Synthesis of Zeolites in The Absence of Organic Structure-Directing Agents

DOI 10.
1515/revce-2013-0020Rev Chem Eng 2014; 30(1): 149
Matthew D. Oleksiak and Jeffrey D. Rimer*
Synthesis of zeolites in the absence of organic

structure-directing agents: factors governing
crystal selection and polymorphism
Abstract: Organic structure-directing agents (OSDAs) Matthew D. Oleksiak: Department of Chemical and Biomolecular
are commonly avoided in commercial zeolite synthesis Engineering, University of Houston, 4800 Calhoun Road, Houston,
TX 77204-4004, USA
because of the economic and environmental disadvantages
associated with the synthesis and removal of organics
occluded within zeolite micropores. Zeolite crystalliza-
tion in OSDA-free media is the route by which microporous 1 Introduction
clays form in nature, and it is also the preferred method
of producing zeolites in bulk for a wide range of applica- Traditional and emerging applications in zeolite science
tions. There are many synthesis parameters that influence have spurred research in the development of novel syn-
zeolite crystallization, among which include the molar thesis methods and rational design approaches to yield
fractions of reagents (silica, alumina, and hydroxide ions), new and/or improved materials for processes that span
water content, temperature, synthesis aging and heating catalysis to medicine. The unique properties of zeolites,
time, the selection of extraframework cations, the choice such as well-defined microporosity and tunable compo-
of silica and alumina sources, and the use of crystal seeds. sition, have contributed to their widespread use as cata-
In this review, we discuss zeolite framework types that lysts, whereas their high surface area and molecular pores
form in OSDA-free solutions at these different synthesis are key factors for their applications in ion-exchange and
conditions in an effort to highlight structure-property rela- selective separations. As heterogeneous catalysts, most
tionships while simultaneously emphasizing the areas of the large-scale commercial processes utilizing zeolites
where further studies are needed to optimize and/or dis- are in petroleum refining and the petrochemical industry
cover new materials. Interestingly, fewer than 15% of the (Martinez and Corma 2011, Zones et al. 2011); however,
total reported zeolite structures have been prepared in there are many emerging fields in catalysis, such as
the absence of OSDAs. For many of these structures, fun- biomass conversion (Huber and Corma 2007, Simonetti
damental mechanisms governing their formation are not and Dumesic 2008, Graca etal. 2009, Mallon etal. 2010,
well understood. In addition, OSDA-free syntheses tend to Roman-Leshkov etal. 2010, Cheng etal. 2012, Zapata etal.
be more susceptible to the formation of crystal polymorphs 2012). Moreover, many areas of zeolite research have been
(or impurities) that can be generated through a series of revitalized by global socioeconomic factors that include
structural transformations during the course of zeolite increased environmental regulations and energy demand,
growth. Here we examine the driving forces for phase tran- which has motivated work on the selective catalytic reduc-
sitions and explore methods to control phase selection and tion of greenhouse gas emissions (Lukyanov et al. 1996,
polymorphism. In order to better facilitate comparisons Long and Yang 2002, Brosius and Martens 2004, Colombo
among zeolite synthesis parameters, we have reinstituted etal. 2010, Kwak etal. 2010, Kim etal. 2013, Wang etal.
the approach of using kinetic phase diagrams to identify 2013), and the impetus use of C1 feedstock (i.e., methane,
conditions of phase stability. syngas, methanol, etc.) for the production of value
added chemicals and fuels, e.g., conversion of methanol
Keywords: crystallization; kinetics; nanomaterials; to olefins or gasoline (MTO or MTG) (Bhawe et al. 2012,
nucleation; Ostwald step rule; polymorphism; structure- Olsbye etal. 2012, Ilias and Bhan 2013).
directing agent; synthesis; thermodynamics; zeolite. Crystal structure, composition, and habit are among
the key characteristics of zeolites that impact their per-
formance in commercial applications. These crystal prop-
*Corresponding author: Jeffrey D. Rimer, Department of Chemical
and Biomolecular Engineering, University of Houston, 4800
erties can often be tailored by the judicious selection of
CalhounRoad, Houston, TX 77204-4004, USA, synthesis parameters and conditions for crystallization.
e-mail: jrimer@central.uh.edu Given the large number of possibilities for parameter
Brought to you by | University of Pittsburgh

Authenticated
Download Date | 1/4/15 8:34 PM
2M.D. Oleksiak and J.D. Rimer: Synthesis of zeolites in the absence of OSDAs
optimization in zeolite crystallization, the influence of any Zeolite Association (IZA) have been prepared in OSDA-
single synthesis parameter on zeolite growth should be free media; and of these zeolites, less than one-third are
considered within the broader context of coupled effects employed in commercial applications. Two factors that
that may occur via simultaneous alteration of multiple hinder more widespread utilization of different zeolite
parameters. It is not uncommon to observe significant framework types for commercial applications is either the
changes in zeolite structure resulting from subtle adjust- difficulty in their preparation or the high cost associated
ments in synthesis temperature, time, composition, or with bulk synthesis. Synthetic routes employing OSDAs
other parameters. This review attempts to quantitatively are impractical as the organics are either commercially
assess the influence of synthesis parameters on zeolite unavailable or expensive to manufacture. Moreover, the
phase(s) in order to better understand, and ultimately occlusion of organics within zeolite pores often requires
define, a parameter space for rational design. Past studies post-synthesis calcination, which eliminates the possi-
have reported the effects of many synthesis parameters on bility for recycling OSDAs; therefore, economic factors
a wide variety of zeolite framework types; however, few predominantly limit their usage in commercial zeolite
studies have systematically investigated the synergistic synthesis. As such, developing OSDA-free methods to
effects of these parameters, and have instead examined produce zeolites with optimal material properties is desir-
changes in zeolite structure or purity by altering only one able. Critical challenges associated with OSDA-free syn-
or at most a few parameters. thesis include the ability to synthesize new structures
There are many parameters that can be varied in with controlled properties, such as composition, size, and
zeolite synthesis, which renders the optimization of mate- morphology, while simultaneously minimizing the forma-
rial properties a challenging task. Pioneering work by tion of unwanted crystal polymorphs (or impurities).
Breck, Flanigen, and others used ternary diagrams of SiO2, In this review, we first discuss the thermodynamic
Al2O3, and M2O fractions (where M is an alkali metal) to and kinetic factors that regulate zeolite crystallization
map regions of zeolite crystallization and phase purity. In and the pathways for polymorph structural transfor-
the last 40 years, this approach has been largely neglected mations. Ternary diagrams are constructed for zeolites
in the published literature. Alternatively, the approach prepared over a range of low, moderate, and high temper-
that has been more commonly used to assess the effects atures. Within the context of these diagrams, we discuss
of synthesis parameters on zeolite crystallization is the the impact of several key synthesis parameters, which
adjustment of molar composition, such as the molar ratios include aging, synthesis time, water content, extraframe-
SiO2:Al2O3:M2O:H2O. This method, however, fails to address work cations, sources of reagents (silica and alumina),
the synergistic effects that cannot be fully captured by and the use of crystal seeds. Collectively, this survey of
changing one mole ratio while holding others fixed. As literature highlights the diverse number of framework
we will discuss, the zeolite crystal phase boundaries can types that can be synthesized in OSDA-free media, while
dramatically change when altering growth conditions. To simultaneously revealing a large knowledge gap in phase
better account for these effects, we have reintroduced the behavior. Developing an improved fundamental under-
concept of ternary plots as kinetic phase diagrams to iden- standing of zeolite crystallization and polymorphism has
tify regions of zeolite crystallization at various reaction the potential to enable rational design of zeolitic mate-
conditions. To this end, we have constructed diagrams rials. Indeed further exploration of the parameter space
using data reported in the literature. Interestingly, we may lead to the identification of synthetic routes capable
observe that many trends in zeolite formation and crystal of producing zeolite structures not yet achieved by OSDA-
phase transformations abide by the often invoked Ostwald free methods.
rule of stages; however, it is also evident that many phe-
nomena cannot easily be described by such correlations.
Likewise, it is apparent that developing an improved fun-
damental understanding of the driving force(s) for zeolite
2 K
inetic and thermodynamic
crystallization and polymorph transformations require factors
detailed knowledge of the thermodynamic and kinetic
factors governing these processes. Developing an improved understanding of zeolite poly-
Herein we focus our discussion on zeolite polymor- morphism in a manner that permits the crystal phase
phism in syntheses that exclude organic structure-direct- purity and properties to be controlled a priori requires
ing agents (OSDAs). Less than 30 of the approximate 200 some knowledge of the interplay between the thermody-
zeolite crystal structures reported by the International namics of formation and the kinetics of crystallization.

Authenticated
M.D. Oleksiak and J.D. Rimer: Synthesis of zeolites in the absence of OSDAs3
Here we discuss the key aspects of both topics prior to framework types is primary attributed to differences in
a detailed description of the parameters that influence enthalpy. Past attempts of correlating the enthalpy of for-
zeolite phase behavior. Prior studies of zeolite thermo- mation with common structural features of the zeolite,
chemistry over a wide range of synthesis conditions such as basic building units or ring structures, have
allows us to make broader generalizations of crystal phase proven to be unsuccessful. An interesting finding by Nav-
transformations, whereby we can describe the overarch- rotsky and coworkers was the positive correlation between
ing trajectory of zeolite structural evolution within the the molar volume (V) of high-silica, anhydrous zeolite
context of the Ostwald rule of stages. Past investigations, frameworks and the heat of formation ( H of , on a TO2
however, reveal that the accuracy required to distinguish basis), which they report as the relative heat of formation
enthalpies of formation among structures of disparate ( H of,zeolite -H f ,quartz ) using a reference value of quartz, the
topology is unattainable by conventional analytical most thermodynamically stable silicate (Navrotsky et al.
tools, thus rendering a full thermodynamic description 2009). As shown in Figure 1, the relative heat of formation
of zeolite phase transitions challenging. Likewise, it is exhibits an approximately linear increase with increas-
apparent that kinetic factors play a key role in many ing molar volume, although fluctuations in data points
phase transformations. There has been significant effort suggest this relationship is not universal for all structures.
to develop rate equations and mechanisms of zeolite For instance, there are cases, such as SiO2 polymorphs,
growth, but most studies focus on only a few crystal where crystals with a higher density than quartz (e.g.,
structures. For the majority of zeolite framework types coesite) exhibit less favorable enthalpies of formation.
discussed in this review, the kinetics of crystal growth This example reveals that the energy of formation does not
is not well established. Although phenomenological rate always scale in a monotonic fashion with molar volume,
expressions can be formulated, the primary obstacle hin- most notably if the energy difference between structures
dering a fundamental description of zeolite crystallization is comparable to the thermal energy (2RT), which spans
is the unknown identity of the growth unit(s). There have 58 kJ/mol for typical zeolite synthesis (i.e., temperatures
been many theories proposed for zeolite nucleation and ranging from 25 to 200C) (Navrotsky etal. 2009). Despite
growth, and a significant body of work in the literature reported anomalies, the correlation in Figure 1 gener-
has identified key constituents in synthesis solutions as ally holds true; zeolite structures with higher framework
being viable growth units; however, there is much more densities (i.e., lower molar volumes) tend to be the most
that must be done to characterize the role and evolution thermodynamically stable. We will refer to this trend in
of aluminosilicate species in synthesis solutions during Section 2.2 to rationalize phase transformations that occur
the course of growth. Coupling this knowledge with what in zeolite synthesis.
we know of the thermodynamics of zeolite formation can The aforementioned studies of anhydrous high-sil-
provide a more complete understanding of phase behav- ica zeolites are not representative of most frameworks
ior and the driving force for structural transformations. formed in organic-free media. Many of the structures we
will discuss in this review have moderate to high alu-
minum content. There are few studies that report H of
2.1 Thermodynamics of zeolite formation
Many factors govern the thermodynamics of zeolite for-

mation. Here we highlight the work of Navrotsky who has 16
investigated the energetics of formation for many zeo-

Htrans (kJ/mol TO2)
12
lites and other oxides using calorimetry. A review article
by Navrotsky and coworkers (2009) provides a thorough 8
discussion of critical parameters influencing the thermo-
298
dynamics of zeolite synthesis, which include framework 4
density, aluminum content, extraframework cations,

0
and hydration all of which are briefly discussed in 32 36 40 44 48
this section. Navrotsky and coworkers reported that the Molar volume (cm3/mol)
entropy of siliceous zeolites is not strongly correlated with
Figure 1Enthalpy of formation for siliceous, anhydrous zeolites
crystal density, which they attribute to similar vibrational as a function of crystal molar volume (reprinted (adapted) from
states of silica and alumina tetrahedral bonds within the Navrotsky etal. 2009, with permission from the copyright holder,
crystal structure. As such, the relative stability of different American Chemical Society).

Authenticated
as a function of aluminum content. Calorimetric meas- enthalpy and unfavorable entropy that collectively tend
urements of anhydrous aluminosilicate framework types to increase the overall thermodynamic stability of zeolites
revealed a linear relationship between H of and alu- (Navrotsky etal. 2009). There are many factors that must
minum content, represented as the molar ratio x=Al/ be considered when assessing the effects of hydration.
(Al+Si), where H of is more negative (i.e., more ther- The pores of high-silica zeolites are more hydrophobic,
modynamically favorable) with increasing Al content whereas the incorporation of aluminum increases frame-
(Navrotsky and Tian 2001). A systematic study of Na-FAU work hydrophilicity (Mallon etal. 2010, Mallon etal. 2011,
performed by Petrovic and Navrotsky (1997) revealed an Xiong etal. 2011, 2012, Copeland etal. 2013). The size of
approximate 70 kJ/mol TO2 difference in H of from one zeolite channels, pores, and cavities can lead to confine-
theoretical limit of zeolite composition (x=0 or SAR=) ment effects, whereas the incorporation of extraframe-
to the other (x=0.5 or SAR=1), where SAR is the silicon- work cations alters water ordering based on both the size
to-aluminum ratio (we use subscripts liq to signify values and charge of the cation. Unlike the systematic trends
of the initial growth solution and s for the solid product). observed in H of with molar volume for all-silica struc-
This analysis included data for Na-forms of MOR, HEU, tures and aluminum content, the energetics of hydration
CHA, and ANA zeolites at different SAR(s). Interestingly, the vary among zeolite frameworks without any obvious trend
grouping of zeolites with similar pore dimension resulted related to the physicochemical properties of the crystal
in energetic trends comparable to glasses, i.e., a similar (Yang and Navrotsky 2000). For a more thorough dis-
change in H of with increasing aluminum content. This cussion of experimental and modeling studies of zeolite
trend was consistent for zeolites with 12-membered ring hydration, we refer the reader to the review by Navrotsky
(MR) pores (FAU and MOR) and a grouping of framework and coworkers (2009).
types with similar density, notably structures with 8-MR In addition to this work, efk and McCormick pro-
(CHA and ANA) and 10-MR (HEU) pores. The parallel trend posed a thermodynamic solution model to predict phase
in H of reported by Navrotsky suggests that the enthalpy transitions between FAU and LTA using the solubility
of Al substitution in anhydrous zeolite frameworks product, s,i, for the condensation of silica and alumina to
(with similar extraframework cations) is approximately produce a zeolite of composition NaAlSinO2n+2, where n is
constant. the silicon-to-aluminum ratio of the crystal (SAR(s)) (efk
Zeolite H of is strongly influenced by the selection and McCormick 1999). Using this model they predicted
of extraframework cations, which are metals employed in regions within a ternary diagram of pure FAU and LTA, as
OSDA-free syntheses to compensate the negative charge well as a binary phase region that was confirmed experi-
of framework aluminum. A majority of zeolites prepared mentally in our previous work (Maldonado et al. 2013).
synthetically contain alkali metals (most commonly Na+, Although the solution model was developed for FAU and
K+, or combinations of both), whereas natural zeolites LTA syntheses, it could be extended to other multiphase
contain both alkali and alkaline earth metals. The ions are zeolite mixtures.
loosely bound to the zeolite structure, which is ideal for
ion-exchange applications that require rapid interchange
of ions (e.g., catalysis, water purification, softening, etc.). 2.2 Phase transformations: Ostwald rule
Calorimetric studies of M-FAU zeolites reveal the following ofstages
trend in enthalpy from least negative (less stable) to most
negative (more stable) values: M=Ca2+<Li+<Na+<K+<Rb+ Crystallization often proceeds in stages according to the
Cs+ (Navrotsky etal. 2009). Calorimetric data for dense Ostwald step rule (or Ostwald rule of stages), which is
glasses (Roy and Navrotsky 1984, Navrotsky et al. 2009) commonly invoked to describe nucleation and polymor-
and additional zeolite framework types, such as HEU and phism in natural and synthetic crystallization (Navrotsky
MOR (Navrotsky and Tian 2001), are consistent with this 2004). The fundamental premise of the Ostwald step rule
trend. It is evident that the selection of extraframework is the evolution of structure with time, beginning with the
cations also plays a role in the type of structures that initial formation of a metastable phase that transforms
can form in OSDA-free media (see Section 3.4 for further through a series of stages along a trajectory that leads to
details). In addition, hydration also influences the ther- more thermodynamically stable structures. The progres-
modynamics of formation. The aforementioned calorim- sion of stages can be distinct, but oftentimes the steps are
etry studies by Navrotsky were performed with anhydrous progressive and less evident (e.g., amorphous-to-crystal-
zeolites, but in hydrothermal synthesis the energet- line transitions). Zeolite crystals are metastable relative
ics of hydration reflects a balance between a favorable to tectosilicate minerals, such as quartz (Navrotsky etal.

Authenticated
2009). The enthalpies of formation for siliceous zeolites There are several factors that potentially contribute to
fall within a narrow range (6.814.4 kJ/mol above quartz), the initial formation of metastable species. Navrotsky sug-
which may explain why kinetic factors play such a signifi- gested that a general correlation exists between increas-
cant role in the structures formed during zeolite crystal- ing metastability and decreasing surface energy, which
lization. The effects of heteroatoms (e.g., Al, P, Ge, etc.), is valid for numerous systems (e.g., TiO2, Al2O3, ZrO2, and
extraframework cations, and hydration are additional SiO2). It was reported that the order of increasing metasta-
factors that contribute to the stability of zeolite structures. bility often correlates to decreasing density of the phase.
Quantitative data for H of as a function of these vari- Calorimetry studies have shown that amorphous phases
ables is not available for most zeolite structures. To this tend to exhibit significantly lower surface enthalpies than
end, a critical challenge for predicting polymorphism a more dense crystalline counterparts. Another factor that
priori is the ability to link the effects of synthesis condi- may contribute to the initial formation of a metastable
tions (e.g., solution composition, pH, water content, ions, phase is a structural similarity with its precursor phase.
temperature, etc.) to the kinetics and thermodynamics of A prevailing theory in zeolite synthesis is that the crystal
crystallization. nucleates from a gel solution that contains one or more
The first structure that forms in zeolite synthesis is basic building units in common with the zeolite frame-
one of any available metastable phases, often an amor- work type. Examples include aluminosilicate (or silicate)
phous or partially disordered phase (Navrotsky 2004). rings, polyhedral cages, and oligomers. For a detailed
For instance, processes in biomineralization generally description of zeolite building units, see the review by
involve the initial formation of an amorphous precursor, Smith (1988). Hypotheses regarding the role of building
e.g., the amorphous calcium carbonate (ACC) precur- units in zeolite crystallization tend to be speculative in
sor phase in nacre (Addadi etal. 2006, Amos etal. 2007, nature as in situ validation of the aluminosilicate species
Gower 2008). Similar mechanisms have been proposed in precursor solutions is challenging to experimentally
for calcium phosphate in bone formation (Termine and measure. For a comprehensive discussion of the proposed
Posner 1966, Posner 1969) and biogenic iron oxide crys- mechanisms of zeolite nucleation and growth, see the
tallization (Lowenstam 1962, Gower 2008). It has been review by Cundy and Cox (2005).
suggested that protein crystallization (e.g., lysozyme Rationalizing zeolite phase selection based solely on
and hemoglobin S) (Vekilov 2004, 2005, Filobelo et al. thermodynamic differences between structures requires
2005, Kashchiev et al. 2005, Pan et al. 2005) occurs via a discerning ability to experimentally measure molar
a multistep pathway involving an initial liquid-liquid enthalpies of formation with accuracies <1 kJ/mol. For
phase separation followed by nucleation within dense instance, in situ calorimetric studies of zeolite crystalliza-
disordered liquid droplets. The physicochemical factors tion (Liu and Narvotsky 2007) revealed no detectable calo-
governing zeolite nucleation from initial metastable rimetric signal during the phase transformation from LTA
phases are not fully understood. Crystal growth seem- (an initial metastable structure) to SOD zeolite. This obser-
ingly occurs by non-classical routes (De Yoreo 2013) that vation by Liu and Navrotsky was attributed to a small dif-
involve the initial formation of precursors (or clusters) of ference in H of between the two structures that is below
aluminosilicate species. Amorphous precursors are ubiq- the detectable limit of the calorimeter. Their result was
uitous in zeolite synthesis. The most widely studied case unexpected given the relatively large disparity in molar
is silicalite-1 (MFI type) nucleation from solutions using volume (6.3 cm3/mol) between LTA and SOD. Many of
tetraethylorthosilicate (TEOS) as a silica source. In these the transformations that will be discussed in this review
systems, spontaneous formation of disordered nanoparti- are far more challenging to explain based on changes
cles (16 nm) (Dokter etal. 1995, Schoeman 1997, Watson in molar volume. It is feasible that subtle differences in
et al. 1997, de Moor et al. 1999, Ravishankar et al. 1999, chemical composition, such as SAR(s), may explain why
Knight and Kinrade 2002, Kragten etal. 2003, Ramanan certain structures are thermodynamically preferred over
etal. 2004, Fedeyko etal. 2005) is followed by a disorder- others, but without experimental validation, such claims
to-order transition (Rimer et al. 2005, Davis et al. 2006) are difficult to confirm. As such, it is our viewpoint that
during solution aging and/or hydrothermal treatment. the Ostwald step rule should be considered as a general
Moreover, amorphous or highly disordered intermediates guideline that establishes the long-term trajectory of
are common in the synthesis of other zeolites and ceram- zeolite transformations from less stable frameworks to
ics, which are typically prepared from amorphous colloi- more stable ones. A full explanation for the exact pathway
dal silicate reagents (Engelhardt etal. 1982, Maniar etal. taken from an initial to final stage that includes all inter-
1990, Navrotsky 2004). mediate metastable structures requires a fundamental

Authenticated
understanding of the kinetics of crystallization. It is rea- depleted by the growing crystals [where n1 in Eq. (1)].
sonable to assume that the rate determining step of a struc- A potential explanation for this phenomenon in zeolite
tural transition is the energetics that dictates the relative growth may be derived from the fact that their growth
rates and timescales of crystal formation, dissolution, and solutions contain three broadly defined phases, which
recrystallization (Engelhardt etal. 1982). In circumstances are solid crystals, soluble species (e.g., monomers and
where the H of values are similar for multiple structures, small oligomers), and amorphous particles. The latter
it is feasible that kinetic factors play a dominant role in refer to aluminosilicate gels (>5 m in dimension) attrib-
zeolite phase selection. uted to undissolved silica reagent (e.g., colloidal or fumed
silica) (Maldonado etal. 2013), or self-assembled nanopar-
ticles (<5m in dimension) that have been identified and
extensively characterized in TEOS-based zeolite synthesis
2.3 Kinetics of zeolite crystallization
(Fedeyko etal. 2004, Rimer etal. 2005). The C variable in
Eq. (1) can be attributed to the concentration(s) of growth
The mechanism and kinetic rates of classical crystalliza-
units that directly attach to the surface of growing zeolite
tion are generally characterized by three theories (Mullin
crystals. This has been a subject of much debate, and a
1972). The phenomenological surface energy theories
variety of theories have been proposed for the mechanism
proposed by Gibbs, Curie, Wulff, and others are often
of zeolite crystal growth (Cundy and Cox 2005). Here we
invoked to predict thermodynamic morphology and sizes
will not recount the details reported in past papers and
of crystals (Wells 1946, Buckley 1951, Constable 1968). The
reviews on this subject, but only point out that hypotheses
adsorption layer theories of Gibbs-Volmer, Kossel, and Bur-
differ with respect to the mechanism of zeolite nucleation
ton-Cabrera-Frank postulated that crystals grow through
(homogeneous or heterogeneous) as well as the nature of
the nucleation and spreading of layers (Read 1953). The
the growth unit. Past studies have predominantly focused
generic rate expression derived for these models is similar
on select framework types, most notably MFI (with OSDA),
to the third approach, diffusion-reaction theory models,
LTA, and FAU. The growth units that have been proposed
which are typically used to characterize bulk crystalliza-
for these structures include (but are not limited to) soluble
tion in industrial-scale processes. The general form of the
oligomers (primary units), n-membered rings (secondary
rate expression for the adsorption layer and diffusion-
units), ternary building units of each framework type
reaction models is
(e.g., sod and lta cages), and amorphous or quasi-ordered
dm nanoparticles (Fan etal. 2007, Maldonado etal. 2013). It is
r= = k ( C ) n (1)
dt reasonable to suggest that the apparent zero-order reac-
tion rates are due to a constant concentration of growth
where r is the rate of reaction (alternatively written as unit(s) maintained during the course of zeolite crystalliza-
dm/dt to represent the change in aqueous solute mass tion (i.e., constant value of (C)n where n0). It is possible
with time), k is the rate constant (or overall mass transfer that this condition is facilitated by amorphous particles
coefficient for diffusion-reaction models, KGA), C is the or gels, which are present throughout crystallization and
relative supersaturation (i.e., difference in concentration likely serve as sources of nutrient that replenish growth
between aqueous solute and its thermodynamic solubil- units as they are consumed during crystallization. For
ity), and n is the order or reaction. Characteristic values of details of proposed mechanisms, we recommend the
n for organic salts crystallizing in aqueous solution range review by Cundy and Cox (2005) or the recent review
from 1.5 to 2. Interestingly, zeolites reportedly crystal- by Valtchev and Tosheva (2013) focusing on nanoscale
lize by a zero-order reaction, independent of solute (i.e., microporous materials.
silica or alumina) concentration. Reaction rate analyses of One aspect that must be considered when analyzing
several zeolites, including MFI and FAU, have revealed a different zeolite polymorphs is that a direct comparison of
linear growth rate during crystallization in supersaturated rate equations for each structure first requires knowledge
solutions (Zhdanov 1971, Zhdanov and Samulevich 1980). of which growth unit(s) participates in the crystallization
Detailed kinetic studies are reported by Suboti, Cundy, of each framework type, and secondly how the growth
and others (Feoktistova and Zhdanov 1989, Cundy et al. unit concentrations change in time with varying synthe-
1990, Bosnar and Suboti 1999, Bosnar et al. 2004). To sis compositions and conditions. It is not fully understood
our knowledge, few examples of linear crystal growth are why certain zeolite framework types are preferred over
reported in the literature. It is more common to observe others at different growth conditions. Similarity in the
a gradually decreasing growth rate with time as solute is thermodynamics of zeolite structures is one of the reasons

Authenticated
why OSDAs are often used to promote the formation of a the effects of synthesis parameters, drawing upon avail-
desired framework type and minimize the formation of able information in the literature to define and character-
unwanted polymorphs. We know of at least 30 frameworks ize zeolite phase behavior.
that can be formed in the absence of an OSDA; however,
the quantitative analysis of their kinetic rates of growth
and dissolution are lacking, which renders a priori predic-
tion of phase transformations a challenging task. As such,
3 I nfluence of synthesis parameters
there is very little information in the literature that suffi- on zeolite phase behavior
ciently elucidates what mechanistically triggers the onset
of structural transformations and the factors most critical At the time this review was written the IZA assigned 213
in determining the trajectory of different framework types framework type codes corresponding to unique zeolite
formed over the course of a zeolite synthesis. The prefer- structures (www.iza-online.org), though considerably
ential formation of structures in OSDA-free media can be fewer (ca. 30) have been synthesized in the absence of
attributed to a myriad of empirical factors, such as water OSDAs, as shown in Table 1. Syntheses in OSDA-free media
content, temperature, molar composition, and extra- have been reported using various techniques. The most
framework cations. In the following sections, we discuss common method, conventional hydrothermal treatment,
Table 1Structural information of zeolite framework types.
Framework Unit cell (nm) Space Rings Building unit(s) Pores Molar volume
group (cm3/mol)
a b c
EMT 1.72 1.72 2.81 P63/mmc 12, 6, 4 d6R, sod 3D 45.3

FAUa 2.44 2.44 2.44 Fd-3m 12, 6, 4 d6R, sod 3D 45.3
LTA 1.19 1.19 1.19 Pm-3m 8, 6, 4 d4R, sod, lta 3D 42.4
RHOa 1.49 1.49 1.49 Im-3m 8, 6, 4 d8R, lta 3D 41.5
BPH 1.31 1.31 1.30 P-62m 12, 8, 6, 4 afs, bph 3D 41.2
CHAa 1.37 1.37 1.48 R-3m 8, 6, 4 d6R, cha 3D 39.9
GMEa 1.37 1.37 0.99 P63/mmc 12, 8, 6, 4 d6R, gme, dcc 3D 39.9
BEAa 1.26 1.26 2.62 P4122 12, 6, 5, 4 mor, bea, mtw 3D 39.4
PAUa 3.48 3.48 3.48 Im-3m 8, 6, 4 d6R, pau, lta, gis 3D 37.9
ERIa 1.31 1.31 1.52 P63/mmc 8, 6, 4 d6R, can 3D 37.4
OFFa 1.31 1.31 0.76 P-6m2 12, 8, 6, 4 d6R, can, gme, dsc 1D 37.4
EDIa 0.69 0.69 0.64 P-4m2 8, 4 nat 3D 36.9
GISa 0.98 0.98 1.02 I41/amd 8, 4 gis, dcc 3D 36.7
PHIa 0.99 1.41 1.41 Cmcm 8, 4 dcc 3D 36.7
MERa 1.40 1.40 1.00 I4/mmm 8, 4 d8R, pau, dcc 3D 36.7
SODa 0.90 0.90 0.90 Im-3m 6, 4 sod 0D 36.1
LTLa 1.81 1.81 0.76 P6/mmm 12, 8, 6, 4 d6R, can, ltl, dsc 1D 36.1
MAZa 1.81 1.81 0.76 P63/mmc 12, 8, 6, 5, 4 gme, dsc 1D 36.1
EONa 0.76 1.82 2.59 Pmmn 12, 8, 6, 5, 4 mor, gme, dsc 2D 35.8
CANa 1.25 1.25 0.53 P63/mmc 12, 6, 4 can, dzc 1D 35.6
LTN 3.56 3.56 3.56 Fd-3m 8,6,4 d6R, can, sod, lta 0D 35.4
MORa 1.83 2.05 0.75 Cmcm 12, 8, 5, 4 mor 1D 35.4
MEL 2.03 2.03 1.35 I-4m2 10, 8, 6, 5, 4 mor, mel, mfi 3D 34.6
FERa 1.90 1.43 0.75 Immm 10, 8, 6, 5 fer 2D 34.2
ABW 0.99 0.53 0.88 Imma 8, 6, 4 abw, dzc 1D 34.2
YUG 1.02 1.38 0.68 C2/m 8, 5, 4 2D 33.5
TON 1.41 1.78 0.53 Cmcm 10, 6, 5 jbw, mtt, bik, ton 1D 33.3
MTW 2.56 0.53 1.21 C2/m 12, 6, 5, 4 jbw, cas, bik, mtw 1D 33.1
MFIa 2.01 1.97 1.31 Pnma 10, 6, 5, 4 mor, cas, mel, mfi 3D 32.7
LTJ 0.93 0.93 1.01 P41212 8, 6, 4 2D 32.6
JBW 0.53 0.75 0.82 Pmma 8, 6, 4 jbw, abw, dzc 1D 32.0
ANAa 1.36 1.36 1.36 Ia-3d 8, 6, 4 3D 31.4
Data were obtained from the IZA Online Structure Database.

Natural zeolites of this framework type have been found.
a

Authenticated
involves the initial creation of a solution or sol gel, fol- Herein, we focus on conventional syntheses where
lowed by stirring at room temperature (or slightly elevated the most critical parameters influencing zeolite phase
temperatures) via a process referred to as aging. Hydro- behavior include aging, crystallization time and tempera-
thermal synthesis typically occurs in high temperature ture, sources of silica and alumina, water content, and the
aqueous solutions at autogenous pressures, which require extraframework cation. In the following sections we will
the use of autoclaves to achieve these conditions. Miner- discuss these parameters individually, bearing in mind
alizing agents employed in these syntheses can be either that their effects on zeolite polymorphism are intercon-
hydroxide or fluoride ions. The latter, although reported nected and should be considered collectively. Pioneering
in some OSDA-free syntheses (Egeblad etal. 2007), is less studies by Breck and Flanigen (1968) identified numer-
common. As such, this review focuses entirely on zeolite ous zeolite polymorphs derived from OSDA-free solutions;
synthesis in nonfluoride basic solutions. Zeolite crystalli- however, their presentation of results makes it difficult
zation can occur over a range of temperatures (60450C) to extract the exact compositions and conditions used to
and synthesis times spanning hours to months. Noncon- achieve these structures. For instance, Breck and Flani-
ventional techniques have been reported, which include gen were among the first to use ternary phase diagrams
solvothermal syntheses (i.e., nonaqueous solvents) to illustrate regions of pure zeolite phase formation.
(Burton etal. 1999, Parnham and Morris 2007) and staged These diagrams as well as the majority of ternary plots
syntheses where the growth solution is heated at differ- reported by other groups thereafter refer to the approxi-
ent temperatures over multiple time intervals (Polak etal. mate regions where different framework types are synthe-
1979, Huang etal. 2010). Moreover, studies have utilized sized based on the molar fractions of SiO2, Al2O3, and Na2O
conventional synthesis conditions in combination with in their synthesis solutions. Interestingly, many of these
the use of substrates (e.g., membrane preparation) (Zhu studies report estimated regions on ternary diagrams
et al. 2008), confined spaces (Yoo et al. 2008), microre- without using numerical axes, rather than listing data
actors (Ju et al. 2006, Pan et al. 2009), and micrograv- points with well-defined molar fractions. Here we report
ity (Sand et al. 1987, Direnzo et al. 1994). More recently, two adapted phase diagrams from the original work of
research efforts have employed microwave heating tech- Breck and Flanigen (see Figure 2) where we estimate the
niques (Li etal. 2006, Zhou etal. 2009), which are sum- placement of phase regions by assigning them numerical
marized in the review by Tompsett et al. (2006). One values based on their spatial location within the original
technique that differs significantly from the others is syn- ternary diagrams, which lacked numerical values. We also
thesis from a gel that has been dried prior to crystalliza- rescaled the diagrams according to molar fractions of Si,
tion, which effectively removes most of the solvent from Al, and NaOH. The two diagrams presented here illustrate
the system (Hu etal. 2008). the disparity in phase behavior according to the selection
A B
Figure 2Ternary phase diagrams adapted from Breck and Flanigen (1968) showing approximate boundaries for zeolite crystals prepared
at 100C with 9098% water and the following silica sources: (A) sodium silicate and (B) colloidal silica. FAU and LTA types form with both
silica sources; sodium silicate promotes SOD and GIS formation; and colloidal silica leads to the formation of GME and CHA. The original
diagrams were plotted with Na2O mole fractions and did not contain numerical axes. Here we estimate the location of each phase based on
their spatial locations within the original ternary diagrams (these phase boundaries should be considered approximate).

Authenticated
of two different silica sources. Syntheses with sodium sili- and the times for aging and crystallization. In many cases,
cate are shown in Figure 2A, whereas those with colloidal temperature and time have similar effects on the formation
silica are shown in Figure 2B. In general, the formation of metastable structures. For instance, crystals that form
of LTA is relatively unchanged by the silica source. The at higher temperature tend to require less time whereas
FAU region is shifted to lower alkalinity (i.e., higher Si/OH the same crystal may be prepared at lower temperatures,
ratios) in Figure 2B. The presence of SOD is noted in Figure but at much longer synthesis time. Such general trends
2A, although it is not entirely clear if the corresponding are difficult to define for all zeolite framework types as
low silica region was analyzed in Figure 2B for syntheses the thermal energy in high-temperature syntheses (ca.
employing colloidal silica. The most notable differences T>150C) may facilitate certain trajectories in structural
between the two ternary diagrams are the lower alkalin- transformations that otherwise would be unattainable
ity regions where sodium silicate promotes the formation at lower temperatures because of kinetic activation bar-
of GIS and colloidal silica promotes the formation of CHA riers. Additionally, aging of the synthesis solution prior
and GME. to heating can affect both the phase and the size of the
Ternary diagrams are an effective and simple plat- crystals formed, keeping in mind that low temperatures
form for visualizing the effects of solution composition on promote nucleation whereas higher temperatures favor
zeolite phase behavior. Literature published since 1990 growth (de Moor et al. 1997, Koroglu et al. 2002, Ogura
rarely presents synthetic conditions within the context et al. 2003). Here we discuss the effects of these three
of ternary diagrams. More recent studies examine the parameters.
effects of solution compositions and conditions on zeolite
crystallization by altering only one or two parameters at
any given time. As we will discuss, such approaches fail 3.1.1 Influence of synthesis temperature
to consider the synergistic effects of multiple parameters.
To this end, we gathered synthesis parameters reported Zeolite syntheses have been reported over a broad range
in the literature in order to collectively plot the data in of temperatures that vary from room temperature (ca.
ternary diagrams to more inclusively identify regions 25C) to 500C and even higher values for solid-state
where different framework types are formed. The data synthesis (i.e., nearly anhydrous). One of the earliest
presented in Figure 2 clearly show that changes in SAR(liq) investigations of temperature effects came from Barrer
dramatically alter the phase space. Likewise, syntheses and White (1952) in which they reported zeolite struc-
at similar SAR(liq) but different alkalinity can result in tures synthesized from 150 to 450C. In these studies, the
different phases. In the remaining sections, we attempt growth solutions were initially evaporated at tempera-
to summarize the existing body of literature within the tures up to 120C, which generated various compositions
context of ternary phase diagrams. This task is quite of unknown water content. Their thorough exploration of
challenging as many studies often use similar synthesis synthesis temperatures revealed the formation of several
conditions; thus, the vast majority of data points overlap zeolites and dense phases, including (but not limited) to
within the phase diagram. This makes it challenging to ANA, MOR, JBW, and CAN types. These studies revealed
define exact boundaries separating phase-pure regions various stages of crystallization, which in some cases
within each diagram. As such, boundaries defined in this included the formation of condensed aluminosilicates,
review should be considered as approximations since the such as albite. Much of the early literature, including
number of data points needed to properly map spatial Barrers work, excludes information on the exact water
regions for different framework types within the ternary content of the growth solutions, which prevents rigorous
diagrams is generally lacking. For some structures, such quantitative analysis of the synthesis conditions for these
as FAU and LTA, these regions are well established, studies.
whereas for others the phase space is unexplored and We have developed ternary diagrams to effectively
insufficient to define regions of stability. display zeolite phases formed at various temperatures.
We subdivided these diagrams based on an arbitrary
selection of low, medium, and high synthesis tempera-
3.1 E
ffects of temperature, aging, and tures. Figure3 shows syntheses at <100C (low tempera-
synthesis time tures); Figure 4 shows syntheses between 100C and
150C (moderate temperatures); and Figure 5 shows prod-
The rates of zeolite nucleation and growth are heavily ucts at temperatures greater than or equal to 150C (high
dependent upon the selection of synthesis temperature temperatures). Here we begin by focusing on syntheses

Authenticated
Figure 3Ternary phase diagram of zeolites formed at temperatures <100C. The cations and three-letter codes for each structure are
labeled (symbols). The lower axis is the total mole fraction of hydroxide (MOH for monovalent cations and M(OH)2 for divalent cations).
Numbers correspond to the listed references, and details of the exact synthesis compositions are provided in Table 2 (note that water con-
tents and synthesis times vary among data).
at low temperatures, which have yielded 13 framework details of EMT synthesis are provided in Section 3.2. One
types: ABW, BPH, EDI, EMT, FAU, LTA, LTN, MFI, MOR, of the questions regarding EMT and FAU formation per-
RHO, and SOD. Details of each synthesis condition identi- tains to the driving force for formation given that these
fied by the points in the phase diagram and similar con- two structures have identical molar volume, which would
ditions omitted from Figure 3 for clarity can be found in suggest that they exhibit similar thermodynamic stabil-
Table 2. Pure and multiphase zeolite structures are formed ity. Interestingly, syntheses in Li+-containing solutions
in distinct regions of the phase diagram based on their Si, promotes a mixture of FAU and EMT, which is commonly
Al, and MOH mole fractions, where M refers to the extra- known as ZSM-2. It is reported that ZSM-2 can remain
framework cation (e.g., M+=Na+, K+, Li+, etc.). The low stable in growth solutions even after periods of 2months
temperature diagram clearly shows that FAU is formed at (Ciric 1968b).
higher alkalinity (i.e., Si/OH<1) and in Si-rich solutions The zeolite structures in Figure 3 are influenced by
(SAR(liq)>1), whereas Al-rich growth solutions (SAR(liq)<1) the selection of the extraframework cation. If we examine
favor the formation of LTA. Within the region of FAU for- the phase boundary between FAU and LTA prepared in
mation, it has been shown by Mintova and coworkers that the presence of Na+, which is located approximately along
EMT is formed within days at 30C (Ng et al. 2012a). At the line of SAR(liq) =1, the substitution of Na+ with Li+ leads
longer times, however, EMT can transform into either FAU to the formation of EDI and mixtures of EDI and ABW.
or SOD (Ng et al. 2012a,b, Maldonado et al. 2013). More Similar growth solution compositions using K+ also favor

Authenticated
Figure 4Ternary phase diagram of zeolites formed at moderate temperature (100150C). The cations and three-letter codes for each
structure are labeled (symbols) and numbers correspond to the listed references. The plots were arbitrarily divided into (A) and (B) to
minimize overlapping data points (for improved visual clarity). Details of the exact synthesis compositions are provided in Table 3 (note that
water contents and synthesis times vary among data).
EDI formation, with the potential to yield binary mixtures degrades via a solid-state transition at temperatures near
of EDI and CHA. It is reported that growth solutions with 160C (Andries etal. 1991, Vaughan 1995). It is critical to
mixtures of Na+ and K+ promote the formation of low-sil- note that structures with such limited thermal stability
ica zeolite X (LSX), which is a FAU framework type with benefit from OSDA-free syntheses as post-synthesis calci-
SAR(s) =1, and inhibit LTA impurity (Iwama et al. 2010). nation to remove the OSDA could easily reduce the percent
Interestingly, the use of K+ does not yield LTA or ABW. The crystallinity or compromise its structural integrity.
former grows in solutions of Na+, whereas the latter forms Another zeolite framework that is scarcely reported
in the presence of Li+. Syntheses utilizing K+ can also yield in the literature using OSDA-free conditions is LTN (also
pure CHA, though the reported conditions appear to be at referred to as Z-21 or Na-V). This crystal structure has been
lower alkalinity and higher silica content than those used formed at short synthesis times (e.g., crystallization for 1h
for EDI (see Table 2). In contrast, BPH-type zeolite forms in at 95C) and in the low silica region of the phase diagram,
K+ solutions that are rich in aluminum content (i.e., lower similar to that of BPH (Duecker et al. 1971). Our discus-
baseline of the ternary diagram). Studies of the alumino- sion thus far has focused on zeolites formed under highly
silicate BPH (zeolite Linde Q) have been limited, which alkaline conditions, which corresponds to the lower left
is likely attributed to the fact that its crystal structure corner of the ternary phase diagram (i.e., Si/OH<1). If we

Authenticated
Figure 5Ternary phase diagram of zeolites formed at temperatures greater than 150C. The lower axis is the total mole fraction of
hydroxide (MOH for monovalent cations and M(OH)2 for divalent cations). The cations and three-letter codes for each structure are labeled
(symbols) and numbers correspond to the listed references. Details of the exact synthesis compositions are provided in Table 4 (note that
water contents and synthesis times vary among data).
trace the FAU phase region along lines of constant SAR(liq), conditions for each data point in Figure 4 and other select
we find that an entirely different set of framework types studies are available in Table 3. The total number of data
form in solutions with lower alkalinity (i.e., top portion of points collected from our literature review far exceeds
the diagram where Si/OH>1). In this region, growth con- those presented in the ternary diagrams as papers com-
ditions at lower temperature favor the formation of CHA, monly repeat synthesis procedures reported in earlier
MFI, MOR, and RHO framework types. Of these struc- bodies of work; therefore, the same set of conditions for
tures, RHO has been formed with mixtures of Na+ and Cs+, zeolite structures are often reproduced without attempt-
whereas pure CHA is reported using either a mixture of Na+ ing to explore alternative compositions. At moderate
and Cs+ or only K+. The formation of MFI and MOR in Na+ temperatures, most of the reported zeolites are synthe-
systems almost always occurs at higher silica concentra- sized within limited regions of the phase diagram, with
tion, lower alkalinity, and markedly higher water content the exception of GIS, which crystallizes at a wide range of
than the structures formed in the high alkalinity region SAR(liq) values. Moreover, there are many instances where
(see Table 2 for a comparison of synthesis conditions). The differences in the synthesis time, water content, and selec-
effect of water content will be discussed in Section 3.2, tion of extraframework cations renders it challenging
and a more detailed discussion of extraframework cations to compare the phase behavior of zeolite structures. For
is provided in Section 3.4. example, FAU undergoes a phase transformation to GIS
The moderate temperature range that we character- at moderate temperatures. As such, the presence of FAU
ized as 100150C is one of the most commonly employed (Figure 4B) in regions where GIS is expected (Figure 4A)
in OSDA-free zeolite synthesis. There are approximately could be explained by a shorter synthesis time, lower tem-
26 framework types reported within this range of temperature, or adjustments in water content. The region in
peratures, which include ABW, ANA, BPH, CAN, CHA, which FAU forms at moderate temperatures is similar to
EDI, EON, ERI, FAU, FER, GIS, GME, KFI, LTA, LTJ, LTL, those presented at lower temperatures (Figure 3), with a
LTN, MAZ, MEL, MER, MFI, MOR, OFF, PHI, RHO, and slight shift to less alkaline conditions. Additionally, the
SOD. Because of the large number of data points in the LTA-to-SOD phase transformation is often incomplete
literature, we have split the phase diagram into two sepa- depending on the selection of synthesis parameters.
rate ternary plots Figure 4A and 4B where data were Higher alkalinity tends to favor SOD formation or binary
randomly partitioned between the figures for easier visu- mixtures of LTA and SOD, whereas higher water content
alization. Detailed information regarding the synthesis results in pure LTA.

Authenticated
Table 2Compositions of points for Figure 3 and similar conditions (omitted from the figure for clarity) crystallized at temperatures <100C given in molar ratios of x Si:y Al:10
[MOH+M(OH)2]:z H2O.
References Molar ratio Mole fraction Temperature (C)c Time (h)d Phasee Cation
x Sia y Alb z H2O Si Al M++M2+
Valtchev and Bozhilov (2004) 1.25f 0.50 245 0.11 0.04 0.85 25 336408d FAU Na+
Ng etal. (2012a) 1.43f 0.57 92 0.12 0.05 0.83 30 36d EMT Na+
Ng etal. (2012a) 1.25f 0.50 165 0.11 0.04 0.85 30 36 EMT, FAU Na+
Ng etal. (2012a) 1.25f 0.50 165 0.11 0.04 0.85 30 50 FAU Na+
Milton (1959) 6.94 0.69 80 0.39 0.04 0.57 50 264 FAU Na+
Ciric (1968b) 10.00g 5.00g 1954 0.40 0.20 0.40 55c 1392 EMT, FAU Li+
Ciric (1968b) 10.00g 3.33g 2556 0.43 0.14 0.43 55c 1392 EMT, FAU Li+
Buhl etal. (2011)h 0.50f 0.75 55 0.04 0.07 0.89 60c 196i SOD Na+
Milton (1959) 3.85f 2.56 200 0.23 0.16 0.61 60 63 FAU Na+
Matsumoto etal. (2006) 2.00j 2.00j 270 0.14 0.14 0.71 60 24 EDI Li+
Ciric (1968a) 4.90f 0.60 130 0.32 0.04 0.65 60 120 EMT, FAU 64% Na+, 36% Li+
Andries etal. (1991) 0.52f 2.76 333 0.04 0.21 0.75 64c 1464 BPH K+
Maldonado etal. (2013) 0.54 0.55 60 0.05 0.05 0.90 65 168d SOD Na+
Authenticated

Maldonado etal. (2013) 0.55 1.09 173 0.05 0.09 0.86 65 168d FAU Na+
Maldonado etal. (2013) 0.79 0.72 173 0.07 0.06 0.87 65 168d LTA Na+

Maldonado etal. (2013) 1.82 0.45 173 0.15 0.04 0.81 65 168d FAU, LTA Na+
(Table 2Continued)
Machado etal. (1999) 26.32 2.92 469 0.67 0.07 0.25 65 48 MOR Na+
Machado etal. (1999) 50.00 5.56 895 0.76 0.08 0.15 65 24 MFI Na+
Machado etal. (1999) 50.00 2.50 895 0.80 0.04 0.16 65 48 Amorphous Na+
Machado etal. (1999) 50.00 5.56 895 0.76 0.08 0.15 65 72 MFI, MOR Na+
Machado etal. (1999) 62.50 6.94 1120 0.79 0.09 0.13 65 48 Amorphous Na+
Barrer etal. (1974) 25.02m 12.51m 1830 0.53 0.26 0.21 80 168 EDI Tl+
Wenqin etal. (1986) 0.45 0.18k 86 0.04 0.02 0.94 80 5 FAU, LTA, SOD Na+
Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 1 LTA Na+
Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 6 LTA, (FAU), (SOD) Na+
Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 9 LTA, (FAU), (SOD) Na+
Authenticated
Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 20 FAU, SOD, (LTA) Na+
Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 24 SOD, (FAU), (LTA) Na+

Wenqin etal. (1986) 0.50 0.20k 95 0.05 0.02 0.93 80 72 SOD, (FAU), (LTA) Na+
Wenqin etal. (1986) 0.50 0.20l 95 0.05 0.02 0.93 80 120 SOD, (FAU), (LTA) Na+

Wenqin etal. (1986) 0.50 0.20l 95 0.05 0.02 0.93 80 168 SOD Na+
Wenqin etal. (1986) 0.63 0.25k 120 0.06 0.02 0.92 80 5 FAU, LTA Na+
Ren etal. (2011) 2.56l 2.56 123 0.17 0.17 0.66 80 3d LTA Na+
Wenqin etal. (1986) 0.83 0.33k 162 0.07 0.03 0.90 80 5 FAU, LTA Na+
Barrer and Mainwaring (1972) 8.08m 4.04m 556 0.37 0.18 0.45 80 96 CHA K+
(Table 2Continued)
Barrer and Mainwaring (1972) 8.08m 4.04m 556 0.37 0.18 0.45 80 96 CHA, LTL 50% Ba2+, 50% K+
Barrer and Mainwaring (1972) 4.04m 4.04m 556 0.22 0.22 0.55 80 96 LTL 20% Ba2+, 80% K+
Warzywoda and Thompson (1991) 1.34n 1.99l 213 0.10 0.15 0.75 86 o CHA, EDI K+
Warzywoda and Thompson (1991) 1.34n 1.99l 213 0.10 0.15 0.75 86 o CHA, EDI 20% Na+, 80% K+
Radulovic et al. (2010) 2.44f 2.71p 106 0.16 0.18 0.66 90 4.5 LTA Na+
Itani et al. (2009) 0.83p 0.84 120 0.07 0.07 0.86 90 2d LTA Na+
Radulovic etal. (2010) 2.44f 2.71p 139 0.16 0.18 0.66 90 4.5 LTA Na+
Radulovic etal. (2010) 2.44f 2.71p 152 0.16 0.18 0.66 90 2.5 LTA Na+
Authenticated
Matsumoto etal. (2006) 3.33j 3.33j 453 0.20 0.20 0.60 90 24 ABW, EDI Li+

Matsumoto etal. (2006) 4.00j 4.00j 545 0.22 0.22 0.56 90 24 ABW, EDI Li+

Mackinnon etal. (2006) 4.35r 4.35r 17 0.23 0.23 0.53 90c 12 EDI K+
Barrer etal. (1980) 14.71 2.94q 157 0.53 0.11 0.36 90 14d ANA, CHA, FAU, LTA, RHO 96% Na+, 4% Cs+
Robson (1975) 15.15 3.03p 165 0.54 0.11 0.35 90 72d RHO 91% Na+, 9% Cs+
Barrer etal. (1980) 11.47 2.94q 157 0.47 0.12 0.41 90 3d ANA, CHA, RHO 88% Na+, 12% Cs+
Barrer etal. (1980) 16.32 2.94q 157 0.56 0.10 0.34 90 6d CHA, RHO 88% Na+, 12% Cs+
Barrer etal. (1980) 17.94 2.94q 157 0.58 0.10 0.32 90 16d CHA, RHO 88% Na+, 12% Cs+
Barrer etal. (1980) 14.71 2.94q 157 0.53 0.11 0.36 90 3d ANA, CHA, FAU, LTA, RHO 87.5% Na+, 12.5% Cs+
Barrer etal. (1980) 16.32 2.94q 157 0.56 0.10 0.34 90 5d RHO, (CHA) 87.5% Na+, 12.5% Cs+
(Table 2Continued)
Barrer etal. (1980) 16.13 2.91q 155 0.56 0.10 0.34 90 5d RHO, (CHA) 86% Na+, 14% Cs+
Barrer etal. (1980) 15.99 2.88q 154 0.55 0.10 0.35 90 5d RHO, (CHA) 85% Na+, 15% Cs+
Barrer etal. (1980) 15.86 2.86q 152 0.55 0.10 0.35 90 5d RHO, (CHA) 84.5% Na+, 15.5% Cs+
Robson (1975) 15.15 3.03p 165 0.54 0.11 0.35 90 96d CHA 71% Na+, 20% K+, 9% Cs+
Robson (1975) 15.15 3.03p 165 0.54 0.11 0.35 90 192d CHA 71% Na+, 20% K+, 9% Cs+
Robson (1975) 15.15 3.03p 165 0.54 0.11 0.35 90 192d ERI, (CHA) 52% Na+, 39% K+, 9% Cs+
Duecker etal. (1971)s 0.21 1.43 79 0.02 0.12 0.86 95 1 LTN Na+
Duecker etal. (1971)s 0.70 0.23 79 0.06 0.02 0.91 95 1 LTN Na+
Maldonado etal. (2013) 2.73 1.82 173 0.19 0.13 0.69 95 168d FAU, GIS, SOD Na+
Jakkula etal. (2006) 5.70 3.80k 180 0.29 0.19 0.51 95 96 EDI K+
a
Unless otherwise noted, the silica source is colloidal.
b
Unless otherwise noted, the aluminum source is sodium or potassium aluminate.
c
Denotes agitation, rotation, or stirring.
d
Denotes aging prior to crystallization.
Authenticated
e
Framework types in parentheses are present in trace amounts.
f
Sodium or potassium silicate.
g
Glass.

h
NaCl added.
i

Listed phased present over range specified.
j
Acidic silica/alumina sol.
k
Metallic aluminum.
l
Water glass.
m
Metakaolin.
n
Fumed silica.
o
Unspecified or unclear.
p
Aluminum hydroxide.
q
Aluminum isopropoxide.
r
Kaolikn.
s
Crystallized under reflux.
Table 3Compositions of points for Figure 4 and similar conditions (omitted from the figure for clarity) crystallized at temperatures from 100 to 140C given in molar ratios of x Si:y Al:10
[MOH+M(OH)2]:z H2O.
References Molar ratio Mole fraction Temperaturec (C) Timed (h) Phasee Cation
x Sia y Alb z H2O Si Al M+(2)
Duecker etal. (1971)f 0.33g 0.33h 79 0.03 0.03 0.94 100 0.75 LTN Na+
Milton (1959) 7.69g 1.06 80 0.41 0.06 0.53 100 24 FAU Na+
Milton (1959) 6.94g 1.22 85 0.38 0.07 0.55 100 6 FAU Na+
Breck (1962)i 12.55 2.51 99 0.50 0.10 0.40 100 j GME Na+
Lin etal. (2004) 6.90k 6.90k 102 0.29 0.29 0.42 100 96 LTA Na+
Milton (1961b) 9.26l 4.75 115 0.39 0.20 0.42 100 65 GIS Na+
Regis etal. (1960)m 0.50 1.00 125 0.04 0.09 0.87 100 24 SOD Na+
Regis etal. (1960)m 0.50 1.00 125 0.04 0.09 0.87 100 168 SOD, (GIS) Na+
Milton (1959) 6.58 2.35 140 0.35 0.12 0.53 100 47 FAU Na+
Milton (1961b) 13.16g 3.76 140 0.49 0.14 0.37 100 47 GIS Na+
Cannan (1989)n 7.38 1.81o 140 0.38 0.09 0.52 100 480d MAZ Na+
Breck (1962)j 16.41g 1.35 141 0.59 0.05 0.36 100 17 GME Na+
Milton (1961b) 9.09 0.91 145 0.45 0.05 0.50 100 52 GIS Na+
Regis etal. (1960)m 2.00 1.00 155 0.15 0.08 0.77 100 168 SOD, MER Na+
Authenticated
Breck (1964) 10.14 0.72 164 0.49 0.03 0.48 100 21 FAU Na+
Regis etal. (1960)m 0.83 3.33 172 0.06 0.24 0.71 100 24 SOD, (CAN) Na+

Regis etal. (1960)m 0.83 3.33 172 0.06 0.24 0.71 100 168 LTA, SOD, (CAN) Na+
Regis etal. (1960)m 0.83 3.33 172 0.06 0.24 0.71 100 504 SOD, (LTA) Na+

Maldonado etal. (2013) 1.82 1.82 173 0.13 0.13 0.73 100 168d GIS, SOD, (CAN) Na+
Maldonado etal. (2013) 3.64 1.82 173 0.24 0.12 0.65 100 168d GIS Na+
Maldonado etal. (2013) 3.64 5.45 173 0.19 0.29 0.52 100 168d LTA, SOD Na+
Maldonado etal. (2013) 4.73 4.18 173 0.25 0.22 0.53 100 168d GIS, SOD Na+
Maldonado etal. (2013) 7.27 7.09 173 0.30 0.29 0.41 100 168d GIS, SOD Na+
(Table 3Continued)
Regis etal. (1960)m 1.17 3.33 178 0.08 0.23 0.69 100 168 CAN Na+
Milton (1961b) 8.20g 0.82 180 0.43 0.04 0.53 100 90 GIS Na+
Koroglu etal. (2002) 9.43p 1.89 188 0.44 0.09 0.47 100 48d FAU Na+
Milton (1961b) 12.20l 2.44 190 0.50 0.10 0.40 100 48 GIS Na+
Skeels and Sears (1993) 12.50 3.13h 195 0.49 0.12 0.39 100 24 FAU Na+
Skeels and Sears (1993) 12.50 6.25h 195 0.43 0.22 0.35 100 24 FAU, GIS, PHI Na+
Breck (1964)i 16.67 4.17 195 0.54 0.14 0.32 100 72d FAU Na+
Breck (1964) 16.67 3.33 195 0.56 0.11 0.33 100 142d FAU Na+
Milton (1959) 3.85g 2.56 200 0.23 0.16 0.61 100 15 FAU Na+
Regis etal. (1960)m 1.25 5.00 208 0.08 0.31 0.62 100 24 LTA Na+
Regis etal. (1960)m 4.00 2.00 212 0.25 0.13 0.63 100 24 FAU, (MER) Na+
Regis etal. (1960)m 4.00 2.00 212 0.25 0.13 0.63 100 336 GIS, (LTA), (SOD) Na+
Authenticated
Regis etal. (1960)m 5.00 1.00 215 0.31 0.06 0.63 100 168 GIS Na+

Regis etal. (1960)m 5.00 1.00 215 0.31 0.06 0.63 100 336 GIS, (SOD) Na+

Regis etal. (1960)m 3.33 3.33 222 0.20 0.20 0.60 100 168 SOD, (GIS), (LTA) Na+
Regis etal. (1960)m 3.33 3.33 222 0.20 0.20 0.60 100 24 CAN Na+
Milton (1961b) 9.80g 5.16 235 0.39 0.21 0.40 100 81 GIS Na+
Milton (1962) 10.00j 3.33j 245 0.43 0.14 0.43 100q 16q CHA Na+
Milton (1959) 3.85g 2.56 245 0.23 0.16 0.61 100 47 FAU Na+
Regis etal. (1960)m 5.00 3.33 255 0.27 0.18 0.55 100 24 FAU, (SOD), (LTA) Na+
(Table 3Continued)
Taylor and Roy (1964) 6.67 1.67 260 0.36 0.09 0.55 100 80q GIS Na+
Regis etal. (1960)m 2.00 8.00 274 0.10 0.40 0.50 100 504 SOD, (LTA) Na+
Regis etal. (1960)m 3.33 6.67 278 0.17 0.33 0.50 100 24 LTA, (SOD) Na+
Regis etal. (1960)m 3.33 6.67 278 0.17 0.33 0.50 100 168 LTA, SOD Na+
Regis etal. (1960)m 6.00 4.00 286 0.30 0.20 0.50 100 24 LTA, (FAU) Na+
Regis etal. (1960)m 6.00 4.00 286 0.30 0.20 0.50 100 504 GIS, (LTA), (SOD) Na+
Regis etal. (1960)m 6.67 3.33 288 0.33 0.17 0.50 100 24 FAU Na+
Authenticated
Regis etal. (1960)m 7.00 4.00 306 0.33 0.19 0.48 100 168 MER Na+

Regis etal. (1960)m 8.00 4.00 326 0.36 0.18 0.45 100 24 FAU, (SOD) Na+

Regis etal. (1960)m 8.00 4.00 326 0.36 0.18 0.45 100 336 GIS, SOD Na+
Regis etal. (1960)m 7.50 5.00 333 0.33 0.22 0.44 100 168 FAU, GIS Na+
Regis etal. (1960)m 6.67 6.67 345 0.29 0.29 0.43 100 24 LTA, (FAU) Na+
Regis etal. (1960)m 6.67 6.67 345 0.29 0.29 0.43 100 168 GIS, LTA Na+
Song etal. (2006)r 17.86l 3.57o 352 0.57 0.11 0.32 100 336d EON, FAU Na+
(Table 3Continued)
Regis etal. (1960)m 6.00 8.00 354 0.25 0.33 0.42 100 168 GIS, (LTA) Na+
Regis etal. (1960)m 6.00 8.00 354 0.25 0.33 0.42 100 336 GIS, SOD Na+
Regis etal. (1960)m 10.00 5.00 384 0.40 0.20 0.40 100 24 (FAU) Na+
Regis etal. (1960)m 10.00 5.00 384 0.40 0.20 0.40 100 504 GIS, MER, (LTA) Na+
Song etal. (2006)r 20.00l 4.00o 390 0.59 0.12 0.29 100 336d EON Na+
Milton (1962) 3.85q 1.28q 420j 0.25 0.08 0.66 100 16 CHA Na+
Regis etal. (1960)m 12.00 8.00 475 0.40 0.27 0.33 100 24 FAU, (GIS) Na+
Authenticated
Regis etal. (1960)m 12.00 8.00 475 0.40 0.27 0.33 100 168 FAU, GIS Na+
Regis etal. (1960)m 12.00 8.00 475 0.40 0.27 0.33 100 504 MER, (LTA) Na+

Regis etal. (1960)m 15.00 5.00 484 0.50 0.17 0.33 100 504 GIS, (LTA) Na+

Skeels and Sears (1993) 25.00 6.25h 795 0.61 0.15 0.24 100 1128 PHI Na+
Skeels and Sears (1993) 25.00 6.25h 795 0.61 0.15 0.24 100 1296 PHI, GIS Na+
Zhang etal. (2012a) 31.25j 2.08 1401 0.72 0.05 0.23 100 j MEL, MFI, MOR Na+
Zhang etal. (2012a) 33.33j 2.22j 1495 0.73 0.05 0.22 100 40 MEL, MFI Na+
Zhang etal. (2012a) 45.45j 0.91j 2040 0.81 0.02 0.18 100 j MEL, MFI Na+
Zhang etal. (2012a) 45.45j 3.03j 2040 0.78 0.05 0.17 100 48 MEL, MFI Na+
Zhang etal. (2012a) 45.45j 4.55j 2040 0.76 0.08 0.17 100 j FER, (MOR) Na+
Matsumoto etal. (2006) 2.00s 2.00s 270 0.14 0.14 0.71 100 24 EDI Li+
Matsumoto etal. (2006) 2.50s 2.50s 339 0.17 0.17 0.67 100 24 EDI Li+
Matsumoto etal. (2006) 3.33s 3.33s 453 0.20 0.20 0.60 100 24 ABW, EDI Li+
Matsumoto etal. (2006) 4.00s 4.00s 540 0.22 0.22 0.56 100 1 EDI, (ABW) Li+
Matsumoto etal. (2006) 4.00s 4.00s 540 0.22 0.22 0.56 100 5 EDI, (ABW) Li+
(Table 3Continued)
Breck and Acara (1961a,b) 1.25j,q 0.63j,q 45 0.11 0.05 0.84 100 j LTJ K+
Milton (1961c) 1.79j,q 1.79j,q 70 0.13 0.13 0.74 100 j EDI K+
Milton (1961a) 8.40g 3.38h 123 0.39 0.16 0.46 100 91 MER K+
Vaughan (1995) 4.76 4.76h 185 0.24 0.24 0.51 100 72 BPH K+
Robson (1975) 15.63 3.13h 128 0.54 0.11 0.35 100 48 RHO, FAU 94% Na+, 6% Cs+
Robson (1975) 15.15 3.03h 162 0.54 0.11 0.35 100 96 RHO, GIS 91% Na+, 9% Cs+
Robson (1975) 15.15 3.03h 147 0.54 0.11 0.35 100d 24 RHO 90% Na+, 10% Cs+
Robson (1975) 15.15 3.03h 147 0.54 0.11 0.35 100 96 RHO 90% Na+, 10% Cs+
Robson (1975) 16.67 3.33h 162 0.56 0.11 0.33 100 72 RHO 90% Na+, 10% Cs+
Xingqiao and Ruren (1985) 15.15j 1.17j 75 0.58 0.04 0.38 100 192 ERI, OFF 75% Na+, 25% K+
Cichocki and Koscielniak (2000) 12.20t 0.98 145 0.53 0.04 0.43 100 168 ERI, OFF 75% Na+, 25% K+
Zhou etal. (2009) 13.89p 1.53h 156 0.55 0.06 0.39 100d 120d ERI, LTL, OFF 75% Na+, 25% K+
Authenticated
Zhou etal. (2009) 16.13 1.77 182 0.58 0.06 0.36 100d 72 ERI, OFF 75% Na+, 25% K+


Zhou etal. (2009) 16.13 2.16 182 0.57 0.08 0.35 100d 120 ERI, OFF, PHI 75% Na+, 25% K+
Breck and Acara (1960a,b) 12.50j 1.25j 195 0.53 0.05 0.42 100 88 ERI, OFF 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 100d 120 MER 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 100d 168 ERI, OFF 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 100d 216 ERI, OFF, MER 75% Na+, 25% K+
Breck and Acara (1960a) 12.50j 0.89j 205 0.53 0.04 0.43 100 166 ERI, OFF 74% Na+, 26% K+
Milton (1961a) 5.53g 2.53 95 0.31 0.14 0.55 100 87.5 MER 71.5% Na+, 28.5% K+
Hayhurst and Sand (1977) 9.57j 0.96j 151 0.47 0.05 0.49 100 68 PHI 66% Na+, 34%K+
Breck etal. (1960)i 6.67 6.67h 95 0.29 0.29 0.43 100 64 ANA 50% Na+, 50% K+
Robson (1973) 26.67j 6.67j 205 0.62 0.15 0.23 100 168 KFI, LTL 90% K+, 10% Cs+
(Table 3Continued)
Robson (1973) 26.67j 6.67j 193 0.62 0.15 0.23 100 168 KFI, LTL 89% K+, 11% Cs+
Robson (1973) 20.00j 6.67j 145 0.55 0.18 0.27 100 192 KFI 89% K+, 11% Cs+
Robson (1973) 20.00j 6.67j 144 0.55 0.18 0.27 100 48 ANA, KFI 80% K+, 20% Cs+
Robson (1973) 26.67j 6.67j 205 0.62 0.15 0.23 100 96 KFI 80% K+, 20% Cs+
Robson (1973) 33.33j 6.67j 257 0.67 0.13 0.20 100 144 KFI 80% K+, 20% Cs+
Robson (1973) 20.00j 6.67j 155 0.55 0.18 0.27 100 48 ANA, CHA 73% K+, 27% Cs+
Robson (1973) 20.00j 6.67j 167 0.55 0.18 0.27 100 48 ANA, CHA 67% K+, 33% Cs+
Robson (1973) 20.00j 6.67j 149 0.55 0.18 0.27 100 384 LTL 89% K+, 11% Li+
Miyake etal. (2005)r 1.67 1.67h 78 0.125 0.125 0.75 110 120d CAN Na+
Barrer and Mainwaring (1972b) 4.71 1.05 144 0.30 0.07 0.63 110c j GIS Na+
Barrer and Mainwaring (1972b) 2.74 1.10 151 0.20 0.08 0.72 110c j GIS, SOD Na+
Barrer and Mainwaring (1972b) 15.00 3.33 458 0.53 0.12 0.35 110c j ANA, GIS Na+
Barrer and Mainwaring (1972b) 8.93 3.57 491 0.40 0.16 0.44 110c j ANA, GIS Na+
Barrer and Mainwaring (1972b) 31.58 7.02 965 0.65 0.14 0.21 110c j GIS Na+
Milton (1959) 3.85g 2.56 185 0.23 0.16 0.61 120 1.5 FAU Na+
Tatlier etal. (2007) 10.00 0.13 195 0.497 0.006 0.497 120 8 ANA, GIS Na+
Tatlier etal. (2007) 10.00 0.09 195 0.498 0.004 0.498 120 16 ANA, GIS Na+
Authenticated
Tatlier etal. (2007) 10.00 0.13 195 0.497 0.006 0.497 120 40 ANA Na+
Tatlier etal. (2007) 10.00 0.09 195 0.498 0.004 0.498 120 48 ANA, (GIS) Na+
Ban etal. (2007) 15.00 1.00 245 0.58 0.04 0.38 120 144d LTL K+

Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 120 168d ERI, OFF 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 120 216d LTL, MER 75% Na+, 25% K+

Breck and Acara (1960a) 10.00j 0.71j 195 0.48 0.03 0.48 120 8 ERI, OFF 74% Na+, 26% K+
Robson (1973) 20.00j 6.67j 135 0.55 0.18 0.27 125 72 CHA, LTL K+
Cichocki and Koscielniak (2000) 12.20t 0.98 145 0.53 0.04 0.43 130 168 (ERI), (OFF) 75% Na+, 25% K+
Ban etal. (2007) 18.00 4.00u 315 0.56 0.13 0.31 130 72d LTL K+
Bajpai etal. (1978) 13.33g 3.33h 360 0.5 0.125 0.375 135 24 MOR Na+
Lin etal. (2004) 6.90k 6.90k 102 0.29 0.29 0.42 140 48 LTA Na+
Lin etal. (2004) 6.90k 6.90k 102 0.29 0.29 0.42 140 96 LTA, (JBW) Na+
Song etal. (2006)r 20.00l 4.00o 395 0.59 0.12 0.29 140 120d EON, GIS Na+
(Table 3Continued)
a b +(2)
x Si y Al z H2O Si Al M
p
Mirfendereski and Mohammadi (2011) 14.29 1.14 195 0.56 0.05 0.39 140 120d LTL, MER 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 140 168d ERI, LTL, MER, OFF 75% Na+, 25% K+
Mirfendereski and Mohammadi (2011) 14.29p 1.14 195 0.56 0.05 0.39 140 216d LTL 75% Na+, 25% K+
Belhekar etal. (1995)v 5.99 6.58w 21 0.27 0.29 0.44 140 96d MER 5.9% Na+, 92.1% K, 2% Sr+2
Belhekar etal. (1995) 6.11 6.71w 22 0.27 0.29 0.44 140 96d CHA 6% Na+, 94% K+
a
b
Unless otherwise noted, the aluminum source is sodium aluminate.
c
d
e
f
Crystallized under reflux.
g
Sodium or potassium silicate.
h
Aluminum hydroxide.
i
Glass reaction vessel used.
j
Source or time unspecified or unclear.
k
Metakaolin.
l
Water glass.
Authenticated
m
Water contents estimated from solid-to-liquid ratio of 1:6 assuming liquid is pure water.
n
Na2SO4 added.
o
Aluminum sulfate.

p
Precipitated silica.
q
Estimated from range/chart.

r
Acid added.
s
Acidic silica or alumina sol.
t
Concentrated silica.
u
Metallic aluminum.
v
SrCl2 added and not included in ratio.
w
Boehmite.
At moderate temperatures, we also observe the forma- of synthesis compositions, which include Si mole frac-
tion of EDI and ABW (Figure 4B) at compositions compara- tions of 0.50.6 and MOH mole fractions of 0.350.5 (see
ble to those reported at lower temperatures, i.e., near the Table 3). It is feasible that the close proximity of other
SAR(liq) =1 line at higher alkalinity. MFI also forms under phases, such as LTL, reduces the stability of ERI-OFF. LTL
similar conditions as those reported at lower tempera- type zeolite readily forms in OSDA-free solutions contain-
tures; however, higher temperatures can yield mixtures of ing K+. A study by Mirfendereski and Mohammadi (2011)
MFI and MEL. The conditions used to synthesize MFI are revealed that solutions heated for 168h at moderate tem-
siliceous, low alkalinity, and high water content growth peratures produced a mixture of ERI, OFF, LTL, and MER,
solutions. A recent study claims that similar conditions which then transformed to pure LTL after 216 h.
also yield FER (also referred to as ZSM-35) with traces of There is a large range of synthesis compositions that
MOR (Zhang etal. 2012a), whereas the same compositions yield GIS crystals (the synthetic form of naturally occur-
at lower water content produce pure MOR (e.g., molar ring gismondine). This structure has been referred to by
ratios 10 MOH:z H2O, where z<1000) (Machado etal. 1999). many names, the most common being zeolite P. Earlier
To our knowledge, this is one of the few OSDA-free synthe- work often distinguished different polymorphs of this
ses of FER reported in the literature. Additional examples framework, referring to the cubic form (Pc, P1, B1), the
of less frequently reported zeolites formed at this tempera- tetragonal form (Pt, P2, Bn with n=2, 3, 5, and 6), and
ture range include GME, LTJ, and MAZ. Breck reported the the orthorhombic form (Po, P3) (Beard 1971). The P2
formation of LTJ and GME at 100C using K+ (Breck and polymorph is the synthetic form of naturally occurring
Acara 1961a) and Na+ (Breck 1962), respectively. Although gobbinsite. The polymorph formerly called P3 is no longer
the synthesis times were not reported in these patents, considered a form of GIS, but is rather the MER frame-
their studies revealed that LTJ crystallizes at high alkalin- work. The difference in structure between P1 and P2,
ity and low water content (z=45), whereas GME is also pro- albeit minor, results in distinctly different X-ray powder
duced at low water content (z=99, see Table 3), but with diffraction patterns. Many studies fail to report the exact
more siliceous and less alkaline growth solutions. MAZ GIS polymorph they have obtained, which makes it chal-
type zeolite was synthesized at conditions slightly more lenging to define the conditions favoring the formation of
alkaline than GME using crystallization times on the order either P1 or P2. In our previous work, we followed similar
of 20days (Cannan 1989). conventions by broadly referring to the structures within
Regis et al. (1960) report the synthesis of multiple phase diagrams as GIS type instead of distinguishing the
zeolites at 100C for periods of 21 days, including GIS, exact polymorph; however, inspection a posteriori of the
LTA, and SOD. Other zeolite framework types produced XRD patterns reveals that all GIS structures in our study
at long synthesis times include PHI and mixtures of PHI were P1 crystals (Maldonado etal. 2013). It is therefore rec-
and GIS, which were reported by Skeels and Sears (1993) ommended that any reproduction of protocols reporting
after 47 and 54days of crystallization, respectively. Longer the synthesis of GIS zeolite also be accompanied by inde-
time is apparently not a prerequisite for PHI formation, pendent validation of the exact polymorph. Additionally,
as this structure is reported by Hayhurst and Sand (1977) particular care should be given while reading the litera-
to form after 68h of hydrothermal treatment. Longer syn- ture before ca. 1970 as many reports of GIS are mislabeled
thesis times can lead to polymorphs, such as mixtures of as phillipsite or harmotome (Beard 1971).
ERI and OFF, which were reported after 120h of heating There are approximately 14 zeolites prepared at tem-
(Zhou et al. 2009). The studies by Zhou et al. and Hay- peratures above 150C, which we refer to as high-temper-
hurst and Sand employed mixtures of Na+ and K+. It is ature synthesis. These conditions produce the following
possible that K+ induces more rapid crystallization of PHI, framework types: ABW, ANA, CAN, EON, ERI, FER, GIS,
although the introduction of K+ also appears to promote HEU, JBW, LTL, MFI, MOR, OFF, and SOD. Growth solu-
the formation of structures such as ERI and OFF, which tions at high alkalinity (Si/OH<1) tend to produce CAN,
are almost always found together as binary mixtures (and ANA, or JBW. The formation of CAN spans both Al- and
often reported as crystal intergrowths). Crystallization Si-rich regions of the ternary phase diagram. In the Al-rich
of ERI-OFF intergrowths with the occasional presence regions, the structural transformation from SOD (which
of impurities is commonly observed when growth solu- forms at lower temperatures) to CAN is often incomplete,
tions consist of mixed cations (e.g., 75% Na+ and 25% even for solutions that have been heated for long periods
K+) (Cichocki and Koscielniak 2000, Zhou et al. 2009, of time (e.g., 21 days). The structure JBW (also referred to
Mirfendereski and Mohammadi 2011). Moreover, ERI-OFF as Na-J) forms in the vicinity of Si/OH=1, oftentimes as a
intergrowths are reported to grow within a narrow range multiphase mixture with CAN and/or SOD. A comparison

Authenticated
of ternary diagrams at SAR(liq)>1 reveals that FAU and GIS more thermodynamically stable structures) crystallize over
form at low temperatures, whereas high temperatures a broad range of temperatures, whereas others form only
result in the synthesis of CAN, ANA, or mixtures thereof at high temperature (see Tables 24). A notable example is
(see Figure 5). ANA-type zeolite crystallizes in Si-rich MFI, which forms at low to high temperature, but requires
solutions that are typically less alkaline than the other high water content. Similarly, MOR forms over a broad
structures. In some instances, ANA synthesis has been range of temperatures, but always within a narrow region
reported at very low MOH mole fraction (i.e., top portion of mole fractions and water contents. The data reported
of the ternary phase diagram). One of the most extreme for ABW, albeit limited, suggest its formation occurs
cases reported in the literature is a LiOH mole fraction of over a range of temperatures in growth solutions with
0.02 (Sand and Sand 1973), which to our knowledge is the SAR(liq) =1. Dense framework types CAN and ANA are syn-
lowest MOH mole fraction reported for any zeolite struc- thesized at high temperature, although the nucleation of
ture. Additional studies report ANA crystallization at low these structures can be induced after longer times at mod-
water content (i.e., 745 H2O:10 NaOH compared to 3945 erate temperatures (Maldonado et al. 2013). Collectively,
H2O:10 LiOH used by Sand and Sand), similar to composi- these observations generate questions regarding the role
tions used in the synthesis of MOR and FER zeolites (Agger of growth solution composition in the formation of high
etal. 2006). density framework structures at low temperatures. As pre-
The ternary diagrams suggest that zeolite synthesis viously mentioned, OSDA-free syntheses typically proceed
in regions of low alkalinity can be performed at either through a series of stages (Ostwald step rule) where the
moderate or high temperature. Notably, the following nucleation of less dense frameworks is followed by struc-
framework types crystallize at similar growth solution tural transitions to more thermodynamically stable frame-
compositions irrespective of the temperature: MFI, MOR, work types. This phenomenon is commonly observed for
FER, LTL, and mixtures of ERI and OFF. Crystals of LTL syntheses at high alkalinity (e.g., the formation of CAN,
type form at lower alkalinity and in Si-rich growth solu- ANA, JBW, etc.), whereas synthesis at low alkalinity often
tions. FER crystallizes at even lower alkalinity and higher involves the nucleation and growth of a single phase (e.g.,
SAR(liq) values than those of LTL. Zeolites ERI and OFF are LTL, MFI, MOR, etc.). In some instances, phase transfor-
reported in similar regions of the phase diagram, clustered mations have been observed at low alkalinity, such as the
around a Si mole fraction of 0.55. MFI crystals grow at very MFI-to-MOR phase transformation reported by Machado
low alkalinity and high water content (as we will discuss etal. at 65C (z=895 and xOH=0.15) (Machado etal. 1999).
in Section 3.2). MOR type zeolite crystallizes in regions Figure 6 depicts common phase transformations in
that overlap with FER and MFI. Past studies comparing growth solutions at high alkalinity (i.e., Si/OH<1). Mal-
MOR and MFI suggest there is a dependence of Al content donado etal. explored zeolite synthesis at multiple com-
on phase selectivity (Dai etal. 1986). A study reported by positions and SAR(liq) values using solutions of constant
Dai et al. compared syntheses at 190C over a period of water content (11 NaOH:190 H2O) and the following sets
24h using compositions with different SAR(liq) and water of temperatures and synthesis times: 65C (7 days), 100C
content. Decoupling the effects of these two parameters (7 days), and 180C (21 days). This study identified pseudo-
from their reported results is difficult as neither variable equilibrium phases in high alkalinity regions of the ternary
was held fixed in their syntheses (see Table 4). Neverthe- diagrams. Maldonado etal. focused on zeolites formed in
less, their study revealed that a reduction in SAR(liq) results solutions using Na+ as the sole extraframework cation (Mal-
in a transition from MFI to MOR. Conversely, their studies donado etal. 2013). At low temperature, the initial phases
also suggested that increasing SAR(liq) (or water content) are primarily FAU and LTA in Si- and Al-rich solutions,
above some threshold value shifts the product from MFI to respectively. Syntheses at temperatures between 80 and
an amorphous material. It is feasible that the 24-h synthe- 100C resulted in the onset of structural transformations.
sis used by Dai etal. was an insufficient time to observe At moderate temperature, a FAU-to-GIS transformation is
the onset of MFI crystallization. For instance, Kim et al. observed in Si-rich solutions, and a LTA-to-SOD transfor-
performed a similar experiment using analogous condi- mation is observed in Al-rich solutions. There is another
tions (but with stirring) and reported that an increase in set of structural transformations that occurs once the tem-
SAR(liq) from 16.5 to 33.5 resulted in reduced rates of MFI perature is raised even further. At high temperatures, the
crystal growth (i.e., a decrease from 0.38 to 0.23 h-1 at predominant structures are ANA and CAN. In general, the
90C) (Kim etal. 2004). sequence of stages observed in Si-rich solutions follows
An interesting observation in the ternary phase dia- the progression FAUGISANA, whereas the sequence
grams is that several high density framework types (i.e., in Al-rich solutions is LTASODCAN (see Figure 6).

Authenticated
Table 4Compositions of points for Figure 5 and similar conditions (omitted from the figure for clarity) crystallized at temperatures of 150C and greater given in molar ratios of x Si:y Al:10
[MOH+M(OH)2]:z H2O.
References Molar composition Mole fraction Temperaturec (C) Timed (h) Phasee Cation
a b + (2)
g h
Bajpai etal. (1978) 13.33 3.33 360 0.5 0.125 0.375 150 24 ANA Na+
Han etal. (2006) 25.00 0.63h 370 0.7 0.02 0.28 150 168d MOR Na+
Han etal. (2006) 25.00 1.25g 370 0.69 0.03 0.28 150 168d MOR Na+
Han etal. (2006) 25.00 2.50g 370 0.67 0.07 0.27 150 168d MOR Na+
Grose and Flanigen (1981) 61.54f 1.54f 2458 0.84 0.02 0.14 150 122 MFI Na+
Han etal. (2006) 25.00 0.00h 370 0.71 0.00 0.29 150 168d Quartz K+
Han etal. (2006) 25.00 0.31h 370 0.71 0.01 0.28 150 168d FER, (LTL) K+
Han etal. (2006) 25.00 0.63h 370 0.7 0.02 0.28 150 168d FER K+
Han etal. (2006) 25.00 1.25g 370 0.69 0.03 0.28 150 168d Amorphous K+
Han etal. (2006) 25.00 2.50g 370 0.67 0.07 0.27 150 168d MER K+
Han etal. (2006) 25.00 5.00h 370 0.62 0.13 0.25 150 168d Amorphous K+
Lowe etal. (1994) 15.00i 1.00j 750 0.58 0.04 0.38 150c 79 Microcline, MER K+
Lowe etal. (1994) 60.00i 1.33l 3000 0.84 0.02 0.14 150c 122.4d TON K+
Lowe etal. (1994) 60.00i 2.00l 3000 0.83 0.03 0.14 150c 163.2 Cristobalite, TON K+
Lowe etal. (1994) 60.00i 4.00l 3000 0.81 0.05 0.14 150c 168 Cristobalite, TON K+
Breck and Acara (1960a) 13.16f 0.94 205 0.55 0.04 0.41 150 22 ERI, OFF 74% Na+, 26% K+
Sand and Sand (1973) 20.00f 10.00f 165 0.50 0.25 0.25 152 67 ANA Li+
Song etal. (2006) 20.00k 4.00l 395 0.59 0.12 0.29 160 24 EON, GIS Na+
Ruiz etal. (2005) 15.70k 3.19h 260 0.54 0.11 0.35 160 42 LTL K+
Authenticated
Itani etal. (2011) 16.67i 3.00j 262 0.56 0.10 0.34 160 24 LTL K+
Ruiz etal. (2005) 17.89k 3.34h 551 0.57 0.11 0.32 160 144 LTL K+
Bajpai etal. (1978) 13.33g 3.33h 360 0.50 0.12 0.38 165 24 ANA Na+

Bellussi etal. (1988) 14.29f 1.59l 1138 0.55 0.06 0.39 165 936 FER, MOR Na+
Maghsoodloorad etal. (2011) 3.25t 1.30h 102 0.22 0.09 0.69 165 72d CHA, MER K+

Maghsoodloorad etal. (2011) 4.16t 1.30h 102 0.27 0.08 0.65 165 72d MER K+
Maghsoodloorad etal. (2011) 8.93t 1.79h 142 0.43 0.09 0.48 165 72d CHA, MER, PHI K+
Maghsoodloorad etal. (2011) 16.67t 3.33h 269 0.56 0.11 0.33 165 72d ERI, MER K+
Linares etal. (2011)m 0.83 0.83j 72 0.070 0.07 0.86 170 168d CAN Na+
Bhat etal. (2004) 12.50i 2.50n 120 0.5 0.1 0.4 170 70 LTL K+
Larlus and Valtchev (2004)p 10.00 1.60j 145 0.46 0.07 0.46 170 72 LTL K+
Bhat etal. (2004) 16.67 4.17n 162 0.54 0.14 0.32 170 45 LTL K+
Larlus and Valtchev (2004)p 20.00 3.20j 295 0.6 0.1 0.3 170 72 LTL K+
Bhat etal. (2004) 20.00 5.00 327 0.57 0.14 0.29 170 65 LTL K+
Larlus and Valtchev (2004)p 20.00 3.20i 495 0.6 0.1 0.3 170 72 LTL K+
Itani etal. (2011) 10.00 1.00j 195 0.48 0.05 0.48 170 24 LTL K+
Ko and Ahn (2004) 13.51f 0.9 170 0.55 0.04 0.41 170 24 LTL 50% Na+, 50% K+
Ko and Ahn (2004) 11.63f 0.78 220 0.52 0.03 0.45 170 24 LTL 50% Na+, 50% K+
(Table 4Continued)
a b + (2)
f
Ko and Ahn (2004) 13.51 0.9 295 0.55 0.04 0.41 170 24 ERI, LTL, OFF 50% Na+, 50% K+
Sand and Sand (1973) 500.00f 50.00f 3945 0.89 0.09 0.02 174 21 ANA Li+
Bellussi etal. (1988)q 10.42f 0.83l 390 0.49 0.04 0.47 175 144 MOR Na+
Bellussi etal. (1988)q 5.88f 2.35l 413 0.32 0.13 0.55 175 240 ANA Na+
Bellussi etal. (1988)q 10.42f 0.69l 568 0.49 0.03 0.47 175 144 MOR Na+
Suzuki etal. (2009) 22.22i 2.22h 778 0.65 0.06 0.29 175 72 MOR Na+
Bellussi etal. (1988)q 13.51f 0.90l 1076 0.55 0.04 0.41 175 168 MFI Na+
Suzuki etal. (2009) 40.00i 4.00h 1400 0.74 0.07 0.19 175 144 FER Na+
Bellussi etal. (1988)q 2.38f 2.38l 209 0.16 0.16 0.68 175 168 ABW Li+
Bellussi etal. (1988)q 4.35f 1.24l 116 0.28 0.08 0.64 175 240 MER K+
Bellussi etal. (1988)q 5.56f 1.59l 122 0.32 0.09 0.58 175 240 LTL K+
Suzuki etal. (2009) 25.00h 2.50g 875 0.67 0.07 0.27 175 192 FER K+
Bellussi etal. (1988)q 12.50f 0.83l 1120 0.54 0.04 0.43 175 240 MOR K+
Suzuki etal. (2009) 22.22i 2.22h 778 0.65 0.06 0.29 175 72 FER 70% Na+, 30% K+
Suzuki etal. (2009) 40.00i 4.00h 1400 0.74 0.07 0.19 175 72 FER 70% Na+, 30% K+
Chi and Sand (1983) 25.00 5.00h 263 0.63 0.13 0.25 175 76 HEU, MOR, PHI 27% Na+, 73% K+
Zhao etal. (1998) 28.13 6.25h 379 0.63 0.14 0.23 180 125 ANA, HEU Rb2+
Maldonado etal. (2013) 3.73 0.09 173 0.27 0.01 0.72 180 504d ANA Na+
Maldonado etal. (2013) 2.27 0.27 173 0.18 0.02 0.8 180 504d CAN Na+
Maldonado etal. (2013) 3.73 0.64 173 0.26 0.04 0.7 180 504d ANA, CAN Na+
Authenticated


Maldonado etal. (2013) 1.36 2.73 173 0.1 0.19 0.71 180 504d CAN, SOD Na+
Maldonado etal. (2013) 5.45 3.64 173 0.29 0.19 0.52 180 504d CAN, ANA Na+
Maldonado etal. (2013) 6.27 6.27 173 0.28 0.28 0.44 180 504d CAN, JBW Na+
Maldonado etal. (2013) 8.64 8.18 173 0.32 0.31 0.37 180 504d ANA, CAN, JBW Na+
(Table 4Continued)
a b + (2)
h
Zhao etal. (1998) 28.13 6.25 339 0.63 0.14 0.23 180 112 HEU Na
Agger etal. (2006) 31.17f 2.45 762 0.71 0.06 0.23 180 72d ANA Na+
Sand and Sand (1973) 33.33f 1.67f 257 0.74 0.04 0.22 180 65 MOR, PHI, (ANA) Li+
Sand and Sand (1973) 66.67f 3.33f 518 0.83 0.04 0.13 180 65 MOR, PHI, (ANA) Li+
Zhao etal. (1998) 28.13 6.25h 344 0.63 0.14 0.23 180 84 HEU K+
Lee etal. (2005) 9.17 0.92l 467 0.46 0.05 0.5 180 72d LTL K+
Lee etal. (2005) 9.62 0.96h,l 490 0.47 0.05 0.49 180 72d LTL K+
Gomez etal. (2011) 9.80 0.98k 499 0.47 0.05 0.48 180 72d LTL, MER K+
Rakoczy etal. (2002) 36.73i 4.08j 566 0.72 0.08 0.2 180 144 FER 50% Na+, 50% K+
Sand and Sand (1973) 20.00f 4.00f 45 0.59 0.12 0.29 185 84 ANA, MOR 50% Na+, 50% Li+
Sand and Sand (1973) 25.00f 10.00f 245 0.56 0.22 0.22 187 78 ANA, MOR 50% Na+, 50% Li+
Dai etal. (1986) 19.23f 0.38f 878 0.65 0.01 0.34 190 24 MFI, MOR Na+
Dai etal. (1986) 19.23f 0.77f 878 0.64 0.03 0.33 190 24 MOR Na+
Dai etal. (1986) 20.83f 0.42f 951 0.67 0.01 0.32 190 24 MFI, (MOR) Na+
Dai etal. (1986) 20.83f 0.83f 951 0.66 0.03 0.32 190 24 MOR Na+
Dai etal. (1986) 22.73f 0.45f 1038 0.68 0.01 0.3 190 24 MFI Na+
Dai etal. (1986) 22.73f 1.52f 1038 0.66 0.04 0.29 190 24 MOR Na+
Authenticated
Dai etal. (1986) 23.81f 1.59f 1088 0.67 0.04 0.28 190 24 MOR Na+

Dai etal. (1986) 25.00f 1.00f 1143 0.69 0.03 0.28 190 24 MFI Na+

Dai etal. (1986) 25.00f 2.00f 1143 0.68 0.05 0.27 190 24 MOR Na+
Dai etal. (1986) 27.78f 1.11f 1270 0.71 0.03 0.26 190 24 MFI Na+
Dai etal. (1986) 27.78f 2.22f 1270 0.69 0.06 0.25 190 24 MOR Na+
Dai etal. (1986) 31.25f 1.25f 1429 0.74 0.03 0.24 190 24 MFI Na+
Dai etal. (1986) 31.25f 2.50f 1429 0.71 0.06 0.23 190 24 MOR Na+
Dai etal. (1986) 38.46f 0.77f 1760 0.78 0.02 0.2 190 24 MFI Na+
Dai etal. (1986) 38.46f 2.56f 1760 0.75 0.05 0.2 190 24 MFI Na+
Dai etal. (1986) 38.46f 3.08f 1760 0.75 0.06 0.19 190 24 Amorphous Na+
Dai etal. (1986) 45.45f 1.30f 2081 0.8 0.02 0.18 190 24 MFI Na+
Aiello etal. (1987) 100.00r 2.22h 3328 0.89 0.02 0.09 190 120 MFI Na+
Zhao etal. (1998) 12.50 2.78h 797 0.49 0.11 0.40 190 194 HEU Li+
Zhao etal. (1998) 1.35 0.30h 34 0.12 0.03 0.86 190 165 HEU 98% Li+, 2% K+
Sand and Sand (1973) 50.00f 10.00f 245 0.71 0.14 0.14 190 48 MOR, Quartz 50% Na+, 50% Li+
Sand and Sand (1973) 50.00f 10.00f 495 0.71 0.14 0.14 190 16 ANA 50% Na+, 50% Li+
Lin etal. (2004) 5.15s 5.15s 67 0.25 0.25 0.49 200 96 JBW Na+
Lin etal. (2004) 6.90s 6.90s 102 0.29 0.29 0.42 200 0.5 LTA Na+
(Table 4Continued)
a b + (2)
s s
Lin etal. (2004) 6.90 6.90 102 0.29 0.29 0.42 200 1 LTA, JBW Na+
Lin etal. (2004) 6.90s 6.90s 102 0.29 0.29 0.42 200 1.5 LTA, JBW Na+
Lin etal. (2004) 6.90s 6.90s 102 0.29 0.29 0.42 200 240 JBW Na+
Lin etal. (2004) 20.83s 20.83s 360 0.40 0.40 0.2 200 96 JBW Na+
Grose and Flanigen (1981) 55.56 1.85 1523 0.82 0.03 0.15 200 70 MFI Na+
Lin etal. (2004) 13.33s 13.33s 207 0.36 0.36 0.27 200 96 ABW Li+
Lowe etal. (1994) 15.00i 1.00j 750 0.58 0.04 0.38 150c 79 Microcline, MER K+
Lowe etal. (1994) 60.00i 1.33l 3000 0.84 0.02 0.14 150c 122.4d TON K+
Lowe etal. (1994) 60.00i 2.00l 3000 0.83 0.03 0.14 150c 163.2 Cristobalite, TON K+
Lowe etal. (1994) 20.00i 0.07j 1000 0.665 0.002 0.333 150c 168 Kenyaite K+
Lowe etal. (1994) 60.00i 4.00l 3000 0.81 0.05 0.14 150c 168 Cristobalite, TON K+
Grose and Flanigen (1981) 48.27 1.19 1902 0.81 0.02 0.17 200 68 MFI 77.4% Na+, 22.6% Ba+2
Grose and Flanigen (1981) 39.37 0.97 1551 0.78 0.02 0.2 200 70 MFI 63% Na+, 37% Li+
Andersen etal. (1991) 2.86 2.86h 138 0.18 0.18 0.64 200 24 ABW 40% Na+, 60% Tl+
Andersen etal. (1991) 2.86 2.86h 138 0.18 0.18 0.64 200 24 ABW 40% K+, 60% Tl+
Andersen etal. (1991) 2.86 2.86h 138 0.18 0.18 0.64 200 24 ABW 40% Li+, 60% Tl+
a
b
Unless otherwise noted, the aluminum source is sodium aluminate.
Authenticated
c
d
e

f
Source not specified or unclear.
g

Sodium silicate.
h
Aluminum hydroxide.
i
Fumed silica.
j
Metallic aluminum.
k
Water glass.
l
Aluminum sulfate.
m
H2CO4 added.
n
Pseudoboehmite.
o
Aluminum isopropoxide.
p
Values estimated from reported range.
q
H2SO4 added.
r
Precipitated silica.
s
Metakaolin.
t
Silicic acid.
A High SAR(liq)
45
FAU 65C
65C
V (cm3/mol)
LTA 40
(Select cases)
GIS 100C 35
B Low SAR(liq)
ANA 180C 30
45
V (cm3/mol)
LTA 65C 40
SOD 100C 35
CAN 180C
Increasing temperature and/or synthesis time
Figure 6Stages of Na-zeolite phase transformation with increasing synthesis temperature and/or time. Structural transitions follow paths
of decreasing molar volume, V, which is consistent with the Ostwald step rule. Select sequences are shown for (A) high SAR(liq) (or Si-rich)
and (B) low SAR(liq) (or Al-rich) growth solutions (reprinted (adapted) from Maldonado etal. 2013, with permission from the copyright holder,
American Chemical Society).
There are many regions within each ternary diagram that in Section 2.1 that we discussed the approximate linear
contain multiple polymorphs, which is an undesirable correlation between the enthalpy of formation and molar
outcome in zeolite synthesis. At low temperature, there volume. On the basis of calorimetry studies, we might
are binary mixtures, but rarely more than two phases. anticipate the progression of zeolite transformations to
At moderate and high temperatures, the observation of follow a general trend from an initial structure with high
multiphase regions containing three or more structures is molar volume to some metastable intermediate or final
more common. There are many factors that contribute to structure with lower molar volume. This trend is true in
the formation of multiphase regions, which include (but some cases, such as those depicted in Figure 6, but it is not
are not limited to) synthesis time, temperature, solution valid for all phase transformations. Examples contrary to
composition, and selection of extraframework cations this trend include the reported transformation from MFI
(see Figure 10 showing the effect of temperature and water (32.7 cm3/mol) to MOR (35.4 cm3/mol) at high temperature
content on phase behavior). (Machado et al. 1999). The reason for such transforma-
The general trends in Figure 6 are consistent with the tions may be due to subtle differences in their solubility
correlation in Figure 1 between molar volume and thermal products (see Section 2.1). Conversely, kinetic factors may
stability. Zeolites formed at low temperature tend to be play a more dominant role in determining which metasta-
low density frameworks that progressively transform to ble structure is formed. For instance, the ternary diagram
more dense, and hence more thermodynamically stable, in Figure 5 reveals a switch from ANA (at low alkalinity) to
structures with increasing temperature and/or synthesis CAN (at high alkalinity) in growth solutions with identical
time. This trend, however, is not observed at all composi- SAR(liq). The CAN framework structure has a higher molar
tions within the ternary phase diagrams. Notable exam- volume, which seemingly contradicts the thermodynamic
ples include (1) the formation of CAN in Si-rich solutions trend; however, such claims cannot be made without suit-
at higher alkalinity, (2) the incomplete transformation of able data to confirm whether one structure is indeed more
SOD-to-CAN at low SAR(liq), and (3) the formation of frame- thermodynamically stable than the other. Information
work types not included in Figure 6 (e.g., JBW, LTN, MAZ, that would satisfy this requirement, such as the solubil-
MER, and EMT). As such, the diagram in Figure 6 is an over- ity product, is challenging to measure experimentally and
simplification of zeolite polymorphic transitions derived rarely reported in the literature. As such, differentiating
from thermodynamic studies of all-silica zeolites. Recall the relative roles of thermodynamic and kinetic factors for

Authenticated
phase transformations is equally challenging. Moreover, Past studies of early stage zeolite growth have focused
there are many questions regarding the mechanisms of on nucleation and the onset of phase transformation(s) for
zeolite nucleation, crystallization, and phase transforma- a variety of framework types, which include FAU (Freund
tion that remain unanswered. Schematics like those in 1976, Lechert and Kacirek 1993, Bosnar et al. 2005), LTA
Figure 6 help rationalize such phenomena, but they are (Valtchev and Bozhilov 2005, Itani et al. 2009, Broni
too simplistic to capture the subtle nuances governing etal. 2012), LTL (Itani etal. 2011), and MFI (ZSM-5, with
zeolite polymorphism. This motivates further investiga- OSDA) (Ren et al. 2012). Depending on synthesis condi-
tions to develop a fundamental understanding of zeolite tions, zeolite crystals may nucleate in a matter of minutes,
crystallization. but may take as long as weeks to fully crystallize. Some
studies have shown that a combination of low tempera-
ture and short synthesis time permits the synthesis of
3.1.2 Timescales for hydrothermal synthesis metastable structures that are otherwise challenging to
prepare in the absence of organics. An exemplary case
The effect of heating time on zeolite polymorphism is is EMT type zeolite where Ng et al. found that synthesis
less apparent than the impact of temperature. The syn- for 36h at low temperature produced pure EMT, whereas
thesis time reported in zeolite literature is often selected more prolonged synthesis time leads to SOD formation (Ng
arbitrarily or is based on prior protocols without exact etal. 2012a,b). For syntheses at high temperatures, iden-
knowledge of the timescales required for complete crys- tifying the first stage and subsequent intermediate stages
tallization. There are studies that have examined time- can be challenging because of the fast rates of growth and
elapsed changes in zeolite crystallinity and report that dissolution. For instance, a study at 200C reported the
variations in synthesis parameters can markedly alter formation of LTA after 30 min, followed by a mixture of
the induction period for zeolite nucleation and the rate LTA and JBW after 1 h, and pure JBW after 3h (Lin etal.
of crystal growth. Any modification to a reported proto- 2004). It should be emphasized that the steps depicted
col in the literature or the ad hoc selection of hydrother- in Figure 6 were analyzed after a set period of time (i.e.,
mal synthesis time may result in a crystallization period 7 days or longer) to examine pseudo-equilibrium struc-
that is either too short, which can yield a partially amor- tures at intermediate stages of phase transformation. The
phous product, or too long, which may lead to the for- exact sequence of stages for structures prepared at high
mation of crystal polymorphs. The timescales for phase temperature, such as CAN, ANA, and JBW, has not been
transformation can be as short as hours or as long as fully characterized. For instance, ANA does not necessar-
weeks. Here we highlight only a fraction of the reported ily have to form through the sequence FAUGISANA,
cases that examined the effects of synthesis time. Basal- but may involve alternative routes, including different
della and Tara (1995) showed that an FAU-LTA binary intermediates and/or fewer stages of transformation.
mixture after 4days of heating (at 56C) will transform Characterizing zeolite nucleation is nontrivial as the
to a mixture of FAU and SOD after 7 days. Komarneni and low mass yield of crystals and small particle size renders
coworkers report the initial formation of RHO followed some common analytical techniques, such as X-ray dif-
by its gradual transformation to CHA and amorphous fraction and scanning electron microscopy, less effec-
material with longer synthesis time (Park et al. 1996). tive. The aforementioned studies of EMT (Ng etal. 2012a)
Other groups report transitions at short timeframes, required X-ray synchrotron measurements and transmis-
such as the transformation from SOD to a binary mixture sion electron microscopy studies to refine the structure.
of SOD and CAN after 16h (Fan etal. 2008, Khajavi etal. At low temperatures, the nucleation and initial steps of
2010). In our own work, we have seen various crystal crystal transformation is usually slow enough to capture
transitions taking place. One example is a syntheses metastable phases, such as EMT. At elevated tempera-
at 95C where an initial FAU-LTA binary mixture trans- tures, the window of time to observe these changes is
forms to a FAU-LTA-GIS-SOD quaternary mixture after often much shorter. The most common timeframe reported
72 h, then a FAU-GIS-SOD ternary mixture after 168 h, for zeolite crystallization in the literature is 17 days. In
and finally with increased temperature (e.g., 180C) some instances, this amount of time may be too short to
the final product is pure CAN (Maldonado et al. 2013). see interesting phenomena. One example is a patent by
From these examples and many others, it is evident that Skeels and Sears (1993) that reports the synthesis of zeolite
the sequence of stages and the number of polymorphs LZ-277 (PHI type) at 100C. The conditions employed in
present at any given time of a zeolite synthesis can vary their study resulted in amorphous material after 30 days,
significantly. pure PHI after 47 days, and the emergence of GIS (minor

Authenticated
impurity) after 54 days. This is an interesting observation during zeolite nucleation is correlated with aging time. A
as PHI and GIS have identical molar volume, which sug- more detailed discussion on the mechanistic aspects of
gests these structures have similar thermodynamic stabil- aging can be found in the review by Cundy and Cox (2005),
ity; however, fundamental investigations like the one used which summarizes syntheses for different silica sources.
to analyze PHI-to-GIS phase transformation over the course Here we focus on the effects of aging for growth solutions
of months are impractical. Nevertheless, such studies do that have been prepared using colloidal silica sources.
suggest that interesting phase behavior may be observed if One of the earliest reported studies of aging was
systems are permitted enough time (i.e., beyond 7 days) to Brecks patent on the crystallization of zeolite Y (FAU
allow structural transformations to occur. type) (Breck 1964). Breck noted that aging growth solu-
To summarize the effect of synthesis time, it is evident tions at ambient temperature resulted in a product that
that the duration of hydrothermal treatment is an impor- was 92% crystalline, whereas the same synthesis condi-
tant factor that regulates zeolite phase behavior. The times tions without aging yielded a product that was only 63%
selected for zeolite synthesis are often arbitrary, which crystalline. A recent study of LTA synthesis by Alfaro etal.
makes it difficult to determine if a transformation has revealed the effects of aging by examining growth solu-
occurred, and if so, the exact sequence of stages over the tions that were heated at 100C for 24 h after first sub-
course of crystallization. The presence of crystal impuri- jecting these solutions to various aging times at room
ties in zeolite synthesis is common, and in certain cases temperature (Alfaro et al. 2007). Powder XRD patterns
polymorphism can be avoided by the prudent adjustment of samples prepared with only 24 h aging contained no
of synthesis time. In other instances, polymorphs are diffi- apparent crystalline peaks, whereas 48 h aging resulted
cult to remove, as evidenced by many multiphase regions in broad (low-intensity) peaks, and additional aging for
in the ternary diagrams. It is reasonable to suggest that if 72144h yielded narrow (high-intensity) peaks in the XRD
provided enough time these multiphase regions may shift patterns. Collectively, these studies reveal that increased
to pure phases or lead to the nucleation of new crystal aging time can reduce the time of hydrothermal treatment
structures. Examples in the literature, however, suggest required to obtain a more fully crystalline product.
the necessary times to observe these changes could be on There are numerous examples in the literature report-
the order of months. ing the effects of aging on zeolite phase behavior. One such
example is the work by Ogura et al. (2003) that reveals
the synthesis of FAU can be shifted to a binary mixture of
3.1.3 Aging of growth solutions ANA and SOD with reduced aging time. In a similar study
of FAU synthesis, Ginter et al. (1992) showed that room
The procedure referred to as aging in zeolite synthesis is temperature aging for a minimum of 2h was required to
the period of time when growth solutions are mixed at obtain FAU as the major phase, whereas NaS (GME type)
a temperature less than the one used for hydrothermal and NaR (CHA type) were formed without any aging.
synthesis. Aging at low temperatures favors nucleation These studies illustrate that a subtle change in aging time
of crystals, rather than growth, which can have a marked (on the order of hours) can have a pronounced effect on
effect on crystal size (Ginter et al. 1992, Koroglu et al. the zeolite phase. Although fundamental explanations
2002, Ogura et al. 2003). Increased aging time has been for these observations are lacking, phenomenological
correlated to a decreased hydrothermal time necessary to associations can be made between the composition of the
achieve the same relative degree of crystallization (Breck initially nonhomogeneous growth solution and zeolite
1964, Ogura etal. 2003, Alfaro etal. 2007). It is important to nucleation. As previously mentioned, colloidal silica
keep in mind that the majority of aging studies in the liter- requires time to dissolve prior to zeolite nucleation and
ature have been conducted using colloidal silica sources, crystallization (Fahlke etal. 1987, Ogura etal. 2003). In the
which produce a nonhomogeneous initial solution where studies by Ginter et al. (1992), the solution composition
much of the silica is contained within the colloidal silica was monitored at periodic times during FAU synthesis. As
particles, thereby resulting in an Al-rich environment shown in Figure 7, the Si concentration at room tempera-
that is not entirely representative of the molar ratio used ture increases with aging time while Al decreases. After
to prepare the initial growth solution or gel (Maldonado heating the solution at 100C for 10 h, changes in Si and Al
et al. 2013). The aging period presumably allows for the concentrations with aging time were negligible.
redistribution of silica via dissolution (or so-called silica Past studies have also shown that increased aging
depolymerization) to create a more homogeneous solu- time generally decreases crystal size (Ginter et al. 1992,
tion. Therefore, the local environment of growth solutions Koroglu etal. 2002, Ogura etal. 2003). It is reasonable to

Authenticated
3 0.5 A review of zeolite literature raises questions as to

Triangle: 0 h Si
what constitutes aging as many studies report experi-
Circle: 10 h Al 0.4
ments at temperatures and times similar to those used for
2
0.3
zeolite growth conditions. Even short aging periods (e.g.,
Si (mol/l)
Al (mol/l)
624 h) commonly used to mix reagents at room tempera-
0.2 ture prior to hydrothermal treatment may be sufficient to
1
induce nucleation and crystal growth. This is certainly
0.1
true for framework types such as FAU, EMT, LTA, and SOD.
0 0
In some instances, aging studies have been reported at
0 20 40 60 80 100 elevated temperatures. A notable example is a study by
Aging time (h) Park etal. (1996) where they investigated RHO synthesis
Figure 7Evolution of Si (gray) and Al (white) concentrations in an using solutions aged for 3days at 25, 35, 45, and 55C. The
FAU growth solution aged for different times. The supernatant was latter case is similar to the temperatures used in other
analyzed by elemental analysis to examine changes in Si and Al RHO crystallization studies. As such, careful considera-
content for solutions aged at room temperature (triangle) and after tion should be given to define what is meant by aging. In
heating for 10h at 100C (circle) (reprinted from Ginter etal. 1992,
situations where prolonged mixing of growth solution at
with permission from the copyright holder, Elsevier).
fixed temperature prior to hydrothermal treatment leads
to nucleation, it may be more appropriate to consider the
process as a two-stage temperature synthesis. Conversely,
suggest that longer aging time increases the rate of nuclei
if the time selected does not exceed the induction period
formation. Moreover, aging can influence the SAR(s) of
(i.e., onset of nucleation) then aging is an appropriate
zeolite crystals. Ogura et al. (2003) systematically meas-
descriptor. Determining the difference between these two
ured the SAR(s) of FAU crystals extracted from growth solu-
cases, however, is not always straightforward.
tions that were heated at 90C for various times. As shown
in Figure 8, their investigation revealed that samples aged
for 2 days yielded FAU crystals with higher SAR(s) than
3.2 Water content
those aged for 7 days. Within the 24-h timeframe of the
study, samples aged for 2days steadily increased in SAR(s)
Extracting information from zeolite literature regarding
by ca. 0.02 h-1. Although Ogura etal. did not examine SAR(s)
the effect of water content can be challenging as there
values beyond a 24-h synthesis time, it is reasonable to
is no established convention for assessing this vari-
expect the SAR(s) would continue to increase with longer
able. As a means of standardization, we have rescaled
heating times (although not beyond a maximum SAR(s),
the molar ratios reported in prior work using the com-
which usually lies between 3.0 and 3.5 for FAU and other
position x Si:y Al:10 MOH:z H2O. The hydroxide source
related structures consisting of 4- and 6-MRs) (Lechert
is often reported as M2O, which is related to MOH by the
2000).
reaction M2O+H2O2MOH (i.e., the consumption of one
water molecule must be accounted for when converting
from M2O to MOH in the mole ratio). The 10 MOH:z H2O
1.4
Triangle: 2 days ratio was selected arbitrarily as a reference for assessing
Circle: 7 days
water content. By fixing the hydroxide concentration, we
SAR(S)
1.2 can compare both the Si-Al-OH mole fractions (i.e., loca-
tion within the ternary diagram) as well as the amount of
1.0 water. The water content, or z, of zeolite syntheses ranges
0 6 12 18 24 30 from 30 to 4400. Our analysis of nearly 200 references
Crystallization time (h)
revealed that the most common water content in zeolite
Figure 8Silicon-to-aluminum ratio, SAR(s), of zeolite powders syntheses ranges from z=100300 (see Figure 9).
extracted from growth solutions as a function of crystallization time. The histogram in Figure 9 shows that a majority of
Data are reported for samples that were aged at room temperature syntheses employ water contents lower than z=300.
for 2days (triangle) and 7days (circle) prior to crystallization at
Conversely, few report syntheses with z>1000, indicat-
90C. Filled symbols represent samples lacking crystallinity in
powder XRD patterns and open symbols correspond to crystalline
ing that compositions of high water content are infre-
samples (reprinted (adapted) from Ogura etal. 2003, with permis- quently used in OSDA-free conditions. The prevalence of
sion from the copyright holder, American Chemical Society). low water content syntheses may be attributed to the fact

Authenticated
300 293
21
Frameworks
250 synthesized
200
167
Frequency
150 18
Frameworks
synthesized
100
81
75
64 66
60 10
14
50 13 12 Frameworks
Frameworks 11
Frameworks Frameworks synthesized
synthesized Frameworks
synthesized synthesized synthesized
0
Water contemt of reaction mixture
50< z 100 100< z 200 200< z 300 300< z 400 400< z 500 500< z 1000 1000 < z
Figure 9Statistical data on the number of zeolite syntheses reported at various water contents (i.e., molar ratios of 10 OH:z H2O). The fre-
quency corresponds to the number of syntheses (based on references in this review). The water content was subdivided into approximately
equal regions with the exception of more dilute growth solutions (z>500), which are less frequently used in zeolite synthesis. Numbers
within each bar correspond to the number of different zeolite framework types that have been synthesized using the corresponding water
contents.
that the most widely studied zeolites, such as FAU (or colloidal silica. For instance, Greenberg and cowork-
zeolites X and Y), are prepared at z=100300. At lower ers demonstrated that silica dissolution at pH >11 is
water content, we observed a limited number of Si-Al-OH independent of pH (i.e., hydroxide concentration), but
mole fractions reported in the literature, which reveals depends on the particle size of colloidal silica and the
that few regions of the ternary phase diagrams have silica concentration (Greenberg 1957, Iler 1979). At lower
been explored. The majority of these studies employ low water content, the silica concentration is larger, thus
Si and high OH fractions, which tend to produce sols providing a higher rate of dissolution. The release of
rather than highly viscous gels. For instance, we have silica from the colloidal source increases its availability
seen that growth solutions with high Si mole fraction for zeolite nucleation and growth. It is therefore reason-
and low water content lead to rapid gelation (Maldonado able to suggest that water content plays a major role in
et al. 2013). We analyzed zeolites grown from an initial regulating the formation of soluble silicate and/or alu-
gel rather than sols and observed the formation of less minosilicate species, and possibly precursors of zeolite
dense frameworks, such as multiphase mixtures of FAU, frameworks.
GIS, and SOD. The water content used in zeolite syntheses prior to
Changes in water content alter the concentrations of ca. 1970 was commonly unspecified in experimental pro-
SiO2 and Al2O3 in growth solutions, and may (but not nec- cedures. More recent studies have placed greater emphasis
essarily) alter the pH. Variations in alkalinity are more on the importance of water content, notably its impact on
difficult to predict a priori as the total concentration of zeolite crystal phase. Lower water content tends to favor
hydroxide ions used in the growth solution is depleted the formation of denser (more thermodynamically stable)
by solution chemistry, i.e., the dissociation of silanol phases whereas higher water content favors the forma-
groups in the zeolite framework or soluble species, such tion of less dense phases (Valtchev et al. 2005, Ng et al.
as silica oligomers. As such, it is not accurate to estimate 2012a, Maldonado etal. 2013). Maldonado etal. explored
the alkalinity using the 10 MOH:z H2O ratio. Instead, a the FAU/LTA kinetic phase diagram using a NaOH-Si-
more practical comparison is the (Si+Al+OH)/H2O molar Al-H2O system at various NaOH:H2O molar ratios (see
ratio. This ratio can have a marked effect on zeolite Figure10B). For syntheses at low temperature, decreased
crystallization, particularly the initial dissolution of water content reduced the binary FAU-LTA region, and

Authenticated
Figure 10Ternary diagrams for Na-zeolites plotted as a function of temperature and water content (or z mole ratio). All data correspond to
zeolite growth solutions using colloidal silica and sodium aluminate as the sources. (A) Growth solutions with a mole ratio of 11 NaOH:190
H2O were heated for 7 days, with the exception of 180C data that was heated for 3 weeks. (B) Growth solutions with mole ratios of 11
NaOH:z H2O were heated at 65C for 7 days. The dark segment of the binary region for z=348 H2O represents the two-phase region predicted
by Sefcik and McCormick (reprinted (adapted) from Maldonadoet al. 2013, with permission from the copyright holder, American Chemical
Society).
eventually resulted in a switch to SOD formation in both 30C). EMT is a challenging zeolite to synthesize in OSDA-
Si- and Al-rich regions of the diagram. This transition to free media. The successful synthesis of EMT was ini-
a more dense SOD framework occurred at ratio 10 NaOH:z tially attributed to the use of low temperature; however,
H2O with z=60100. Similar observations by Bosnar etal. the authors also reported that syntheses at higher water
(2012) revealed that low water content (i.e., z=90) induced content using the same Si-Al-OH mole fractions (i.e., the
a partial LTA-to-SOD transition. Valtchev et al. (2005) same point in the ternary diagram) resulted in mixed EMT
observed the same transition, which is shown in Table5 and FAU phases. In a separate study, Ng et al. asserted
listing the compositions (on the order of decreased water that low temperature facilitates the formation of pure
content) and the resulting zeolite phase(s). A general EMT because of slower reaction kinetics (Ng etal. 2012b).
trend observed in this study was a reduction in the onset Our investigations of FAU synthesis at higher temperature
of amorphous-to-LTA transformations with decreasing also revealed the initial formation of EMT, but at shorter
water content. times, suggesting the low water content of the growth
Ng et al. (2012a) reported the formation of EMT-type solution is the dominant factor governing EMT formation
zeolite at low water content and low temperature (ca. (Maldonado etal. 2013).
As previously mentioned, zeolite structures with
lower molar volume tend to crystallize in growth solu-
Table 5Synthesis of LTA crystals at 25C (Valtchev etal. 2005). tions with reduced water content. An exception is MFI,
which is synthesized at high water content (z>1000)
Water content, z Mole fraction Time (days) Phasea
over a wide range of temperatures and a narrow region
10 NaOH:z H2O Si Al NaOH of mole fractions within the ternary diagram. Interest-
328.3 0.13 0.13 0.75 12 LTA ingly, almost all syntheses in highly siliceous regions of
245.0 0.10 0.10 0.80 7 LTA the ternary diagram are performed at high water content
195.0 0.08 0.08 0.83 5 LTA (typically z>800). There are exceptions to this trend,
161.7 0.07 0.07 0.86 4 LTA which include the formation of FER and MER in Si-rich
161.7 0.07 0.08 0.85 4 LTA
solution with z=370 (Han etal. 2006). It was shown that
161.7 0.07 0.07 0.86 5 LTA, (Ub)
161.7 0.07 0.06 0.87 6 LTA, Ub a decrease in water content promotes the formation of
120.0 0.07 0.08 0.85 3 LTA MER, which has a lower molar volume than the struc-
120.0 0.06 0.06 0.89 4 LTA, SOD tures formed from Si-rich solutions with higher water
103.3 0.07 0.08 0.85 3 LTA, SOD contents (e.g., MFI, FER, MOR, and MEL; see Table 1).
Phases in parentheses are in trace amounts.
a To better understand the role of water in highly siliceous
U, unidentified phase.
b
syntheses, we refer to a study on the formation of ZSM-5

Authenticated
by Dai etal. (1986) in which they varied SAR(liq) and water 3.3 Sources of silica and alumina
content and formed both MOR and MFI. Their data, which
is presented in Table 4, suggest that high water content There are many silica sources used in zeolite synthesis,
promotes pure MFI, whereas a reduction in water content among which include colloidal forms (e.g., LUDOXTM),
(i.e., z<1000) yields either pure MOR or mixtures of MOR fumed silica (e.g., Cab-O-Sil), silicic acid, and silicate solu-
and MFI (depending on the selection of SAR(liq)). The syn- tions such as sodium metasilicate and TEOS (or tetraeth-
theses of Dai et al. yielded MFI at water contents that oxysilane). The selection of a silica source can influence
typically form MOR. This phenomenon was also observed how rapidly silica is released into solution, which in turn
by Machado etal. (1999), although their studies revealed regulates the homogeneity of the initial growth solution.
an amorphous-to-MFI-to-MOR transition with increased We discussed in Section 3.1.3 the effects of silica avail-
synthesis time, which suggests that the more dense MFI ability via aging (notably for colloidal sources), which
structure is metastable relative to MOR. Similarly, Dai impacts the induction period. For example, so-called
et al. (1986) showed that MOR was more favorable with aluminosilicate gels may act as sites for heterogeneous
increasing Al content (see Table 4). Collectively, these nucleation, or may dissolve to provide solute for homo-
studies highlight three observations for the selective crys- geneous nucleation and growth of zeolite crystals. Bein,
tallization of MFI over MOR: (1) high water content favors Mintova, Valtchev, and others have investigated FAU and
MFI formation; (2) Si-rich growth solutions promote MFI LTA nucleation using colloidal silica sources (Mintova
crystallization; and (3) MFI is an inherently metastable et al. 1999a,b). These studies have relied on analytical
phase relative to MOR at certain synthesis conditions, techniques such as TEM to monitor the temporal evolution
whereby reduced synthesis time appears to suppress of aluminosilicate precursors and examine their amor-
MOR formation. phous-to-crystalline transitions. Their studies suggest
When evaluating data gathered from the litera- that each amorphous particle serves as a nucleation site
ture, we must consider the fundamental role water for a single (or possibly multiple) crystals. Interestingly,
content has on zeolite formation. We discussed how the final crystal size often equals that of the initial alumi-
changes in water content can influence the composi- nosilicate precursor, which was attributed to nucleation
tion of the reaction mixtures, such as the concentrations occurring within the amorphous particle interior followed
of soluble species and solution pH; however, the lack by consumption of the amorphous aluminosilicate parti-
of in situ measurements to assess temporal changes of cle during LTA or FAU crystallization. The selection of a
zeolite growth solution speciation renders it challeng- silica source in many ways controls the homogeneity of
ing to quantify the effects of water content. Along these precursor growth solutions, and thus impacts zeolite
lines, the mechanism of zeolite crystallization and more nucleation and perhaps even the final crystal size.
quantitative rate expressions of growth at various reac- The use of TEOS as a silica source is less common in
tion conditions are needed. According to classic theo- OSDA-free synthesis, and for many growth solution com-
ries of crystallization, growth is highly dependent on positions it results in either amorphous or non-zeolitic
solute supersaturation. Zeolite crystallization is rarely products. Our studies have shown that LTA and FAU crys-
discussed in these terms because of the linear rate of tallization can be achieved using either colloidal silica or
crystal growth observed for different framework types TEOS (without any noticeable differences in the physi-
(as discussed in Section 2.3). To this end, it is uncertain cal properties of the final crystal product). The effect of
what role the silica and alumina concentrations have TEOS on crystal phase purity was examined by Wiersema
in mediating zeolite crystallization and phase selectiv- and Thompson (1996) while attempting to grow ANA.
ity. Within this context, it can be asked what effect con- They found that if the growth solution was subjected to
centrated solutions have on the growth mechanism(s) hydrothermal treatment prior to the complete hydroly-
considering zeolite growth kinetics is seemingly inde- sis of TEOS, the final product contained multiple crystal
pendent of silica or alumina concentration. Clearly, the impurities. Conversely, if the solution was stirred at room
water content plays a major role in zeolite phase behav- temperature for 110days to permit TEOS hydrolysis, the
ior, but it is uncertain if its effect is attributed to tempo- final product was pure ANA (although the time required
ral changes in precursor species, such as basic building to achieve a crystalline product was noticeably longer
units, which are presumed to be growth units in zeolite than syntheses employing colloidal silica). Furthermore,
crystallization. Without these basic understandings, Wiersema and Thompson performed an experiment that
fundamental questions regarding the effects of water mimicked TEOS growth solutions wherein fumed silica
content remain largely unanswered. was used as the silica source and ethanol was added to

Authenticated
the solution to simulate the by-product of TEOS hydroly- Table 6Phase selection based on the choice of silica source
(Krznari etal. 2003).
sis. Interestingly, this synthesis produced similar zeolite
impurities as the TEOS synthesis an outcome that could
Sample Si Al OH H2O Heating Major Silica source
potentially be attributed to slow dissolution of fumed timea (h) phaseb
silica, which mimics the slow hydrolysis and release of
I 4.28 1.74 10.0 283 4.0 FAU Water glass
silica from the immiscible organic layer (TEOS) to the
II 3.96 1.63 10.0 276 3.0 LTA Na2SiO3
aqueous solution. III 4.24 1.68 10.0 276 2.7 FAU Na2SiO35H2O
The slow dissolution of silica generates a non-homo- IV 4.24 1.69 10.0 285 1.8 LTA Fumed silica
geneous solution comprised of Si-rich colloidal particles a
Heating times at 80C following 48h aging at room temperature.
and Al-rich aqueous solution. As previously discussed, b
Each sample contained a mixture of LTA, FAU, and GIS.
aging helps facilitate the homogenization of growth
solutions, but not entirely. As such, the Al-rich solutions
present an environment for zeolite nucleation that is not
representative of the overall molar composition used to Another class of materials that have been used as
prepare the growth solution. Our studies have shown that silica or alumina sources are naturally occurring alumi-
solutions prepared with SAR(liq) >1 can induce the forma- nosilicates, such as kaolin (Basaldella and Tara 1995,
tion of zeolite frameworks that tend to only crystallize in Mackinnon et al. 2006, Rios et al. 2009a) and metakao-
Al-rich solutions. For example, the synthesis of FAU near lin (a dehydroxylated form of kaolin) (Lin et al. 2004).
the two-phase FAU-LTA boundary (see Figure 10) resulted Kaolin is a natural clay that is mined by various compa-
in the initial formation of LTA, followed by a transforma- nies. There is an inherent lack of control associated with
tion to FAU as the growth solution was enriched in silica using clay due to the presence of impurities, such as Fe2O3
(Maldonado et al. 2013). The progression of stages illus- (ca. 0.21%) or TiO2 (ca. 0.49%) (Basaldella and Tara 1995).
trated in Figure 6 seemingly defies the Ostwald step rule Dehydration of kaolin by heat treatment can produce a
as the LTA-to-FAU transition involves the switch from a more Si-rich source (Kazemimoghadam and Mohammadi
structure with lower molar volume to one that has higher 2011). Additionally, there has been interest in utilizing
molar volume (less thermodynamically stable). We attrib- waste materials, such as rice husk or fly ash, as silica and/
uted this phenomenon to the slow dissolution of colloidal or alumina sources (Bajpai etal. 1981, Rios etal. 2009b,
silica during the induction period. Navrotsky and cowork- Azizi and Yousefpour 2010, Naskar etal. 2011). Recovery
ers have suggested that the amorphous precursors (com- of silica from rice husk ash has proven to be an effective
monly referred to as gels in the literature) are composed method to obtain a nearly pure silica source (Kalapathy
of undissolved colloidal silica (Yang et al. 2000). The etal. 2002). Problems associated with the use of rice husk
slow dissolution of silica might explain why the study by are the excess Na+ ions retained within the product and
Wiersema and Thompson reported crystal impurities with its variable composition based on the degree of washing.
reduced aging time. The excess cations in rice husk ash may explain observa-
It is not uncommon to observe a switch in crystal poly- tions that the use of rice husk reduced the Na2O content
morphs when changing silica sources. An example is the in zeolite growth solutions necessary to achieve a desired
study by Krznari et al. (2003) in which they compared crystalline product compared to other silica sources
the products obtained from four different silica sources: (Bajpai etal. 1981). On the basis of variability in different
Na2SiO3, Na2SiO35H2O, water glass, and fumed silica. rice husk or ash feedstock, one may wish to analyze the
This study compared two batches with different composi- silica recovered from these sources for elemental impuri-
tions that were heated at 80C until no amorphous phase ties; however, such pre-treatment or analysis steps raise
was present. The syntheses were performed at differ- the cost of using these sources. Moreover, a lack of consist-
ent heating times (see Table 6), resulting in multiphase ency among batches of ash or clay leads to the inclusion
mixtures of LTA, FAU, and GIS; however, the dominant of various metals or other species, which is problematic
phase (either LTA or FAU) was heavily dependent upon for use in fundamental studies. For instance, Ruiz et al.
the choice of silica source. The authors rationalized their added Mg(NO3)26H2O to their silica source and observed
observations based on potential differences in nuclei, the an overall decrease in the size of LTL crystals, as well
secondary building units (e.g., d4R of d6R), and/or the as increased agglomeration of crystals when Mg2+ was
different growth rates of each framework type (meanwhile present in amounts greater than 10ppm (Ruiz etal. 2005).
emphasizing that these factors are interrelated, but not A similar effect reported by Lee et al. revealed that the
fully understood). addition of MgCl2 in an amount corresponding to 8.210-5

Authenticated
mol% of the growth solution resulted in an approximate

50% reduction in the length and width of LTL crystals Alo(OH)
compared to the same conditions in the absence of MgCl2
(Lee etal. 2005). As such, it is evident that trace quantities NaAlO2 solution
of chemical impurities in silica and alumina sources can
Intensity (a.u.)
impact zeolite crystallization. Al(OH)3
The vast majority of zeolite synthesis is performed in
NaAlO2 solid
either plastic or Teflon containers; however, the older lit-
Al(C3H7O)3
erature often reported OSDA-free synthesis in glass con-
tainers. Although this procedure is now less common, it Al(NO3)3
is important to note that the glass surface can (1) serve Al2(SO4)3
as a site for heterogeneous nucleation and (2) dissolve in 10 20 30 40 50
highly alkaline growth solutions to alter the concentration 2 ()
of silica. This latter effect is difficult to quantify, but has
Figure 11Powder X-ray diffraction patterns of products from zeolite
been studied by Cichocki and coworkers during zeolite T
syntheses employing various alumina sources. Bragg peaks for the
(ERI-OFF) synthesis (Cichocki 1985). This study examined AlO(OH), NaAlO2(aq), and Al(OH)3 samples were indexed as mixtures
the effects of glass containers by adding pieces of glass to of ZSM-5 (MFI) and ZSM-11 (MEL). The patterns for samples prepared
growth solutions and performing the synthesis in either with NaAlO2(s) and Al(C3H7O)3 appear amorphous, whereas the XRD
a glass or steel container. Cichocki observed that glass pattern for Al2(SO4)3 appears to be a mixture of amorphous material
and some unreported crystalline phase (reprinted from Zhang etal.
dissolution favored the formation of PHI-type impurity
2012a, with permission from the copyright holder, Elsevier).
and increased crystal yield. Although it was not explicitly
considered in earlier studies, glasses contain impurities,
such as boron, that can potentially influence zeolite for-
mation. To this end, the early literature using glass bottles and aluminum isopropoxide both yielded amorphous
typically fail to account for silica or impurities potentially material; aluminum oxyhydroxide [also referred to as
leached from the bottle. aluminum hydroxide oxide, AlO(OH)], alumina hydrox-
Few studies in the literature have thoroughly exam- ide, and sodium aluminate (aqueous) formed a crystal-
ined the effects of alumina sources on zeolite synthesis. line material; and both aluminum nitrate and aluminum
Common sources include aluminum hydroxide (Al(OH3)), sulfate yielded a structured, but unknown product.
alumina, sodium aluminate (Al2O3Na2O or NaAlO2), Al Interestingly, the use of solid and aqueous sodium alu-
metal (e.g., powder, ribbon, foil, etc.), aluminum nitrate minate resulted in amorphous product and fully crystal-
(Al(NO3)3), aluminum sulfate (Al2(SO4)3), and aluminum line zeolite, respectively. Possible reasons why Al sources
isopropoxide (Al(C3H7O)3). The latter hydrolyzes to resulted in different products were not discussed. Answers
produce an organic product (propanol), which although to these questions seemingly require further studies to
present in low quantity, has the potential to alter crystal- elucidate the effect of the alumina sources on zeolite
lization. Our group and others have shown that organics phase behavior.
can act as modifiers of crystal habit, and may induce poly-
morphism (Carr and Shantz 2005, Ban et al. 2007, Brent
et al. 2010, Gomez et al. 2011, Gaona-Gomez and Cheng 3.4 Extraframework cations
2012, Lupulescu and Rimer 2012, Lupulescu et al. 2013).
The use of aluminum salts, such as Al(NO3)3 or Al2(SO4)2, The choice of extraframework cation(s) used in a growth
can alter the solution alkalinity via the formation of acidic solution has a significant impact on zeolite crystalliza-
compounds. Sodium aluminate accumulates carbonate if tion, as discussed in Section 3.1.1 when comparing trends
exposed to the atmosphere for long periods of time, which in the ternary diagrams. Naturally occurring zeolites
can lead to the possible sequestration of Na+ in solution often have multiple extraframework cations within their
via the formation of either sodium carbonate, Na2CO3, or structures. Examples include natural faujasite, which is
sodium bicarbonate, NaHCO3. A recent study by Zhang composed of four cations ((Na,K,Ca0.5,Mg0.5)56[Al56Si136O384]
et al. (2012a) examined the effect of several Al sources 235H2O), and offretite, which contains three cations
on phase behavior. This study showed that changes in Al (CaMgK[Al5Si13O36]16H2O) (Passaglia and Sheppard
source resulted in a wide variety of products (see the XRD 2001). Many crystal phases obtained in OSDA-free syn-
patterns in Figure11). Notably, sodium aluminate (solid) theses are analogues of natural zeolites. Table 1 lists the

Authenticated
different zeolite structures obtained from OSDA-free syn- 2006). In the case of MFI crystallization, switching from
thesis (where natural zeolites are marked with an aster- Na+ to K+ results in different products, including MER,
isk). Typical syntheses employ molar ratios of the general TON, non-zeolitic minerals (e.g., kenyaite, cristobalite,
form SiO2:Al2O3:M2O:H2O, where M is the extraframework and microcline), and trace quantities of MFI (Lowe etal.
cation. The most commonly used cations are Na+ and 1994). Past studies suggest that Na+ promotes MFI forma-
K+; however, there have been studies that utilize other tion. Conversely, the presence of Na+ appears to suppress
cations, including those reported in natural zeolites (e.g., the formation of EDI, which readily forms in solutions of
Li+, Cs+, Tl+, Ca2+, Sr2+, and Ba2+). There are significantly K+, Li+, and Tl+. Another example is the formation of JBW
fewer studies employing divalent cations compared to in Na+ growth solutions, and the formation of the closely
monovalent cations, presumably because of the difficulty related zeolite structure ABW in the same growth solu-
of maintaining a stable growth solution with the addition tions employing Li+ as the cation. Interestingly, a binary
of divalent cations. For instance, the inclusion of calcium mixture of Tl+ with a host of other alkali metals (e.g., Li+,
in growth solutions may screen electrostatic interactions Na+, or K+) also yields ABW so long as Tl+ accounts for 60%
between negatively charged precursor species, which can or more of the cation content (Andersen etal. 1991).
induce the aggregation of aluminosilicate sols. Interest- There is a relatively large body of work examining
ingly, the majority of natural zeolites contain divalent binary mixtures of Na+ and K+ cations. A thorough inves-
cations in trace quantities. As such, it is reasonable to tigation of cation effects was presented by Basaldella and
suggest that further studies of zeolite synthesis with diva- Tara (1995) in which they systematically observed the
lent cations may lead to discoveries of new zeolites or syn- impact of various blends of Na2O and K2O in the synthe-
thetic analogues of natural zeolites that are unattainable sis of FAU. Starting from growth solutions in which Na2O
by conventional methods. was used in the absence of K2O, mixtures of FAU, LTA, and
The majority of OSDA-free syntheses in the litera- SOD were formed (depending on the synthesis time). The
ture use Na+ as the cation. There are often notable differ- gradual substitution of Na+ with K+ (while maintaining a
ences when the cation is changed to K+. These changes fixed hydroxide concentration) promoted the formation
are evident in the phase diagrams (Figures 35), such of pure FAU. When the amount of K+ in the binary cation
as the transformation from MOR to LTL when the cation mixture reached 18%, only FAU was formed. Further
is switched from Na+ to K+. An interesting change was increase in K+ content subsequently increased the synthe-
observed by Lowe etal. (1994) in which they studied the sis time necessary to form a crystalline phase; however,
synthesis of K+-MFI. Few samples in their study yielded once an equimolar ratio of Na+:K+ was reached, Basal-
MFI in the presence of K+, but instead resulted in the for- della and Tara observed no crystal formation (even after
mation of NU-10 (TON type) under conditions where MFI 198h of heating). These results suggest that crystal purity
would readily form if Na+ was used as the cation. This is can be tuned by utilizing mixtures of cations, perhaps
one of the few systems in which MFI was unable to crys- because of their kinetic effects on zeolite crystallization
tallize. As previously discussed in Section 3.1.1, MFI has since cations may act as inorganic structure-directing
been synthesized using Na+ and mixtures of Na+ with Li+ agents in zeolite synthesis. Analogous effects on crystal
or Ba2+, although further studies of pure mono- and diva- phase purity were observed by Warzywoda and Thomp-
lent cations would be necessary to elucidate the differ- son (1991) who showed that EDI and CHA were produced
ent effects of these cations in MFI formation. Additional from K+ growth solutions, whereas a mixture of 80% K+
studies have shown that the selection of cations other and 20% Na+ resulted in the formation of pure EDI.
than Na+ can yield structures, such as zeolite K-H (MER Additional systems of mixed cations have been
type), cristobalite, kenyaite, and microline, which are not studied, including Robsons work on zeolite RHO crys-
often reported. tallization (Robson 1975) using mixtures of Na+ and Cs+
A comparison of various cations in the ternary (see Table 7). These studies revealed that as the percent-
diagram for low-temperature syntheses (see Figure 3) age of Na+ was increased above 91%, syntheses produced
reveals that zeolite growth solutions using Na+ result in RHO with trace to minor amounts of GIS and FAU impu-
pure LTA (Maldonado et al. 2013), whereas similar con- rity. Conversely, as the percentage of Na+ in the mixture
ditions using Li+ resulted in the formation of both EDI was reduced below 90%, a binary RHO-CHA mixture was
and mixtures of EDI and ABW (Matsumoto et al. 2006). obtained; and Na+ content <80% yielded pure CHA. Syn-
Similarly, replacing Na+ with K+ (even at high synthesis theses employing a ternary cationic mixture of Na+, K+, and
temperature) promotes the formation of EDI at condi- Cs+ had a tendency to yield CHA. Moreover, substitution of
tions where pure Na+ solutions yield LTA (Jakkula et al. K+ with Rb+ did not appear to affect CHA crystallization.

Authenticated
Table 7Synthesis of RHO- and CHA-type zeolite with cation mixtures (Robson 1975).
Molar ratio SAR(liq) t (h) (at 90C) Phase Cation
Si Al OH H2O
15.2 3.0 10.0 164.7 5 72 RHO 0.91:0.09 Na:Cs

15.2 3.0 10.0 161.7 5 288 RHO 0.91:0.09 Na:Cs
15.6 3.9 10.0 182.5 4 48 CHA, RHO 0.85:0.15 Na:Cs
15.6 3.9 10.0 182.5 4 144 CHA 0.7:0.3 Na:Cs
15.6 3.9 10.0 182.5 4 144 CHA 0.7:0.15:0.15 Na:Rb:Cs
15.6 3.9 10.0 182.5 4 96 CHA 0.7:0.15:0.15 Na:K:Cs
15.2 3.0 10.0 164.7 5 96 CHA 0.71:0.2:0.09 Na:K:Cs
15.2 3.0 10.0 164.7 5 192 CHA 0.71:0.2:0.09 Na:K:Cs
Barrer et al. (1980) observed different effects in the syn- GME (Sr-F), CHA (Sr-G), HEU (Sr-R), and YUG (Sr-Q). Barrer
thesis of RHO using mixtures of Na+ and Cs+ at similar and coworkers also explored systems of mixed cations
temperature. They noted that decreasing Na+ to 83% of the (Aiello and Barrer 1970), though in the presence of an
total cation content and crystallizing for 7 days favored OSDA. They reported that mixtures of Na+ and K+ yielded
the formation of an apparent mixture of RHO, CHA, and both MER and LTL, whereas mixtures of K+ and Ba2+ pro-
ANA, whereas higher Na+ content (i.e., greater than 90%) duced CHA, LTL, and SOD (Barrer and Mainwaring 1972).
yielded mixtures of RHO, FAU, LTA, CHA, and ANA with Some of their data for K+-CHA is presented in Figure 3;
514days of heating. It is important to note that many of however, upon addition of Ba2+ (1020% of total cation
the indexed ANA peaks in their powder XRD data seemed content) they reported that the same growth solution com-
to overlap with those of FAU. Their observations suggest positions produced either pure LTL (Ba-G,L) or mixtures
that increased Na+ content favors the formation of LTA and of LTL and CHA. Additional compositions were analyzed,
FAU. including mixtures of Ba2+ and Li+, Ba2+ and Na+, Tl+ and
Barrer and coworkers performed numerous studies of Ba2+, and pure Tl+. Results of their studies revealed the for-
pure and mixed cation syntheses, though many of their mation of a variety of framework types, which included
earlier reports prior to ca. 1970 lack specific details regard- EDI, ABW, LTL, MER, YUG, and GME (Barrer etal. 1974).
ing the composition of growth solutions, such as the water Moreover, studies of binary Ba2+ and Na+ synthesis mix-
content. In the first part of their series of papers entitled tures revealed the formation of LTL (G, L), GIS (P), and MER
The Hydrothermal Chemistry of Silicates, Barrer and White (Ba-M) framework types (Barrer and Sieber 1978). Further
investigated zeolite crystals formed in SiO2-Al2O3-Li2O-H2O details of these syntheses can be found in a review of Bar-
systems at temperatures ranging from 130 to 450C (Barrer rers work (Barrer 1982). It should be noted that almost all
and White 1951). The most frequent structure reported in of the work on divalent cations and a majority of the more
this study was Li-ABW, whereas other (minor) products infrequently studied monovalent cations (e.g., Li+, Cs+,
were predominantly non-zeolitic phases. Barrer later pub- and Rb+) have not been documented with enough detail
lished studies that examined the following cations: Na+ to permit a proper comparison (or reproduction) of the
(Barrer and White 1952), Rb+ and Cs+ (Barrer and McCallum exact synthesis conditions. To this end, there is consider-
1953), Ca2+ (Barrer and Denny 1961), Sr2+ (Barrer and Mar- ably more research that is required to fully understand the
shall 1964a), and Ba2+ (Barrer and Marshall 1964b). The effects of extraframework cations on zeolite phase purity.
notation used for zeolite framework types in these studies
was a single letter, which differs from the current three-
letter code established by the IZA. Here we report both 4 A
lternative routes to synthesize
notations for clarity. Among the collective results reported
by Barrer and White, there were several interesting obser-
zeolite framework types
vations, which included rubidium promotion of ANA
(Rb-B and Rb-H), calcium promotion of ANA (Ca-D and 4.1 Seeded growth
Ca-E) and MOR (Ca-Q), barium promotion of LTL (Ba-G,L),
and strontium mediated formation of the following frame- A common method to achieve a desired zeolite structure is
work types: FER (Sr-D), ANA (Sr-I), CAN (Sr-J), MOR (Sr-M), the use of seed crystals. This route to produce zeolites has

Authenticated
been performed with and without the addition of OSDAs A B Mordenite (MOR)
(gel)
to the growth medium; however, it is important to preface
this discussion by emphasizing that a relatively high per-
centage of studies claiming to examine OSDA-free seeded
mor
growth are, in fact, not completely organic free as the syn- mtw
thesis of seed crystals often uses organic agents. Notably, mor
in most cases these seed crystals are not calcined. Thus, bea mel mfi cas
claims of being OSDA-free can be misleading as seed beta (*BEA) mordenite (MOR) ZSM-11 (MEL) ZSM-5 (MFI)
dissolution can release organics into the growth solu- (seed and target) (gel) (seed and target) (seed and target)
tion (Majano et al. 2009, Kamimura et al. 2012). If seeds
Figure 12Comparison of building units for seed crystals and
are produced from OSDA-free syntheses or the occluded desired products of zeolite growth solutions. Shaded regions
organic compounds within the seeds are removed through indicate a typical growth solution used for MOR synthesis. (A)
post-synthesis calcination, the seeded growth solution is Introduction of BEA seeds into a MOR growth solution results in the
indeed OSDA-free (Wu etal. 2008). continued growth of BEA. (B) Introduction of either MEL or MFI seeds
into the MOR growth solution results in the continued growth of the
The mechanism of seed promoted zeolite crystalliza-
seeds. It was suggested that seeds sharing at least one common
tion is debatable, analogous to mechanisms of non-seeded building unit with a crystal obtained from a non-seeded growth
zeolite crystallization. Dutta and Broni (1994) attempted to solution will promote the formation of crystals equal to that of the
study the interactions between the seeds and the reaction seed [reprinted (adapted) from Itabashi etal. 2012, with permission
mixture using a reaction vessel with a membrane to sepa- from the copyright holder, American Chemical Society].
rate the seeds from the mixture. They observed the forma-
tion of different zeolite framework types above and below
the membrane, and suggest the presence of seeds influ- solutions, the trend does not hold true in every instance.
enced the synthesis pathway. It is possible that seed crystals For example, the transition from a metastable structure to
interact with the growth solution in several ways, including a more thermodynamically stable structure often occurs
(1) seed dissolution to produce silica and alumina nutrients between zeolites that do not share a common building unit.
(soluble species, building units, etc.) for homogeneous Examples include (but are not limited to) the FAU-to-GIS,
nucleation and growth of a new crystalline phase, or (2) SOD-to-CAN, and GIS-to-ANA transformations. It is interest-
the presentation of an interface with the growth solution to ing to consider whether these phase transformations are, in
promote heterogeneous crystallization via epitaxial growth fact, seed solutions as the new (more stable) crystal phase
of the new crystal phase on the surface of the seed. Seeds nucleates and grows from a suspension of the initial (less
provide a significant amount of surface area in growth solu- stable) phase. In such instances, one may ask if it is reason-
tions when introduced in moderate quantities. If the seeds able to consider the initial metastable phase a seed crystal.
are unstable in the growth solution and tend to dissolve, To this end, further investigation of crystal transformations
they likely do not serve as heterogeneous nucleation sites, between zeolite framework types with similar and different
but may affect the formation of precursor species. For more building units may lead to heuristic guidelines capable of
details and examples of seeded growth, we refer the reader explaining such transitions.
to the review by Cundy and Cox (2005).
Okubo and coworkers recently proposed a hypothesis
for OSDA-free seeding that focused on framework types that 4.2 Organic structure-directing agents
possess similar building units (Itabashi etal. 2012). Their
studies suggest the use of seeds for a desired crystal sus- A large percentage of papers published in the area of zeolite
pended in a growth medium that favors the formation of a synthesis employ OSDAs to achieve a desired framework
framework type sharing at least one similar building unit type. In many cases, the synthesis of these structures cannot
will result in the growth of the seed structure, as shown in be achieved in the absence of the OSDA (Corma etal. 2004,
Figure 12. To this end, they successfully grew ZSM-11 (MEL), Simancas et al. 2010, Jiang et al. 2011, Hernandez-Rodri-
ZSM-5 (MFI), and BEA crystals from growth solutions that guez etal. 2012). In other instances, the use of novel OSDAs
are typically employed in non-seeded MOR synthesis. Inter- can lead to very interesting and/or unique properties,
estingly, the crystal structures of all four zeolites consist such as tailored crystal size, shape, and orientation (Choi
of mor building units. There are additional examples pro- etal. 2009, Na etal. 2011, Zhang etal. 2012b, Chaikittisilp
vided by Itabashi etal.; however, if we were to extend this etal. 2013). There are many articles that discuss the use of
hypothesis to polymorph transitions in non-seeded growth OSDAs in zeolite synthesis. The topic of polymorphism in

Authenticated
the presence of organics could be the subject of an entirely (e.g., crystal size and habit), and the discovery of synthetic
separate review. Here we have intentionally avoided routes capable of producing new framework types with
this subject and focused solely on OSDA-free synthesis; tunable composition (e.g., SAR). Our review of OSDA-free
however, it is of interest to note that many groups have synthesis reveals trends in zeolite polymorphism, but also
studied phase transformations in the presence of organ- emphasizes a general lack of knowledge regarding phase
ics. These studies often employ zeolite seeds (e.g., BEA, selection and transformation. The Ostwald step rule pro-
FAU, etc.) and convert them to new phases in the presence vides a loose framework for understanding structural tran-
of different OSDAs. Papers published by Zones, Sano, and sitions, but cannot account for all observed phenomena
others provide many examples of OSDA-mediated phase (particularly in the absence of empirical thermodynamic
transformations (Zones 1991, Zones etal. 1992, Zones and data to identify the most stable structures at different syn-
Nakagawa 1994, Jon etal. 2006, 2008, Itakura etal. 2008, thesis conditions). The solution composition and possibly
2010, Inoue etal. 2009, Sasaki etal. 2009). It is reasonable the nature of the soluble species play a role in the final or
to suggest that zeolite synthesis employing a combination intermediate zeolite structure, but to what extent these
of parameter selection (as discussed in previous sections effects control zeolite crystallization is not fully under-
for OSDA-free solutions) and the judicious selection of an stood. The construction of ternary diagrams revealed that
OSDA could lead to the discovery of new framework types, much of the phase space remains unexplored, due in part
or potentially synthetic routes to achieve zeolite structures to the limited range of conditions reported in prior work,
that are otherwise challenging to produce by conventional i.e., studies tend to simply repeat synthesis conditions used
methods. by other groups rather than test new conditions. In older
references (ca. before 1970), it is challenging to extract the
exact conditions used in experimental procedures. Moreo-
5 Conclusion ver, there are many studies that alter multiple parameters
simultaneously, thus making it challenging to attribute the
The synthesis of zeolites from OSDA-free media dates back effects to a particular parameter.
to the pioneering research in this field during the mid-20th Future advancement and research in zeolite synthe-
century. This process represents the most common route sis would benefit from a more systematic examination of
to produce commercial zeolites for applications spanning the phase space in the ternary diagrams presented here.
catalysis to ion-exchange. This review highlights the influ- Efforts to identify and quantify the temporal changes in
ence of various synthesis parameters on crystal phase selec- soluble species, such as the formation and depletion of
tion and polymorphic transformations that are observed potential building units, may lead to greater insight into
in OSDA-free syntheses. Our analyses largely emphasized the mechanisms regulating zeolite nucleation and phase
the use of kinetic phase diagrams to distinguish regions of transformation. Elucidating the relative role(s) of thermo-
composition (notably the aluminum, silicon, and hydroxide dynamics and kinetics is necessary if we wish to predict
molar fractions) where different framework types crystal- and ultimately control zeolite polymorphism. There is
lize. These ternary diagrams can be constructed at different significant room for improvement in zeolite synthesis
conditions, such as temperature and time, as well as dif- to design and optimize materials for current industrial
ferent solution compositions, such as water content and processes and emerging technologies. In particular, the
extraframework cation(s). Extending the list of synthesis ability to do so using OSDA-free methods has economic
parameters to additional factors, such as aging, silica and and environmental benefits for commercial realization.
alumina sources, and the use of seeds, poses significant
challenges for selecting the most optimal set of conditions. Acknowledgments: We wish to thank the National Science
Identifying these conditions via combinatorial approaches Foundation (CAREER 1151098), the Norman-Hackerman
or experimental design is both time and cost intensive. Advanced Research Program (Award 003652-0024-2011),
Industrial research and development centers often have the American Chemical Society Petroleum Research Fund
the resources to mount large-scale combinatorial synthe- (Award 52422-DNI5), and the Welch Foundation (Award
sis although a full-scale investigation of all possible syn- E-1794) for funding. We are grateful to M. Maldonado for
thesis parameters is still a daunting task. Indeed, a more assistance preparing ternary diagrams.
rational approach based on fundamental understandings
of structure-property relationships that govern zeolite
polymorphism would be better suited for the optimization Received May 30, 2013; accepted August 4, 2013; previously pub-
of crystal purity, the design of tailored material properties lished online October 22, 2013

Authenticated
References
Addadi L, Joester D, Nudelman F, Weiner S. Mollusk shell formation: Barrer RM, White EAD. The hydrothermal chemistry of silicates.
a source of new concepts for understanding biomineralization Part I. Synthetic lithium aluminosilicates. J Chem Soc 1951;
processes. Chem-Eur J 2006; 12: 981987. 12671278.
Agger JR, Shoaee M, Mistry M, Slater B. Crystal growth of analcime Barrer RM, White EAD. The hydrothermal chemistry of silicates.
studied by AFM and atomistic simulation. J Cryst Growth 2006; PartII. Synthetic crystalline sodium aluminosilicates. J Chem
294: 7882. Soc 1952; 15611571.
Aiello R, Barrer RM. Hydrothermal chemistry of silicates. Part. XIV. Barrer RM, Beaumont R, Collela C. Chemistry of soil minerals.
Zeolite crystallisation in presence of mixed bases. J Chem Soc PartXIV. Action of some basic solutions on metakaolinite and
A 1970; 14701475. kaolinite. J Chem Soc Dalton 1974; 934941.
Aiello R, Crea F, Nastro A, Pellegrino C. Zeolite crystallization from Barrer RM, Barri S, Klinowski J. Zeolite RHO (Part I) synthesis
high-silica monocationic or bicationic alkali (Li, Na, or K) gels and characterisation. Proceedings of the fifth international
in presence and in absence of TPA ions. Zeolites 1987; 7: conference on zeolites, Naples, Italy, June 26, 1980.
549553. Basaldella EI, Tara JC. Synthesis of LSX zeoltie in the Na/K system
Alfaro S, Rodriguez C, Valenzuela MA, Bosch P. Aging time effect influence of the Na/K ratio. Zeolites 1995; 15: 243246.
on the synthesis of small crystal LTA zeolites in the absence of Beard WC. Linde type B zeolties an related mineral and synthetic
organic template. Mater Lett 2007; 61: 46554658. phases. Adv Chem Ser 1971; 237249.
Amos FF, Sharbaugh DM, Talham DR, Gower LB, Fricke M, Volkmer D. Belhekar AA, Chandwadkar AJ, Hegde SG. Physicochemical
Formation of single-crystalline aragonite tablets/films via an characterization of a synthetic melinoite (Linde W-like) zeolite
amorphous precursor. Langmuir 2007; 23: 19881994. containing Na K, and Sr cations. Zeolites 1995; 15: 535539.
Andersen IGK, Andersen EK, Norby P, Colella C, DegennaroM. Bellussi G, Perego G, Carati A, Cornaro U, Fattore V. 51 SBU
Synthesis and structure of an ABW type thallium based zeolites from wholly inorganic systems. In: Grobet PJ,
aluminosilicate. Zeolites 1991; 11: 149154. MortierWJ, Vansant EF, Schulz-Ekloff G, editors. Innovation
Andries KJ, Dewit B, Grobet PJ, Bosmans HJ. The synthesis and in zeolite materials science, Studies in Surface Science and
properties of synthetic zeolite Linde-Q. Zeolites 1991; 11: 116123. Catalysis. Amsterdam, Netherlands: Elsevier, 1988: 3744.
Azizi SN, Yousefpour M. Synthesis of zeolites NaA and analcime Bhat SD, Niphadkar PS, Gaydhankar TR, Awate SV, Belhekar AA,
using rice husk ash as silica source without using organic Joshi PN. High temperature hydrothermal crystallization,
template. J Mater Sci 2010; 45: 56925697. morphology and yield control of zeolite type K-LTL. Micropor
Bajpai PK, Rao MS, Gokhale K. Synthesis of mordenite type zeolite. Mesopor Mater 2004; 76: 8189.
Ind Eng Chem Prod RD 1978; 17: 223227. Bhawe Y, Moliner-Marin M, Lunn JD, Liu Y, Malek A, Davis M. Effect
Bajpai PK, Rao MS, Gokhale K. Synthesis of mordenite type zeolite of cage size on the selective conversion of methanol to light
using silica from rice husk ash. Ind Eng Chem Prod RD 1981; olefins. ACS Catal 2012; 2: 24902495.
20: 721726. Bosnar S, Suboti B. Mechanism and kinetics of the growth of
Ban T, Saito H, Naito M, Ohya Y, Takahashi Y. Synthesis of zeolite L zeolite microcrystals Part 1: influence of the alkalinity of
crystals with different shapes. J Porous Mat 2007; 14: 119126. the system on the growth kinetics of zeolite A microcrystals.
Barrer RM. Hydrothermal chemistry of zeolites. New York: Academic Micropor Mesopor Mater 1999; 28: 483493.
Press, 1982. Bosnar S, Antoni T, Broni J, Suboti B. Mechanism and kinetics of
Barrer RM, Denny PJ. Hydrothermal chemistry of silicates. Part X. the growth of zeolite microcrystals. Part 2: influence of sodium
Partial study of field CaO-Al2O3-SiO2-H2O. J Chem Soc 1961; ions concentration in the liquid phase on the growth kinetics
9831000. of zeolite A microcrystals. Micropor Mesopor Mater 2004; 76:
Barrer RM, Mainwaring DE. Chemistry of Soil Minerals. Part XII. 157165.
Transformations of metakaolinite with solutions containing Bosnar S, Broni J, Krznari I, Suboti B. Influence of the
barium hydroxide. J Chem Soc Dalton 1972; 12591265. concentrations of aluminium and silicon in the liquid phase
Barrer RM, Marcilly C. Hydrothermal chemistry of silicates. Part XV. on the growth kinetics of zeolite A and X microcrystals. Croat
Synthesis and nature of some salt-bearing aluminosilicates. J Chem Acta 2005; 78: 18.
Chem Soc A 1970; 27352745. Bosnar S, Broni J, Jeli TA, Suboti B. Anomalous nucleation events
Barrer RM, Marshall DJ. Hydrothermal chemistry of silicates. Part during crystallization of zeolite A under marginal alkalinities:
XII. Synthetic strontium aluminosilicates. J Chem Soc 1964a; a population balance analysis. Crystengcomm 2012; 14:
485497. 30693079.
Barrer RM, Marshall DJ. Hydrothermal chemistry of silicates. Part Breck DW. Crystalline zeolite S. US Patent 3054657, 1962.
XIII. Synthetic barium aluminosilicates. J Chem Soc 1964b; Breck DW. Crystalline zeolite Y. US Patent 3130007, 1964.
22962305. Breck DW, Acara NA. Crystalline zeolite T. US Patent 2950952,
Barrer RM, McCallum N. Hydrothermal chemistry of silicates. Part 1960a.
IV. Rubidium and coesium aluminosilicates. J Chem Soc 1953; Breck DW, Acara NA. Crystalline zeolite E. US Patent 2962355,
40294035. 1960b.
Barrer RM, Sieber W. Hydrothermal chemistry of silicates. Part 22. Breck DW, Acara NA. Crystalline zeolite J. US Patent 3011869, 1961a.
Hydrated barium-sodium aluminosilicates. J Chem Soc Dalton Breck DW, Acara NA. Crystalline zeolite M. US Patent 2995423,
1978; 598601. 1961b.

Authenticated
Breck DW, Flanigen EM. Molecular sieves: papers read at the Corma A, Diaz-Cabanas MJ, Rey F, Nicolooulas S, Boulahya K. ITQ-15:
conference held at the school of pharmacy. Society of Chemical the first ultralarge pore zeolite with a bi-directional pore
Industry, 1968. system formed by intersecting 14- and 12-ring channels, and its
Brent R, Lobo AJW, Lewis DW, Anderson MW. Modifying the crystal catalytic implications. Chem Commun 2004; 13561357.
habit of zeolite L by addition of an organic space filler. J Phys Cundy CS, Cox PA. The hydrothermal synthesis of zeolites:
Chem C 2010; 114: 1824018246. precursors, intermediates and reaction mechanism. Micropor
Broni J, Pali A, Suboti B, Itani L, Valtchev V. Influence of Mesopor Mater 2005; 82: 178.
alkalinity of the starting system on size and morphology of the Cundy CS, Lowe BM, Sinclair DM. Direct measurements of the
zeolite A crystals. Mater Chem Phys 2012; 132: 973976. crystal-growth rate and nucleation behavior of silicalite, a
Brosius R, Martens JA. Reaction mechanisms of lean-burn hydrocarbon zeolitic silica polymorph. J Cryst Growth 1990; 100: 189202.
SCR over zeolite catalysts. Top Catal 2004; 28: 119130. Dai FY, Suzuki M, Takahashi H, Saito I. Mechanism of zeolite
Buckley HE. Crystal growth. New York: John Wiley and Sons, 1951. crystallization without using template reagents of organic bases.
Buhl J-C, Schuster K, Robben L. Nanocrystalline sodalite grown from In: Murakami Y, Iijima A, Ward JW, editors. New developments in
superalkaline NaCl bearing gels at low temperature (333 K) zeolite science and technology, Studies in Surface Science and
and the influence of TEA on crystallization process. Micropor Catalysis. Amsterdam, Netherlands: Elsevier, 1986: 223230.
Mesopor Mater 2011; 142: 666671. Davis TM, Drews TO, Ramanan H, He C, Dong JS, Schnablegger H,
Burton A, Feuerstein M, Lobo RF, Chan JCC. Characterization of Katsoulakis MA, Kokkoli E, McCormick AV, Penn RL, Tsapatsis
cancrinite synthesized in 1,3-butanediol by Rietveld analysis M. Mechanistic principles of nanoparticle evolution to zeolite
of powder neutron diffraction data and solid-state Na-23 crystals. Nat Mater 2006; 5: 400408.
NMR spectroscopy. Microporous Mesoporous Mat 1999; 30: de Moor P, Beelen TPM, van Santen RA. Influence of aging and
293305. dilution on the crystallization of silicalite-1. J Appl Crystallogr
Cannan TR. Crystalline zeolite LZ-202 and process for preparing 1997; 30: 675679.
same. US Patent 4840779, 1989. de Moor P, Beelen TPM, van Santen RA, Tsuji K, Davis ME. SAXS
Carr CS, Shantz DF. Synthesis of high aspect ratio low-silica zeolite and USAXS investigation on nanometer-scaled precursors in
L rods in oil/water/surfactant mixtures. Chem Mater 2005; 17: organic-mediated zeolite crystallization from gelating systems.
61926197. Chem Mater 1999; 11: 3643.
Chaikittisilp W, Suzuki Y, Mukti RR, Suzuki T, Sugita K, Itabashi K, De Yoreo J. Crystal nucleation: more than one pathway. Nat Mater
Shimojima A, Okubo T. Formation of hierarchically organized 2013; 12: 284285.
zeolites by sequential intergrowth. Angew Chem-Int Edit 2013; Direnzo F, Fajula F, Espiau P, Nicolle MA, Dutartre R. The influecne
52: 33553359. of microgravity on zeolite crystallization. Zeolites 1994; 14:
Cheng YT, Wang ZP, Gilbert CJ, Fan W, Huber GW. Production of 256261.
p-Xylene from biomass by catalytic fast pyrolysis using ZSM-5 Dokter WH, Vangarderen HF, Beelen TPM, Vansanten RA, Bras W.
catalysts with reduced pore openings. Angew Chem-Int Edit Homogeneous versus heterogeneous zeolite nucleation.
2012; 51: 1109711100. Angew Chem-Int Edit Engl 1995; 34: 7375.
Chi CH, Sand LB. Synthesis of Na-clinoptilolite and K-clinoptilolite Duecker HC, Weiss A, Guerra CR. Synthetic crystalline zeolite.
endmembers. Nature 1983; 304: 255257. USPatent 3567372, 1971.
Choi M, Na K, Kim J, Sakamoto Y, Terasaki O, Ryoo R. Stable single- Dutta PK, Broni J. Mechanism of zeolite formation seed gel
unit-cell nanosheets of zeolite MFI as active and long-lived intereaction. Zeolites 1994; 14: 250255.
catalysts. Nature 2009; 461: 246U120. Dwyer FG, Chu P. ZSM-4 crystallization via faujasite metamorphosis.
Cichocki A. Effect of glass corrosion on the synthesis of zeolite-T. J Catal 1979; 59: 263271.
Zeolites 1985; 5: 2630. Egeblad K, Kustova M, Klitgaard SK, Zhu K, Christensen CH.
Cichocki A, Koscielniak P. Experimental designs applied to Mesoporous zeolite and zeotype single crystals synthesized in
hydrothermal synthesis of zeolite ERI plus OFF (T) in the fluoride media. Micropor Mesopor Mater 2007; 101: 214223.
Na2O-K2O-Al2O3-SiO2-H2O system Part 3. Mathematical models Engelhardt G, Hoebbel D, Tarmak M, Samoson A, Lippmaa E. Si-29
and geometrical forms of the relationship between product NMR investigations on the anion structure of crystalline
properties and synthesis parameters: an attempt to optimize tetramethylammonium-aluminosilicates and aluminosilicate
synthesis conditions. Micropor Mesopor Mater 2000; 41: solutions. Z Anorg Allg Chem 1982; 484: 2232.
241251. Fahlke B, Starke P, Seefeld V, Wieker W, Wendlandt KP. On the
Ciric J. Lithium-containing crystalline aluminosilicate. US Patent intermediates in zeolite Y snythesis. Zeolites 1987; 7: 209213.
3415736, 1968a. Fan W, Ogura M, Sankar G, Okubo T. In situ small-angle and
Ciric J. ZSM-2 zeolite and preparation thereof. US Patent 3411874, wide-angle X-ray scattering investigation on nucleation and
1968b. crystal growth of nanosized zeolite A. Chem Mater 2007; 19:
Colombo M, Nova I, Tronconi EA. Comparative study of the NH3-SCR 19061917.
reactions over a Cu-zeolite and a Fe-zeolite catalyst. Catal Fan W, Morozumi K, Kimura R, Yokoi T, Okubo T. Synthesis of
Today 2010; 151: 223230. nanometer-sized sodalite without adding organic additives.
Constable RFS. Kinetics and mechanism of crystallization. Langmuir 2008; 24: 69526958.
New York: Academic Press, 1968. Fedeyko JM, Rimer JD, Lobo RF, Vlachos DG. Spontaneous
Copeland JR, Shi X-R, Sholl DS, Sievers C. Surface interactions of C-2 formation of silica nanoparticles in basic solutions of small
and C-3 polyols with gamma-Al2O3 and the role of coadsorbed tetraalkylammonium cations. J Phys Chem B 2004; 108:
water. Langmuir 2013; 29: 581593. 1227112275.

Authenticated
Fedeyko JM, Vlachos DG, Lobo RF. Formation and structure of seed-assisted synthesis without organic structure-directing
self-assembled silica nanoparticles in basic solutions of agent. J Am Chem Soc 2012; 134: 1154211549.
organic and inorganic cations. Langmuir 2005; 21: 51975206. Itakura M, Inoue T, Takahashi A, Fujitani T, Oumi Y, Sano T. Synthesis
Feoktistova NN, Zhdanov SP. On the kinetics of crystallization of of high-silica CHA zeolite from FAU zeolite in the presence of
silicalite-1. Zeolites 1989; 9: 136139. benzyltrimethylammonium hydroxide. Chem Lett 2008; 37:
Filobelo LF, Galkin O, Vekilov PG. Spinodal for the solution-to- 908909.
crystal phase transformation. J Chem Phys 2005; 123: Itakura M, Oumi Y, Sadakane M, Sano T. Synthesis of high-silica
014904-1014904-7. offretite by the interzeolite conversion method. Mater Res Bull
Freund EF. Mechanism of crystallization of zeolite X. J Cryst Growth 2010; 45: 646650.
1976; 34: 1123. Itani L, Bozhilov KN, Clet G, Delmotte L, Valtchev V. Factors that
Gaona-Gomez A, Cheng C-H. Modification of zeolite L (LTL) control zeolite L crystal size. Chem-Eur J 2011; 17: 21992210.
morphology using diols, (OH)(2)(CH2)(2n+2)O-n (n=0, 1, and2). Itani L, Liu Y, Zhang W, Bozhilov KN, Delmotte L, Valtchev V.
Micropor Mesopor Mater 2012; 153: 227235. Investigation of the physicochemical changes preceding
Ginter DM, Bell AT, Radke CJ. The effects of gel aging on the synthesis zeolite nucleation in a sodium-rich aluminosilicate gel. J Am
of NaY zeolite from colloidal silica. Zeolites 1992; 12: 742749. Chem Soc 2009; 131: 1012710139.
Gomez AG, de Silveira G, Doan H, Cheng CH. A facile method to tune Iwama M, Suzuki Y, Plevert J, Itabashi K, Ogura M, Okubo T. Location
zeolite L crystals with low aspect ratio. Chem Commun 2011; of alkali ions and their relevance to crystallization of low silica
47: 58765878. X zeolite. Cryst Growth Des 2010; 10: 34713479.
Gower LB. Biomimetic model systems for investigating Jakkula VS, Williams CD, Hocking TJ, Fullen MA. High selectivity and
the amorphous precursor pathway and its role in affinity of Linde type F towards NH4+ on application as a soil
biomineralization. Chem Rev 2008; 108: 45514627. amendment for maize growth. Micropor Mesopor Mater 2006;
Graca I, Ribeiro FR, Cerqueira HS, Lam YL, de Almeida MBB. Catalytic 88: 101104.
cracking of mixtures of model bio-oil compounds and gasoil. Jiang JX, Jorda JL, Yu JH, Baumes LA, Mugnaioli E, Diaz-Cabanas MJ,
Appl Catal B-Environ 2009; 90: 556563. Kolb U, Corma A. Synthesis and structure determination of the
Greenberg SA. The depolymerization of silica in sodium hydroxide hierarchical meso-microporous zeolite ITQ-43. Science 2011;
solutions. J Phys Chem 1957; 61: 960965. 333: 11311134.
Grose RW, Flanigen EM. Novel zeolite compositions and processes Jon H, Nakahata K, Lu BW, Oumi Y, Sano T. Hydrothermal conversion
for preparing and using same. US Patent 4257885, 1981. of FAU into (*)BEA zeolites. Micropor Mesopor Mater 2006; 96:
Han B, Shin CH, Warrender SJ, Lightfoot P, Wright PA, Camblor MA, 7278.
Hong SB. Structural chemical zoning in the boundary phase Jon H, Takahashi S, Sasaki H, Oumi Y, Sano T. Hydrothermal
zeolite TNU-7 (EON). Chem Mater 2006; 18: 30233033. conversion of FAU zeolite into RUT zeolite in TMAOH system.
Hayhurst David T, Sand LB. Crystallization kinetics and properties of Micropor Mesopor Mater 2008; 113: 5663.
Na, K-phillipsites. In: Gould RF, editor. Molecular Sieves II, Ju JX, Zeng CF, Zhang LX, Xu NP. Continuous synthesis of zeolite
ACS Symposium Series. American Chemical Society 1977; NaAin a microchannel reactor. Chem Eng J 2006; 116: 115121.
219232. Kalapathy U, Proctor A, Shultz J. An improved method for production of
Hernandez-Rodriguez M, Jorda JL, Rey F, Corma A. Synthesis and silica from rice hull ash. Bioresour Technol 2002; 85: 285289.
structure determination of a new microporous zeolite with Kamimura Y, Iyoki K, Elangovan SP, Itabashi K, Shimojima A,
large cavities connected by small pores. J Am Chem Soc 2012; OkuboT. OSDA-free synthesis of MTW-type zeolite from sodium
134: 1323213235. aluminosilicate gels with zeolite beta seeds. Micropor Mesopor
Hu D, Xia QH, Lu XH, Luo XB, Liu ZM. Synthesis of ultrafine zeolites Mater 2012; 163: 282290.
by dry-gel conversion without any organic additive. Mater Res Kashchiev D, Vekilov PG, Kolomeisky AB. Kinetics of two-step nucleation
Bull 2008; 43: 35533561. of crystals. J Chem Phys 2005; 122: 244706-1244706-6.
Huang Y, Wang K, Dong D, Li D, Hill MR, Hill AJ, Wang H. Synthesis Kazemimoghadam M, Mohammadi T. Preparation of nano pore
of hierarchical porous zeolite NaY particles with controllable hydroxysodalite zeolite membranes using of kaolin clay and
particle sizes. Micropor Mesopor Mater 2010; 127: 167175. chemical sources. Desalination 2011; 278: 438442.
Huber GW, Corma A. Synergies between bio- and oil refineries for Khajavi S, Sartipi S, Gascon J, Jansen JC, Kapteijn F. Thermostability
the production of fuels from biomass. Angew Chem-Int Edit of hydroxy sodalite in view of membrane applications.
2007; 46: 71847201. Micropor Mesopor Mater 2010; 132: 510517.
Iler RK. The chemistry of silica: solubility, polymerization, colloid Kim SD, Noh SH, Seong KH, Kim WJ. Compositional and kinetic study
and surface properties and biochemistry of silica. New York: on the rapid crystallization of ZSM-5 in the absence of organic
Wiley, 1979. template under stirring. Micropor Mesopor Mater 2004; 72:
Ilias S, Bhan A. Mechanism of the catalytic conversion of methanol 185192.
to hydrocarbons. ACS Catal 2013; 3: 1831. Kim J, Jentys A, Maier SM, Lercher JA. Characterization of
Inoue T, Itakura M, Jon H, Oumi Y, Takahashi A, Fujitani T, Sano T. Fe-exchanged BEA zeolite under NH3 selective catalytic
Synthesis of LEV zeolite by interzeolite conversion method reduction conditions. J Phys Chem C 2013; 117: 986993.
and its catalytic performance in ethanol to olefins reaction. Knight CTG, Kinrade SD. Comment on Identification of precursor
Micropor Mesopor Mater 2009; 122: 149154. species in the formation of MFI zeolite in the TPAOH-TEOS-H2O
International Zeolite Association, www.iza-online.org. system. J Phys Chem B 2002; 106: 33293332.
Itabashi K, Kamimura Y, Iyoki K, Shimojima A, Okubo T. A working Ko YS, Ahn WS. Crystallization of zeolite L from Na2O-K2O-Al2O3-
hypothesis for broadening framework types of zeolites in SiO2-H2O system. Powder Technol 2004; 145: 1019.

Authenticated
Koroglu HJ, Sarioglan A, Tatlier M, Erdem-Senatalar A, Savasci OT. Majano G, Delmotte L, Valtchev V, Mintova S. Al-rich zeolite beta by
Effects of low-temperature gel aging on the synthesis of seeding in the absence of organic template. Chem Mater 2009;
zeolite Y at different alkalinities. J Crystal Growth 2002; 241: 21: 41844191.
481488. Maldonado M, Oleksiak MD, Chinta S, Rimer JD. Controlling crystal
Kragten DD, Fedeyko JM, Sawant KR, Rimer JD, Vlachos DG, Lobo RF, polymorphism in organic-free synthesis of Na-zeolites. J Am
Tsapatsis M. Structure of the silica phase extracted from silica/ Chem Soc 2013; 135: 26412652.
(TPA)OH solutions containing nanoparticles. J Phys Chem B Mallon EE, Bhan A, Tsapatsis M. Driving forces for adsorption of
2003; 107: 1000610016. polyols onto zeolites from aqueous solutions. J Phys Chem B
Krznari I, Antoni T, Broni J, Suboti B, Thompson RW. Influence of 2010; 114: 19391945.
silica sources on the chemical composition of aluminosilicate Mallon EE, Babineau IJ, Kranz JI, Guefrachi Y, Siepmann JI, Bhan A,
hydrogels and the results of their hydrothermal treatment. Tsapatsis M. Correlations for adsorption of oxygenates onto
Croat Chem Acta 2003; 76: 717. zeolites from aqueous solutions. J Phys Chem B 2011; 115:
Kwak JH, Tonkyn RG, Kim DH, Szanyi J, Peden CHF. Excellent activity 1143111438.
and selectivity of Cu-SSZ-13 in the selective catalytic reduction Maniar PD, Navrotsky A, Rabinovich EM, Ying JY, Benziger JB.
of NOx with NH3. J Catal 2010; 275: 187190. Energetics and structure of sol-gel silicas. J Non-cryst Solids
Larlus O, Valtchev VP. Crystal morphology control of LTL-type zeolite 1990; 124: 101111.
crystals. Chem Mater 2004; 16: 33813389. Martinez C, Corma A. Inorganic molecular sieves: preparation,
Lechert H. Possibilities and limitations of the prediction of the Si/ modification and industrial application in catalytic processes.
Al ratios of zeolites from the batch composition. Micropor Coordin Chem Rev 2011; 255: 15581580.
Mesopor Mater 2000; 40: 181196. Matsumoto T, Miyazaki I, Goto Y. Synthesis and characterization
Lechert H, Kacirek H. The kinetics of nucleation of X zeolites. ofLi-type EDI zeolite. J Eur Ceram Soc 2006; 26:
Zeolites 1993; 13: 192200. 455458.
Lee YJ, Lee JS, Yoon KB. Synthesis of long zeolite-L crystals with flat Milton RM. Molecular sieve adsorbents. US Patent 2882244, 1959.
facets. Micropor Mesopor Mater 2005; 80: 237246. Milton RM. Crystalline zeolite. US Patent 3012853, 1961a.
Li YS, Chen HL, Liu J, Yang WS. Microwave synthesis of LTA zeolite Milton RM. Crystalline zeolite B. US Patent 3008803, 1961b.
membranes without seeding. J Membrane Sci 2006; 277: Milton RM. Crystallline zeolite F. US Patent 2996358, 1961c.
230239. Milton RM. Crystalline zeolite R. US Patent 3030181, 1962.
Lin DC, Xu XW, Zuo F, Long YC. Crystallization of JBW, CAN, SOD and Mintova S, Olson NH, Bein T. Electron microscopy reveals the
ABW type zeolite from transformation of meta-kaolin. Micropor nucleation mechanism of zeolite Y from precursor colloids.
Mesopor Mater 2004; 70: 6370. Angew Chem-Int Edit 1999a; 38: 32013204.
Linares CF, Simon C, Weller MT. Synthesis and characterization of Mintova S, Olson NH, Valtchev V, Bein T. Mechanism of zeolite a
the oxalate cancrinite-type zeolite. Micropor Mesopor Mater nanocrystal growth from colloids at room temperature. Science
2011; 137: 3235. 1999b; 283: 958960.
Liu Q, Navrotsky A. Synthesis of nitrate sodalite: an in situ scanning Mirfendereski M, Mohammadi T. Investigation of
calorimetric study. Geochim Cosmochim Acta 2007; 71: hydrothermalsynthesis parameters on characteristics
20722078. of T type zeolite crystal structure. Powder Technol 2011;
Long RQ, Yang RT. Selective catalytic oxidation of ammonia to 206:345352.
nitrogen over Fe2O3-TiO2 prepared with a sol-gel method. J Catal Miyake M, Akachi T, Matsuda M. Preparation, structure and
2002; 207: 158165. photocatalytic properties of cancrinite encapsulating lead and
Lowe BM, Nee JRD, Casci JL. Crystallization of inorganic ZSM-5 in the sulfide ions. J Mater Chem 2005; 15: 791797.
system K2O-Al2O3-SiO2-H2O. Zeolites 1994; 14: 610619. Mullin JW. Crystallisation. London: Butterworths, 1972.
Lowenstam HA. Magnetite in denticle capping in recent chitons Na K, Jo C, Kim J, Cho K, Jung J, Seo Y, Messinger RJ,
(polyacophora). Geol Soc Am Bull 1962; 73: 435438. ChmelkaBF,Ryoo R. Directing zeolite structures into
Lukyanov DB, Lombardo EA, Sill GA, dItri JL, Hall WK. Selective hierarchically nanoporous architectures. Science 2011;
catalytic reduction (SCR) of NO with methane over CoZSM-5 and 333:328332.
HZSM-5 zeolites: on the role of free radicals and competitive Naskar MK, Kundu D, Chatterjee M. Coral-like hydroxy sodalite
oxidation reactions. J Catal 1996; 163: 447456. particles from rice husk ash as silica source. Mater Lett 2011;
Lupulescu AI, Rimer JD. Tailoring silicalite-1 crystal morphology with 65: 34083410.
molecular modifiers. Angew Chem-Int Edit 2012; 51: 33453349. Navrotsky A. Energetic clues to pathways to biomineralization:
Lupulescu AI, Kumar M, Rimer JD. A facile strategy to design zeolite precursors, clusters, and nanoparticles. Proc Natl Acad Sci USA
L crystals with tunable morphology and surface architecture. 2004; 101: 1209612101.
JAm Chem Soc 2013; 135: 66086617. Navrotsky A, Tian ZR. Systematics in the enthalpies of formation
Machado FJ, Lopez CM, Centeno MA, Urbina C. Template-free of anhydrous aluminosilicate zeolites, glasses, and dense
synthesis and catalytic behaviour of aluminium-rich MFI-type phases. Chem-Eur J 2001; 7: 769774.
zeolites. Appl Catal A-Gen 1999; 181: 2938. Navrotsky A, Trofymluk O, Levchenko AA. Thermochemistry of
Mackinnon I, Millar G, Stolz W. Aluminosilicate of zeolite N microporous and mesoporous materials. Chem Rev 2009; 109:
structure. US Patent 0269472 A1, 2006. 38853902.
Maghsoodloorad H, Mirfendereski SM, Mohammadi T, Pak A. Effects Ng E-P, Chateigner D, Bein T, Valtchev V, Mintova S. Capturing
of gel parameters on the synthesis and characteristics of ultrasmall EMT zeolite from template-free systems. Science
W-type zeolite nanoparticles. Clay Clay Min 2011; 59: 328335. 2012a; 335: 7073.

Authenticated
Ng E-P, Goupil JM, Vicente A, Fernandez C, Retoux R, Valtchev V, Regis AJ, Sand LB, Calmon C, Gilwood ME. Phase studies in the
Mintova S. Nucleation and crystal growth features of EMT-type portion of the soda-alumina-silica-water system producing
zeolite synthesized from an organic-template-tree system. zeolites. J Phys Chem 1960; 64: 15671571.
Chem Mater 2012b; 24: 47584765. Ren L, Li C, Fan F, Guo Q, Liang D, Feng Z, Li C, Li S, Xiao, F-S.
Ogura M, Kawazu Y, Takahashi H, Okubo T. Aluminosilicate species UV-raman and NMR spectroscopic studies on the crystallization
in the hydrogel phase formed during the aging process for of zeolite A and a new synthetic route. Chem-Eur J 2011; 17:
the crystallization of FAU zeolite. Chem Mater 2003; 15: 61626169.
26612667. Ren N, Suboti B, Broni J, Tang Y, Sikiri MD, Mii T, SvetliiV,
Olsbye U, Svelle S, Bjorgen M, Beato P, Janssens TVW, Bosnar S, Jeli TA. Unusual pathway of crystallization of zeolite
JoensenF, Bordiga S, Lillerud KP. Conversion of methanol ZSM-5 in a heterogeneous system: phenomenology and
to hydrocarbons: how zeolite cavity and pore size controls starting considerations. Chem Mater 2012; 24: 17261737.
product selectivity. Angew Chem-Int Edit 2012; 51: 58105831. Rimer JD, Vlachos DG, Lobo RF. Evolution of self-assembled silica-
Osada M, Sasaki I, Nishioka M, Sadakata M, Okubo T. Synthesis tetrapropylammonium nanoparticles at elevated temperatures.
of a faujasite thin layer and its application for SO2 sensing J Phys Chem B 2005; 109: 1276212771.
at elevated temperatures. Micropor Mesopor Mater 1998; 23: Rios CA, Williams CD, Fullen MA. Nucleation and growth history
287294. of zeolite LTA synthesized from kaolinite by two different
Pan WC, Kolomeisky AB, Vekilov PG. Nucleation of ordered solid methods. Appl Clay Sci 2009a; 42: 446454.
phases of proteins via a disordered high-density state: Rios RCA, Williams CD, Roberts CL. A comparative study of two
phenomenological approach. J Chem Phys 2005; 122: 174905. methods for the synthesis of fly ash-based sodium and
Pan Y, Ju M, Yao J, Zhang L, Xu N. Preparation of uniform nano-sized potassium type zeolites. Fuel 2009b; 88: 14031416.
zeolite A crystals in microstructured reactors using Robson HE. Method for preparing a small pore synthetic zeolite. US
manipulated organic template-free synthesis solutions. Chem Patent 3720753, 1973.
Commun 2009; 122: 72337235. Robson HE. Zeolite RHO. US Patent 3904738, 1975.
Park M, Kim SH, Heo NH, Komarneni S. Synthesis of zeolite rho: Roman-Leshkov Y, Moliner M, Labinger JA, Davis ME. Mechanism of
aging temperature effect. J Porous Mat 1996; 3: 151155. glucose isomerization using a solid lewis acid catalyst in water.
Parnham ER, Morris RE. Ionothermal synthesis of zeolites, Angew Chem-Int Edit 2010; 49: 89548957.
metal-organic frameworks, and inorganic-organic hybrids. Roy BN, Navrotsky A. Thermochemistry of charge-coupled
Accounts Chem Res 2007; 40: 10051013. substitutions in silicate-glasses: the systems M1/nn+ AlO2-SiO2
Passaglia E, Sheppard RA. The crystal chemistry of zeolites. (M=Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Pb). J Am Ceram Soc 1984;
In: BishD, Ming D, editors. Natural zeolites: occurrence, 67: 606610.
properties, applications, reviews in mineralogy and Ruiz AZ, Bruhwiler D, Ban T, Calzaferri G. Synthesis of zeolite L:
geochemistry. Mineralogical Society of America and The tuning size and morphology. Monatsh Chem 2005; 136: 7789.
Geochemical Society, 2001; 69116. Sand LB, Sand ML. Synthetic zeolite. US Patent 3760062, 1973.
Petrovic I, Navrotsky A. Thermochemistry of Na-faujasites with Sand LB, Sacco A, Thompson RW, Dixon AG. Large zeolite crystals:
varying Si/Al ratios. Micropor Mater 1997; 9: 112. their potential growth in space. Zeolites 1987; 7: 387392.
Polak F, Ptak J, Cichocki A. Sposb wytwarzania syntetycznego Sasaki H, Jon H, Itakura M, Inoue T, Ikeda T, Oumi Y, Sano T.
zeolitu-mordenitu o rednicy porw 67 A (A process for Hydrothermal conversion of FAU zeolite into aluminous MTN
preparing synthetic zeolite-mordenite a proe size of 6-7 A). zeolite. J Porous Mat 2009; 16: 465471.
Poland Patent 100913, 1979 (in Polish). Schoeman BJ. A high temperature in situ laser light-scattering study
Posner AS. Crystal chemistry of bone mineral. Physiol Rev 1969; 49: of the initial stage in the crystallization of TPA-silicalite-1.
760792. Zeolites 1997; 18: 97105.
Radulovic A, Dondur V, Dimitrijevic R, Arandjelovic D. Thermal efk J, McCormick AV. Prediction of crystallization diagrams for
transformation of Na-LTA zeolite into low-carnegieite: synthesis of zeolites. Chem Eng Sci 1999; 54: 35133519.
the influence of residual sodium and aluminium species. Simancas R, Dari D, Velamazan N, Navarro MT, Cantin A, Jorda JL,
Thermochim Acta 2010; 511: 3742. Sastre G, Corma A, Rey F. Modular organic structure-directing
Rakoczy RA, Breuninger M, Hunger M, Traa Y, Weitkamp agents for the synthesis of zeolites. Science 2010; 330:
J. Template-free synthesis of zeolite ferrierite and 12191222.
characterization of its acid sites (Reprinted from Chem. Ing. Simonetti DA, Dumesic JA. Catalytic strategies for changing the
Tech., 73, 10241027, 2001). Chem Eng Technol 2002; 25: energy content and cchieving C-C coupling in biomass-derived
273275. oxygenated hydrocarbons. ChemSusChem 2008; 1: 725733.
Ramanan H, Kokkoli E, Tsapatsis M. On the TEM and AFM evidence Skeels GW, Sears MR. Zeolite LZ-277 and process for preparing
of zeosil nanoslabs present during the synthesis of silicalite-1. same. US Patent 5192522, 1993.
Angew Chem-Int Edit 2004; 43: 45584561. Smith JV. Topochemistry of zeolites and related materials 1.
Ravishankar R, Kirschhock CEA, Knops-Gerrits PP, Feijen EJP, Topology and geometry. Chem Rev 1988; 88: 149182.
GrobetPJ, Vanoppen P, De Schryver FC, Miehe G, Fuess H, Song JW, Dai L, Ji YY, Xiao FS. Organic template free synthesis
Schoeman BJ, Jacobs PA, Martens JA. Characterization of of aluminosilicate zeolite ECR-1. Chem Mater 2006; 18:
nanosized material extracted from clear suspensions for 27752777.
MFIzeolite synthesis. J Phys Chem B 1999; 103: Suzuki Y, Wakihara T, Itabashi K, Ogura M, Okubo T. Cooperative
49604964. effect of sodium and potassium cations on synthesis of
Read WT. Dislocations in crystals. New York: McGraw-Hill, 1953. ferrierite. Top Catal 2009; 52: 6774.

Authenticated
Tatlier M, Baris K, Tokay CB, Erdem-Senatalar A. Microwave vs. Xiong R, Sandler SI, Vlachos DG. Molecular screening of alcohol and
conventional synthesis of analcime from clear solutions. J Cryst polyol adsorption onto MFI-type zeolites. Langmuir 2012; 28:
Growth 2007; 306: 146151. 44914499.
Taylor AM, Roy R. Zeolite studies IV: Na-P zeolites and Yang SY, Navrotsky A. Energetics of formation and hydration of
ionexchanged derivatives of tetragonal Na-P. Am Miner 1964; ion-exchanged zeolite Y. Micropor Mesopor Mater 2000; 37:
49: 656682. 175186.
Termine JD, Posner AS. Infrared analysis of rat bone: age Yang SY, Navrotsky A, Phillips BL. In situ calorimetric, structural,
dependency of amorphous and crystalline mineral fractions. and compositional study of zeolite synthesis in the system
Science 1966; 153: 15231525. 5.15Na2O-1.00Al2O3-3.28SiO2-165H2O. J Phys Chem B 2000;
Tompsett GA, Conner WC, Yngvesson KS. Microwave synthesis of 104: 60716080.
nanoporous materials. Chemphyschem 2006; 7: 296319. Yoo WC, Kumar S, Wang ZY, Ergang NS, Fan W, Karanikolos GN,
Valtchev VP, Bozhilov KN. Transmission electron microscopy study McCormick AV, Penn RL, Tsapatsis M, Stein A. Nanoscale
of the formation of FAU-type zeolite at room temperature. reactor engineering: hydrothermal synthesis of uniform zeolite
JPhys Chem B 2004; 108: 1558715598. particles in massively parallel reaction chambers. Angew
Valtchev VP, Bozhilov KN. Evidences for zeolite nucleation at the Chem-Int Edit 2008; 47: 90969099.
solid-liquid interface of gel cavities. J Am Chem Soc 2005; 127: Zapata PA, Faria J, Ruiz MP, Jentoft RE, Resasco DE. Hydrophobic
1617116177. zeolites for biofuel upgrading reactions at the liquid-liquid
Valtchev VP, Tosheva L. Porous nanosized particles: preparation, interface in water/oil emulsions. J Am Chem Soc 2012; 134:
properties, and applications. Chem Rev 2013; 113: 67346760. 85708578.
Valtchev VP, Tosheva L, Bozhilov KN. Synthesis of zeolite Zhang L, Liu SL, Xie SJ, Xu LY. Organic template-free synthesis of
nanocrystals at room temperature. Langmuir 2005; 21: ZSM-5/ZSM-11 co-crystalline zeolite. Micropor Mesopor Mater
1072410729. 2012a; 147: 117126.
Vaughan DEW. ECR-33: a stabilized rare-earth exchanged Q type Zhang XY, Liu DX, Xu DD, Asahina S, Cychosz KA, Agrawal KV, Al
zeolite. US Patent 5382420, 1995. Wahedi Y, Bhan A, Al Hashimi S, Terasaki O, Thommes M,
Vekilov PG. Dense liquid precursor for the nucleation of ordered Tsapatsis M. Synthesis of self-pillared zeolite nanosheets by
solid phases from solution. Cryst Growth Des 2004; 4: repetitive branching. Science 2012b; 336: 16841687.
671685. Zhao DY, Szostak R, Kevan L. Role of alkali-metal cations and seeds
Vekilov PG. Two-step mechanism for the nucleation of crystals from in the synthesis of silica-rich heulandite-type zeolites. J Mater
solution. J Cryst Growth 2005; 275: 6576. Chem 1998; 8: 233239.
Wang D, Zhang L, Kamasamudram K, Epling WS. In situ DRIFTS Zhdanov SP. Some problems of zeolite crystallization. Adv Chem Ser
study of selective catalytic reduction of NOx by NH3 over 1971; 101: 2043.
Cu-exchanged SAPO-34. ACS Catal 2013; 3: 871881. Zhdanov SP, Samulevich NN. Nucleation and crystal growth of
Warzywoda J, Thompson RW. Synthesis of zeoltie A in the Na/K zeolites in crystallizing aluminosilicate gels. Proceedings of the
system and the effect of seeding. Zeolites 1991; 11: 577582. fifth international conference on zeolites, Naples, Italy, 1980.
Watson JN, Iton LE, Keir RI, Thomas JC, Dowling TL, White JW. Zhou RF, Zhong SL, Lin X, Xu NP. Synthesis of zeolite T by microwave
TPA-silicalite crystallization from homogeneous solution: and conventional heating. Micropor Mesopor Mater 2009; 124:
kinetics and mechanism of nucleation and growth. J Phys Chem 117122.
B 1997; 101: 1009410104. Zhu GQ, Li YS, Chen HL, Liu J, Yang WS. An in situ approach to
Wells A. Crystal growth. Annu Rep Chem Soc 1946; 43: 62. synthesize pure phase FAU-type zeolite membranes: effect
Wenqin P, Ueda S, Koizumi M. The synthesis of zeolite NaA from of aging and formation mechanism. J Mater Sci 2008; 43:
homogeneous solutions and studies of its properties. In: 32793288.
Murakami AIY, Ward JW, editors. New developments in zeolite Zones SI. Conversion of faujasites to high-silica chabazite SSZ-13 in
science and technology, Studies in Surface Science and the presence of N,N,N-trimethyl-1-adamantammonium iodide.
Catalysis. Amsterdam, Netherlands: Elsevier, 1986: 177184. JChem Soc-Faraday Trans 1991; 87: 37093716.
Wiersema GS, Thompson RW. Nucleation and crystal growth of Zones SI, Nakagawa Y. Boron-beta zeolite hydrothermal conversions:
analcime from clear aluminosilicate solutions. J Mater Chem the influence of template structure and of boron concentration
1996; 6: 16931699. and source. Microporous Mater 1994; 2: 557562.
Wu Z, Song J, Ji Y, Ren L, Xiao F-S. Organic template-free synthesis of Zones SI, Vannordstrand RA. Novel zeolite transformations: the
ZSM-34 zeolite from an assistance of zeolite L seeds solution. template-mediated conversion of cubic-P zeolite to SSZ-13.
Chem Mater 2008; 20: 357359. Zeolites 1988; 8: 166174.
Xingqiao W, Ruren X. Studies on the transformation between Zones SI, Yuen LT, Nakagawa Y, van Nordstrand RA, Toto SD.
erionite and effretite in T-type zeolite. In: Draj B, Hoevar S, An unexpected and highly versatile new zeolite synthesis
Pejovnik S, editors. Zeolites: synthesis, structure, technology route leading to large pore alumino and borosilicate sieves.
and application, Studies in Surface Science and Catalysis. Proceedings from the ninth international zeolite conference,
Amsterdam, Netherlands: Elsevier, 1985: 111118. Montreal, 1992.
Xiong R, Sandler SI, Vlachos DG. Alcohol adsorption onto Zones SI, Ruan J, Elomari S, Terasaki O, Chen CY, Corma A. Studies
silicalitefrom aqueous solution. J Phys Chem C 2011; 115: on zeolite SSZ-57: a structural enigma. Solid State Sci 2011; 13:
1865918669. 706713.

Authenticated
Matthew Dowd Oleksiak received his BS degree in Chemical Engi- Jeffrey Daniel Rimer received dual BS degrees in Chemistry from
neering from the University of Delaware. He is currently pursuing Allegheny College in 1999 and Chemical Engineering from Washing-
his PhD in Chemical Engineering at the University of Houston. His ton University in St. Louis in 2001. He received his PhD in Chemical
research interests include rational approaches in zeolite synthesis Engineering from the University of Delaware in 2006 and began
and catalysis. his position at the University of Houston in 2009, where he now
serves as the Ernest J. and Barbara M. Henley Assistant Professor of
Chemical Engineering. His research interests in the area of crystal
engineering include studies of zeolite and biogenic crystal forma-
tion with applications that span catalysis to drug design.

Authenticated

Synthesis of Zeolites in The Absence of Organic Structure-Directing Agents

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Synthesis of Zeolites in The Absence of Organic Structure-Directing Agents

Diunggah oleh

Hak Cipta:

Format Tersedia

DOI 10.

1515/revce-2013-0020Rev Chem Eng 2014; 30(1): 149

Matthew D. Oleksiak and Jeffrey D. Rimer*

Synthesis of zeolites in the absence of organic

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Many factors govern the thermodynamics of zeolite for-

investigated the energetics of formation for many zeo-

dynamics of zeolite synthesis, which include framework 4

density, aluminum content, extraframework cations,

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Table 1Structural information of zeolite framework types.

EMT 1.72 1.72 2.81 P63/mmc 12, 6, 4 d6R, sod 3D 45.3

Data were obtained from the IZA Online Structure Database.

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M++M2+

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M++M2+

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M++M2+

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M++M2+

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

x Sia y Alb z H2O Si Al M+(2)

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Brought to you by | University of Pittsburgh

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh

Download Date | 1/4/15 8:34 PM

Brought to you by | University of Pittsburgh