Insights into the Chemistry of Organic Structure-Directing Agents in the Synthesis of Zeolitic Materials

255 Pages·2018·13.93 MB·English

by  Luis Gómez-Hortigüela

Structure and Bonding 175
Series Editor: D.M.P. Mingos
Luis Gómez-Hortigüela Editor
Insights into the
Chemistry of Organic
Structure-Directing
Agents in the Synthesis
of Zeolitic Materials
175
Structure and Bonding
SeriesEditor:
D.M.P.Mingos,Oxford,UnitedKingdom
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L.H.Gade,Heidelberg,Germany
Y.Lu,Urbana,IL,USA
F.Neese,M€ulheimanderRuhr,Germany
J.Pe´rez-Pariente,Madrid,Spain
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Luis Go´mez-Hortiguela
Editor
Insights into the Chemistry of
Organic Structure-Directing
Agents in the Synthesis of
Zeolitic Materials
With contributions by
(cid:1) ´ (cid:1) (cid:1)
B. Bernardo-Maestro M.A. Camblor P.A. Cox
L. Go´mez-Hortig€uela (cid:1) L.B. McCusker (cid:1) M. Moliner (cid:1)
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
C. Paris F. Rey J. Simancas S. Smeets A. Turrina
(cid:1)
A.E. Watts P.A. Wright
Editor
LuisGo´mez-Hortig€uela
InstitutodeCata´lisisyPetroleoqu´ımica-CSIC
Madrid,Spain
ISSN0081-5993 ISSN1616-8550 (electronic)
StructureandBonding
ISBN978-3-319-74288-5 ISBN978-3-319-74289-2 (eBook)
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Preface
Sincetheirfirstuse,theadditionoforganicspecies(usuallyorganiccations)tothe
synthesisgelsofzeolitematerialshastriggeredthemostimportantrevolutioninthe
preparationanddiscoveryofnewzeoliticmaterialswithunprecedentedproperties.
Theseorganicspeciesdrivethecrystallizationpathwaytowardaparticularzeolite
frameworktypewithspecificchemicalproperties,andhencetheyarereferredtoas
organicstructure-directingagents.Duringthecrystallizationprocess,theseorganic
agents organize the inorganic units into a particular geometry from which viable
nuclei of the host-guest system will be produced, which will promote the crystal-
lizationofacertainzeoliticmaterial.Theuseoforganicstructure-directingagents
has enabled the discovery of a large number of new zeolite topologies, with very
different pore shapes and sizes; in addition, they have made accessible particular
chemical compositions of zeolite networks. Both of these factors have greatly
amplifiedthenumberofapplicationsofthisimportantclassofmaterialsindifferent
sectorsofthechemicalindustry.
Traditionally, the main properties whereby researchers designed new organic
structure-directingagentsfocusedontheirsize,shape,andhydrophobicity(chapter
“IntroductiontotheZeoliteStructure-Directing Phenomenon byOrganicSpecies:
General Aspects”). However, and due to the complexity of the crystallization
process of zeolite materials, a deep knowledge of the chemical role played by
these organic species was notavailable. Asa consequence, research onthe use of
organic structure-directing agents was mainly based on a trial-and-error basis,
carrying out systematic explorations of the structure-directing ability of different
organicspeciesandsynthesizingnewmaterials,butbasingtheresearcheffortsonly
onempiricalevidenceandchemicalintuition.Nevertheless,oneofthemajoraims
inthisresearchfieldistherationaldesignoforganicstructure-directingagentsfor
thesynthesisofatargetedzeolitematerial.This,whichwasnotpossiblejustafew
years ago, is starting to become accessible thanks to the great advancement of
mainlytwophysico-chemicaltechniquesthathavegreatlyenhancedourknowledge
oftheorganicstructure-directingphenomenon:(1)diffractiontechniques(chapter
“Location of Organic Structure-Directing Agents in Zeolites Using Diffraction
v
vi Preface
Techniques”), which now allow to find the location of the organic species within
zeoliteframeworks,enablingtheestablishmentofstructuralrelationshipsbetween
zeolitetopologiesandthegeometricalpropertiesoftheorganicstructure-directing
agents that drive their crystallization, and (2) molecular modeling techniques
(chapter “Molecular Modelling of Structure Direction Phenomena”), which have
allowed to understand, from a molecular level, the structure-directing mode of
action of these organic species. In addition, and based in part on the knowledge
gainedthroughthesetechniques,inrecentyearsnewchemicalconceptsareemerg-
inginstructure-directionofzeoliteframeworksbyorganicspecies.Inthiscontext,
thespectrumoforganiccompounds,whichwasoriginallyalmostexclusivelybased
onquaternaryammoniumcations(based onnitrogen),has been notablyamplified
bytheuseofalternativeorganiccationsbasedonphosphoniumorsulfoniumions
(chapter “Beyond Nitrogen OSDAs”), or by organometallic compounds (chapter
“Metal Complexes as Structure-Directing Agents for Zeolites and Related Micro
porous Materials”), providing new structure-directing agents with novel chemical
properties that can be transferred into zeolite materials. Not only the use of new
typesoforganiccompoundsbutalsotheappropriateuseofintermolecularinterac-
tions that trigger a remarkable supramolecular chemistry during the structure-
direction phenomenonhasprovidedwith new zeolitic materials (chapter “Role of
SupramolecularChemistryDuringTemplatingPhenomenoninZeoliteSynthesis”).
The geometrical correspondence between organic structure-directing agents and
zeoliteframeworkshasadditionallyenabledastrategytotackleoneofthegreatest
challenges in zeolite (and materials) science, the search for enantiopure chiral
solids able to perform enantioselective operations (chapter “Chiral Organic Struc
ture-Directing Agents”). All these aspects that will be covered in the different
chapters of this book have notably enhanced our knowledge on the organic struc-
ture-directing phenomenon during the crystallization of zeolites, and have led to
new complex materials with novel and sometimes unprecedented properties that
havegreatlyexpandedtherangeofapplicationsofzeolitesindifferentfields.
Madrid,Spain LuisGo´mez-Hortig€uela
Contents
IntroductiontotheZeoliteStructure-DirectingPhenomenon
byOrganicSpecies:GeneralAspects. . . . . . . . . . . . . . . . . . . . . . . . . . . 1
LuisGo´mez-Hortig€uelaandMiguelA´.Camblor
LocationofOrganicStructure-DirectingAgentsinZeolitesUsing
DiffractionTechniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
StefSmeetsandLynneB.McCusker
MolecularModellingofStructureDirectionPhenomena. . . . . . . . . . . . 75
AlessandroTurrinaandPaulA.Cox
BeyondNitrogenOSDAs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
FernandoReyandJorgeSimancas
RoleofSupramolecularChemistryDuringTemplatingPhenomenon
inZeoliteSynthesis.. . . . .. . . . .. . . . .. . . .. . . . .. . . . .. . . . .. . . . .. 139
CeciliaParisandManuelMoliner
MetalComplexesasStructure-DirectingAgentsforZeolites
andRelatedMicroporousMaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
AbigailE.Watts,AlessandroTurrina,andPaulA.Wright
ChiralOrganicStructure-DirectingAgents. . . . . . . . . . . . . . . . . . . . . . 201
LuisGo´mez-Hortig€uelaandBeatrizBernardo-Maestro
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
vii
StructBond(2018)175:1–42
DOI:10.1007/430_2017_8
#SpringerInternationalPublishingAG2017
Publishedonline:10October2017
Introduction to the Zeolite Structure-
Directing Phenomenon by Organic Species:
General Aspects
LuisGo´mez-Hortigu€elaandMiguelA´.Camblor
Abstract During the last years, a tremendous progress has been achieved in the
application of new zeolite materials in many different sectors through different
pioneering innovations in the field of zeolite synthesis. At the very core of the
production of these new zeolite materials lies the use of organic species as
structure-directingagents(SDA),whichhasbeenrecognizedasthemostimportant
factor to determine the zeolite product rendered after the crystallization process.
Theseorganicspeciesorganizetheinorganiczeoliticunitsanddrivethecrystalli-
zationpathwaytowardstheproductionofparticularzeoliteframeworktypes.This
structure-direction phenomenon frequently works in combination with several
otherfactorsrelatedtothechemicalcompositionofthesynthesisgels,mainlyuse
of fluoride, concentration (H O/T ratio), and presence of different heteroatoms,
2
whicharealsorelevantforthecrystallizationofparticularzeolitematerials.Several
properties determine the structure-directing effect of these organic species, espe-
cially their molecular size and shape, hydrophobicity, rigidity vs flexibility, and
hydrothermal stability. The properties of the zeolitic materials synthesized can be
tuned up to a certain point through the use of rationally selected organic species
withparticularphysico-chemicalfeaturesasSDA.Inthisintroductorychapter,we
briefly review the history of the use of organic cations as SDAs, and give the
fundamentsofthedifferentaspectsrelatedtothisstructure-directionphenomenon
and factors affecting it, explaining the main properties of SDAs, providing some
examples of recent uses and trends of organic SDAs, as well as the host–guest
chemistry involved. In addition, we pay particular attention to the use of
L.Go´mez-Hortigüela(*)
InstitutodeCata´lisisyPetroleoqu´ımica(ICP-CSIC),C/MarieCurie2,28049Madrid,Spain
e-mail:[email protected]
M.A´.Camblor(*)
InstitutodeCienciadeMaterialesdeMadrid(ICMM-CSIC),C/SorJuanaIne´sdelaCruz3,
28049Madrid,Spain
e-mail:[email protected]
2 L.Go´mez-HortigüelaandM.A´.Camblor
imidazolium-based organic cations as SDAs because of their current relevance in
thesynthesisofnewzeolitematerials.
Keywords Host–guest (cid:129) Imidazolium (cid:129) Structure-directing agents (cid:129) Templates (cid:129)
Zeolites
Contents
1 Introduction:UseofOrganicCationsintheSynthesisofZeolites......................... 2
2 PropertiesofOrganicStructure-DirectingAgents.......................................... 4
2.1 SizeandShape.......................................................................... 5
2.2 Hydrophobicity/Hydrophilicity........................................................ 10
2.3 HydrothermalStability................................................................. 14
2.4 RigidityvsFlexibility.................................................................. 15
3 FactorsAffectingtheStructure-DirectingPhenomenon.................................... 19
3.1 SynthesisinFluorideMedia........................................................... 20
3.2 EffectofConcentration(AmountofWater).......................................... 20
3.3 HeteroatomSubstitution................................................................ 21
4 Host/GuestInteractionsDuringStructure-Direction........................................ 22
5 Imidazolium-BasedCationsasStructure-DirectingAgents................................ 26
5.1 NewZeolitesDiscoveredUsingImidazoliumCations............................... 26
5.2 NewCompositionsAttainedwithImidazoliumCations.............................. 32
5.3 AchievingHomochirality.............................................................. 33
6 Conclusions................................................................................... 34
References........................................................................................ 34
1 Introduction: Use of Organic Cations in the Synthesis
of Zeolites
Zeolites are an important class of inorganic microporous crystalline materials
whose oxide-based network is composed of corner-sharing TO atoms, where T
4
refers to a tetrahedral atom, most commonly Si and Al. Since their discovery,
zeolites havefoundwidespreadapplicationsinmanydifferentareas,especiallyin
catalysis,adsorption/separation,andion-exchangeprocesses[1].Apartfromthese
traditional uses of zeolites that have met a tremendous economic impact on
differentsectorsofthechemicalindustry,remarkablyonthepetrochemicalsector,
newusesofzeoliticmaterialsareemerginginthelastyearsindifferentapplications
such as in luminescence, electricity, magnetism, medicine, and microelectronics
[2]. Such a wide range of applications in very different processes is directly
associated with the particular characteristics of these materials: (1) Their unique
microporous structure, with porous systems of channels and/or cavities of mole-
cular dimensions which allow them to behave as molecular sieves or as shape-
selective catalysts, and (2) their versatile range of compositions of the oxide
networks that can build up the different frameworks, most commonly Si and Al,
butalsoextendedtoalargevarietyofothertetrahedralatomssuchasB,Ge,P,and