pubs.acs.org/acscatalysis
1. INTRODUCTION is corrosive and poor for waste discharge.17 Thus solid acid
Open framework porous materials have attracted a great deal catalysts are preferable, which could eliminate the corrosion
of interests over the years because of their potential as green problems and offer easy separation of catalysts from the products
adsorbent and catalysts, which could resolve the environmental through simple filtration. For solid acid catalysts, the carboxylic
concern and waste management.13 Mesoporous materials can acid first adsorbs on the catalytic site, and this is followed by
reaction with the alcohol from the bulk phase.1820 To date,
fulfill this area owing to their distinctive properties like high
several groups have developed various solid acids for the ester-
surface area, uniform pore size distribution (PSD), plenty of well
ification of long chain fatty acids; these include zeolites,2123
distributed active sites,46 and ease of diffusion for large reacting
sulfonated carbonized sugar,7,8 sulfated zirconia,21,22 sulfated
molecules through their channels.7,8 Functionalized porous solids
silica-zirconia,24 functional ionic liquid,25 zirconium phosphate
have been employed as heterogeneous catalysts because they are
supported over different metal oxides,26 and organosulfonic acid
environmentally green with respect to corrosiveness, nonhazar-
mesoporous silica27 and so forth. These solid acids catalyze the
dous in nature, and offer ease of catalyst recovery and reus- esterification of fatty acids with methanol at 453 K. Kiss et al. have
ability.7,912 Solid acid catalysts can be used in biodiesel produc- also developed another class of interesting biodiesel catalysts
tion, which is an environment-friendly fuel as it is made from such as metal oxides, which include niobic acid, sulfated zirconia,
renewable resources and low cost feedstocks, like yellow greases, sulfated titania, and sulfated tin oxide.22 Cheng et al. have
rendered animal fats, and trap greases that contain a significant developed a sulfated zirconia anchored mesoporous silica catalyst
concentration of free fatty acids. It is usually derived from the for the esterification of long-chain free fatty acids heterogeously
esterification of free fatty acids or the transesterification of trigly- at 341 K in 2007.24
cerides with methanol or ethanol.13,14 Industrial trans-esterifica- On the other hand the mesoporous metallophosphates have
tion processes using homogeneous base catalysts are associated been invented either post-synthesis method or direct method by
with higher production cost for biodiesel manufacture because of several group of researchers.28,29 Mesoporous zirconium oxo-
neutralization and separation problems.15 phosphate/phosphates have been synthesized through the post-
Moreover, the base catalyzed process suffers from some synthesis method by employing CTAB as structure directing
limitations of feedstock. The contents of free fatty acid in the agent.30,31 Later, Wu and his co-workers have synthesized porous
feedstock need to be lower than 0.5 wt %, otherwise soap zirconium phosphate through the post-synthesis surface reaction
formation seriously hinders the production of biodiesel.16 Ester-
ification is thus needed for converting long-chain free fatty acids Received: January 8, 2011
into esters. Esterifications are conventionally catalyzed under Revised: March 23, 2011
homogeneous conditions using concentrated sulfuric acid, which Published: March 25, 2011
r 2011 American Chemical Society 493 dx.doi.org/10.1021/cs200005z | ACS Catal. 2011, 1, 493–501
ACS Catalysis RESEARCH ARTICLE
between mesoporous zirconium oxide, prepared by using CTAB as 2.2. Preparation of Mesoporous Zirconium Oxopho-
surfactant, and phosphoric acid.32 Very recently, Sinhamahapatra sphate (MZrP). In a typical synthesis of mesoporous zirconium
et al. have developed mesoporous zirconium phosphate by oxophosphate, 30 mL absolute ethanol was acidified with 3.30 g
utilizing CTAB as structure directing agent in aqueous medium (35 wt %) hydrochloric acid. Then 2.0 g triblock copolymer
with pore dimensions ranging 23 nm, which have active acidic pluronic F127 was added to this acidic ethanol medium and
sites to catalyze FriedelCraft benzylation reaction.11 Rao et al. allowed to stir until dissolution. Then 3.84 g (0.01 M) zirconium-
have developed porous zirconium phosphate, which catalyzes (IV) butoxide (taken in 5 mL ethanol) was added slowly under
esterification reaction of palmitic acid with methanol to only 20% vigorous stirring and allowed to stir for 30 min. During stirring
conversion. However, this zirconium phosphate when supported precipitation should be avoided. Then, to this clear solution 1.16 g
with WO3 behaves as a strong acid catalyst and convert the of (0.01 M) orthophosphoric acid (88 wt %, taken in 5 mL
palmitic acid to its corresponding ester more efficiently.26 ethanol) was slowly dropwise added under vigorous stirring at
In this context, herein we have developed new mesoporous ambient temperature. Then the reaction mixture was covered
zirconium oxophosphate materials through the evaporation- and allowed to stir overnight at room temperature. The mixture
induced self-assembly (EISA) method by using non-ionic Pluro- was placed inside the oven at 343 K to undergo the EISA process.
nic F127 as structure directing agent in acidic nonaqueous Finally, the obtained solid sample was calcined through slow
medium. These materials possess high surface areas with pore increase of the temperature to 773 K (1 K min1 ramping rate)
dimensions in the range of large mesopores. To the best of our followed by heating at 773 K for 5 h in the presence of air
knowledge fabrication of mesoporous zirconium oxophosphate to obtain template-free mesoporous zirconium oxophosphate.
with large pore dimension by using Pluronic F127 as structure Similarly, two other MZrP samples have been synthesized
directing agent through the EISA method and their use as through the above-mentioned method just by varying the
heterogeneous solid acid catalyst in biodiesel formation reaction zirconium to phosphorus ratio of 2:1 and 4:1. These three
has not been explored. In most of the cases, mesoporous metallo- synthesized mesoporous zirconium oxophosphate materials hav-
phosphates and other known biodiesel catalysts have been ing the zirconium to phosphorus ratio of 1:1, 2:1, and 4:1 are
synthesized mainly through a post-synthesis method with rela- abbreviated as samples 1, 2 and 3, respectively.
tively small pore (23 nm) dimension.7,8,2123,32 Furthermore,
in all the catalysts prepared by the post-synthesis method the
active sites are not easy accessible to the reactants because of the 3. CHARACTERIZATION TECHNIQUES
pore blocking and inhomogeneous distribution of active sites, Powder XRD of the samples were recorded on a Bruker AXS
and consequently is responsible for their low reactivity. Here, we D-8 Advance diffractometer operated at 40 kV voltage and 40 mA
have synthesized mesoporous zirconium oxophosphate with current and calibrated with a standard silicon sample, using
large pore (∼5.0 nm) and high surface area in one pot, which Ni-filtered Cu KR (λ = 0.15406 nm) radiation. TEM images were
reduces the probability of pore blocking and inhomogeneity recorded on a JEOL 2010 TEM operated at 200 kV. A Jeol JEM
problem. Furthermore, NH3-TPD analysis suggests the presence 6700 field emission scanning electron microscope (FESEM)
of reasonable amount of Lewis and Br€onsted acid sites. High with an energy dispersive X-ray spectroscopic (EDS) attachment
surface area together with large pores and presence of strong was used for the determination of morphology of the particles
Lewis and Br€ onsted acid sites have motivated us to explore the and its surface chemical compositions, respectively. Nitrogen
catalytic potential of the mesoporous zirconium oxophosphate adsorption/desorption isotherms of the samples were recorded
materials in biodiesel reaction between different alcohols as well on a Quantachrome Autosorb 1C, at 77 K. Prior to the gas
as several long-chain free fatty acids into their corresponding adsorption measurements, the samples were degassed at 423 K
esters. Here large pore dimension favors the diffusion of long for 4 h under high vacuum. Fourier transform infrared (FT IR)
chain fatty acid molecules. The materials are characterized spectra of these samples, pyridine adsorption/desorption studies
thoroughly by using different characterization tools such as powder including variable temperature pyridine desorption were re-
X-ray diffraction (XRD), transmission electron microscopy (TEM), corded on KBr pellets by using Perkin-Elmer Spectrum 100
scanning electron microscopy (SEM)-energy dispersive spec- spectrophotometer. UVvisible diffuse reflectance spectra were
troscopy (EDS), thermogravimetry (TG)-differential thermal recorded on a Shimadzu UV 2401PC with an integrating sphere
analysis (DTA), UVvisible reflectance, and FT IR spectroscopy. attachment, and BaSO4 was used as background standard.
Thermogravimetric analysis (TGA) and DTA of the sample
were carried out in a TGA instrument thermal analyzer TA-SDT
2. EXPERIMENTAL SECTION Q-600 under N2 flow. Temperature programmed desorption of
ammonia (TPD-NH3) was carried out in a Micromeritics
2.1. Chemicals. Triblock copolymer poly(ethylene glycol)- Instrument Corporation ChemiSoft Unit 1. In a typical experi-
block-poly-(propylene glycol)-block-poly(ethylene glycol) (Plur- ment for the TPD measurement, mesoporous zirconium oxo-
onic F127, Mav = 12600, EO106PO70EO106) was used as the phosphate samples 1 and 2 were activated under the flow of He
structure-directing agent and zirconium(IV) butoxide [Zr(OC4- gas at 873 K (3 h) followed by cooling at 298 K and then
H9)4] were purchased from Sigma-Aldrich. Hydrochloric acid adsorbing ammonia through injection until complete saturation
(HCl) and orthophosphoric acid (H3PO4) were obtained from (observed from the respective thermal conductivity detector
Merck. In catalytic reactions different alcohols and fatty acids (TCD) signal). Physically adsorbed ammonia was then removed
were used. Cyclohexanol, 2-ethylhexanol were procured from by desorbing it in He at 373 K. TPD experiment was then carried
Loba Chemie, benzyl alcohol, methanol from Merck, all fatty out by raising the temperature of the catalyst in a programmed
acids (lauric acid, myrestic acid, palmitic acid, stearic acid) manner (10 deg/min). Areas under the peaks were converted to
obtained from Loba Chemie and were used without further equivalent ammonia per gram on the basis of injection of known
purification. volumes of ammonia at similar conditions.
494 dx.doi.org/10.1021/cs200005z |ACS Catal. 2011, 1, 493–501
ACS Catalysis RESEARCH ARTICLE
Table 3. Esterification Reaction of Different Alcohols with Table 4. Esterification Reaction of Different Long-Chain
Acetic Acid Catalyzed by Mesoporous Zirconium Oxopho- Free Fatty Acids with Methanol Catalyzed by Mesoporous
sphate Materialsa Zirconium Oxophosphate Materialsa
a
Reaction conditions: The esterification of long-chain fatty acids with
a
Reaction conditions: The esterification of alcohols with acetic acid was methanol was carried out with a mole ratio of fatty acid/methanol of
carried out with a mole ratio of alcohol/acetic acid of 1:3. Here acetic 1:10. Here methanol acts as reactant as well as solvent. Temperature at of
acid acts as reactant as well as solvent. Temperature of the reaction was the reaction was maintained at 338 K. Catalyst was taken as 5% (w/w)
maintained at 373 K. Catalyst was taken 3% (w/w) based on alcohol. based on fatty acid. b Esterification reaction was carried out with sample
TON (turn over number) = moles of substrate converted/mol of acid 2 as catalyst. c Esterification reaction was carried out with sample 3 as
site of catalyst (estimated from the NH3-TPD). b Esterification reaction catalyst. d Esterification reaction was carried out without catalyst. In
was carried out with sample 2 as catalyst. c Esterification reaction was every case product selectivity is 100% and conversion of all the products
carried out with sample 3 as catalyst. d Esterification reaction was carried were measured after 10 h.
out without catalyst. In every case product selectivity was 100% and
conversions of all the products were measured after 6 h reaction time.
30.63 and 20.03 cm3 g1, respectively. Thus, this result suggests
that with an increase in Zr:P molar ratio from sample 1 to 2, the
acid site can be related to the corresponding desorption tem- surface acidity for the mesoporous zirconium oxophosphate
perature. Sample 1 shows a little higher intensity and desorption framework decreased. The decrease in total acidity from MZrP
in the temperature range of 363435 K indicating higher sample 1 to 2 in the NH3-TPD study could be attributed to the
number of weak acid sites than sample 2. Furthermore, from lowering of surface area and phosphorus content in the meso-
the figure it is clear that the medium strength acid sites are much porous frameworks. During biodiesel synthesis through the
higher for sample 1 than for sample 2. The higher amount of heterogeneous esterification reaction, acid sites of the solid acid
weak and medium acid sites in sample 1 is mainly due to the catalysts play a crucial role and as a result sample 1 should show
presence of high phosphate content within the mesoporous better catalytic efficiency than sample 2. This trend is similar to
framework. High phosphate content could be responsible of that observed for zeolites, wherein the acid strength is higher at
geminal P(OH)2 sites. Furthermore, both samples showed the higher Si/Al ratio because of the larger number of isolated Al sites
presence of strong acid sites, as their respective desorption tem- in the silica framework.49
peratures are quite high (737835 K). Total acidity (calculated 4.9. Catalytic Study. The catalytic performance of mesopor-
from total area under the peaks) for MZrP samples 1 and 2 are ous zirconium oxophosphate with different nZr/nP ratio in
498 dx.doi.org/10.1021/cs200005z |ACS Catal. 2011, 1, 493–501
ACS Catalysis RESEARCH ARTICLE
Table 5. Comparative Catalytic Performance of Reported Bio-Diesel Catalysts with Our Materials
entry catalyst fatty acid alcohol: fatty acid catalyst (wt %) temp (K) time (h) conv. ref.
subsequent acid catalyzed elimination of water yields the desired of the zirconium sites present in these samples are tetrahedrally
ester.51 coordinated Zr(IV). In addition to tetrahedral coordination
The stability as well as heterogeneous nature of mesoporous there is considerable extent of five or six coordinated zirconium
zirconium oxophosphate was investigated by performing a hot present in the extra-framework of the materials, which could
filtration test utilizing the sample 1 catalyst under the optimized result because of its synthesis under strong acidic conditions.
reaction conditions. In this case the reaction was stopped when NH3-TPD analysis suggests the presence of Lewis and Br€onsted
the conversion reached 30% and quickly removed the catalyst by acid sites, and pyridine adsorbed FT IR spectral studies also
filtration. The filtrate was immediately reused in the same confirm this observation. The high acid density and large surface
reaction in an identical condition, and it was found that there area could be employed for an efficient biodiesel catalyst.
was no further increase in substrate conversion. The filtered Furthermore, large pore size that favors the diffusion of large
catalyst was also reused with fresh reagents after applying suitable organic molecules contributes to the enhancement of catalytic
conditions and negligible loss of its catalytic activity was ob- ability. These catalysts efficiently converted the long chain fatty
served. Further, when the reaction was carried out in the absence acids to their corresponding methyl ester with methanol as well
of catalyst, almost no conversion was found. These results as different alcohols to their corresponding ester with glacial
confirmed that during the reaction no catalyst leaching occurs, acetic acid. In a typical reaction the observed biodiesel yield was
and the reaction is a purely heterogeneous one in nature.912 over 91% under an optimal reaction conditions. Moreover, this
The activity of a regenerated catalyst was inspected by filtration mesoporous solid acid catalyst has been recycled five times with
of the catalyst from an optimized reaction and then washing negligible loss of activity, suggesting high chemical stability
several times with methanol and anhydrous acetone followed by and reusability of the mesoporous zirconium oxophosphate
drying in an oven at 373 K overnight. The catalyst was subse- framework.
quently activated at 673 K for 4 h under air flow and utilized for
the above reaction. The same procedure was repeated an addi- ’ ASSOCIATED CONTENT
tional four times, and the kinetic plots for the conversion12 in the
esterification of different alcohols with acetic acid and several bS Supporting Information. Wide angle PXRD, FE-SEM
long-chain free fatty acids with methanol in the recycling images, UVvis diffuse reflectance spectrum, Nitrogen adsorp-
process are shown in Figures 8A and 8B, respectively. The tion/desorption isotherms and corresponding pore size of
rate of conversion of different alcohols as well as different sample 1 and sample 2 calcined at 1173 K, band gap, FT IR
fatty acids into their corresponding products did not show and TG-DTA profile have been given. This material is available
any noticeable change during the progress of the reaction free of charge via the Internet at http://pubs.acs.org.
throughout five reaction cycles. Thus the mesoporous zirconium
oxophosphate materials described herein have great potential to ’ AUTHOR INFORMATION
be a stable and highly active recyclable solid acid catalyst. In
Corresponding Author
Table 5 we have provided a comparative catalytic performance of
reported biodiesel catalysts with our mesoporous zirconium *E-mail: msab@iacs.res.in.
oxophosphate materials. Results suggested that our mesoporous
zirconium phosphate material is a superior catalyst for the ’ ACKNOWLEDGMENT
production of biodiesel over the existing catalysts known in the
literature (Table 5). S.K.D. and M.K.B. wish to thank CSIR, New Delhi for their
respective Senior Research Fellowships.
5. CONCLUSION
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