10 2307@43424246

Properties and applications of zeolites
Author(s): CHRISTOPHER J. RHODES

Source: Science Progress (1933-), Vol. 93, No. 3 (2010), pp. 223-284
Published by: Science Reviews 2000 Ltd.
Stable URL: http://www.jstor.org/stable/43424246
Accessed: 17-02-2016 07:04 UTC
REFERENCES
Linked references are available on JSTOR for this article:
http://www.jstor.org/stable/43424246?seq=1&cid=pdf-reference#references_tab_contents
You may need to log in to JSTOR to access the linked references.
Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at http://www.jstor.org/page/
info/about/policies/terms.jsp
JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of content
in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms of scholarship.
For more information about JSTOR, please contact support@jstor.org.
Science Reviews 2000 Ltd. is collaborating with JSTOR to digitize, preserve and extend access to Science Progress (1933-).
http://www.jstor.org
This content downloaded from 128.111.121.42 on Wed, 17 Feb 2016 07:04:40 UTC
All use subject to JSTOR Terms and Conditions
(2010),93(3),223-284
ScienceProgress
doi:10.3184/0036850
10X12800828 155007
Properties and applications of zeolites
CHRISTOPHERJ.RHODES
ABSTRACT
solidsbearinga negatively
Zeolitesare aluminosilicate chargedhoneycomb
framework of microporesinto whichmoleculesmay be adsorbedfor
environmental decontamination, and to catalysechemicalreactions.They
are centralto green-chemistry since the necessityfor organicsolventsis
minimised. Proton-exchanged (H) zeolitesare extensively employed in the
petrochemical industryfor cracking crude oil fractions intofuels and
chemical feedstocksfor other industrialprocesses.Due to their abilityto
perform cation-exchange,in which thecationsthatare originallypresentto
counterbalance theframework negative be
chargemay exchanged outofthe
zeolite by cationspresentin aqueous solution,zeolitesare usefulas
industrial in the removalof radioactiveCs+ and Sr^+
water-softeners,
cationsfromliquidnuclearwasteand in theremovalof toxicheavymetal
cationsfromgroundwaters and run-off waters.Surfactant-modifiedzeolites
(SMZ)findparticular application in theco-removalofbothtoxicanionsand
organicpollutants.Toxic anions such as arsenite,arsenate,chromáte,
cyanideand radioactiveiodide can also be removedby adsorptioninto
zeolitesthathavebeenpreviously loadedwithco-precipitatingmetalcations
suchas Ag+ and Pb2+ whichformpractically insolublecomplexes thatare
contained withinthezeolitematrix.
Keywords:zeolite,cation-exchange,Chernobyl, radioactivewaste,stron-
tium,strontium, caesium,catalyticcracking,oil, petroleum,solid acid
iodine,cadmium,
catalysts, lead,zinc,surfactant-modifiedzeolites,decon-
tamination,pollution
www.
sciencepr co.uk
ogress, 223
ProfessorChrisRhodeshas a visiting positionat the
Universityof Readingand is Directorof Fresh-lands
EnvironmentalActions.He has catholicscientific
interests
(www.fresh-lands.com)whichcoverradiation chemistry,
zeolites,
catalysis, freeradicalsandelectron
radioisotopes,
spinresonance spectroscopy, whichmorerecently have
developedintoaspectsof environmental decontamination
andtheproduction of sustainable
fuels.Chrishas given
numerous radioandtelevised interviews
concerning envir-
onmentalissues,bothinEuropeandintheUnited -
States
includingonBBC Radio4's MaterialWorld. Latestinvitations
include a seriesof
international lectures
CaféScientifique regardingtheimpending depletion ofworld
oil and the need to developoil-independent,sustainablesocieties.He has
publishedmorethan200 peer-reviewed scientific
articlesandfivebooks.He is
also a published
novelist, andpoet.E-mail:cjrhodes@fresh-lands.com
journalist
1. Introduction
Zeolites constitutea unique class of solid substances with multi-
farious applications to industrialprocesses and to the control of
environmental pollution1-11.They may be used in bothpre-emptive
decontamination strategiesand to clean-uptoxic spillages of various
kinds. The workingstructure of a zeolite consistsof a microporous,
aluminosilicate framework,bearing a formal negative electric
charge,which contains an exact numberof cations as requiredto
counterbalance that framework charge. The cations may be
exchanged out of the zeolite by other types of cation introduced
in solution-phase,rendering zeolites as effective ion-exchange
+
materials, for softeningwater (by removing Ca2+ and Mg2
cations, and replacing them, e.g. by Na+ cations), for cleaning
radioactive Sr2^ and Cs+ cations fromliquid nuclear waste, for
+ + +
removingtoxic heavy-metalcations (e.g. Pb2 , Cd2 , Zn2 ) from
+
wastewater,and as exchanged by protons(H ) to formsolid acid
catalystswhich are used extensivelyin the petrochemicalindustry
forcrackinghydrocarbonfractionsinto fuels and in the preparation
of raw chemical feedstocksforvariousmanufacturing processes1.In
consequence of the factthatzeolites are microporous(meaningthat
theycontaina honeycomb-likestructure withpores typicallyof less
than 13 Angstroms[1.3 nm] in diameter,and can thereforereadily
accommodate simple organic molecules) they can provide micro-
reactors in which a range of "green" chemical reactions, e.g.
oxidations and otheruseful processes, may be carriedout, with a
smaller environmentalimpact than would otherwisebe the case
since the use of organicsolventsis minimised.The firstzeolite was
identifiedin 1756 by the Swedish mineralogist(Baron) Friedrich
Axel Cronstedt,who observed that on heating the stones he had
224 Christopher
J.Rhodes
gatheredin a blow-pipe flame,theydanced about in a frothof hot
liquid and steam, appearing as if the stones themselves were
boiling. He thus coined the name "zeolite" which from Greek
derivation( zein, "to boil"; lithos, "a stone") means "stones that
boil"4. The phenomenonhe observed provides a vital clue to an
essential propertyof zeolites, which is their ability to absorb a
substantialproportion -perhaps half theirown volume, depending
on the type of zeolite-of water,and indeed of otherliquids. The
combinationof cation-exchangeand microporouscapacity confers
particularpropertiesto zeolites and a wealth of applications for
them.Four milliontonnesof naturalzeolites are mined annually,of
which 2.5 million tonnes are shipped to China, mainly to make
concreteto supply a constructionindustrythatexpands to meet an
unprecedentedswathe of industrialand economic growth7.
The worldmustcome out of denial over therealityof a finiteand
dwindlingresource of crude oil, and developmentsin the use of
zeolites as catalysts to render known hydrocarboncracking and
oxidation chemistrymore efficient,and the discovery of new
catalyticprocesses, both for the procurementand modificationof
hydrocarbonsare of the essence5. Some 50 different typesof zeolite
are known to occur naturally,while around another150 have been
artificiallysynthesised5.Synthetic zeolites can be designed to
selectively to performspecific tasks, and with a typicallymore
homogeneous composition than is the case for their naturally
occurringcounterparts. A superlativeexample of a tailoredsynthetic
zeolite is H-ZSM-5 (Figure 1), developed6 by Mobil in the early
1970s. H-ZSM-5 is designated "H" because it is the hydrogen
(proton) exchanged form that is referredto, "ZSM", so it is
rumouredbecause these are the initial lettersof the surnamesof
the threescientistswho createdthe frameworkmaterial,or simply
"Zeolite Synthesisedby Mobil", and "5" because it was the fifth
attemptthatworked,accordingto the oftenserendipitousnatureof
zeolite synthesis. H-ZSM-5 was introduced to catalyse the
"methanol to gasoline" (MTG) process, in which methanol is
convertedinto hydrocarbonmixturesof a suitable compositionto
be burnedin internalcombustionengines.H-ZSM-5 is also used on
a large scale to feed the "polyester" industry,by producing"pure"
para-xylene(which diffusesout of the microporesof ZSM-5 nearly
10,000 timesfasterthanthe othertwo xylene isomersdo), which is
oxidised to terephthalic acid and thenesterifiedwithglycolsto form
synthetic"polyester" fabricsforthe clothingindustry7.
For large-scaleenvironmentalapplications,it is preferableto use
a naturalzeolite-containing mineral(Figure 2), which can be mined
www.scienceprogress.co.uk andapplications
Properties ofzeolites225
Fig. 1. Schematic ofzeoliteZSM-5.Thishas an intersecting
representation two-
dimensional channel Thefirstsetofchannels
structure. is straight
andelliptical
in
crosssection.Thesecondsetofchannels intersects
thestraight
channels at right
angles,in a zig-zagpattern
and are circularin crosssection.Thisuniquetwo-
dimensionalporestructure
allowsa moleculetomove from onepointinthecatalyst
toanywhere elseintheparticle.
ucsd.
http.V/chemelab. edu/methanol/imagesMTG/schematicZSM-5.gif Reproduced
withpermission
(ideally locally to minimisetransportationcosts) and used with the

minimumof processing: merely crushingthe raw mineral into a
powder may be all that is needed. Native sodalite often has an
attractiveblue colour due to unpaired electronsthathave become
trappedwithinits structure and is made intojewelry and ornamants
(e.g. Figure 3). Natural zeolites are produced by the forces of
volcanism (Figure 4), and are often associated with mountainous
Fig. 2. Cagestructure
ofsodalite.http://wikis.lib.ncsu.edU/images/8/8c/Z-s-l.png
Reproduced with
permission.
226 Christopher
J.Rhodes
Fig.3. Anornamental carved
hippopotamus fromnatural Thebluecolour
sodalite.
isfromtrapped inthesodalitecages.Thefracture-planes
electrons ofthematerial
areevident.
http: wikimedia.
//upload, org/wikipedia/commons/8/8d/Sodalite.
hippo,arp.75Opix.jpg
regions, e.g. the Caucasus and the Balkans, while there are also
depositsfoundin the Himalayas and in Switzerland,and in theU.S.
aroundthe Gulf of Mexico (includingCuba), which has a volcanic
history. When molten magma, the force of which pushes up
mountains,can escape througha volcanic vent,the volcanic rocks
(solidified lava) and ash layers that are produced may transform
(crystallize)into a zeolite if they come into contact and reaction
Fig. 4. Volcanism
at work:Cleveland in theAleutian
Volcano IslandsofAlaska
photographedfromtheInternational May2006.
SpaceStation,
http wikimedia.
.//upload, commons/
org/wikipedia/ 4/4a/MtCleveland_ISS01
3-E-24184.jpg
www.scienceprogress.co.uk Properties ofzeolites227

andapplications
Fig.5. Natural
zeolite
formation,
http://www.zeoinc.com/images/zeolite
Jormation.jpg
Reproducedwith fromZeo,Inc.
permission
with alkaline/saline lake or ground-waters(Figure 5). Beds of

zeolites may be hundreds of meters thick (Figure 6). Zeolites
have also crystallized in post-depositional environmentsover
periods ranging from thousands to millions of years in shallow
zeolite:theCuchillo
Fig.6. Bedofnatural Negroclinoptilolite
deposit theSt.
from
CloudMining Company (thelargest
producerofnatural
zeoliteinNorth
America),
NewMexico.
locatednearWinston,
ees.nmt.
//www.
http: .html Reproduced
edu/bowman/research/SMZ/StCloudZeolitel
withpermissionfromProf.R. Bowman
J.Rhodes
228 Christopher
Squarein Yerevan,
Fig. 7. Republic whichis constructed
Armenia, fromlocally
mined volcanic Photocoutesy
tuff. toAmasiaFilm.
ofVoyage
http://www.voyagetoamasia.com
marine basins, and are found in some ocean sediments1'2'5.

Naturallyoccurringzeolites are rarelypure and are contaminated
to varying degrees by other minerals, metals, quartz or other
zeolites. For this reason, naturallyoccurringzeolites are excluded
from many importantcommercial applications where uniformity
and purityare essential. Some of the more commonnaturalzeolites
are: analcime, chabazite, heulandite,clinoptilolite,natrolite,soda-
lite,phillipsiteand stilbite.Stilbiteis the moderndesignationof the
mineraloriginallydiscovered by Cronstedt4.
Some of the more importantapplicationsof zeolites are among
the following1-3'5"11:
• Buildings:fourmilliontonnesof naturalzeolitesare minedannually
mainlyto be used in theconstruction industry,of which2.5 million
tonnes are shipped to China to make a light-weightconcrete.
Volcanic tuffmay be cut with handsaws and used directlyto
fabricatehouses and indeed all kinds of buildings,in regions
where it is plentiful,e.g. Republic Square in Yerevan, Armenia,
withits architectural
splendour(Figure7).
• Around1.4 milliontonnesof zeoliteA are synthesised each yearfor
to removeand encapsulateCa2 +
use as a "builder" in detergents,
and Mg2+ cationswhichmake water"hard", ratherthanpolypho-
sphateswhichcause algal bloom in lakes and rivers.

andapplications
• Toxic heavy metal cations,e.g. Pb2+ , Cd2+ , Zn2+ , may also be
removedfromtheenvironment by cation-exchange intozeolites.
• H+ exchangedzeolites,e.g. ultrastable zeoliteY (USY) are used as
solid acid catalystsin the petrochemicalindustry. Around300,000
tonnes of syntheticzeolites are manufacturedannually for his
purpose.
• e.g. Ni2+ -exchangedzeolites have been demonstrated to absorb
sulfurcompounds(thiophenederivativesand thiols) frommodel
"diesel" in accord witha desire to to reduce transportation-based
S02 emissions,and hence the damagingeffectsof "acid rain" on
riversand thefacadesof buildings.
• Reductionin NOx emissions fromvehicles, using zeolite-loaded
"catalyticconverters".
• Surfactant-modified zeoliteshave a potentialto removetoxicanions,
e.g. chromáteand organicpollutants, simulta-
e.g. trichloroethylene,
neously fromthe environment. It is commonthata regionis co-
contaminated witha mixtureofpollutantsand sucha multifunctional
decontamination agentmightbe veryuseful.Contaminated ground-
watersare a good example.
• Anionabsorption. Environmental contamination by toxicanionsmay
also be eliminated,by reactionwithheavymetalcationspreviously
exchangedintothezeolite,e.g.:
Ag+ - zeolite+ Na+I - ^Na+ - zeolite+ Agi (precipated).
In this example, a silver exchanged zeolite can be used for

removingradioactiveiodine (in the formof iodide ions) as insoluble
Agi, which is both formedand held withinthe zeolite matrix.When
it is saturated,the zeolite may be removed for disposal. The
principle may be adapted for the management of other toxic
anions, e.g. cyanide,arsenic (both arseniteand arsenate),chromáte,
molybdateand others.
• Molecularsieves: smallpore zeolites(such as zeolite-A)selectively
absorbsmallpolarmolecules,e.g. water,and so zeolite "molecular
sieves" are highlyefficientdryingagents for removingtraces of
waterfromothersolvents.
• Hydrocarbonsieving:linearn-alkanes(needed to make detergents)
can be separatedfrombranchedalkanes, since the formerpass
more slowly through a column packed with zeolite 5A in
consequenceof theirpreferential penetrationof the zeolite pores,
which resultsin a more tortuouspassage throughthe material.
Millions of tonnes of n-alkanes are produced annually by this
method.
J.Rhodes
230 Christopher
• Medical applications: Hemosorb and QuikClot are commercial
productsbased on zeolites which, when applied to wounds (in
accidentsor surgery),are said to cause an "instant" cessationof
bleeding. Zeolites are also used in kidney dialysis machines,to
absorbammoniafromblood and preventit frombuildingup in the
body (a job thathealthykidneysnormallydo).
• Separationof gases: thereare commercialunits thatcan provide
oxygen of 95% purityfor use in hospitals or for patientse.g.
sufferingfrom emphysema and other forms of Obstructive
PulmonaryDisease (OPD), by separatingit fromair. Nitrogen
(80% of air) is preferentiallyabsorbed over oxygenby a zeolite
because of its much largermolecularelectricquadrupolemoment,
and so enables oxygen to separatefromair almost in a state of
purity.
• Agriculture: forsupplyingK+ and NH4+ to plantsfromsoils that
have been enrichedwithzeolites exchangedspecificallywiththese
cations.It is suggestedthatsuch "zeoponics", as the strategyis
called,mightbe used to growfoodon long space missions,e.g. ifwe
ever send "a man to Mars".
• Contaminated,e.g. Brown Field land, may be renderedfit for
buildingand even foragriculture by treatingthesoil withsufficient
quantitiesof zeolites1'4.
• Use in more efficientheating systems.Essentially,the adsorbed
water can be driven out of a zeolite by heat, but when the
water is readsorbed,heat is given out. The principle can be
incorporatedinto a heat-pumpsystemwhich uses more of the
available energy for actual heating, most of which would
otherwisebe wasted.
• Zeolites are also effectivein environmental decontamination stra-
tegies, e.g. around 500,000 tonnes of zeolites were used in the
at
clean-upafterthenuclearpowerplantdisaster Chernobyl, which
involvedmonopolisingvirtuallyeveryzeoliteproductionfacilityin
theentireformerU.S.S.R. Zeoliteswere fedto cattlein an effort to
keep the radioactiveions out of the milk, and were baked into
bread and intobiscuits(cookies) forchildrensimilarlyin an effort
to minimiseradioactivecontamination in humans4,7.Albeit on a
smallerscale since the problemwas far more contained,zeolites
were also used at "Three Mile Island", a decade or so before
Chernobyl.

andapplications
2. "Ship-in-a-bottle" complexes in zeolites
The mysteryof a "ship-in-a-bottle"languishes among the many
shatteredillusions of adults who learn beyond childhood that the
essentialframeworkcomponentsof the ship-mast and all -are first
broughttogetherand assembled inside the bottle, and finallythe
mast is "pulled-up" from outside as a pièce de résistance thus
presentingthe fullgloryof the finalvessel, apparentlytoo big to fit
throughthebottle'snarrowneck. In a reasonable analogy,relatively
large molecules may be assembled inside the supercagesof zeolites
fromcondensationand coordinationreactionsof smaller adsorbed
species. There are various reportsof potentiallyuseful materials
created using ship-in-a-bottle methods. For instance,the prefluor-
escent probe dansyl-TEMPO (DT) was produced withinthe super-
cages of NaY by means of a base-catalysedreaction to yield the
supramolecularassembly DT@NaY, which is furthermore the first
example of base-catalysed reaction within a zeolite. [The termi-
nology A@X means that A is the encapsulated species while X is
the zeolite concerned.] This material was successfullyused as a
solid state sensor to monitorthe intercavitydiffusionof carbon-
centredradicals produced by AIBN thermolysisand in a slurryto
studytheinter-pore diffusionof carbon-centred radicals producedin
solution from a 3,3'-diphenyl-3H,3 'H-[3,3 /]bibenzofuranyl-2,2/-
dione. The dynamics of hydrogen atom transferfrom a good
donor, such as the syntheticantioxidant3-phenyl-2-coumaranone,
to DT@NaY were also investigated in a benzene slurry12.3-
Hydroxyfiavone(3 -HOF) was incorporatedin zeolite micropores
by ship-in-a-bottlesynthesis. 3-HOF molecules were found to
exhibitexcited-stateintramolecular protontransferand a tautomeric
equilibrium was observed between the 3-HOF-excitedstructures N*
and T*. The position of equilibriumis affectedstronglyby the
protonie nature and polarity of the surroundingmedium. The
physical and spectroscopic characterizationof the dye-loaded
zeolite colloids enabled a correlationto be established between
the optical propertiesof the dye and the environmentof the zeolite
micropores13.The 2,4,6-triphenylthiapyrylium cation was encapsu-
lated in the supercages of the 3-dimensionallarge pore zeolites Y
and beta via ship-in-a-bottlesynthesisfromchalcone and acetophe-
none, in the presence of hydrogen sulfide. The resultingsolids
furnishefficientand robustphoto-catalyststhatcan degradephenol
and aniline in waterwitha higherefficiencythanthe standardP-25
Ti02 catalystcan. There is further evidence thatthese encapsulated
dye materials may also be efficientphoto-catalystsforthe oxidative
232 Christopher
J.Rhodes
Fig. 8. Structure
offaujasiteshowingcentral
supercage bysodalite
surrounded
cages,along withcation
sites.
3.chem.
http://turmacl Columbia. Reproduced
edu/images/publications/NJT728.gif
withpermissionofProf.N. Turro.
degradation of malodorous sulfur-containingmolecules14. 2-(6-

hydroxy-3 -oxo-(3H)-xanthen-9-yl)benzoicacid (fluorescein) has
been prepared inside the pores of zeolite-Y, even though the
fluorescein molecules are too large to pass through the 8 Â
windows of the faujasitezeolite used (Figure 8). This was accom-
plished by the acid-catalysed reaction of resorcinoland phthalic
anhydridecontainedwithinthe zeolite micropores.
Spectroscopic data are presentedalong with one example that
these fluorescence-labellednano-particlesmightserve for imaging
applicationssuch as confocal fluorescencemicroscopy15.Similarly,
a [2]-catenane consisting of a bipyridiniumcyclophane and a
dioxybenzenemacrocyclicpolyetherhas been encapsulatedwithin
the supercages of zeolite Y. Laser flashphotolysisreveals thatthe
charge-separatedspecies decays over a period of hundreds of
microsecondsin contrastto the few picoseconds previouslyreported
for the same transientin acetonitrilesolution. It is deduced that
photochemical quenching is largely precluded in the zeolite
matrix16.Many and various differentcatalytic centres can be
encapsulated into zeolite micropores,frequentlyusing ship-in-a-
bottlemethods,to create materialsthatare especially effectivefor
use in oxidation reactions. Sometimes the resultingmaterialsare
termedzeozymes, " zeolite mimics of enzymes" in analogy with
enzymes, though none of these syntheticcounterpartsbased on

andapplications
zeolites quite matchthe specificityand rate accelerationof the real
McCoy.
Two recentreviews of materialsof this kind are available17'18.
The firstfocuses on aspects of "green chemistry",and stresses
the currentneed for cleaner fuels (i.e. those freeor aromaticsand
of minimal sulfurcontent)or fuels that convertchemical energy
directly to electricity,with minimum noise and avoiding the
productionof toxic oxides and particulates;chemical, petrochem-
ical and pharmaceuticalprocesses thatmay be conductedin a one-
step, solvent-free mannerand thatuse air as the preferredoxidant;
and industrialprocesses thatminimizeenergy-costs,waste-produc-
tion, or the use of corrosive,explosive, volatile, and non-biode-
gradable materials. Nanoporous catalysts based on zeolites are
highlightedfor specific examples which include the productionof
adipic acid thatneitheruses concentratednitricacid nor produces
greenhouse gases such as nitrous oxide; the production of
caprolactam(the precursorof nylon) withoutneeding oleum and
hydroxylaminesulfate; and the oxy-functionalization at the term-
inal carbon atom of linear alkanes in air, which is importanton a
practical scale for detergentmanufacture17.The second review
refersmore generallyto supramolecularhost- guest complexes in
zeolites prepared by ship-in-a-bottlesynthesis,and provides an
excellent overview and coverage of history, characterisation,
synthesisand currentapplications of zeolites with an emphasis
on ship-in-a-bottlemethods18. It is significant to note that
pioneering thinking behind the synthesis of zeolites, as was
achived by Barrer in the 1950s, originatedfrom an attemptto
mimic the conditionsthatwere thoughtto prevail in the Earth to
form zeolite minerals by natural processes. This led to the
synthesis of zeolite Y 19, which surely is one of the most
significantpractical breakthroughsin the chemistryof the 20th
century,and Barrer is considered by many in the field to have
been passed-over for the Nobel Prize for this discovery and his
many otherseminal contributionsto zeolite chemistry.Two other
highly informativereviews on zeolite-encapsulatedcatalysts for
use in selective liquid phase oxidation reactions have also been
published20'21.
An early example of a ship-in-a-bottlesynthesis was the
productionof the 2,4,6-triphenylpyrylium cation, as encapsulated
in the zeolite HY22. This cation may be generatedin solutionby
the treatmentof chalcone with acetophenone in the presence of
strong acids such as perchloric or tetrafluoroboric acid. In the
solid-acid zeolite medium,a similaracid-catalysedaldol condensa-
J.Rhodes
234 Christopher
tion takes place, followed by an aromatizationto yield the 2,4,6-
triphenylpyrylium cation. The chalcone need not be independently
pre-synthesised, since it can be generatedin situ in the HY zeolite
by an acid-catalysed condensation between benzadehyde and
acetophenone.The acidity of the particularHY sample is key to
the success of the process, since it must be strong enough to
promotethe intial aldol condensation22.As an alternativeroute to
the zeolite-cationsupramolecularcomplex, the commerciallyavail-
able HS04~ salt of 2,4,6-triphenylpyrylium cation may be added
to NaY zeolite, in aqueous suspension,whereuponthe large cation
is absorbed into the zeolite. This mightappear as a normalcation-
exchange process, but involving a cation which should be
excluded from the zeolite on the basis of its large size.
Rathermore,the evidence is that under the reaction conditions,
the initiallyadded pyryliumcation undergoes a ring-openingto
form l,3,5-triphenyl-2-pentene-l,5-dione, which is far less steri-
cally demanding and can penetrate the zeolite easily. Having
enteredthe zeolite supercage, mild heating is sufficientto cause
dehydrationof the molecule and restitution of the pyryliumcation.
The latter method has the advantage thatthe degree of loading of
the organic cation into the zeolite can be controlledpreciselyand
the lattermay be filledso thatone cation is presentper supercage.
Furthermore,since a neutral zeolite can be used, the system is
more reproducibleto construct,ratherthan using samples of HY
which may differfrombatch to batch in their acidic nature and
hence vary in theirabilityto promotethe desired reaction23.
The zeolite-encapsulated solid catalyst (2,4,6-triphenyl-
pyrylium@Y) can performphotocatalyticelectron-transfer reac-
tions in organic solvents. It may, however, be used in aqueous
solutions, whereas standard salts of the cation, e.g. the HS04~
salt, are unstable in neutral or alkaline solutions in water where
hydrolyticring-openingoccurs24.In zeolite-encapsulatedform,the
2,4,6-triphenylpyrylium cation is an effectivephotocatalystfor the
degradation and partial mineralisationof pesticides in water on
exposure to ambient solar light, e.g. phenol, aniline and 4-
chlorophenoxyaceticacid25, methylparathion26, fenvalerate27and
propoxur28have all been degraded successfullyby means of it. In
analogy with the mechanism by which Ti02 photocatalysts
work11,it appears that the photocatalyticmechanism for 2,4,6-
triphenylpyrylium@Yinvolves the formationof • OH radicals,
which are formedby the photoinducedoxidation of water when
the transferof a single electron occurs fromH20 to an excited
state of the trapped cation molecule24. The encapsulation serves

andapplications
furtherto protect the organic component from degradation by
• OH radicals, and the irradiationof an aqueous suspension of
2,4,6-triphenylpyrylium@Y resultsin the formationof H202 to an
accumulated concentrationof 10~3-10_2M.24 The phenomenon
is interestingand makes one wonder why the cation is protected
to such a degree in the encapsulated state. A simple matrix
isolation effectmight be invoked, but the water molecules must
of course enterthe zeolite cages in order for the electrontransfer
to take place; thus the resulting • OH radicals are in potential
directcontactwith the organic component.Results frommolecular
modelling calculations suggest that the 2,4,6-triphenylpyrylium
cation is held tightlyby the zeolite cavity, so that the necessary
increase in dimension incurred by the overall addition of a
hydroxylanion is prevented[viz., transferof one electronto the
2,4,6-triphenylpyrylium cation followed by combination with
• OH, is equivalent to an overall addition of ~ OH]24. This is a
useful facet, since in homogeneous solutions the degradationof
the photocatalysttends to thwartattemptsto degrade pesticidesby
means of it. A restrictionin the overall 2,4,6-triphenylpyrylium
cation configurationby the zeolite explains too the unexpected
observationof an ambienttemperaturephosphorescence29.
+
Triphenylmethyl (trityl)carbenium cations (Ar3C ) are arche-
typal examples of stable carbocations.This is in partbecause they
can délocalisé the positive charge over the entire molecular
7i-electronframework.This tends to diminish their reactivity
+
compared to more localised carbenium cations (e.g. CH3 ), in
addition to renderingthe species intrinsicallymore stable and so
more readilyformed.The presenceof tritylcations may be inferred
from the colours impartedto various media that contain them,
which range fromyellow for the unsubstitutedPh3C+ cation to
orange,accordingto the natureof substituents thatare present.The
particular colour follows an additive shiftin maximum absorption
wavelength which can be predicted using the Woodward rules:
interestingly, the well-known pigments malachite green and rose
aniline are based around tritylcations30.
3. Diffusion of molecules in zeolites

The diffusionof molecules within zeolites (Figure 9) is a key
featurein the essential processes of adsorption and catalysis by
these materials1-11.For this reason, there is great concern to
determinefundamentaldetails of diffusionprocesses in zeolites,
most often using selected probe-molecules. As is clear in the
J.Rhodes
236 Christopher
Fig. 9. Diffusion inzeolites.
processes
//www.
http: co2crc.
com.
au/images/imagelibrary/cap_diag/membrane_separationtype_m
Reproduced with fromC02CRC
permission
following section, there are a range and a diversityof experi-

mental and theoreticalapproaches adopted in this aim. A combi-
nation of pulsed field gradient (PFG) NMR and quasi-elastic
neutronscattering(QENS) was employed to measure the diffusion
of an homologous series of n-alkane molecules, up to n-tetra-
decane, in MFI-type zeolites. The diffusivitiesare of an inter-
mediate magnitudebetween those measured for NaCaA and NaX
zeolites, and in orderof theirrespectivepore diameters.As forthe
zeolite NaA, the diffusionrates decrease in a monotonie fashion
as the carbon chain length increases, as might be expected.
However, this does contrastthe behaviour of n-alkanes adsorbed
into NaCaA which shows a strikingdeviation fromthis trendfor
chain lengths of six carbon atoms and above. Accepting that a
general agreement is found between the two methods, the
diffusivitiesmeasured by PFG NMR are smaller than those
determinedusing QENS by one orderof magnitude.This apparent
contradictionmay be explained in termsof the different motional
"distance" thatis accessed by these methods,as is fairlycommon
when using differentmethods with differentmeasurementtime-
scales. Thus, PFG NMR monitorsmolecular scale displacements
typically of micron (10~6m) distance, and hence may reflect
additional transportresistances and diffusion barriers imposed
throughoutthe entirezeolite grain. These are inconsequentialfor
QENS, which instead measures excursions of molecules over far
lesser distances31.

andapplications
There are two recentdevelopmentsof the PFG NMR technique
that have been proposed for the measurementof the diffusionof
molecules in zeolites as absorbed in the formof multi-component
liquids. This approach is of potentialpracticalimportancesince in
almost all real applications,the zeolite interactswith a mixtureof
components rather than with a single substance. The methods
include options for enhancing the sensitivitywith respect to
displacementsover reduced dimensions by a novel principle of
fieldgradientpulse matchingand withrespectto selectivitybetween
different componentsby combiningPFG NMR with magic angle
spinning(MAS) NMR and with a micro-imaginggradientsystem.
The diffusioncoefficients were determinedforethane,ethene,water
and benzene adsorbed in zeolite NaX, and the resultsare compared
with those measured previously for these materials as presentin
simpleradsorbed systems32.
The energies and entropies which control the adsorption of
benzene on acidic (H/ZSM-5) and non-acidic (Silicalite-1) MFI
(ZSM-5) type materialshave been studied using both gravimetric
and calorimetricmethods along with in situ IR spectroscopyin
orderto make both a qualitativeand quantitativeevaluation of the
way benzene interactswiththe pores and the functionalSi(OH) and
Si(OH)Al groups withinthe structure.According to an interpreta-
tion of the adsorption isotherms,there are adsorption sites for
benzene present in MFI type materials that are sterically
constrained.It is the interactionbetween benzene molecules and
the pore walls which dominatesthe adsorptionenergetics,while the
more localized interactionwith the bridginghydroxylgroups is of
little significance. When a benzene molecule is close to an
-
Si(OH)Al group O H stretchingfrequencyshiftsare observed,
in reflectionof the local adsorption geometry of the benzene
molecules in addition to the acid strengthof the OH group and
the base strengthof benzene. Two kinds of OH perturbation were
observed which are accounted for in terms of their being two
orientationsof the benzene molecules inside the pores. One
orientationhas the ring parallel to the pore wall and in the other
the ringis orientedtowardsthe bridgingOH groups.As the surface
coverage increases,benzene molecules become adsorbed addition-
ally at Si(OH)Al groups whose environmentis unconstrained,it is
thoughtmost likely at the openings of the pores33.
Transportdiffusivitieshave been determinedfor perdeuterated
benzene adsorbed in NaX zeolite using neutronspin-echomeasure-
ments.In orderto aid comparisonwithrecentlyreportedmolecular
dynamics simulations,correcteddiffusivitieswere employed. The
J.Rhodes
238 Christopher
diffusivities were measured forbenzene loadings of 1, 2, 3 and 4.5
molecules per NaX supercage,and at temperatures of 300, 350 and
400 K. Both corrected and transportdiffusivitieswere seen to
increase as the loading rose from 1 to 3 benzene molecules per
cage, but thento decrease sharplyfor an average of 4.5 molecules
in each cage. An excellent accord was found between the experi-
mental and simulatedresultsfor both the loading dependence and
the overall values for the correcteddiffusivities.The latter are
12 11
mostlyin the range 10" - 10" m2 s-1.34
The heat capacity behaviour of benzene and hexafluorobenzene
confinedin the pores of NaY zeolite has been determined,both for
the individual compounds and as a 1:1 binary mixture35.Both
molecules are planar and non-polar,withmolecularelectricquadru-
pole moments that are of similar magnitude36but opposite sign
( - 29 C m2 forbenzene and + 31.7C m2 forhexafluorobenzene).
As solids, bothmeltat the same temperature to withinhalf a degree
C, and have preciselythe same boiling point (80.2°C). The heat of
vapourisationis the same forboth too, while the heat of fusionfor
C6H6 is only 86% thatof C6F6. Strongloading dependencieswere
found,and the heat capacities determinedat intermediateloadings
were verylarge, indicatingthatmore energylevels become rapidly
accessible after a firstenergy gap has been overcome. This is
reasonable if excitation of shallow ("soft") highly anharmonic
surface-vibrational modes of the adsórbate species occurs. In an
adsorbed 1 : 1 mixture of C6H6 and C6F6 the heat capacity is
dominatedlargely by intramolecularinteractionsbetween separate
C6H6 and C6F6 molecules, ratherthanby theirinteractions withthe
zeolite. Notably,thereare no phase transitionsobservedover a very
large range of temperatureand loading-levels,as is reminiscentof
the behaviour of supercriticalfluids35.
In anotherstudy,the ostensiblydifferent diffusionbehaviour of
alkanes adsorbed in zeolites thatmay be deduced dependingon the
particulartechnique employed to measure it, was explained. The
resultsshow that when various data-setsreportedin the literature
are correctedfor the loading of the alkane used in the particular
kind of measurement,a much closer agreementis obtainedbetween
them37.Using the zero lengthcolumn (ZLC) method,the diffusion
of linearalkanes (n-hexaneto n-tetradecane)in zeolite NaCaA was
measured. There was a monotoniedecrease found with increasing
chain lengthfromn-hexaneto n-undecane,a slightincreasefromn-
undecane to n-tridecane,and a finalplateau at n-tetradecane.While
the agreementwithresultsobtainedfromPFG-NMR measurements
is reasonable,the pronouncedmaximumthatwas foundin a recent
neutronspin echo studywas not apparent.The differencebetween
the infinitedilution ZLC data and the microscopic techniques
cannot be explained by the intrusionof surface resistancessince
it is clear frompartialloading measurementsthatinternaldiffusion
is the controllingfactor.The activationenergiesforthe diffusionof
linear alkanes in NaCaA all lie in the range 20-26kJ mol-1.37
QENS data have been measured forthe self-diffusion of n-alkanes
(up to hexadecane) in silicalite.At 300 K, the measureddiffusivities
are greater in silicalite than in Na-ZSM-5, in agreement with
molecular dynamics calculations and with hierarchicaltransition-
state theory/Browniandynamics calculations. Activation energies
~1
for diffusionare close to 5 kJ mol fora carbon chain of one to
six units,but rise as the carbonnumberincreasesthroughthe series
-1
Cs~Ci6 to approximately15kJmol forC16. A possible explana-
tion emergesfromthe hierarchicalsimulation,which indicatesthat
Cļ-C6 alkanes tendto be located entirelywithinthe voids of single
channel segments and diffuseby jumps across energeticallyless
favourable channel intersections.Molecules of greaterlength are
forcedto straddlechannelintersectionsand in orderfordiffusionto
take place, theymust firstundergo conformationalchanges. Since
the QENS measurementsand the simulationsboth probe motion
over the same small (nm) dimensions,good agreementis found
between them. When PFG-NMR is used to measure self-diffusiv-
ities in the same systems, appreciably lower values are found,
because (as noted earlier) the technique measures motion over
significantlylonger (micron; 10~6m) distances and is therefore
more sensitiveto defectsin the silicalite crystals38.The force-field
used to describe the interactionsbetween linear alkanes and Na+
cations in faujasitetypezeolites (Figure 8), has been enlargedso as
to include Ca2+ cations. The forcefieldwas fittedto reproducethe
Na+ and Ca2+ cation positions in zeolite LTA along with the
adsorptionpropertiesof n-alkanestaken over all available tempera-
turesand pressuresfromthe enormousliteratureprevailingon the
topic39.
There has been made a criticalre-examinationof experimental
data, which was reported originally in 197340 and showed an
unusual oscillatoryvariationof the apparentmicrocrystalline diffu-
sivity of n-alkanes in zeolite-T with carbon number41. This
phenomenon was termed the "window effect". In contrast,the
recentevaluationshows thatthe source of the variationwas in fact
an artefactof the originalanalysis42.The observedpatternof uptake
ratescan be explainedin termsof the intrusionof finiteheat transfer
resistance and isothermnon-linearity,taking only the expected
J.Rhodes
240 Christopher
monotonie dependence of the intrinsic diffusivitywith chain
length43.A series of Grand Canonical Monte Carlo simulationsof
water adsorptionin the faujasitesNaY and NaX and in silicalite-1
has been reported44.It is proposed thatthe method and forcefield
used in this work should be useful for practically important
applicationssuch as the adsorptionand separationof multi-compo-
nentmixturesin various stablezeolites, since it providesa means to
predictthe effectof the small quantitiesof waterwhich are virtually
presentin all such media44.A similarinvestigationwas made of the
adsorption of water from the vapour phase into silicalite. The
simulations predict that when the micropores are completely
hydrophobic,essentiallyno adsorption of water should occur at
low pressures,but as the pressureis increasedthe degree of filling
should follow suit.Using simulationsbased around "seeded" water
molecules to model hydrophilicdefects,the effectof silanol defects
in real silicalite samples was investigated.Water molecules form
hydrogen-bondedclustersaround these defects,and also cause the
pores to fillat a lower pressurethan is the case forthe completely
hydrophobicmaterial45.Molecular dynamicssimulationshave been
used to investigatecation migrationupon adsorptionof methanolin
NaY and NaX faujasitesas a functionof loading. Accordingto the
calculationsforNaY, at low and intermediateloadings, Sn cations
can migrate toward the centre of the supercage due to strong
interactionswith the adsorbates, followed by a hopping of
cations fromthe sodalite cage into the supercage to fillthe vacant
Sn site. An Sn cation can also migrateacross the double six ring,
where it takes a vacant position. Si cations mainly remain
trapped their initial sites irrespectiveof the loading. At high
in
loadings, only limitedmotionsare foundfor Sn cations because of
steric effectsinduced by the presence of adsorbates within the
supercage. For NaX, the Sin/ cations which occupy the most
accessible adsorption sites are found to shift their position
throughcoordinationto the methanolmolecules, and a maximum
displacementis found at a loading of 48 methanolmolecules per
unit cell. At higher loadings the displacementis amelioratedby
stericeffects.In contrast,the and Sn cationsremainpracticallyat
theirinitialsites whateverloading is introduced.It is proposed that
the cations migratevia Sni' cation displacementsinto neighbouring
Snr sites46.Molecular dynamicssimulationswere extendedby the
same researchgroup to elucidate the concentrationdependence of
the self-diffusion of methanolin the faujasites.Changes in the self-
diffusivity were studied as a functionof coverage for DAY and
NaY systems, with a particular focus on the effect of pore

andapplications
confinement and the presenceof the extra-framework cationswithin
the supercage.The self-diffixsivity
was foundto decrease according
to loading for DAY, while for NaY a maximum is observed at
intermediatecoverages. This is fully in accord with results from
PFG NMR and QENS reported in similar systems. When the
materialsare fullyloaded, the methanolmolecules formeda one-
dimensional hydrogen-bondedchain along the channels in DAY,
but only dimerswere formedin NaY47.
A combinationof Monte Carlo and molecular dynamicssimula-
tions and neutronscatteringexperimentswas employed to investi-
gate the adsorptionand diffusionof H2 and D2 in zeolite Rho in the
temperaturerange 30- 150 K. Within the theoretical algorithm,
quantumeffectsare incorporatedvia the Feynman-Hibbsvariational
approach. A new set of potential parametersfor hydrogen are
introduced,which are compatible with the Feynman-Hibbsvaria-
tionalapproachas it is used forquantumcorrections.The molecular
dynamicssimulationsshow thatthe quantumeffectis verysensitive
to pore dimensions and can lead to a reverse kinetic molecular
sieving effectin which strikinglydeuteriumdiffuses fasterthan
hydrogen48.By means of the virial expansion of the chemical shift
in relationto the densityof xenon atoms adsorbed in zeolites at
pressuresof up to lOMPa, the pressure and local densitydepen-
dence of the 129Xechemical shiftwas analysed. The second virial
coefficientis foundto be sensitiveboth to the pore size and shape,
and the void space to influence Xe-Xe interactionsin both
microporousand mesoporous materials.An analysis was made of
the local structure
of adsorbed xenon in zeolite 5A in termsof Xen
clusters,so to give a descriptionof the densitydependence of the
chemical shift.The validity of the cluster model was proven by
applying it to 13X and ZSM-5 zeolites. It was shown thatxenon
adsorbedin the ZSM-5 microporesexists as an atomicmonomerup
to a loading of about 0.6, but thatclustersof up to n = 4 may be
produced at higherdensities49.CO molecules were produced in the
channelsof the mesoporousMCM-41 silica by photodissociationof
diphenylcyclopropenoneusing a nanosecond laser pulse, and
monitoredusing time-resolvedFourier transforminfrared(FTIR)
spectroscopyin both step-scanand rapid-scanmodes. A verybroad
absorption band from CO was observed in the region 2200-
2080 cm-1 at room temperaturewhich demonstrateda biphasic
decay. Two-thirdsof theband's intensitydecayed on a microsecond
rimescale (lifetime= 344 + 70 ļis) as a result of the molecules
escaping throughthe mesopores into the surroundinggas phase,
with a diffusionconstantofl.5xl0~9m2s_1. The broadness of
242 Christopher
J.Rhodes
the absorption profile is attributedto randomly hopping CO
molecules coming into contact with siloxane and silanol groups
on the surfaceof the pore50.
4. Adsorbed gases in zeolites

Homonuclear diatomicmolecules like H2, 02, N2 do not normally
show infra-redabsorptionspectrabecause theyhave no permanent
electricdipole moment,and so froma classical viewpointcannot
interactwith the oscillatingelectriccomponentof the electromag-
netic wave. It has, however been known since 195351 that the
application of an external electric field to dihydrogengas could
induce IR absorptions from it. Forster and his co-workersfirst
reported crystal-field-induced transmittancespectra of hydrogen
adsorbed in Na-A and NaCa-A zeolites at low temperatures52'53.
In the unperturbedhomonucleardiatomic molecule, the electronic
centreof gravityand the molecular centreof mass coincide. The
applied field acts to polarise the molecule thus displacing electron
density from the centre of mass and inducing a dipole moment
which can couple withthe electromagnetic radiationfield,resulting
in the absorptionof IR frequenciesthatcorrespondto the stretching
mode of the polarised molecule. It is usually found that the
stretchingfrequenciesare lowered as compared with those for the
unperturbeddiatomics, as measured from their Raman spectra.
Satellitebands54may further be observed,symmetrically displaced
fromthe main absorption,which are thoughtto originatefromthe
translationalmotion of hydrogenmolecules moving parallel to the
cavitywalls. Rotationalstructure may also be resolved,on both the
fundamentaland overtone bands from H2 adsorbed in various
zeolites, by means of a high-resolutionIR diffuse reflectance
method.Indeed, a splittingof frequenciesof 5.8 cm-1 fromortho
and para hydrogenisotopes adsorbed in zeolite NaY was detected
on boththe fundamentaland overtonebands54.Molecular hydrogen
has been employed as a simple molecular probe to explore cation
sites in zeolites A, X, Y, ZSM-5 and mordenite,as adsorbed at
77 K. It was found that the degree of H - H bond polarisation,
estimatedfromthe size of the low-frequencyshiftof the funda-
mental H - H stretchingvibration in perturbed H2 molecules,
depended stronglyon the basicity of the neighbouringframework
oxygen atoms. Thus it is not only the cation and the site of its
location that is importantbut also the structureof the zeolite
frameworkin determininghow the molecular probe is coordi-
nated55. In a related study of zeolites A, X and Y, the H - H

andapplications
stretching frequencieswere foundto be relatedclosely to the charge
on the cations.For alkaline-earthmetal cation (Mg2 + , Ca2 + , Sr2+ ,
Ba2 + )-exchangedformsof high-silicazeolites the frequencyshifts
were found to correlate well with the polarising power of the
cations. The importanceof any "hydrolysis" of the cations, i.e.
the reaction
Mn+ + H20 -M(OH)(n_1)+ + H+,

in determining the extentof hydrogenpolarisationis emphasised56.
Various weakly interactingmolecular probes have been used to
characterisethe acid and base sites in zeolites. Brenstedaciditycan
be determinedby the effectof hydrogen-bonding(to the probe
-
molecule) on surfaceO H frequencyshiftswhen N2 and CO are
-
employedas the probes. Additionally,shiftsin the C O stretching
-
frequencyare found which generallyparallel those of the O H
groups. In the case of N2, the interactioninduces an absorptionby
themolecule, as noted above forhomonucleardiatomics.In zeolites
+
exchangedwith small cations such as Li+ and Na , Lewis acidity
was foundto dominatethe process, and as the cation increased in
size, more basic propertiesbecame important.In all cases of CO,
C02, N2 and CH4 interacting withcationsin zeolites,the interaction
energy was found to decrease as the cation radius increased, in
accord with the fall in polarisingpower (<e/r) of the cation. At very
low equilibriumpressuresof CO, the sitingof Na+ cations and the
Al (Lewis site) distributionin the six-rings(Sn-sites) could be
investigated;CH4 was found to interactwith cations in a C3v-
symmetricconfiguration of the kind M+-H3CH. It is also shown
thatthereis a potentialuse forC - H acids such as CI3CH (CI3CD),
acetylene and methylacetylene as a probe for base sites at zeolite
surfaces,on the basis of observed C - H frequencyshiftswhen
adsorptionhas taken place57.
Variable-temperatureIR measurements have been adapted
successfullyto the determination of the thermodynamic parameters
for weak gas-solid interactions58.By equating the van't Hoff
equation, the Beer- Lambert law and the Langmuir isotherm,and
measuringthetemperature dependenceof theintensity of an IR band
characteristic of the adsorbed state(the band becomes more intense
as the temperature is decreased), the enthalpy,AH and entropy,AS
for the equilibriumbetween the gas-phase and adsorbed state of a
probe molecule can be determined(Figure 10). Proton-exchanged
zeolites oftenexhibitabsorptionbands fromO - H groupsassociated
with Bronsted sites Si(OH)Al, and they appear in two frequency
ranges,3650-3600 and 35 80 -3530 cm"1. The higherwavenumber
244 Christopher
J.Rhodes
Fig. 10. Determination andentropy
oftheenthalpy forH2 inNa-
ofadsorption
ZSM-5usingvariable-temperature measurements.
infra-red
with from
permission
http://www.rsc.org/ejga/CS/2005/b407049f-ga.gifReproduced
theRoyalSocietyofChemistry
@2005.
-
range correspondsto Bronsted acid O H groups located within
-
large cavities while the lower range representsO H groups
vibratingin smaller voids. Adsorbed molecules may be denied
adsorptionin the smaller cavities (formedby rings of lower than
eightmembers).When N2 is adsorbed into H-ZSM-5, the band at
3616 cm" 1 fromBranstedacid sites begins to decrease in intensity
while the band from silanols at 3747 cm-1 is barely affected.
However, a new broad band from hydrogen-bondedOH - N2
complexes grows-inat around 3500 cm- ' simultaneouslywiththe
activationof theN - N stretchingvibrationat 2331 cm" ' From the
temperaturedependence of these band intensities,values58 of
AH = - 19.7(±0.5)kJmol-1 and AS = -125 (±0.5) J mol" Vk
were obtainedforthe enthalpyand entropyof adsorptionforN2 on
H-ZSM-5 which is close to theheat of adsorptionof - 19kJmol" 1
deduced frommicrocalorimetry measurements59.When molecular
hydrogenis adsorbed in alkali-metalcation exchanged zeolites at
77 K, the main adsorptionband is observed in the region 4070-
4100 cm-1, fromthe fundamentalH - H stretchingmode of the
adsorbed H2 molecule. Cations and theirneighbouringframework
oxygen atoms provide centresfor adsorptionof H2 for which the
vibrationalfrequencyis reduced fromthe 4136cm- 1 Raman-active
band measured for the free molecule in the gas phase. Values of
AH = - 10.3(±0.5) kJ mol-1 and AS = - 121( + 10) J mol-1
K-1 were obtained for H2 adsorbed in Na-HSM-5 (Figure 10) 60.
The enthalpyof adsorptionmay be comparedwiththe enthalpyfor
the liquefactionof hydrogengas, which at a temperatureof 20.45 K

andapplications
is - 0.9 kJ mol-1. Thus, the much larger energy involved in
confiningH2 in the zeolite than in liquid hydrogenofferspromise
that zeolites might be used as storage media for hydrogen,the
validityof which is discussed in the followingsection. The value
of AH = - 10.3(±0.5)kJ mol-1 for H2 in Na-ZSM-5 can be
compared with its equivalent of AH = - 6.5(±0.5)kJ mol-1 for
H2 in Li-ZSM-560 and AH = -9.1(±0.5)kJ mol"1 for H2 in K-
ZSM-561. A useful comparison may also be made between the
entropychange that occurs for adsorption of H2 in Na-ZSM-5,
AS = -121 (± 10) J mol-1 K-1, and the absolute entropy for
dihydrogenof 163 J mol-1/K-1 at a temperatureof 100K and a
pressureof 1 mm Hg, which are close to theprevailingconditionsin
the zeolite/H2 measurements.We may deduce thereforethat the
1
standardentropyof the adsorbed phase is about 40 J mol" K~ l,
probablydue to the conversionof translationalmodes (gas) to low-
lyingvibrationalmodes (of surface"bonds") with the retentionof
considerablerotationalfreedom58.
5. Zeolites as hydrogen storage materials

In an effortto address the twin-problemsof dependence of nations
upon importedhydrocarbonfuel and climatechange forcing/global
warminginduced by emissions of C02 fromburningfossil fuels,
hydrogenis being investigatedas a clean, carbon-freefuel that
could be made on a national (or regional) basis7. However,
hydrogen is not actually a "fuel" but an energy carrier.
Hydrogenis not available in its aboriginalformas are oil, coal or
gas, (which are known as "primaryfuels"), but ratherit must be
"made" by some artificialmeans. Most of the hydrogencurrently
used in the world (mainly for chemical purposes, such as the
wholesale manufactureof ammonia for fertilisersand hydrocarbon
reformingin the petrochemicalindustry)is produced fromnatural
gas by a process known as "steam reforming"sometimeswiththe
use of a zeolite either as a catalyst or to separate62the carbon
monoxide formedwhen the carbon is "extracted" frommethaneby
its reactionwith steam:
CH4 + H20 -»CO + 3H2,

or to separatecarbon dioxide when thatCO is used to squeeze-out
another molecule of H2 by adaptations of the "water-gas shift
reaction":
co + h2o^co2 + h2.
J.Rhodes
246 Christopher
Zeolites are also used more generallyto remove C02 fromnatural
gas62. Ideally, hydrogenshould be "green", i.e. made by electro-
lysis of water using electricityproduced fromrenewable sources,
e.g. wind power, but it is arguable that those electronswould be
more effectivelyused in formsof batterytechnologyfor driving
vehicles and otherelectricalappliances. Nonetheless,effortstoward
theputativehydrogeneconomy continue,and of greatestconcernis
the developmentof materialsin which hydrogenmightbe effec-
tivelystored,includingzeolites7.
Researchers in Spain63 have found that a zeolite-Y partially
+
exchangedwithmagnesiumcations(Mg2 ~) has an unprecedentedly
- 1 for
high adsorptionenthalpyof 17.5 kJmol H2, which is close
1
to the value of - 15kJ mol" recentlyproposed as optimum64for
a materialthatwill efficientlybothbind and release H2 accordingto
the storage/releasedemands forit. Thus the gas should neitherbe
too stronglyadsorbed otherwise it will not be released in a
"fuelling station" situation,nor too weakly adsorbed otherwise
the materialis ineffectivefor storingit in the firstplace. The high
adsorptionenthalpyis attributed to the high polarisingpower (<e/r)
of the Mg2+ cations. Here, the effectof polarisation(Section 4)
reduces the fundamentalH - H stretchingfrequencydetermined
from Raman spectroscopy in the gas phase for unperturbed
molecules at 4163cm-1 to 4056 cm-1. The value of - 17.5 kJ
-
mol 1 is significantly greaterthanthose previouslyreportedforthe
adsorptionof H2 in alkali-metalcation exchanged zeolites60'61'65,
and is around20-foldhigherthantheliquefactionenthalpyof H2 of
- 0.9 kJ mol-1 (at 20.45 K). However, this does not answer the
questionof exactlyhow much hydrogencan be imbibedby a zeolite
for practical purposes. For commercial applications, a workable
energydensityfor a hydrogenstorage tank is accounted as being
able to efficientlyhold an amountof hydrogenequal to 6.5 wt% of
the weight of the tank or 62kg H2 m- 3 in termsof volume65'66.
Although investigationsof hydrogen storage methods have been
ongoing for more than 30 years, no single method has yet arisen
which fulfilsthese demandingcriteria.Some approaches meet the
weighttarget,but the H2 occupies unacceptablylarge volumes (e.g.
tanks of compressed hydrogen gas). Others achieve the volume
targetbut fail to meet the weightratio criterion(e.g. metal hydride
absorbents).A molecular mechanics study has been made of the
thermodynamic limits on hydrogenstorage in sodalite framework
materials,builtup fromT04 (where T = Al, Si, Ge, P) tetrahedra67,
fromwhich it is concluded thatcation-freesodalite structures could
accommodate eight hydrogenmolecules per cage as an optimum
loading, whereuponthe quantityof hydrogenper unit volume is
almostequal to thatin liquid hydrogen,such thatthe limitinguseful
practical density of 65kg H2 m-3 may be possible for most
structuresbased on sodalite. For pure liquid hydrogenthe density
is 70.8kg H2 m~3 which is the normal densityof the liquid at a
temperatureof 20.28 K. Liquefying hydrogen consumes around
30% of the energythatmightbe recoveredfromthe materialas a
fuel,which is a considerabledrawbackto the strategy68. Despite the
optimistic theoretical estimate of how much hydrogencan be put
into a zeolite, the experimentalresultsfall far shortof it69,at 0.26
and 0.4 wt% forall-Si (Si960192) and AIP (Al48P48Oi92),given the
calculated68capacities of 4.8 and 5.2 wt% respectively.The source
of this discrepancyis thatthe theoreticalmaximum capacities are
based solely on energetic considerations,and do not address
influencesfromions, water or otherimpuritieswhich mightserve
to block access to portionsof the overall internalvolume of the
sodalite cages. Nor do the calculationsaccount forentropieeffects,
since in effecttheyreferto zero Kelvin. Adsorptionisothermsof H2
in various sodalitematerialshave also been calculatedusing a grand
canonical Monte Carlo method70.It is concluded that for loading
capacities of technical interest,573 K and 100 bar, a storage
capacity of around 0.1 wt% might be achieved for each type of
sodalite structure.However, in the practical situation,capacities of
greaterthan 4% will most likely be met only under conditionsof
extremelylow temperature and/orextremelyhigh pressure70.When
hydrogenis absorbed in a zeolite, to all intentsand purposes the
adsorptionmay be consideredas a facilitatedliquefaction,wherethe
solid-gas interactionaids liquid condensation at more readily
accessible temperatures and pressuresthanare requiredto condense
hydrogengas into the bulk liquid phase.
A theoreticalstudy71was made which employed the force-field
method within the Discover module of the Materials Studio 2.2
package of AccelerysInc.72The progressivefillingof twelvepurely
siliceous models of common zeolite frameworkswith H2 was
simulatedin orderto determinethe effectof frameworkproperties
including flexibilityon the maximum adsorption capacity for
hydrogen.The conclusions are that the highest capacities, in the
range 2.65 -2.86 wt% of H2, are exhibited by the flexible non-
pentasil zeolites (RHO, FAU, KFI, LTA and CHA)71. A respect-
able correlation was found between the calculated adsorption
capacities and those determined experimentally at 77 K.
Nonetheless, these materials fall distinctlyshort of the 6.5 wt%
targetlimitagreed forpracticalhydrogenstorage.
J.Rhodes
248 Christopher
The zeolite chabazite (CHA) was rated as having the largest
capacity of any zeolite as a storagemedium forhydrogen68'73. An
adsorptioncapacity of 1.28% was determined at 77 K for a sample
of H-SSZ-13 (Si/Al= 11.8),and slightlyabove that for zeolite-A
(1.24wt%) and forH-CHA itself(Si/Al ratio= 2.1) at 1.10wt%68.
The paper describes the zeolite-adsorbed hydrogen as "liquid
hydrogen",and it is shown thatthe workingvolume of a chabazite
(H-SSZ-13) cage can contain seven hydrogen molecules at the
density of liquid hydrogen.Experimentalresults indicate that at
77 K, which is 57 K above the boiling point of liquid hydrogen,
around five hydrogenmolecules are confinedto each cage, which
indicatesthatconditionsclose to the liquefactionof hydrogengas
are met when hydrogen is adsorbed into H-SSZ-13 zeolite at
77 K68. The volumetricuptake of H2 was determinedat 77 K and
a transmissionIR measurementof H2 absorptionmade at 15K, in
H-SSZ-13, (which is an isostructural silico-aluminophosphate mate-
rial withthe same Bronstedsite density),H-SAPO-34, and H-CHA
itself.It was found that the H2 uptake increased as the Bransted
sites became more stronglyacidic (in the orderH-SAPO-34 to H-
SSZ-13). Conversely,increasingthe densityof Bransted sites (in
the orderH-SSZ-13 to H-CHA) is foundto hamperthe adsorption
process. The latter result is counter-intuitive but possibly the
additional Bronsted sites interactconcertedlyvia H-bonds inside
the small chabazite cages and the energyrequiredto displace the
adjacentOH ligand is greaterthanthe adsorptionenthalpygained in
-
formingthe OH H2 complex73.The 1.28 wt%73 at 77 K and one
atmospherepressureworldrecordset by H-SSZ-13 has been broken
using low silica type-X zeolites (LSX, Si/Al = 1) which are fully
+ +
exchangedwith alkali-metalcations (Li , Na , K+)74. Hydrogen
adsorption isotherms were determined separately at 77 K and
pressuresbelow 1 atmosphere,and at 298 K and less than lOMPa
(about 100 atm). The adsorptioncapacity of the zeolite depended
stronglyon the radius of the exchange-cationand on the densityof
cations located on the exposed sites. The interactionenergies
between H2 and the cations follow the series Li+>Na+>K+,
in order of the increasing cation radii: 0.068, 0.097, 0.133 nm,
respectively.Li-LSX had an adsorptioncapacityof 1.5 wt% at 77 K
and 1 atmospherepressure,and a capacityof 0.6 wt% at 298 K and
lOMPa pressure,which places it among the best of known sorbents
forH2. By bridgedhydrogenspilloveronto carbonbridgesbetween
the dissociation catalyst and the zeolite, the hydrogen storage
capacity could be increased to 1.6 wt% at 298 K and lOMPa
pressure of hydrogen gas. This is by far the greatesthydrogen
Storage capacity achieved using a zeolite material at ambient
temperaturebut still the material is nowhere near to providing
conditionsfor a practicalstoragedevice74.
Calculations were performedfor twelve known clathrasils (a
clathrasilis a frameworkwith Si606 as its largest ring aperture)
and seven hypotheticalenergeticallystable analogues. Under all
temperatureand pressure conditions investigated,high adsorption
energies were predicted for small volume cages (<400 A3) in
consequence of the largercontactarea between the cage wall and
H2. However,H2 loading intothe materialremainsrelativelylow in
consequence of the large internalsurface-to-volumeratio which
means thereis littlevoid space forthe H2 molecules to occupy, and
thereforeclathrasils are unlikely to become of practical use as
hydrogenstoragemedia75.
In conclusion, the prospect of using zeolites for practical
hydrogenstorage appears limited. Some zeolite-templatedporous
carbons seem to offer greaterpromise, and for one example a
hydrogenuptake of 4.5 wt% and 45g/L weight and volumetric
densities, was reported at 77 K and 20 atmospheres (2MPa)
pressure76.Greatercapacities still are reportedforporous coordina-
tion-framework materialsgiving uptakes forH2 of up to 6 wt%, at
78 K and pressures less than 20atm77. Hence these will almost
certainlybe furtherinvestigatedas potential practical hydrogen
storage systems. However hydrogenmight be used, either as a
pure substance or as adsorbed into zeolites or other porous
materials,the energycosts of cryogeniccooling and compression
mustbe born and factoredinto the energybalance equation forthe
hydrogen economy. All such effortsto find a substitutefor
hydrocarbonfuels have broughthome exactly how ideal the latter
are as fuels, both in terms of energy densityand theirhandling
properties,and findinga substituteforthemwill be a hard act if it
can be done at all5.
6. Chemical oxidations
Various metal ion complexes have been incorporated into
constrainedenvironmentsto mimic the kind of chemistryknown
for related reagentsin solution phase78. Oxidation fundamentally,
provides the means by which hydrocarbonsmay be functionalised
to produce both bulk and finechemicals but when freeradicals are
involved the approach is usually messy and leads to multiple
substitutionand mixtures of products. When transitionmetal
cations are present, cheap oxidants like 02, H202 or organic
J.Rhodes
250 Christopher
hydroperoxides,R02H, e.g. tert- butyl hydroperoxideor cumyl
hydroperoxide,may be used successfullyto promoteoxidationsin
both the gas and liquid phases. Heterogeneouscatalystsare often
furtheradvantageous in that they are readily recovered afterthe
reactionis completed,and so may be recycled,and are easily used
in continuousprocesses. This is beneficialin the design of "green
chemistry"in order to diminishthe environmentalimpact of the
chemical industry.When a metal centre in placed inside an
inorganicmatrix,a catalystcan be obtained which allows specific
activitiesand specificitiesto be retainedby preventingthe oligo-
merisationof activemonomelicoxometal(M=0) or relatedspecies
to 1LI-OXO complexes. The pronounced propensityfor oxometal
complexes to undergo such transformations is one main reason
forthe low activitiesoftenfoundin solution.Titanium(IV)catalysts
provide an apposite example of this and are most effectiveas
isolated in polymer matrices which preventthem formingoligo-
mers, or a redox-activemetal centre may be incorporatedat the
surface of an oxide support material, e.g. the heterogeneous
Ti(rV)/Si02 catalystsused by Shell to promote the formationof
propylene oxide (1,2-epoxypropane) by reacting propylene
(propene) with ethylbenzenehydroperoxide79.
The redox centre may be incorporatedin the aluminosilicate
frameworkor withinthe cavities of zeolites and othermolecular
sieves. Such "redox molecular sieves" have a regular arrange-
ment of micropores with homogeneous internal cavities and
channels of molecular size80-82. It is possible to tailor-make
catalysts where the reaction dimension is tightlycontrolled by
the pore size of the zeolite, and also by the degree of hydro-
phobicitywhich in combinationact to sieve the kind of molecules
for access to the active centre on the basis of their size and
relative hydrophobic/hydrophiliccharacter. There is a clear
analogy between such materials and enzymes, and thus they
have been termed"zeozymes" 83. For many decades, the strategy
relied almost entirelyon the introductionof redox-activemetal
ions into zeolites by cation-exchange,but here the metal cation is
susceptible to leaching and escapes, often quite rapidly,into the
prevailing liquid medium. In 1983, researchers at Enichem
found84that the framework-substituted titaniumsilicalite (TS-1)
was stable for the selective oxidation of a range of organic
substrateswith a 30% aqueous solution of H202. This resulted
in a surge of activityto find alternativetitanium(IV) molecular
sieves and indeed those containing other metal ions for use in
organic synthesis85-88.

andapplications
Molecular sieves may be created by hydrothermalsynthesis,
where an aqueous gel containing a source of the framework
composing elements,i.e. Al, Si, P, and a templatearound which
the frameworkstructure can be composed, are allowed to crystallize
under self-generating pressuresat temperatures of up to 200°C. An
amine or an alkylammoniumsalt usually furnishesthe template.If a
source of the redox metal ion is also present,the expected overall
frameworkstructureis formed but with periodic isomorphous
replacementsof an Al, Si or P atom by the metal ion, so thatthe
metal occupies T04 tetrahedraand is hence an integralpart of that
structure.The rule89is thatisomorphoussubstitutionis possible if
the radius ratio rcationAoxygen lies within the range 0.225-0.414;
however, this ratio may vary considerably and accordingly the
frameworkstructureand charge may also alter when the initial
productis calcined in orderto decompose and flush-outthe organic
template.In chromium-substituted molecularsieves, it is the Cr(III)
state that is present initially,but this is convertedto Cr(IV) on
calcination. The latter comprises two extra-frameworkCr=0
moieties and hence can only be bound to a surface defect and
cannotbe substitutedisomorphouslyinto the framework.Indeed, a
wide range of redox-activemetal centreshas been incorporatedinto
a variety of zeolites, silicalites, AlPOs and SAPO 's using such
methods90,althoughit mustbe notedthattrueisomorphoussubstitu-
tion has not been proved in all cases. Indeed one reviewer has
stressedthatphysical/chemicalcharacterisation of theprecisenature
of thesubstitutionhas notbeen adequatelydone or describedin most
papers reportingon the topic. Accordingly,comparingthe reactivity
of apparentlysimilarbut actuallyverydifferent materialswould tend
to compromisemechanisticinterpretations of such materials91.
A metal complex may be bound onto the internalsurface of a
molecular sieve by means of a covalent bond either directly
(grafting)or by means of a spacer ligand (tethering)92.Methods
to forma covalent bond between organometalliccomplexes and a
silica surface by reacting an appropriatefunctionalgroup with
silanol (Si-OH) groups are well known93, and hence metal
complexes mightbe equivalentlygraftedonto the internalsurface
of mesoporous sieves such as MCM-41. A surface-grafted Ti(IV)
and an oxomanganesecatalysthave been preparedby the respective
reaction of MCM-41 with with titanocenedichloride94and with
95
Mn2(CO)xo ■
Reactions that involve H202 or R02H as the oxidant and
catalysed by metals may be either homolytic and involve free
radical intermediates(reactive oxygen species, ROS, as they are
252 Christopher
J.Rhodes
described in the biological literature),such as HO*, H02*, RO,
R02*, or heterolyticand involve oxygen-atomtransfer processes,or
indeed a mixtureof them,dependingmainly on the type of metal.
When the metal in its highestoxidation state is both a Lewis Acid
and a weak oxidant, e.g. early transitionmetal ions with a d°
configuration,such as Mo(VI), W(VI) and Ti(IV), heterolytic
peroxometal(M-OOR) routesare favoured.The metal ion functions
as a Lewis Acid and so its oxidation level remains constant
throughoutthe catalytic cycle. Strong single-electronoxidants,
such as Cr(VI), Mn(III), Co(III), Fe(III), encourage oxometal path-
ways and/or homolyticdecompositionof R02H. Vanadium(V) is
somethingof an all-rounder,since its mechanisticrole appears to
involve all three types of activity,on account that it is a strong
Lewis Acid in addition to being a fairly strong single-electron
oxidant82.When hydrocarbonsare oxidised using 02, hydroper-
oxides are formedaccording to the classical mechanismof auto-
xidationwith R02H species as intermediates78. These species may
undergo subsequent heterolyticoxygen-atom transfers,and in
oxidations with R02H or H202 as reagents,homolyticreactions
may resultin the formationof free 02 as a resultof bimolecular
terminations of R02* or H02* radicals (Russell Mechanism) e.g.
•
R02 + R02* -ROOR + 02.
The 02 can feed-back into an autoxidationtype mechanism by
reactingfurther with freeradicals presentin the system.
It is not always an easy matterto distinguishbetweenhomolytic
and heterolyticpathways, because the same products can be
produced fromboth routes. There are simple means for inquiring
systemsabout freeradicals, for example adding radical scavengers
which necessarily inhibit a genuine homolytic chain-mechanism,
and if the productconcentrationis reduced on deoxygenation,e.g.
withargon,thereis the stronglikelihoodthat02 is involved in the
reaction.The relativerates at which secondaryand tertiaryC - H
bonds are oxidised may also be used to indicate the natureof the
attackingspecies, and is is in the range 2-3 forHO* reactingwith
R3CH/R2CH296,bearing in mind thatthe relativerates depend on
the choice of solvent and on other factors.Among peroxometal
mediatedpathwaysare the epoxidation,sulfoxidationand oxidation
of alkenes, while typical oxometal-mediatedor autoxidationreac-
tions include the oxidation of allylic and benzylic compounds and
the oxidationof alkanes, where the two mechanismsare oftenhard
to distinguish.Alcohol oxidationmay involve both peroxometalor
oxometal intermediates,and titanium-substituted molecular sieves

andapplications
act via peroxometalpathwaysand effectthe epoxidationof alkenes.
They would not, however, work well in allylic or benzylic
oxidations,and using titaniumor vanadium-substituted molecular
sieves to promote the oxidation of alkenes with H202 would be
unlikelyto involve heterolyticoxygen-atomtransfer.More reason-
ably, hydroxyl and hydroperoxylradicals are formed in these
systems,by the metal ion induced homolysis of H202, as is the
case in homogeneous vanadium catalysts97.
7. Photooxidation in zeolite cages

The oxidation of small alkanes, alkenes and aromaticcompounds
(derived fromcrude oil and naturalgas) is pivotal to much of the
chemicalindustry.Molecular oxygenis an ideal oxidantin principle
because it is so widely and readily available, but it tends to lack
selectivity,and almost invariably results in the production of
unwanted by-productswhich require separation using processes
that are demanding in terms of their energy costs. This lack of
selectivityis due to the factthatoxidationreactionsin gas or liquid
phases tend to proceed via free radical intermediates,and are
notorious for resulting in over-oxidation and other products
resultingfromradical coupling and disproportionation. A relative
exothermicity is also a of
feature reactionswith 02, and unrestricted
mobilityof freeradicals encourages indiscriminateattackon initial
hydrocarbonchains and theirprimaryoxidation products.It is an
unluckydispensationof naturethatthe oxidised productmolecules
tend to be more reactive toward free radicals than their parent
hydrocarbonsare, and hence the kinetic competitionfavours the
formationof poly-substitution or over-oxidationproducts. As the
reactionproceeds and its productsaccumulate,the effectbecomes
more pronouncedand in most practicalsituationsconversionto the
desired products is limited to just a few percent78.Various
approaches have been explored by which to optimisethe outcome
of oxidationreactionsmore viably. An 02 molecule and a hydro-
carbon molecule may be togetheractivated to induce an electron
transferfromthe latterto the former,resultingin the formationof
the hydrocarbonradical cation along with the superoxide radical
anion (02 *). The resultingalkane and alkene radical cations are
highlyacidic and so can transfera protonto the superoxidemoiety,
yielding an alkyl or allyl radical and the hydroperoxylradical
(HOO*). Althoughthese are the same radicals as are produced in
normal gas-phase or liquid-phase oxidation reactions,at ambient
temperatureand in a restrictedenvironment, theirreactivitymight
J.Rhodes
254 Christopher
be controlled so that a greater selectivityprevails in the final
products.A charge-transfer of this kind can be induced when a
photon is absorbed by a collisional complex of a hydrocarbon
molecule and an 02 molecule. Light-inducedproductionof hydro-
carbon- 02 charge-transfer (CT) states was firstobserved in the
1950s by Evans98 and by Mulliken" and their co-workers.In
oxygen-saturatedliquid hydrocarbonsand gas-02 mixturesunder
high pressures,optical absorptionswere recordedin the UV region
fromcollisional CT pairs, which are revealed as long, structureless
absorption-tails. Nonetheless,a multitudeof different productswas
always produced100-103.
Frei and his co-workershave managed to performphotochemical
oxidationsof hydrocarbonsin zeolites using 02. The resultsof this
work are summarised in two overlapping reviews104'105.In the
absence of solvent, a cation-exchangedzeolite provides a micro-
porous environmentin which reactantmolecules may be adsorbed
so to restricttheirmobility,and hence discourageradical coupling
reactions that tend to dominate the chemistryof gas or liquid
phase systems.An analogy of the zeolite-containedmolecules is
with a "matrix-isolated" system, in which contained molecules
may react with other very local species, but are otherwise
diffusionallyprecluded from undergoing undesired furtherreac-
tions, as is used to make spectroscopicmeasurementson reactive
species11.
The alkali metal or alkaline earthmetal cationspresentin zeolites
are poorly "solvated" by the zeolite framework, and hence provide
large surface electrostaticfields which tend to stabilise the highly
polar CT states of hydrocarbon -02 collisional complexes.
Depending on the extent of the stabilisation,oxidation reactions
via CT mightbe promotedusing only visible light.Use of longer-
wavelength visible radiation ratherthan UV, would ensure the
formationof primaryphoto-productswith a minimumamount of
excess energy,thusminimisingbond homolysis(especially of weak
bonds e.g. O - O in peroxides or hydroperoxides)and random
coupling reactionsof resultingfreeradicals. Hence the decomposi-
tion of sensitivecompounds such as peroxides,and over-oxidation
would be limited.In termsof costs, visible lightis much cheaperto
produce than is light at UV wavelengths,and is less draconianto
use in regardto Health and Safetyregulations.The success of this
approach is summarisedin the followingexamples.
The firstreportwas of the oxidation of 2,3-dimethylbut-2-ene
adsorbedin zeolite-NaY (Si/Al = 2.4). BaY was also used and both
Na+ and Ba2 + -exchanged forms of zeolite-L. These particular

andapplications
zeolites were used as hosts formost of the subsequentexperiments
too. Zeolite-Y has the faujasite structure(Figure 8) with a 3-
dimensional network (honeycomb) of spherical supercages of
diameter 13 A, and connected by "windows" of 8 A aperture.In
contrast,zeolite-L has a uni-dimensionalstructureof channelswith
a diameterof 7 A. Zeolites Y and L are very useful in studies of
photoxidationreactions,because theycan be preparedfreeof either
Bronstedor Lewis acid sites when dehydratedunder vacuum, the
presenceof which could otherwisecomplicatedevisingmechanisms
forthem.On average therewere 1-2 molecules of hydrocarbonfor
each supercage of zeolite-Y, and one 02 molecule per 3-4 super-
cages. It was foundthatirradiationof 2,3-dimethylbut-2-ene even at
light wavelengths of 750 nm resulted in oxidation of the alkene,
yielding the product 2,3-dimethyl-3-hydroperoxyl-l-butene, along
with a small quantity(2%) of acetone which originatedfromthe
thermaldecompositionof the primaryalkene hydroperoxide106'107.
The optical spectrumof this system shows a long absorptiontail
which extendsinto the red regionof the spectrum(to 750 nm) from
the CT absorption108.When 2,3-dimethylbut-2-ene and 02 are
presenttogether in the liquid or the gas phase, the CT tail begins
only at 400 nm, which implies thereis a stabilisationof the excited
CT complex by the zeolite surface electrostaticfield by up to
350 nm which amountsto 3.5 eV. The formalnegative charge per
supercagewall in zeolite-Y is -7, and is located on the framework
oxygen atoms, but counterbalancedby poorly shielded cations
resultingin an electrostaticfield strengthof 0.3 V/A and 0.9 V/A
forNaY and BaY, respectively105. Thus the large dipole of the CT
ion pair of around 15 Debye units will interactstronglywith the
internal surface field, providing stabilisation for it and greatly
assistingits formationin the zeolite matrix.
The oxidationof propylene109 requiredrathershorterwavelengths
in
( < 520 nm), accord with the fact thatthe ionisationpotentialof
propylene(9.7 eV) is greaterthanthat(8.3 eV) for2,3-dimethylbut-
2-ene, but product selectivityproved harder to achieve in this
system. The initial product allyl hydroperoxidewas stable when
the zeolite was maintainedat a temperatureof - 100°C and was
formedalong with 13% of propyleneoxide as a minorproduct.If
the zeolite containingallyl hydroperoxidewas allowed to warm
with excess propylenestill present,propyleneoxide was produced,
but only acrolein if the excess propylenewas pumped-offbefore
warming.A reasonable mechanismcan be invoked if allyl hydro-
peroxide is the primaryproduct of photo-oxidationof propylene,
but is convertedto acrolein by dehydration.Propylene oxide is
J.Rhodes
256 Christopher
more reasonablyproduced by a "dark" reactioninvolvingtransfer
of an "O" atom from the hydroperoxideto excess propylene,
yielding allyl alcohol as an additional product. A quantum effi-
ciency of 20% was deduced for the formationof the primary
hydroperoxidewith a selectivity of 98%, both of which are
remarkableand unprecedentedfor the oxidation of propyleneor
any othersimple alkene109.
The conversionof toluene to benzaldehyde,an importantindus-
trial chemical used in the manufacture of various flavours,
fragrancesand agrochemicals,is not as straightforward as might
be imagined115,since thereis no reactionknown that can oxidise
toluene selectivelyto benzaldehyde,which is prone to overoxida-
tion to benzoic acid as in the autoxidationof toluene,catalysedby
Co3+ ions110.Yet, when toluene is incorporatedwith molecular
oxygen in eitherzeolite BaY or CaY and irradiatedwith light of
wavelengths<600nm, benzaldehydeis the sole organicproduct110.
When the process was contained in a zeolite cooled to - 60°C,
benzyl hydroperoxidewas trappedbut this was seen to dehydrate
spontaneouslyon warming the matrixto room temperature.The
indicationthus is thatthe hydroperoxideis both the primaryphoto-
productand the criticalintermediatein the formationof benzalde-
hyde. Even at a toluene conversion of 50% the selectivitywas
retained.Over-oxidationof benzaldehydeto benzoic acid is avoided
because the latterhas a substantiallygreaterionisation potential
(9.5 eV) than toluene (8.8 eV), and so the benzaldehydes-02 CT
absorptiondoes not reach into the visible region, renderingthe
material inaccessible to photolysis at these wavelengths111.A
similarconversionof ethylbenzeneto acetophenonewas achieved
also with complete selectivityin zeolite BaY105.
Alkanes can also be oxidised in zeolites using molecular
oxygen112-114. Cyclohexane has almost the same ionisationpoten-
tial as propyleneand irradiationof a cyclohexane and 02-loaded
zeolite NaY with green or blue light (<520nm) resulted in
oxidation of the alkane solely to cyclohexyl hydroperoxideand
cyclohexanone plus water. The cyclohexyl hydroperoxidewas
foundto undergoa clean thermalrearrangement to formcyclohex-
anone. The selectivityremains even at high conversionsof cyclo-
hexane, above 40%. The reaction was monitoredby in-situFT-
infrared spectroscopy and the visible reactant absorption was
detected by diffuse reflectance spectroscopy with an onset at
about 500 nm. The absorptionis attributedto the cyclohexane-02
CT transition, which is shiftedfromthe UV into the visible region
by the veryhigh electrostaticfieldof the zeolite cage112.Similarly,

andapplications
zso-butaneand oxygen gas loaded into zeolite BaY were caused to
react by irradiationwith green or blue light to yield tert- butyl
hydroperoxidein a single-photonprocess. The selectivitywas 98%,
even at 50% conversionof the reactantsloaded into the zeolites113.
When propane was similarlyoxidised114,acetone and water were
detectedby reflectanceIR as the finalproductswhen 150-300 mm
Hg of propane and 1 atm pressureof 02 were adsorbed into zeolite
BaY and exposed to blue or greenlightfromeithera tungstenlamp
or a laser. Some additional bands were ascribed to isopropyl
hydroperoxide,a species that disappeared under dark conditions
along with the concomitantincrease in featuresfromacetone and
water. Thus isopropyl hydroperoxideappears to be the primary
photo-product, as is confirmedfromthe resultsof identicalexperi-
ments repeated using perdeuteropropane114. The possibility that
thermaloxidations of alkanes might take place in zeolites in the
absence of lightwas also exploredand forpropane in CaY, even at
room temperature some oxidationwas foundto occur114.
The effectof zeolite Y cation-exchangedwitha seriesof alkaline-
earth cations on selective propane oxidation at room temperature
was studied using in situ infrared spectroscopy, from which
isopropylhydroperoxidewas observed as a reaction intermediate
which may decompose to formacetone and water. In contrastto
previous reports,BaY was active at room temperature. The rate of
reactionwas seen to increase in the orderBaY < MgY < SrY < CaY
as gauged by the rate of formationof adsorbed acetone. The
acetone/waterratio was found to increase with cation size, with
no other detectableproducts,while the acetone/isopropylhydro-
peroxide ratio was found to decrease as the number of Bransted
acid sites decreased. Both observations provide evidence that
Br0nsted acid sites are involved in this reaction, in addition to
the alkaline earthmetal cations.A two-stepmechanismis suggested
in which the conversionof propane into isopropylhydroperoxide
takes place on the cations, while the decompositioninto acetone
occurs at Bronstedacid sites115.
An investigationof the number of supercages involved in the
visible light-inducedreaction between 2,3-dimethylbut-2-ene and
02 in NaY zeolite was made in which the growth of the sole
product, 2,3-dimethyl-3-hydroperoxy-but-l-ene was studied using
rapid-scan FT-IR spectroscopy with a 150 ms photolysis pulse.
Since the pulse durationis shortin comparisonwith the estimated
rimescaleover which cage-to-cagediffusionoccurs,it is possible to
determinethe numberof cages involved. It was estimatedthat a
minimumof 1% of all NaY supercages actually take part in the
J.Rhodes
258 Christopher
photo-reaction.Since this is between 1 and 3 ordersof magnitude
greaterthanthe concentration of any defectsites (Lewis acid or free
radical sites) thatmightbe presentin the zeolite, theresultconfirms
that the sole relevantphysical propertyof the zeolite cage in the
photo-reactionis the high electrostaticfield in the vicinityof the
Na+ cations,which is responsibleforinducingthe reaction,as has
been previouslyassumed116.Frei has published a note in Science
which emphasises the importanceof the rate of diffusionof the
productsout of thezeolite in any practicalpreparativeapplicationof
these photooxidations and that this poses a major obstacle to
commercialscale-up117.The importanceof the relativeorientation
of the photo-reactantsin the zeolite cage to accessing the CT
complex is also discussed. Interestingly, a paper by anothergroup
reportsDensity Functional Theory(DFT) calculationson the initial
CT step foralkene photo-oxidationin zeolite Y. The model system
used representsa partof the Y-zeolite supercagecontainingtwo Sn
sites with alkaline-earthcations and 2,3-dimeťhylbutene-2 (DMB)
and 02 co-adsorbed on them. It is predictedthat the electrostatic
fieldof the zeolite cavityplays only a minorrole in the stabilization
of a charge-transfer state, while the relative orientationand the
distancebetweentheDMB and 02 molecules are thecriticalfactors.
On the basis of these results,the photo-oxidationis consideredas
being due to a confinement effectin which the reagentsare oriented
in a suitable "pre-transitionstate" configuration118. The same
group have reporteda furtherDFT studyof the conformationsof
akanes adsorbed on zeolite cations119.
8. Novel zeolites
Post-synthetic modification120'121
is a method thatis employed to
reduce the effectivechannel dimensions of a zeolite, to reduce
the numberof frameworkacid sites or to introducesome desired
new reactive functionality.Haw and his coworkers recently
functionalisedthe large-pore zeolite H-beta by reaction with
trimethylphenylsilane at 648 K, which was found to convert
some of the acid sites to their trimethylsilylderivatives122.This
work has been extended to a two-steppost-synthetic sequence in
which HZSM-5 is functionalised with a high selectivity at
ambient temperatures.The frameworkacid sites of the zeolite
are initiallyreacted with phenylsilaneto replace the acidic proton
with a hydrosilyl(-SiH3) group covalently linked to the frame-
work (step 1). This group readily couples to acetone in a step 2
to forma framework-bound hydrosilylisopropylether.While this
is thermallystable at 473 K under dry conditions, it undergoes
decomposition in the presence of moisture. Theoretical studies
using DFT and cluster models of the zeolite acid site affirmed
that both reaction steps are exothermicand predicted chemical
shifts that were in excellent agreementwith their experimental
values123. A portion of the silicon may be removed from a
zeolite by treatmentwith alkaline solutions as a simple way to
obtain mesoporous ZSM-5 zeolites in which the integrityof the
essential structureis preserved.The process of frameworksilicon
extraction is controlled by frameworkaluminium and makes
desilication selective towards the creation of intracrystallinç
mesopores. The process is optimal at a range of Si/Al ratios
of 25-50 while at higher Si/Al ratios the loss of framework
silicon becomes excessive and unselective; at lower ratios
comparativelylittle extractionof silicon occurs.
The presence of non-frameworkaluminium species, as are
formedby steam treatment(as in USY), is found to inhibitthe
formation of mesopores on treatmentwith alkaline solutions
because these species become reinsertedinto the zeolite frame-
work. It is thoughtthatmesoporous zeolites should induce a more
efficientuse of the zeolite crystal since the accessibility is
improved along with more facile transportto and from the
active sites124. The technique of dry-gel conversion involves
treatingthe pre-driedgel powder with water vapour at elevated
temperatureand pressure,and though water vapour is known to
be involved in the process the mechanismfor this is not clear. In
one study, 170-labelled water vapour was used in the crystal-
lization of A1P04-11 and the process was monitoredusing 170
MAS NMR spectroscopy.The results show that water fromthe
vapour phase initiallyexchanges slowly with water molecules that
are stronglybound to the AIPO intermediatesand that gradually
170 atoms become incorporatedin both P- O - H and P- O - Al
units in the layered intermediate125.
The effectof particle size in the range of 0.16-2.01 microns
on the hydrothermal stabilityof H-Y zeolite under hydrothermal
treatmentconditions similar to those used in Fluidised Catalytic
Cracking (FCC) processes has been investigated.It was found
that the optimumparticle size for zeolite H-Y to retain a high
percentage of crystallinityupon hydrothermaltreatmentis 0.45
microns. The relative crystallinity(C/C0) could be correlated
with the reciprocal of the square root of the zeolite particle size
(d0) and hence provides an accurate prediction of the hydro-
thermalstabilityof zeolite Y in the small to medium particlesize
260 Christopher
J.Rhodes
ranges at a given temperature.The correlationwas found not to
hold for the larger particles of Y zeolite (>0.45 microns),
probably due to the presence of a greaternumber of structural
defects in the zeolite, according to the higher Bronsted/Lewis
acid ratios which pertain126. There is a controversy about
whether the H-form of natrolite actually exists. To cast light
on the matter, the thermal decomposition of NH4-exchanged
natrolite (as a precursor of the H-form) was studied by gas
chromatography, IR spectroscopyand X-ray diffraction,leading
to the conclusion that throughoutthe decomposition, the de-
ammoniationis followed rapidly by dehydroxylation,in accord
with an intrinsicinstabilityfor H-natroliteformedonce NH3 has
been removed. The final step of the decompositioninvolves the
adsorptionof NH3 onto Lewis acid centreswhich have accumu-
lated in the now amorphousframeworkand this hampersthe loss
of ammonia. In accord with this interpretation, the activation
energy observed for NH3 desorption increases from an initial 117
( + 13) kJ mol-1 to a final value of 270 ( 20) kJ mol-1. If
+
the NH4-exchangednatroliteis degassed smoothlyunder vacuum
at 550 K, a partial de-ammoniation is observed rather than
formationof H-natrolite127.
A deep-eutecticsolvent (DES) is a mixtureof two compounds
which togetherresultin a depression in the freezingpoint of the
mixturecompared with those for the separate components.In one
study,the controlleduse is described of DES which are unstable
at high temperaturesand so the organic templateis not added in
the normalmannerto the reactionmixturebut is deliveredthusby
the decompositionof one of the componentsin the DES itself128.
Weckhuysen et al. have used a multi-techniqueapproach to
unravellingthe mechanism of formationof zeolites and obtained
resultsthatsupportthe inferencethatmolecular organisationtakes
place before crystallisationoccurs. Thus it is molecular recogni-
tion thatcreates the seeds of order around which complex lattices
grow129-131, remarkablylike the self-assemblingsystemsthat are
believed to be key to the origin of life on earth132.The presence
of phosphorus atoms is found to stabilize the ZSM-5 zeolite
structureby preventingthe separationof the frameworkAl atoms
duringhydrothermal treatment.In addition to the classical frame-
work tetracoordinatedaluminium, which is a major factor in
determiningthe acidity of the zeolites, a second tetrahedral
aluminium (probably in a distortedenvironment)also seems to
be active in n-hexane cracking, in addition to favouring the
formationof light olefins duringgasoil cracking133.
8.1 Zeolite-containing membranes
Zeolite membraneshave been preparedwith the aim of providing
molecularseparators,e.g. forthe dryingof bioethanol,by separating
waterfromit,foruse as a fuel (Figure 11). Zeolite NaA membranes
have been preparedwith reproduciblestructuresby seeded hydro-
thermalsynthesison the inner-sideof porous alpha-aluminatubular
supports,using a semi-continuoussystem in which the gel was
periodically renewed inside the tubes. A cross-flow filtration
technique was used which permitteda controlled seeding of
zeolite NaA crystals from a suspension. The influence of the
renewal rate duringthe synthesis,as well as the seeding weight
gain (SWG), on the pervaporationperformanceof the membranes
preparedwas investigated.An optimalSWG value was foundto be
around 0.15 mg cm-2 of membrane area. The use of a semi-
continuous system was able to furnishzeolite membranes with
selectivitiesup to 16,000 at fluxesof 0.50kg m~2 h~ 1 at 323 K for
the pervaporationof 90 : 10 wt% ethanol/watermixtures134. Zeolite
NaA membraneswere investigatedfor the pervaporation(PV) of
Fig. 11. Dehydration

system a zeolitemembrane,
employing advancedbyMitsui
andEngineeringandShipbuilding
Co.fordryingbioethanol
foruseas a fuel.
http://sl69.photobucket.com/albums/u238/biopact2/th_biopact_zeolite_memb
Reproduced with
permission
fromBiopact.
262 Christopher
J.Rhodes
ethanol/watermixtures.The PV performanceof the as-synthesized
membraneswas explored at 303-363 K for water contentsof 1-
60wt% and for feed and permeatepressuresin the range 0-7 bar
and 2-70 mbar,respectively.The selectivitywas foundto show a
maximumat a water feed compositionin the range 5-10wt% and
to rise withtemperature.Waterand ethanolfluxeswere successfully
fittedto an adsorption-solution model derived fromthe Maxwell-
Stefantheory,wherethe ethanolfluxis coupled withthewaterflux.
It appears thatthe PV performanceof zeolite NaA membranesis
determinedmainlyby the adsorptionof water and ethanol135.
ZSM-5 zeolite membranes were synthesizedby means of the
secondary growthprocedure over porous alpha-alumina supports
from clear template-freeprecursorsolution and their permeation
properties were compared with membranes prepared using
templates.The templatedmembrane(Ml) was shown to contain
smallercrystalswith a greaternumberof faces thantheirtemplate-
free counterpart(M2). The expected size selectivitycould not be
achieved for Ml as this membranepossessed some micro-defects
formedduringthe calcinationprocedure.The required size selec-
tivitywas however achieved for M2 at ambienttemperaturesand
shape selectivityfound at 200° C. A selectivityratio of 44 was
achieved forbutane isomers throughM2 with n-butanemolecules
experiencing a maximum activation energy of 43 kJ mol-1,
resultingfroman activated diffusionmechanism. The permeation
values measured forM2 membraneswere normallyan orderlower
thanthose forMl membranes136. Two methodswere comparedfor
the preparationof zeolite beta membranes with a thickness of
around lOOOnmon beta seeded, commercialTrumemdisk supports.
The firstmethod produced an alkali-freezeolite beta layer with a
Si/Al ratioof 40. By means of the second method,a Na-containing
zeolite beta layer with a Si/Al ratio of 13 was obtained. The
mechanism for permeationwas controlled by surface diffusion.
Significantly,only those membranespreparedby the firstmethod
were effective in separating di- from mono-branchedalkanes,
according to PV experimentsat 303 K with a 50:50wt% 2-
methylpentane(2 MP) and 2,2-dimethylbutane (22DMB) mixture,
giving a selectivityof 1.5 in favourof 2 MP which is greaterthan
that expected on the basis of Knudsen diffusion. Respective
adsorptionenergiesfor2 MP and 22DMB of - 48 kJmol-1 and
- 42 kJmol-1 in zeolite beta were determined137.
Asymmetricallystructuredzeolite membranesof a hydrophobic
MFI (ZSM-5) typeand hydrophilictype,NaA were preparedas thin
layers of thickness 10-30 microns on ceramic substratesand

andapplications
examinedby pervaporationwithbinarywater-ethanolmixturesand
withpure waterand pure ethanol.By comparingsingle and mixture
permeance, it was deduced that differentseparation mechanisms
operate for MFI and NaA membranes, which were influenced
stronglyby the structureof the membranesupport138.
An H-ZSM-5 membranehas been employed for xylene isomer-
ization and forthe separationof /7-xylenefromits otherisomers.In
this work, MFI membranes (silicalite-1 and H-ZSM-5) were
preparedby seeded growthon porous stainless steel supports.The
membraneswere testedfor separationof the xylene isomers in the
temperaturerange 100-400°C. The H-ZSM-5 membraneshowed
higher/7-xylene permselectivity[(para/ ortho) = 4.3 at 300°C] and
lower permeanceto /7-xylene(3.55 x 10" 8mol m-2 s-1 Pa-1 at
300°C) comparedto the silicalite-1membrane(para/ortho) =2.1,
7
permeanceto /7-xylene(7.4 x 10" mol m~2 s_1 Pa-1 at 300°C).
However, neitherwere entirelydefect-free139.
A method for preparingNafion/acid functionalizedzeolite Beta
(NAFB) nanocompositemembranesby in situ hydrothermal crystal-
lizationhas been reportedintendedforuse in a directmethanolfuel
cell (DMFC). When testedwith a 1 M methanolfeed, the DMFCs
with the NAFB composite membranes demonstrateda slightly
higher open circuit voltage (OCV; 3%) and much higher
maximum power density(21%) than those with the pure Nafion
115 membranes.When a highermethanolconcentration(5M) was
used, the DMFCs with the NAFB compositemembranesshowed a
14% higherOCV and a 93% highermaximumpower densitythan
those with the pure Nafion 115 membranes140.The pervaporative
dehydrationof ethyleneglycol (EG)/ watermixturesusing commer-
cial nanoporousNaA zeolite membraneshas been investigated.The
concentrationrange (C-EG>70wt%) was selected according to
existing industrialrequirements,and at 70°C with an initial EG
concentrationof 70 wt%, largerfluxesand separationfactorscould
be obtained, i.e., 0.94kg m-2 h-1 and 1177, respectively.The
PervaporationSeparationIndex (PSI) of the membranewas found
to be high comparedto thatof polymericmembranes141.
Other applications of pervaporationthroughzeolite membranes
include the separationof water fromethanol-watermixturesusing
NaA and NaY membranes142,the separation of xylene isomers
using polyurethane membranes containing ZSM-5143 and the
separation of various dichlorinatedcompounds (dichloromethane,
1,2-dichloroethaneand ¿rarcs-l,2-dichloroethylene)from water in
their aqueous solutions using a silicalite-1 membrane144.In the
latter example, fluxes of dichlorinatedcompounds in the range
J.Rhodes
264 Christopher
0.2 -71g m-2 h-1 were measured with separationfactorsin the
range 12-332, depending on the mole fractionof the organic
material.It is concluded that the silicalite-1membraneis suitable
for the selective removal of dichlorinatedorganic compounds
fromtheir dilute solutions in water and at a comparativelylow
temperature,which may have applications in cleaning contami-
nated groundwatersand wastewaters144.
9. The acid strength of zeolites and its implication

in catalysis
Prior to 1994, H-exchanged zeolites were referredto as "super-
acids", i.e. withan acidic strengthgreaterthanthatof concentrated
sulfuricacid. Consequently,the mechanismsof reactionscatalysed
by H-zeolites such as hydrocarboncracking,were ascribedin terms
involvingsimple carbeniumions and rationalisedaccordingto the
known chemistryof these exotic high energy intermediates,as
gleaned from studies made of reactions in true liquid superacid
media. However, in the lightof new evidence, it is probablymore
reasonable to referto H-zeolites as "solid acids" or "solid acid
catalysts",ratherthanto specifya particulardegree of thatacidity.
The subject has been reviewed by Haw who has made seminal
contributionsto the topic145.It is difficultto define the acidic
strengthof solid materialssince a given substancemay contain a
mixtureof Bransted (proton) acid sites and Lewis acid sites, and
some zeolites also contain polyvalent cations and surface defect
sites that can also functionin the manner of an acid. Hence the
propertyis furthermore ratherdifficultto measure. A number of
spectroscopic methods have been employed,in conjunctionwiththe
adsorption of a probe base molecule, to measure the strength of the
resulting base-acid "neutralisation" of Bronsted sites. Indeed it is
now thoughtthat the use of Hammettindicatorsadsorbed on the
surfacesof zeolites and othersolid acids may have been the cause
of much of the confusion about the acid strengthof these
materials145.The Hammettacidity (Hbh + ) of 100% sulfuricacid
is - 12, and this is regardedas the thresholdvalue above which a
systemis definedas a superacid. Zeolite acid strengthswere often
cited as being in the range - 12 to - 24 and so clearlytheywould
be consideredas solid superacids.
Rather than relyingon colour changes of indicators,which are
difficultto determinein solid media, Haw et al. used NMR as a
direct measure of the degree of protonationfor four common
Hammett indicators. The conclusions are that while the strong

andapplications
base p-fluoroaniline (HBh+ = +2.4) is protonatedin both HY and
H-ZSM-5 zeolites, the weak base p-fluoronitrobenzene
(Hbh+ = - 12.4) is not, and so zeolites are not superacids
according to the Hammett definition146.This conclusion is
supported by 15N MAS NMR studies which show that other
Hammett indicatorsclose to - 12 are not protonatedin normal
zeolites145.Haw's groupused NMR to measureproductsformedin
zeolite catalysedreactionsat temperatures of 523 K or less because
the materialsused in the constructionof the NMR probe precluded
more elevatedtemperatures. Generally,Haw145foundno significant
differencebetween measurementsmade at room temperatureand
523 K, but thepossibilitydid remainthatthe zeolites mightdevelop
a much greateracidityat the highertemperatureswhen theywere
typicallyemployed forreal catalyticconversions.
Rodunerand Dilger147studiedthe entropychange associated with
deprotonationof a zeolite which showed thatH-zeolites are in fact
less stronglyacidic at elevated temperatures, as indeed are aqueous
solutionsof mineralacids. Therefore,if a zeolite is not a superacid
at ambienttemperatureit is most unlikelyto become one at more
elevated temperatures.If zeolites are not superacids, other more
complex mechanismsmust be invoked to explain theirchemistry.
Solid state 13C NMR spectra of benzene in zeolite HY were
compared with those measured in solid and in frozen "magic
acid" and confirmthat there is little or no proton transferto
benzene fromthe zeolite148.Hydrogen-deuterium isotope exchange
has been observedto occur fora varietyof hydrocarbonswhen they
are adsorbed in H/D-zeolites, which generally is attributedto
protonationof the hydrocarbonwith the formationof carbocation
(carbeniumor carboniumion) intermediates accordingto the super-
acidic natureof the zeolite. In a studyof H-D exchange formethane
adsorbed in zeolites, it was concluded thata concertedmechanism
was responsible and not a five-coordinatefree carbonium ion
intermediate149. A study was made of perdeuteriobenzene(C6D6)
adsorbed on H-zeolites using :H MAS NMR, in which the benzene
proton signal, formed by D-H exchange with the zeolite, was
monitored.For the zeolites H-ZSM-5, USY and Na,HY activation
energies of 60.2 kJ mol-1, 84.9 kJ mol-1, 107kJ mol-1 were
determinedrespectively148, and are close to those determinedfrom
a theoretical model. It has been shown that the gas-phase proton
-1
affinityof n-hexane is 665 kJ mol which is too weak for
complete proton transferto occur in a zeolite150. Theoretical
studies have provided convincing model mechanisms in which
alkane cracking occurs throughtransitionstates in which basic
J.Rhodes
266 Christopher
frameworkoxygen atoms near to the Bransted site act to stabilise
both the protonand an activatedfragmentof the hydrocarbon.The
significantdifferencefrom the accepted mechanism is that only
partialcharge transferis requiredratherthanthe generationof fully
free carbocations,thus lower-energypathways are available than
those requiredto create such high-energyintermediates151'152.
The Methanolto Gasoline (MTG) process6is a way of converting
methanolto hydrocarbonmixturessuitable for burningin internal
combustion engines, and is catalysed by the zeolite H-SZM-5.
Despite the elapse of thirtyyears since its development,during
which a massive researchefforton the topic has been mountedin
academia and in industry,the precise mechanismforit remainsthe
subjectof controversy153-155. There has been a more recentshiftof
interestin the general process of convertingmethanolto hydro-
carbons from the original goal of making syntheticfuel to the
conversion of methanol into light olefins using the less strongly
acidic silico-aluminophosphate catalyst(HSAPO-34). Interestin this
methanol-to-olefins (MTO) process arises fromthe prospectthatit
may provide a means for the conversion of methane to polyole-
fins154.The complete strategywould involve steam-reforming
methanefromnaturalgas to forma mixtureof H2, CO and C02
("synthesis gas") fromwhich methanolcan be synthesisedusing a
Cu/Zn0/Al203 catalyst.If an economicallyviable methodis found
to convertmethanolto lightolefins,the world plastics industryhas
only to depend on naturalgas ratherthan importedoil. However,
gas is importedincreasinglyintomany countriesincludingthe U.K.
which is now a net energyimporterratherthanthe exporterit once
was as the North Sea fields are in decline, so a dependence on
importedresourcesis not necessarilyobviated5.
Either MTG or MTO process poses the mechanisticpuzzle of
how the firstC - C bond is formedfroma feedstockof molecules
containingjust a single carbon atom, i.e. methanol. There have
been at least 20 different mechanismsproposed to account forthis
those based on +
including CH3 carbeniumions, oxonium ylides,
e.g. Si20+-CH2~, and free radical species153"155.The latterare
particularly attractivein their simplicity,since formationof a
-
C C bond from CH3OCH2* radicals derived frommethanol in
H-ZSM-5 involves a simple radical combination step156. Spin-
trapping experiments combined with ESR spectroscopy have
provided evidence that radicals are formed in the gas-phase
when dimethylether(the primaryproduct formedby dehydration
of methanol) interactswith H-ZSM-5156, although it is not clear
that they are key intermediatesin the MTG process157.For that

andapplications
matter,free radical species may be spin-trappedfrom the gas-
phase froma varietyof different model catalyticsystems,but how
importantthey are in real catalyticreactionsis unknown158.A co-
catalyticaffectwas demonstratedwhen a mixtureof methanoland
toluene was injected into the reactor containingH-ZSM-5159'160.
To account for this observation, the formationof resonance-
stabilised carbenium ion intermediatesin the zeolite by a side-
chain alkylationmechanismwas proposed159'160.
Little further progresswas made untilthe mid-1990s when Dahl
and Kolboe advanced the "hydrocarbonpool" mechanismin which
the functionof methanolis to methylatehydrocarbonmolecules of
unknown structureadsorbed on the catalyst's surface, and leads
ultimately to olefins through parallel reaction pathways161'162.
Haw's group began to search for key intermediatesin the hydro-
carbonpool using experimentalpulse-quenchin situNMR methods.
Methanol conversions catalysed by both H-ZSM-5163'164and H-
SAPO-34165'166were investigated.Among the species identifiedin
H-ZSM-5 were the 1,3-dimethylcyclopentenyl carbenium ion in
equilibrium with a relatedneutral cyclic diene, and methylsubsti-
tuted benzenium carbenium ions in equilibrium with neutral
methylatedbenzene derivatives.On H-SAPO-34, the criticalreac-
tion centresappear to be methylatedbenzene derivatives.Haw has
concluded thatthe initiationstep in MTO/MTG catalysisis reallya
phantom,and thatthe firsthydrocarbonpool species are formedby
organic impurities.He contends that only an "indirect" hydro-
carbon pool mechanism accounts for the observed outcome of
MTO/MTG methanol conversion catalysis, and if any "direct"
reaction happens at all it is much slower than those processes
involvingthehydrocarbonpool. Hence initiationof the MTO/MTG
reactionis generallycaused by organicimpuritiesthatformthe first
few reaction centres167.The impuritiesin the mixtureundergo
repeated methylationand subsequent olefin eliminationwith re-
initialisationof the catalyticcycle. The impuritiesare largerorganic
molecules termed"organic reaction centres" which functionas a
scaffold onto which the reactants are tacked togetherand the
products are removed therefrom.This circumstanceavoids the
need to invoke the high-energyintermediatesrequired by all of
the "direct" mechanisms. The rate of formationof the initial
reaction centres and hence the duration of the inductionperiod
depend on the natureof the impurityspecies. Secondaryreactions
of primaryolefinproductsare determinedby the topologyand acid
strengthof the porous catalysts.It is proposed thatreactioncentres
formvia some secondaryroutesthat"age" intopolycyclicaromatic
J.Rhodes
268 Christopher
hydrocarbonswhich eventuallydeactivate("poison") the catalyst.
Each cage or channel with its occluded organic and inorganic
species in its entiretymay be considered as a supramolecule
which acts as a reactantto formvarious product species, leading
to structure-activityand structure-selectivityrelationshipswhich
permitthe modificationof the catalyst with degrees of freedom
that appear closer to homogeneous catalysts than heterogeneous
catalysts168.However, closure over this matteris not unequivocal
and the issue of formingthe very firstC - C bond remains the
subject of investigationand speculation,althoughthismay be more
or less a matterof "fine-tuning",if the most importantelements
really are comprehended.
The hydrocarbonpool model implies that reactions occurring
during an initial kinetic inductionphase need not necessarilybe
similar to those on a working catalyst. It remains unresolved
however, which inductionreactions- if any - mightcontributeto
the hydrocarbonpool. The results of a theoreticalstudy169have
been publishedwhich aims to integratea large range and varietyof
possible directreactionsand so to deduce whetherethylenecan be
produced solely from methanol, and which stable intermediates
mighttherebybe formeddirectly,to provide an understandingof
how that vexed first C - C bond is indeed formed. Over 80
stationarypoints in the MTO process were calculated which
provided both rate coefficientsat 720 K and reaction barriersat
0 K. However, no directpathwaycould be identifiedthatled from
frommethanolto ethylene(or for that matterto any intermediate
-
containing a C C bond), in accord with the observation that
methanol/dimethylether are relatively unreactive on H-ZSM-5
when there are no organic impuritiespresentthat can provide a
hydrocarbon pool. Two bottlenecks were identified from the
calculations: one being the instabilityof ylide intermediates,and
also that the frequentlyinvoked concertedC - C bond formation
reactionsactually have very high energybarriers,which is due to
the weakly basic character of the zeolite oxygen bridge. The
calculations allow a clear definitionof those intermediatespecies
which are likely to interactwith the hydrocarbonpool, which are
not only the mixtureof methanol and its condensationproducts
dimethylether and water, but also the trimethyloxonium cation,
which mightact as a source of methylgroups,and also of methane
and formaldehyde.In summary,the authors note that neithera
single mechanismnor a combinationof steps among the calculated
scheme of reactionscan link methanolto ethylene.They conclude
that the theoreticalwork provides hence strong support for the
hydrocarbonpool view of the MTO process since it does not
demand any highlyactivatedconcertedsteps169.
Some details of the H-D exchange reactionsof propene over D-
ZSM-5, its boron analogue D-(B)ZSM-5 and D-SAPO-34 have
been reported.Given the huge excess of exchangeable deuterium
atoms on the catalystin relationto the numberof hydrogenatoms
in the propene molecules loaded onto it, completeexchange would
be expected to yield C3D6 as the exclusive equilibriumproductof
the reaction.However, a distributionof exchanged propene isoto-
pomers was measuredby mass spectrometry: 6% D4, 72% D5 and
22% D6 propene. By increasingthe size of the propene pulse, the
deuteriumdistribution was substantiallybut reproduciblydifferent:
28% D4, 44% D5 and 29% D6 propene.The productswere foundto
include not only propene but additional substances arising from
crackingand oligomerisation,i.e. butenes,pentenesand hexenes. A
mechanismis suggestedto account forthese changes170.
In a separatestudy,the H-D exchange reactionof 2,2-dimethyl-
propane (neopentane) over D20-exchanged zeolites (MOR, FAU,
BEA, MFI) in a batchrecirculationreactorwas studiedby means of
gas chromatography/mass spectrometry.It was found that H-D
exchangeproceedswithoutany side reactionsat shortcontacttimes,
in the temperature range 473-573 K. The activationenergiesof the
H/D exchangebetweenneopentaneand zeolites are the same forall
zeolites which may indicate a common carboniumion type transi-
tion state,in analogywiththe exchangebetweenmethaneand liquid
superacids. Accordingly,the deuteriumexchange rates in neopen-
tane were tentativelyrelated to the acidity of the solids. However
the orderof activityMOR > MFI > BEA > FAU seems to be related
to the size of the pores, which may suggest that a confinement
effectin the zeolite cavities is critical171.However, as we have
already discussed, a genuine carbocation mechanism appears
dubious.
Ivanova et al. have writtena shortreview on the impactof in situ
13C and :H MAS NMR on the elucidationof the mechanismsby
which alkylaromatic compounds are transformedover zeolite
catalysts.Conversions of deuteratedbenzene and eumene deriva-
tives on protonie formsof zeolites are used to account for H-D
exchange both in the aromatic ring and in the alkyl chain. The
natureof 13C label transfersduringthe course of therearrangements
of specifically labeled benzene, eumene, n-propylbenzeneand
ethylbenzeneare evaluatedto providedeeper insightin themechan-
isms of transalkylation,disproportionate, skeletaland nonskeletal
rearrangements of alkyl chain, fragmentationand dealkyla-
J.Rhodes
270 Christopher
tion/alkylationprocesses over zeolites. The selectivityof zeolite
catalystsin alkylbenzenetransformations are thusevaluated,and the
results suggest that the dominantfactorcontrollingthe particular
reaction pathway is the zeolite geometry,i.e. that "shape-selec-
tivity" is at work. The paper provides a convincingdemonstration
that in situ MAS NMR, and specific isotopie labelling of organic
reactants,can provide greatinsightinto the detailedmechanismsof
catalyticreactions172.
10. Environmental pollution control using zeolites

Zeolites and zeolite-basedmaterialsare used as sorbentseitherpre-
emptivelyto keep toxic materials out of the environmentor in
remediationstrategiesto clean-up toxic spillages afterthe event.
Cleaning-up afterthe Chernobylnuclear disaster (Figure 12) is a
superlativeexample of thelatterin which 500,000 tonnesof zeolites
were employed to take-upby cation-exchangeradioactivecations,
principally134Cs, 137Cs and 90Sr,thathad been spewed out from
the brokenUnit 4 reactor(by a steam-explosionof sufficient force
to throwthe 1,000 tonne concretelid offthe top of its containment
building), in the formof a cloud that contaminatedUkraine and
much of western Europe5'7'8.Radioactivityfrom Chernobyl was
detectedas far as the east coast of the USA. Zeolites were baked
into bread and biscuits and fed to childrenin an effortto remove
radioactivecontaminationfromtheirbodies. Cattlewere fed zeolites
in an effortto minimisethe level of radioactivematerialin their
milk.I workedin Russia duringthe aftermath of Chernobyl,when it
was extremelydifficultto get any local informationabout what had
happened, and most of what we did know came from our colleagues
in the West via the Janetcomputernetwork.We were however
advised by health physicistsnot to eat "anythinggreen", but to
stick to meat, as this would probably be less contaminatedwith
radioactiveisotopes (iodine in particularwhich concentratesin the
thyroidgland) than freshvegetables would be, given the circum-
stances. The words "sorbent(s)", "sorb" and "sorption" are used
in the literature,presumablybecause not all uptake occurs onto a
surfaceper se as in "adsorb" and "adsorption". In the followingI
have adopted this manner of expression. Surfactant-modified
zeolites (SMZ) offerpromise in environmentalremediation,and
Bowman has published a review of the preparation,properties,
characterisationand effectivenessof SMZs in thisregard.SMZs are
interestingmaterials and have multiplesorbentfeaturesso thatthey
Fig. 12. Aftermath : destroyed
nucleardisaster
ofChernobyl Unit4 reactor
and
reactor turbine
(centre);
building (lowerleft);reactor
building 3 (centre
right).
/1b/Chernobyl_Disaster.
org/wikipedia/en/1
http.V/upload.wikimedia. jpg
may simultaneouslysorb mixturesof toxic inorganic anions and

organic species, e.g. chromáteand perchloroethylene (Figure 13).
The sorption capacity is relatively low, and they are most
effectivefor the removal of toxic agents presentin relativelylow
concentrations,for example in water173.The sorptionof ionisable
organic solutes (phenol and aniline) by clinoptilolitemodifiedby
hexadecyltrimethylammonium(HDTMA) cations has been
reported174.It was found that planar nitrateanions sorb more
effectivelyon the SMZ surfaces than do chromáteanions which
are tetrahedral.Indeed when sulfateor nitrateanions were present
simultaneously,the sorptionof chromátewas found to be inhib-
ited75.The processes involved in the sorptionof chromáte,selenate
and sulfateanions by SMZ have been studiedin some detail from
which the sorptiondata foreach anion were fittedwell accordingto
the Langmuirisothermadsorptionequation176.It has been demon-
J.Rhodes
272 Christopher
Fig.13. Partitioning
ofa mixture
oftoxicchromáte
anionsandperchloroethylene
duringtheir
combined bya surfactant-modified
sorption zeolite(SMZ).
//www.
http: clu-in.
org/products/newsltrs/gwc/images/fig30399.gifwith
Reproduced
fromClu-in.
permission
stratedthat arsenic fromsoil-washingleachate is sorbed by SMZ

witha maximumadsorptioncapacityof 72.0 mmol kg" 1 of arsenic
~1 ~
kg (5.4 g kg l) of SMZ at 25°C177. Surfactant-modified
sorbents
have also been proposed for the removal of organic compounds
fromaqueous solution. In one study,one cationic (HDTMA) and
three anionic (DOWFAX-8390, STEOL-CS330, and Aerosol-OT)
surfactantswere tested for theirsorptivebehaviour onto different
Fig.14. Metsamor
nuclear
powerplant(NPP)inArmenia,
viewed Mount
against
Araratinthebackground.
com.tr/resim/site/metsamorl
http://yenisafak. 1c4052by.
044a642504 jpg
sorbents(alumina, zeolite, and Canadian River Alluvium). These
materialswere then used to sorb a range of hydrophobicorganic
compounds of varyingnature(benzene, toluene,ethylbenzene,1,2-
dichlorobenzene,naphthalene,and phenanthrene), and theirsorption
capacityand affinity forthemwere quantified.The HDTMA-zeolite
system proved to be the most stable surfactant-modified sorbent
studiedbecause of the limiteddesorptionof surfactant. Both anionic
and cationic surfactantsresultedin modifiedsorbentswith higher
sorptioncapacity and affinity than the unmodifiedCanadian River
Alluvium which contained only natural organic matter178.It has
been shownthatSMZ may be regeneratedafterit has been saturated
with chromáteand perchloroethylene179. SMZ have also been used
to remove BTEX (benzene, toluene,and xylenes) as a contaminant
fromwater180.
Toxic cations may be removed from an aqueous medium by
cation-exchangeusing zeolites, includingradioactive cations from
the cooling etc. watersof a nuclearpower plant (NPP). In particular,
radioactive 137Cs+ and ^Sr24" are always present among the
productsarising fromthe fission of uranium-23 5 (235U). 134Cs is
also produced but it is less of a problem for long-termdisposal
since it has a half-lifeof about 2 years, compared with around 30
years each for 137Cs and 90Sr,and hence loses most of its radio-
activityin 20 years ratherthan 300 years (10 half-lives each).
Natural zeolites are most frequentlyused for this purpose; clin-
optilolite,forexample is used in cleaning the watersfromthe NPP
at Metsamor in Armenia (Figure 14), using zeolite-rich tuffs
(geologically modifiedvolcanic rocks) mined in the northof the
country5'8.Similarly,tuffsmined in Mongolia have been evaluated
fortheirabilityto take-upradioactivecations (137Cs, 90Sr,90Y) in
competitionwithothercationspresentin aqueous media. The order
of elemental cation uptake normally follows the series:
Cs+>K+>Sr2+>Ca2+>Na+>Mg2+, although, depending on
the precise Si/Al ratio and the concentrationand nature of the
cations presentaltogether,the ability of a zeolite to take-up Cs +
and Sr2+ may vary,as is discussed. The typicalselectivityand high
affinityof clinoptiloliteforCs + and Sr2+ among thebimodal range
of productnuclei resultingfromthe fission of a 235U nucleus is
demonstrated, however181.Anotherpaper reportsthatclinoptilolite
mined in Iran (in its Na+ -exchangedform)is particularlyeffective
forremovingradioactiveCs + and Sr2+ fromnuclear-powerplant
wastewaters and in removing Ni2+ and Ba2+ from municipal
wastewatersince the affinityof the mineral for these cations is
relatively high182. A comparison is made between different
274 Christopher
J.Rhodes
sorbent/ion-exchange materialsforremovingradioactivestrontium
fromliquid radioactivewaste and very hard groundwaters.In hard
groundwaters,the presence of fairlyhigh concentrationsof e.g.
Ca2+ and Mg2+ cations competes for and reduces the uptake of
Sr2+ . This is a very informativepaper, and covers the background
to this topic well183.
The use of natural zeolites for the purpose of radioactive
decontaminationon the large scale (using 500,000 tonnes of
zeolite) after the Chernobyl disaster was referredto earlier5'7'8.
Nano-pore titaniumsilicate materials ETS-10 and ETAS- 10 with
different Ti/Al ratioswere used successfullyto removeheavy-metal
cations (Cu2 + , Co2 + , Mn2+ and Zn2+ ) from their aqueous
solutions,and the data were fittedby various adsorptionequations
of which the Langmuir-Freundlich isotherm proved best.
Thermodynamicmeasurementssuggest that while the adsorption
is endothermic(positive AH, negativeAG), the positive entropyof
adsorptionindicatesthatthe cations are not taken-upin stable sites
on the surfacesof these materials,probablybecause of the increase
in translationalenergythatis gained when theyare displaced from
theirprimaryadsorptionsites184.
The contaminationof soils and groundwatersby Zn2+ and Pb2+
(from tin-solder)fromrun-offof rain fromgalvanised roofs is a
matterof growingconcern.Both clinoptiloliteand geotextilefilters
have been employed in attemptsto interceptthese toxic cations.
While the geotextile filteris ineffectiveis retainingthese heavy
metal cations, perhaps not surprisingly,the clinoptilolitefilter
retained97% of theirinitial concentration185. Naturallyoccurring
Turkish zeolite minerals which contained 45% clinoptiloliteand
35% mordenitewere used to remove lead and zinc cations from
their aqueous solutions186.The potential application of natural
Turkishclinoptiloliteto removingCo2 + , Cu2 + , Zn2+ and Mn2+
fromthe wastewatersof metal finishingprocesses has also been
described187.A significantimprovementof the ability of natural
clinoptiloliteto take-upZn2+ was reportedif the zeolite was first
exchanged with Na+ cations by chemical conditioningwith 1M
NaCl solution188.
The "radiation removal" of lead from aqueous solutions has
been described.In essence, an aqueous solutionof Pb2+ cations is
treatedwith various sorbentmaterials(activated carbon, bentonite
and zeolite) and exposed to radiationfroman electronbeam. While
theresultsare somewhatvariable as to the efficacyof the irradiation
in its effecton lead removal,a substantialincrease in the effective-
ness of the process is indicatedwhen the solutionis saturatedwith
nitrous oxide. This to my mind suggests the involvement of
hydroxylradicals the yield of which is enhanced in N20 saturated
aqueous media189. It's an interestingpaper but the method it
describes will never become a practical decontaminationmethod
on the large scale, since it is too demandingin termsof electricity
and only small volumes of liquid could be sensibly treatedby
means of it.
Unmodifiedzeolite surfacesshow no affinityfor anions, and in
fact repel thembecause of the formalnegative frameworkelectric
change. However,if thezeolite is initiallyexchangedwithparticular
cations which form practically insoluble complexes with those
anions it is desired to remove froma particularaqueous medium,
the resultingcomplexes will precipitatewithin the zeolite matrix
and tend to remain there.When chromáteanions were sorbed by
clinoptilolite,the degree of uptake was foundto be proportionalto
the solubilityproduct( Ksp) of the particularchromátesalt, and to
the amountof the exchangeable cation presentin the zeolite. In the
series of cations studied, Pb2+ was found most effective in
removingchromáte190.The removal of iodide anions, particularly
131I~ with a half-lifeof just 8 days (hence highly radioactive)
formedin 2.77% yield among theproductsfromthe fissionof 235U,
using zeolites has been investigated.It was foundthatclinoptilolite
is a morepromisingmaterialforthispurposethannatrolite,and that
the adsorptionwas highestin its Ag + , Pb2+ and TI + -exchanged
forms191.Faghihian et al. based in Tehran, have reported the
following studies, which may be taken as representativeof the
field of environmentaldecontaminationusing zeolites as a whole:
adsorptionof arsenate anions by Fe, Pb and Ag-exchanged clin-
optilolites192,uptake of ceriumcations by zeolite A preparedfrom
natural tuffs193,thorium cation uptake again using zeolite A
prepared from natural clinoptilolitetuffs194, removal of cyanide
anions fromindustrialliquid wastes using cation-exchangedclin-
optilolite(the cobalt formof the zeolite showed the highestuptake
of 1.95 meq of cyanide per gram of zeolite, whereas the uptake of
naturalformsis 0.070 meq/g) 195,synthesisof Na-P-c zeolite from
perliteand its use in cyanide adsorption196, removal of radioactive
iodide anions using a surfactant-modified zeolite (SMZ) 197,adsorp-
tion of molybdateanions by natroliteand clinoptilolite-richtuffs198.
Catalyticconvertersare implementedinto the exhaust-systems of
vehicles to reduce theirtoxic gas emissions, especially NOx. Cu-
ZSM-5 catalystsare used fordirectNO decompositionof which it
is found that Cu-SZM-11 and Cu-SZM-12 have about twice the
efficiencyof Cu-ZSM-5 forthispurpose199.In a followingpaper,it
J.Rhodes
276 Christopher
is concluded thata higheractivityis conferredby the presence of
only straightmicroporouschannels which eithercontain a greater
numberof catalyticcentresor theyare more accessible in thehigher
zeolite, whereas ZSM-5 contains both straightand sinusoidal
channels200.
A catalyticapplication for the eliminationof a pollutantis the
oxidationof 1,2-dichlorobenzeneover various protoniezeolites (H-
FAU, H-BEA, H-MFI, H-MCM-22 and ITQ2) and their corre-
spondingPt-loadedequivalents.The process is foundto be effective
at 350-400°C, and while the presence of platinumenhances the
activityof the catalyst,it largelyincreases the yield of by-products
such as 1,2,4-trichlorobenzene201. It is also reportedthatammonium
cations can be removed as a contaminantfromaqueous solutions
using a Romanian natural volcanic tuffeven in the presence of
Zn2+ and Cd2+ which appear not to decrease the ammonium
adsorptioncapacity of the material202.
Broadly in relationto the runningof the Metsamornuclearpower
plant(NPP) in Armenia,is one paper reportingon the adsorptionof
tritiatedwater by Armenian natural zeolites203, and another
reportingon the modificationof the sorptivepropertiesof natural
Armenian zeolites by exposure to radiation from an electron
accelerator204.A bactericidal activity has been reported for a
silver-exchangedzeolite and which is found to be of the same
orderas silvernitratesolution.It is proposed thatthe contactof the
bacterial cell with the zeolite causes the transferof Ag+ cations
into the cell and thatreactiveoxygen species which are involved in
the mode of bactericidalaction of the Ag-zeolite are thengenerated
in situ205. Hemostatic dressings for wounds in battle situations
which are based on zeolites (e.g. QuikClot) have been reported.
However, the effectivenessof these new dressings on wounds
actually sustained in combat is still questionable according to
studies and anecdotal reportsfromOperation Iraqi Freedom. It is
concluded thatmore researchis needed to draw definiteconclusions
about the effectivenessof these materialsin a combat setting206.
Doubtless there will be no lack of such futureopportunitiesas
humansclamourforwhat remainsof the earth'sbestowal of energy
sources, metals and water.
As this review aims to show, zeolites are remarkablematerials
with a great varietyof practical uses. I call attentionto the the
Cuban designation1 "La Roca Magica" which accolades them
superlatively.I recall that synonyms in Spanish for "Magica"
(the adjective form of "Magico") include "Estupenda" and
"Maravillosa", and both would seem to suit.

andapplications
Acknowledgements
I thank Karen Blakeman for her invaluable I.T. skills, the
InternationalScience and Technology Centre (I.S.T.C) in Moscow
and the Galvanisers Association for their support of projects
concerningradioactivewaste managementand heavy metal cation
decontaminationusing zeolites.
References
1. Mumpton, F.A.(1999)Proc.Natl.Acad.Sci. USA,96,3463.
2. Barrer, R.M. (1978)Zeolitesand ClayMinerals as Sorbents and Molecular
Sieves
, Academic Press, London.
3. http://en.wikipedia.org/wiki/Zeoliteandlinkstherein.
4. Cronstedt, A.F.(1756)Kongl.Vetenskaps Akad.Handl.Stockholm , 17,120.
5. Rhodes, C.J.(2007)Annu. Rep.Prog.Chem., Sect.C: Phys.Chem., 103,287.
6. Meisel,S.L.,McCullogh, J.P.,Lechthaler,C.H. andWeisz,P.B.(1976)Chem.
Technol., 6, 86.
7. Rhodes, C.J."Energy Balance":http://ergobalance.blogspot.com
8. Armbruster, T. (2001)In: Galarnau, Di Renzo,F.,Faujula,F. andVédrine, J.
(eds.),Studies insurface science andcatalysis135zeolites andmesoporous solids
at thedawnofthe21stcentury. A. Elsevier,
Amsterdam, p. 13.
9. http://www.bbc.co.uk/radio4/science/thematerialworld_20060119.shtml
10. Sherman, J.D.(1999)Proc.Natl.Acad.Sci. USA, 96,3471.
11. Rhodes, C.J.(2005)Prog.React.Kinet.Mech ., 30, 145.
12. Ricci,A.,Chretien, M.N.andSciano,J.C.(2004)Chem. Mater., 16,2669.
13. Doussineau, T., Smaihi, M., Balme,S. andJanot, J.-M.(2006)Chem.Phys.
Chem., 7, 583.
14. Alvaro,M., Carbonell, E., Garcia,H., Lamaza,C. andPillai,M.N. (2004)
Photochem. Photobiol. Sci., 3, 189.
15. Chretien, M.N.,Shen,B., Garcia, H., English, A.M.andScaiano,J.C.(2004)
Photochem. Photobiol ., 80,434.
16. Alvaro, M.,Chretien, M.N.,Ferrer, B., Fornes, V, Garcia,H. andScaiano, J.C.
(2001)Chem.Commun ., 2106.
17. Thomas, J.M.andRaja,R. (2005)Ann.Rev.Mater. Res.,35,315.
18. Corma, A. andGarcia, H. (2004)Eur.J.Chem., 1143.
19. Barrer, R.M.(1968)Mol.SievesPap.Conf,39.
20. Sheldon, R.A.,Arends, I.W.C.E. andLempers, H.E.B.(1998)Catalysis Today,41,
387.
21. Arends, I.W.C.E.andSheldon, R.A.(2001)Appl.Catai.A,212,175.
22. Corma, A.,Fornes, V, Garcia, H., Miranda, M.A.,Primo, J.andSabater, M.J.
(1994)J.Am.Chem. Soc., 116,2276.
23. Amat, A.M.,Arques, A.,Bossmann, S.H.,Braun, A.M.,Gob,S. andMiranda,
M.A.(2003)Angew. Chem. Int.Ed.,42, 1653.
24. Sanjuan, A.,Alvaro, M.,Aguirre, G.,Garcia, H. andScaiano, J.C.(1998)J.Am.
Chem. Soc.,120,7351.
25. Sanjuan, A.,Aguirre, G.,Alvaro, M. andGarcia, H. (1998)Appl.Catai.B, 15,
247.
26. Sanjuan, A.,Guillermo, G.,Alvaro, M.andGarcia, H. (2000)Water Res.,34,320.
J.Rhodes
278 Christopher
27. Sanjuan, A.,Aguirre, G.,Alvaro, M.,Garcia, H., Scaiano, J.C.,Chretien, M.N.
andFocsaneanu, K.-S.(2002)Photochem. Photobiol. Sci.,1,955.
28. Sanjuan, A.,Aguirre, G.,Alvaro, M.,Garcia,H. andScaiano, J.C.(2000)Appl.
Catai.B, 25,257.
29. Cano,M.L.,Cozens, F.L.,Garcia, H.,Marti,V andScaiano, J.C.(1996)J.Phys.
Chem., 100,18152.
30. Duxbury, D.F.(1993)Chem. Rev.,93,381.
31. Jobie,H., Schmidt, W., Krause,C.B. and Karger, J. (2006) Microporous,
Mesoporous Mater.,90,299.
32. Pampel, A.,Engelke, F.,Galvosas,P.,Krause, C., Stallmach, F.,Michel,D. and
Karger, J.(2006)Microporous, Mesoporous Mater., 90,271.
33. Jentys, A., Mukti, R.R.,Tanaka,H. and Lercher, J.A. (2006)Microporous,
Mesoporous Mater.,90,284.
34. Jobic,H.,Ramanan, H., Auerbach, S.M.,Tsapatsis, M. andFouquet, P. (2006)
Microporous, Mesoporous Mater.,90,307.
35. Zhao,G.,Gross, B.,Dilger, H. andRoduner, E. (2002)Phys.Chem. Chem. Phys.,
4, 974.
36. Williams, J.H.(1993)Acc.Chem. Res.,26,593.
37. Beerdsen, E. andSmit, B. (2006)J.Phys.Chem. B, 110,14529.
38. Gunadi,A. and Brandani, S. (2006) Microporous, Mesoporous Mater.,90,
278.
39. Jobic,H. andTheodorou, D.N.(2006)J.Phys.Chem. B, 110,1964.
40. Garcia-Perez,E.,Dubbeldam, D.,Maesen, T.L.M.andCalero, S. (2006)J.Phys.
Chem. B, 110,23968.
41. Gorring,R.L.(1973)J.Catai,31, 13.
42. Ruthven,D.M.(2006)Microporous, Mesoporous Mater., 96,262.
43. Di Lella,A.,Desbiens, N.,Boutin, A.,Demachy, I.,Ungerer, P.,Bellat,J.-P.and
Fuchs,A. (2006)Phys.Chem.Chem. 8, 5396.
Phys.,
44. Hunger, J.,Beta,I.A.,Bohlig, H.,Ling,C., Jobic, H. andHunger, B. (2006)J.
Phys.Chem. B, 110,342.
45. Ramachandran, C.E., Chempath, S., Broadbelt,L.J.and Snurr, R.Q. (2006)
Microporous, Mesoporous Mater., 90,293.
46. Maurin, G.,Plant, D.F.,Henn,F. andBell,R.G.(2006)J.Phys.Chem. B, 110,
18447.
47. Plant,D.F.,Maurin, G. andBell,R.G.(2006)J.Phys.Chem., 110,15926.
48. Kumar, A.VA.,Jobic,H. and Bhatia,S.K. (2006)J. Phys.Chem.B, 110,
16666.
49. Omi,H.,Ueda,T.,Kato,N.,Miyakubo, K. andEguchi, T. (2006)Phys.Chem.
Chem. Phys., 8, 3857.
50. Andersen, L.K. andFrei,H. (2006)J.Phys.Chem. B, 110,22601.
51. Crawford, M.F.andDagg,I.R.(1953)Phys.Rev.,91, 1569.
52. Forster,
H. andSchmidt, M. (1978)J Mol.Struct ., 47,339.
53. Bose,H.,Forster, H. andFrede, W.(1987)Chem. Phys.Lett., 138,401.
54. Beck,K.,Pfeifer, H. andStaudte, B. (1993)J.Chem. Soc.,FaradayTrans., 89,
3995.
55. Kustov,L.M.andKazansky, VB. (1991)J.Chem. Soc.,Faraday Trans.,87,2675.
56. Khodakov, A.Yu.,Kustov, L.M.,Kazansky, VB. andWilliams, C. (1991)J Chem.
Soc.,FaradayTrans., 88,3251.
57. Knozinger, H. andHuber, S. (1998)J.Chem. Soc.,FaradayTrans., 94,2047.
58. Garrone,E. andOteroArean, C. (2005)Chem. Soc.Rev.,34,846.
59. Savitz,S., Myers, A.L. andGorte, R.J.(1999)J.Phys.Chem.B, 103,3687.
60. OteroArean, C.,Rodriguez Delgado, M.,Turnes Palomino, G.,TomasRubio, M.,
Tsyganenko, N.M.,Tsyganenko, A.A. and Garrone, E. (2005)Microporous,
Mesoporous Mater ., 80,247.
61. OteroArean, C., Manoilova, O.V,Bonelli, B., Rodriguez Delgado,M.,Turnez
Palomino, G. andGarrone, E. (2003)Chem. Phys.Lett., 370,631.
62. en.wikipedia.org/wiki/Adsorption
63. Turnes Palomino, C., LlopCarayol, M.R.andOteroArean, C. (2006)J.Mater.
Chem., 16,2884.
64. Bhatia,S.K.andMyers, A.L.(2006)Langmuir , 22, 1688.
65. Nachtigall, P., Garrone, E., TurnesPalomino, G., Rodriguez Delgado,M.,
Nachtigallova,D. andOteroArean, C. (2006)Phys.Chem.Chem.Phys.,110,
2286.
66. James, B.D.,Baum,G.N.,Lomax, F.D.Jr.,Thomas, C.E.andKuhn, I.E Jr.
(1996)
Comparison ofonboard hydrogen storageforfuelcellvehicles, Task4.2Final
Report under subcontract 47-2-R31 148,prepared forFordMotorCompany and
U.S.Department ofEnergy, Arlington, Virginia, May1996,p. 2-2.
67. vandenBerg,A.W.C. , Bromley, S.T. andJansen, J.C.(2005)Microporous,
Mesoporous Mater., 78,63.
68. Zecchina, A.,Bordiga, S., Vitillo,J.G.,Ricchiardi, G.,Lamberti, C., Spoto,G.,
Bjorgen,M. andPetter Lillerud,K. (2005)J.Am.Chem. Soc.,127,6361.
69. Weitkamp, J.,Schmid, D., Fritz,M.,Cubero, F. andErnst, S. (1994)Wasserst.
Energietraeger, Kolloq.1994Sondersforschungbereichs 270 Univ.Stuttgart, p.
287-300.
70. vandenBerg,A.W.C.,Bromley, S.T.,Wojdel,J.C.andJansen, J.C.(2006)
Microporous, Mesoporous Mater., 87,235.
71. Vitello,J.G.,Ricchiardi, G., Spoto,G. andZecchina, A. (2005)Phys.Chem.
Chem. Phys., 7, 3954.
72. Materials Studio 2.2,Discover module, Accelerys Incorporated, SanDiego,CA,
2002.
73. Regli,L.,Zecchina, A.,Vitillo, J.G.,Cocina, D.,Spoto, G.,Lamberti,C.,Lillerud,
K.P.,Olsbye, U. andBordiga, S. (2005)Phys.Chem.Chem. Phys., 1, 3197.
74. Li,Y. andYang,R.T.(2006)J.Phys.Chem. B, 110,17175.
75. vandenBerg,A.W.C.,Zwijnenburg, M.A.,Bromley, S.T.,Flikkema, E., Bell,
R.G.,Jansen, J.C.andSchoonman, J.(2006)J.Mater. Chem., 16,3285.
76. Yang,Z.-X.,Xia,Y.-D.,Sun,X.-Z.andMokaya, R. (2006)J Phys.Chem. B,110,
18424.
77. Lin,X.,Jia,J.,Zhao,X.,Thomas, K.M.,Blake,A.J.,Walker, G.S.,Champness,
N.R.,Hubberstey, P.andSchroder, M. (2006)Angew. Chem. Int.Ed.,45,7358.
78. Fossey,J.,Lefort, D. andSorba,J.(1995)Freeradicalsin organic chemistry,
Wiley,Chichester.
79. Sheldon, R.A.(1980)J.Mol.Catai,7, 107.
80. Sheldon, R.A.,Chen,J.D.,Dakka,J.andNeelmen, E. (1994)Stud.SurfSci.
Catai,82,515.
81. Sheldon, R.A.,Chen,J.D.,Dakka,J.andNeelmen, E. (1994)Stud.Surf.Sci.
Catai, 83, 107.
82. Sheldon, R.A.andDakka,J.(1994)Catalysis Today, 19,215.
83. Parton,R.,De Vos,D. andJacobs, P.A.(1992)In:Zeolite Microporous Solids:
Synthesis, Structure and Reactivity, Derouanne, E.G. et al. (ed.), Kluwer,
Dordecht, TheNetherlands, p. 555.
84. Taramasso, M., Perego, G. andNotāri, B. US Patent 4410501(1983);Notāri,
B.(1987) Stud.Surf. Sei. Catai, 37, 413.
280 Christopher
J.Rhodes
85. Arends, I.W.C.E., Sheldon,R.A.,Wallau, M. andSchuchardt, U. (1997)Angew.
Chem., Int.Ed., 36, 1144.
86. Bellusi,G. andRigutto, M.S.(1994)Stud.Surf. Sei.Catai.,85,177.
87. Ratnasamy, P.andKumar, R. (1995)Stud.Surf. Sci.Catai.,97,367.
88. De Vos,D.E.,Buskens, P.L.,Vanoppen, D.L.,Knops-Gerrits, P.P.andJacobs,
P.A.(1996)Compr. Supramol. Chem., 7, 647.
89. Pauling, L. (1960)Thenature ofthechemical bond , Cornell UniversityPress,
NewYork.
Ithaca,
90. Szostak, R. (1989)Molecular sieves, vanNostrand, NewYork.
91. Sheldon, R.A.,Arends, I.W.C.E.andLempers, H.E.B.(1998)Catalysis Today,
41,387.
92. Thomas, J.M.(1997)J.Mol.Catai.A: Chemical , 115,371.
93. Bassat,J.M.andNiccolai, G.P.(1996)In:Applied homogeneous catalysiswith
organometallic compounds , Cornilis, B. and Hermann, W.A.(eds.),VCH,
Weinheim, Vol.2, p. 624.
94. Maschmeyer, T., Rey,F., Sankar, G. andThomas, J.M.(1995)Nature , 378,
159.
95. Burch,R.,Cruise, N.,Gleeson, D. andTsang, S.C.(1996)J.Chem. Soc.,Chem.
Commun ., 951.
96. SubbaRao,Y.V,De Vos,D., Bein,T. andJacobs, P.A.(1997)J.Chem. Soc.,
Chem.Commun ., 355.
97. Shul'pin, G.B.,Guerreiro, M.C. andSchuchardt, U. (1996)Tetrahedron , 52,
13051.
98. Evans,D.F.(1953)J.Chem. Soc., 345.
99. Taubomura, H. andMulliken, R.S.(1960)J.Am.Chem. Soc.,82,5966.
100.Wei,K.S. andAdelman, A.H.(1969)Tetrahedron Lett.,3297.
101.Chien, J.C.W. (1965)J.Phys.Chem., 4317.
102.Onodera, K., Furusawa, G.,Kojima, M.,Tsuchiya, M.,Aihara, S., Akaba,R.,
Sakuragi, H. andTokumaru, K. (1985)Tetrahedron , 41,2215.
103.Kulevsky, N.,Sneeringer, P.V,Grina, L.D.andStenberg, V.l.(1970)Photochem.
Photobiol., 12,395.
104.Frei,H.,Blatter, F. andSun,H. (1996)CHEMTECH, 26,24.
105.Blatter,F.,Sun,H.,Vasenkov, S. andFrei,H. (1998)Catalysis Today, 41,297.
106.Blatter,F.andFrei,H. (1993)J.Am.Chem. Soc.,115,7501.
107.Blatter,F. andFrei,H. (1994)J.Am.Chem. Soc.,116,1812.
108.Blatter,F.,Moreau, F. andFrei,H. (1994)J.Phys.Chem., 98, 13403.
109.Blatter,F.,Sun,H. andFrei,H. (1995)Catal.Lett., 35, 1.
110.Sheldon, R.A. andKochi,J.K.(1981)Metal-catalysed oxidation oforganic
compounds, chap.11,Academic Press, NewYork.
111.Sun,H.,Blatter, F.andFrei,H. (1994)J.Am.Chem. Soc.,116,7951.
112.Sun,H.,Blatter, F.andFrei,H. (1996)J.Am.Chem. Soc.,118,6873.
113.Blatter,F.,Sun,H. andFrei,H. (1996)Chem. Eur.J.,2, 385.
114.Sun,H.,Blatter, F.andFrei,H. (1997)Catal.Lett., 44,247.
115.Xu,J.,Mojet, B.L.,vanOmmen, J.G.andLefferts, L. (2003)Phys.Chem. Chem.
Phys.,5, 4407.
116.Vasenkov, S. andFrei,H. (1998)J.Phys.Chem. B, 102,8177.
117.Frei,H. (2006)Science, 313,309.
118.Pidko, E.A.andvanSanten, R.A.(2006)J.Phys.Chem. B, 110,2963.
119.Pidko,E.A.andvanSanten, R.A.(2006)Chem. Phys.Chem., 7, 1657.
120.Niwa,M.,Kato,S.,Hattori, T.andMurakami, Y. (1984)J.Chem. Soc.,Faraday
Trans.2, 80,3135.

andapplications
121.Impens,N.R.E.N.,vanderVoort, P. andVansant, E.F. (1999)Microporous,
122.Song,W.,Marcus, D.M.,Abubakar, S.M.,Jani, E. andHaw,J.E(2003)J Am.
Chem. Soc., 125,13964.
123.Abubakar,S.M.,Lee,J.C.,Marcus, D.M.,Ehresmann, J.O.andHaw,J.F.(2006)
J.Phys.Chem. B, 110,14598.
124.Groen,J.C.,Moulijn, J.A.andPerez-Ramirez, J.(2006)J.Mater.Chem., 16,
2121.
125.Chen,B.H.andHuang, Y.N.(2006)J.Am.Chem. Soc.,128,6437.
126.Sombatchaisak, S., Praserthdam,P.,Chaisuk, C. andPanpranot, J.(2004)Ind.
Eng. Chem. Res., 43, 4066.
127.Likhacheva, A.Y.,Veniaminov, S.A.,Paushtis, E.A. andBelitsky, J.A.(2006)
Eur.J.Mineral., 18,345.
128.Parnham, E.R.,Drylie, E.A.,Wheatley, P.S.,Slawin, A.M.Z.andMorris, R.E.
(2006)Angew. Chem. Int.Ed.,45,4962.
129.Beale,A.M.,vanderEerden, A.M.J.,Jacques, S.D.M.,Simon, D.M.,Leynaud,
O.,O'Brien, M.G.,Meneau, E, Nikitenko, S.,Bras,W.andWeckhuysen, B.M.
(2006)J.Am.Chem. Soc.,128,12386.
130.O'Brien,M.G.,Beale,A.M.,Catlow, C.R.A.andWeckhuysen, B.M.(2006)J.
Am.Chem. Soc.,128,11744.
131.vanSanten, R.A.(2006)Nature, 444,46.
132.Rebek,J.(2005)Angewandte Chem. Int.Ed.,44(14),2068.
133.Caeiro,
G.,Magnoux, P.,Lopes,J.M.,Ribero, E.R.,Menezes, S.,Costa,A.F.and
H.S. (2996)Appl.Catai.A,314,160.
Cerqueira,
134.Pera-Titus,
M.,Mallada, R.,Llorens, J.,Cunill,F. andSantamaria, J.(2006)J.
Membrane Sci.,278,401.
135.Pera-Titus,
M.,Llorens, J.andCunill,
J.,Tejero, F.(2006)Catalysis Today, 118,
73.
136.Gopalakrishnan,S.,Yamagichi, T.andNakao,S.I.(2006)./Membrane Sci.,274,
102.
137.Maloncy,M.L.,vandenBerg,A.W.C,andJansen, J.C.(2005)Microporous,
138.Weyd, M.,Richter, H.,Voigt, I.,Hamel,C. andSeidel-Morgenstern, A. (2006)
Desalination,199,308.
139.Haag,S., Hanebuth, M., Mabande, G.T.P.,Avhale, A., Schwieger, W. and
R. (2006)Microporous,
Dittmeyer, Mesoporous Mater.,96, 168.
140.Chen,Z.-W,Holmberg, B.,Li,W.-Z., Wang, X.,Deng,W.-Q., Munoz, R. and
Yan,Y.-S.(2006)Chem. Mater.,18,5669.
141.Nik,O.G.,Moheb,A. andMahannnnadi, T. (2006) Chem.Eng. Tech.,29,
1340.
142.Ahn,H.,Lee,H.,Lee,S.B.andLee,Y. (2006)Desalination, 193,244.
143.Lue,S.J.andLiaw,T.H.(2006)Desalination, 193,137.
144.Ahn,H. andLee,Y. (2006)J.Membrane Sci.,279,459.
145.Haw,J.F.(2002)Phys.Chem.Chem. Phys., 4, 5431.
146.Nicholas,
J.B., Haw,J.F., Beck,L.W.,Krawietz, T.R.andFerguson, D.B.(1995)
J.Am.Chem. Soc.,117,12350.
147.Roduner,E. andDilger, H. (2001)J.Am.Chem. Soc.,123,7717.
148.Beck,L.W.,Xu,T.,Nicholas, J.B.andHaw,J.F.(1995)J.Am.Chem. Soc.,117,
11594.
149.Kramer,G.J.andvanSanten, R.A.(1995)J.Am.Chem. Soc.,117,1766.
150.Hunter,K.C.andEast,A.L.L.(2002)J.Phys.Chem. A,106,1346.
282 Christopher
J.Rhodes
151.Zygmunt, S.A.,Curtiss, L.A.,Zapol,P.andIton,L.E. (2000)J.Phys.Chem. B,
104,1944.
152.Blaszkowski, S.R.,Nascimento, M.A.C,andvanSanton, R.A.(1996)J Phys.
Chem., 100,3463.
153.Chang, C.D. (1983)Catal.Rev. , 25,1.
154.Stocker,M. (1999)Microporous, Mesoporous Mater., 29,3.
155.Keil,F.J.(1999)Microporous, Mesoporous Mater.,29,49.
156.Clarke,J.K.A.,Darcy, R.,Hegarty,B.F.E.,O Donoghue, B.F.,Amir-Ebrahimi, V
andRooney, J.J.(1986)J.Chem. Soc.,Chem.Commun .,425.
157.Rhodes, C.J.andHinds,C.S. (1995)In:Radicalson Surfaces , Lund,A. and
Rhodes, C.J.(eds.),Kluwer, Dordrecht, p. 119.
158.Rooney, R.J.personal communication.
159.Mole,T.,Whiteside, J.A.andSeddon, D. (1983)J.Catal.,82,261.
160.Mole,T.,Bott,G. andSeddon, D. (1983)J.Catal.,82,435.
161.Dahl,I.M.andKolboe,S. (1994)J Catal.,149,458.
162.Dahl,I.M.andKolboe,S. (1996)J Catal.,161,304.
163.Haw,J.F.,Nicholas, J.B.,Song,W.G.,Deng,F., Wang,Z.K., Xu, T. and
Heneghan, C.S. (2000)J.Am.Chem. Soc.,122,4763.
164.Goguen, P.W.,Xu,T.,Barich, D.H.,Skloss,T.W.,Song,W.G.,Wang,Z.K.,
Nicholas, J.B.andHaw,J.F.(1998)J.Am.Chem. Soc.,120,2650.
165.Song,W.G.,Haw,J.F., Nicholas,J.B.andHeneghan, C.S. (2000)J.Am.Chem.
Soc.,122,10726.
166.Song,W.,Fu,H. andHaw,J.F.(2001)J.Am.Chem. Soc.,123,4749.
167.Song,W.,Marcus, D.M.,Fu,H.,Ehresmann, J.O.andHaw,J.F.(2002)J.Am.
Chem. Soc.,124,3844.
168.Haw,J.F., Song,W.,Marcus, D.M.andNicholas, J.B.(2003)Acc.Chem. Res.,
36,317.
169.Lesthaeghe, D., VanSpeybroeck, V, Martin,G.B.andWaroquier, M. (2006)
Angew. Chem. Int.Ed.,45, 1714.
170.Marcus, D.M.,Hayman, M.J.,Blau,Y.M.,Guenther, D.R.,Ehresmann, J.O.,
Kletnieks,P.W.andHaw,J.F.(2006)Angew. Chem. Int.Ed.,45,1933.
171.Walspurger, S.,Sun,Y.Y.,Sido,A.S.S.andSommer, J.(2006)J.Phys.Chem. B,
110,18368.
172.Ivanova,I.I.,Nesterenko, N.S.andFernandez, C. (2006)Catalysis Today,113,
115.
173.Bowman, R.S.(2003)Microporous, Mesoporous Mater., 61,43.
174.Li,Z., Burt,T. andBowman, R.S.(2000)Environ. Sci.Technol ., 34,3756.
175.Li,Z.H.,Anghel, I. andBowman, R.S. (1998)J.Disp.Sci. Technol., 19,843.
176.Haggarty, G.M.andBowman, R.S. (1994)Environ. Sci.Technol. , 28,3756.
177.Sullivan, E.J.,Bowman, R.S. and Legiac,I.A. (2003) J. Env.Qual.,32,
2387.
178.Karapangioti, H.K.,Sabatini, D.A. andBowman, R.S. (2005)Water Res.,39,
699.
179.Li,Z.H.andBowman, R.S.(2001)Water Res.,35,322.
180.Ranck, J.M., Bowman, R.S.,Weeber, J.L.,Katz,L.E.andSullivan, E.J.(2005)J.
Env.Eng.,131,432.
181.Dyer,A.,Chimedtsogzol, A.,Campbell, L. andWilliams, C. (2006)Micropor-
ous,Mesoporous Mater.,95, 172.
182.Faghihian, H., Marageh, M.G.andKazemian, H. (1999)App.Rad.Isot., 50,
655.
183.Marinin,D.V andBrown, G.N.(2000)Waste Management, 20,545.

andapplications
184.Choi,J.H., Kim,S.D.,Kwon, Y.J.andWha,W.J. (2006)Microporous, Mesopor-
ousMater., 96, 157.
185.Athanasiadis, K.,Helmreich, B. andWilderer, P.A.(2004)Actahydrochemica et
hydrobiologica, 32,419.
186.Beyazit,N.,Ibrahim, P.andNuri,O. (2003)Int.J.Env.Poll., 19,160.
187.Erdem, Karapinar, N. andDonat,R. (2004)J ColloidInterface Sci.,280,309.
188.Athanasiadis, K. andHelmreich, B. (2005)Water Res.,39, 1527.
189.Pospisil,
M.,Cuba,V, Mucka, V andDrtinová, B. (2006)Radiai.Phys.Chem.,
75,403.
190.Faghihian, H. andBowman, R.S. (2005)Water Res.,39, 1099.
191.Faghihian, H.,Maragheh, M.G.andMalekpour, A. (2002)J.Radioanal. Nuci
Chem.,254,545.
192.Faghihian, H. (2005)Iran.J.Sci.Tech. A,29,189.
193.Faghihian, H.,Amini, M.K.andNezamzadeh, A.R.(2005)J.Radioanal. Nuci.
Chem.,264,577.
194.Faghihian, H., Maragheh, M.G.,Amini, M.K. andNezamzadeh, A.R.(2004)
Adsorption Sci. Tech.,
22, 707.
195.Faghihian, H. (2004)Int.J.Env.Pollut., 22,732.
196.Faghihian, H. andKamali, M. (2003)Int.J.Env.Pollut., 19,732.
197.Faghihian, H.,Malekpour, A. andMaragheh, M.G.(2003) Adsorption Sci.Tech.,
21,373.
198.Faghihian,H.,Malekpour, A. andMaragheh, M.G.(2002)Int.J.Env.Pollut .,18,
181.
199.Kustova, M.Y.,Kustov, A.,Christiansen, S.E.,Leth,K.T.,Rasmussen, S.B.and
Christansen,C.H.(2006)Catal.Comm., 7, 705.
200. Kustova,M.Y.,Rasmussen, S.B.,Kustov, A.L. andChristansen, C.H. (2006)
App.Catal.B, 67,60.
201. Taralunga,M.,Mijoin, J.andMagnoux, P.(2006)Catal.Comm., 1, 115.
202. Maranon, E.,Ulmaņu, M.,Fernandez, Y.,Anger, I. andCastrillon,
L. (2006)J.
Hazard.Mater., 137,1402.
203. Keheyan, Y., Khachatryan, S., Christidis,G., Moraetis,D., Gevorkyan, R.,
H.,Yeritsyan,
Sarkisyan, H.,Nikoghosyan, S.,Hovhannisyan, A.,Sahakyan, A.,
Kekelidze,N. andAkhalbedashvili, L. (2005)J.Radioanal. Nuci.Chem., 264,
671.
204. Gevorkyan, R.G.,Sargsyan, H.H.,Karamyan, G.G.,Keheyan, Y.M.,Yeritsyan,
H.N.,Hovhannesyan, A.S. and Sahakyan, A.A. (2002) Chemieder Erde
Geochemistry,62,237.
205. Matsumura, Y.,Yoshikata, K.,Kunisaki, S.-I.andTsuchido, T.(2003)App.Env.
Microbiol
., 69,4278.
206. Neuffer,
M.C.,McDivitt, J.,Rose,D., King,K., Cloonan, C.C. andVayer, J.S.
(2004)Military Medicine, 169,716.
284 Christopher
J.Rhodes

10 2307@43424246

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

10 2307@43424246

Diunggah oleh

Hak Cipta:

Format Tersedia

Properties and applications of zeolites

Author(s): CHRISTOPHER J. RHODES

You may need to log in to JSTOR to access the linked references.

Properties and applications of zeolites

(ideally locally to minimisetransportationcosts) and used with the

www.scienceprogress.co.uk Properties ofzeolites227

with alkaline/saline lake or ground-waters(Figure 5). Beds of

marine basins, and are found in some ocean sediments1'2'5.

www.scienceprogress.co.uk Properties ofzeolites229

Ag+ - zeolite+ Na+I - ^Na+ - zeolite+ Agi (precipated).

In this example, a silver exchanged zeolite can be used for

www.scienceprogress.co.uk Properties ofzeolites231

degradation of malodorous sulfur-containingmolecules14. 2-(6-

www.scienceprogress.co.uk Properties ofzeolites233

www.scienceprogress.co.uk Properties ofzeolites235

3. Diffusion of molecules in zeolites

following section, there are a range and a diversityof experi-

www.scienceprogress.co.uk Properties ofzeolites237

www.scienceprogress.co.uk Properties ofzeolites241

4. Adsorbed gases in zeolites

www.scienceprogress.co.uk Properties ofzeolites243

Mn+ + H20 -M(OH)(n_1)+ + H+,

www.scienceprogress.co.uk Properties ofzeolites245

5. Zeolites as hydrogen storage materials

CH4 + H20 -»CO + 3H2,

www.scienceprogress.co.uk Properties ofzeolites251

www.scienceprogress.co.uk Properties ofzeolites253

7. Photooxidation in zeolite cages

www.scienceprogress.co.uk Properties ofzeolites255

www.scienceprogress.co.uk Properties ofzeolites257

Fig. 11. Dehydration

www.scienceprogress.co.uk Properties ofzeolites263

9. The acid strength of zeolites and its implication

www.scienceprogress.co.uk Properties ofzeolites265

www.scienceprogress.co.uk Properties ofzeolites267

10. Environmental pollution control using zeolites

may simultaneouslysorb mixturesof toxic inorganic anions and

stratedthat arsenic fromsoil-washingleachate is sorbed by SMZ

www.scienceprogress.co.uk Properties ofzeolites277

www.scienceprogress.co.uk Properties ofzeolites281

www.scienceprogress.co.uk Properties ofzeolites283

Anda mungkin juga menyukai