HYDROTHERMAL SYNTHESIS AND CRYSTALLIZATION OF ZEOLITES Typical zeolite synthesis NaAl(OH)4(aq) + Na2SiO3(aq) + NaOH(aq), 25oC, condensation-polymerization, Na(H2O)n+ template  Naa(AlO2)b(SiO2)c.NaOH.H2O(gel)  25-175oC, hydrothermal crystallization of amorphous gel Nax(AlO2)x(SiO2)y.zH2O(crystals)

HYDROTHERMAL SYNTHESIS AND CRYSTALLIZATION OF ZEOLITES Nax(AlO2)x(SiO2)y.zH2O(crystals) Extraframework charge-balancing cations, templates, ion-exchangeable Framework Al(III)O4 and Si(IV)O4 tetrahedral primary building-blocks (AlO2)- and SiO2 stoichiometry for building blocks as bridging O Occluded water, removed by 25-500oC vacuum thermal dehydration Organic cationic templates, quaternary alkylammonium, structure-directing, space-filling, charge-balancing, discovery of new structures

ZEOLITE BUILDING UNITS SHORTHAND NOTATION Mq+ Cation binding site in six ring resembles crown ether-cation complex Corner sharing SiO4/AlO4 tetrahedra Six ring shorthand notation

BUILDING-BLOCK APPROACH TO ZEOLITE SYNTHESIS, STRUCTURES AND PROPERTIES Primary tetrahedral units, AlO2-, SiO2, PO2+ and so forth, combined to give open-framework and framework charge, balanced by extraframework cations Existence of primary and secondary units in a synthesis mixture including: 4R, 6R, 8R, D4R, D6R, 5-1, cubooctahedron

ZEOLITE POST MODIFICATION FOR CONTROLLING PROPERTIES OF ZEOLITES Tailoring channel, cage, window dimensions, adsorbents, gas separation, purification Tuning Brnsted acidity, hydrocarbon cracking Ion exchange capacity, Lewis acid-base character, water softening, detergents Size-shape selective catalysis, separations, sensing -reactant, product, transition state selectivity

ZEOLITE POST MODIFICATION FOR CONTROLLING PROPERTIES OF ZEOLITES Host-guest inclusion, atoms, ions, molecules, radicals, organometallics, coordination compounds, clusters, polymers (conducting, insulating), nanoreaction chambers Advanced zeolite devices, electronic, optical, magnetic applications Entry to nanoscale materials, size tunable properties, QSEs

SHAPE SELECTIVE CATALYSIS - REACTANT, PRODUCT, TRANSITION STATE SELECTIVITY

ALKYLATION OF TOLUENE BY METHANOL - SHAPE SELECTIVE CATALYTIC PRODUCTION OF p-XYLENE Used for manufacture of terephthalic acid for production of polyester fibers Snug fit can diffuse through channels

Shape slective dehydration of normal and iso-butanols to butenes over calcium ion exchanged zeolite A and zeolite Y

DIAMOND LATTICE OF 1.3 nm SPHERICAL SUPERCAGES IN ZEOLITE Y

SIMPLIFIED NOTATION FOR ZEOLITE ION EXCHANGE, BRNSTED ACID SITE FORMATION AND DEALUMINATION TO HIGH SILICA ZEOLITES

The changing face of zeolite science and technology - pore and channel dimensions way beyond 1 nm - periodic table of compositions

LAYER-BY-LAYER GROWTH OF ZEOLITE THIN FILMS FOR PERMSELECTIVE MEMBRANES

ORGANICS ORGANIZING INORGANICS ABIOGENIC

ARCHITECTURAL CONTROL - TEMPLATE DIRECTED TRANSFORMATION OF BUILDING BLOCKS TO OPEN FRAMEWORK SOLIDS Ge4S104- adamantanoid building block Mq+ links building blocks via S binding and structure directed by Me4N+ template

LEARNING FROM NATURE - TEMPLATING INORGANICS WITH SINGLE MOLECULES AND SUPRAMOLECULAR ASSEMBLIES