- Email: [email protected]
Hydrothermal chemistry of zeolites
Intercalation Chemistry Eds. M. S. Whittingham and A. J. Jacobson Academic Press, 1982; ISBN 0-12-747380-7; pp. xvi + 595; price US ~87.50 This monograph is a cooperative effort in the Material Science and Technology Series under the general editorship of Drs. Nowick and Libowitz. It is in some respects a sequel to 'Non-stoichiometric Compounds', also published by the Academic Press, in 1964, but in many areas the subject matter and emphasis are very different. The intensive study of reactions involving guest molecules or ions and host crystals has developed in a remarkable way over recent decades and this book which ably develops the theme of intercalation chemistry, will find a place on many bookshelves. There are 18 chapters which, in serial order, deal with the following topics: a general introduction to intercalation (Whittingham); graphite intercalation chemistry (Bartlett and Mcquillan); sheet silicate intercalates (Thomas); diffusion and shape-selective catalysis in zeolites (Derouane); intercalation in acid salts of tetravalent metals (Alberti and Constantino); intercalation in ~-alumina (Tofield); organic and organometallic intercalation compounds of transition metal dichalcogenides (Jacobson); intercalation in metal phosphorus trichalcogenides (Johnson); structural aspects of monovalent cation intercalates of dichalcogenides (Hibma); solvated intercalation compounds of layered chalcogenides and oxide bronzes (Schollhorn); intercalation chemistry of metal chalco-
genides (Halbert); hydrogen containing materials (Buschow and van Mal); intercalation in biological systems (Wilson and Jones); reactions in crystallographic sheet structures (Anderson); oxide insertion compounds (Dickens and Pye); lithium intercalation compounds of vanadium chalcogenides (Murphy); and physical properties of intercalation compounds of transition metal chalcogenides (Thompson and Di Salvo). It will be seen from the above headings that the main thrust is in the direction of the layered chalcogenides to which seven of the 18 chapters are devoted. Nevertheless, graphite, layer silicates, zeolites, ~-alumina and certain other oxides, acid salts and metals all receive attention as host crystals. Biological intercalates introduce a novel theme, and, while not closely connected with intercalation, the chapter on crystallographic shear structures makes interesting reading. Chemical and structural aspects have been emphasized more than actual and potential applications. The book is well produced and relatively few printing errors have been observed by this Reviewer. Authors, editors and publishers have produced an up-to-date survey of an important area of chemical endeavour.
R. M. Barfer
Hydrothermal Chemistry of Zeolites R. M. Barrer, FRS Academic Press, London 1982, ISBN 0-12-079360-1,360 pp, price £31.00/US ~57.50 The Zeolite scientific community again profits from the continuing contributions of Professor Barrer to zeolite chemistry. The monograph covers hydrothermal synthesis with emphasis on the formation and transformation of zeolites. It includes a comprehensive compilation and collation of the life-long work of Professor Barrer and associates in hydrothermal silicate chemistry and zeolite synthesis, highlighted by his latest insights and suggestions for future directions. The volume begins with a concise review of the occurrence, structure and classification, and properties of zeolites (42 pp). The next chapter on Introduction to the Hydrothermal Chemistry of Silicates (57 pp) develops basic principles and convincingly illustrates the immense scope and power of hydrothermal reactions of silicates and oxides. Subjects covered include phase equilibria, stabilization of porous crystals by guest molecules, solubility and alkalinity. Examples of hydrothermal reactions broadly span the structural classes from clays to dense tectosilicates and oxides such as corundum (e-AI203).
278 ZEOLITES, 1983, Vol 3, July
The next several chapters (145 pp) cover zeolite synthesis. The concept of metastability in zeolite formation is introduced as typified by reactant effects, heterogeneous reaction mixtures, kinetic rather than thermodynamic control of nucleation, and Ostwald's rule of successive transformations. The stages of pre-nucleation, nucleation, cyrstallization and transformations are systematically developed. The discussion of reactant and synthesis variables focuses on the need for information about precursor states and species. It includes sections on aluminate and silicate solution species and techniques for their determination including recent 29Si NMR methods. Barrer then reviews nucleation theory, the kinetics of zeolite nucleation and crystal growth, and the effect of reaction variables. The structure-directing roles of cations, organic bases, and cation templates, are developed in detail. An assessment of the present best mechanistic picture of zeolite formation supports the view that nucleation occurs from dissolved precursor species, that crystal growth involves condensa-
Book
tion-polymerization of dissolved species on the growing surface, and that crystal growth primarily involves deposition of dissolved species on the crystals. The last chapter (5) on zeolite synthesis covers the mapping of crystallization fields, comparison of different source materials for zeolite production, and transformation reactions involving zeolites. It includes a systematic review of synthesis in various cations and mixed cation-aluminosilicate systems, at higher and lower synthesis temperatures, and synthesis from layer silicates, glasses,and other non-gel reactant systems. The next chapter (6, 54 pp) on isomorphous substitution is, in this reviewer's opinion, one of the highlights of the monograph and a much needed contribution in hydrothermal silicate and zeolite synthesis literature. The scope of isomorphous replacements covered includes cation exchange, replacement of Si in anionic frameworks by a wide variety of other elements, replacement of framework oxygen, and replacement of intracrystalline salts or molecular water by other species. The literature on isomorphous substitution of AI for Si is reviewed and classified. A statistical thermodynamic formulation consistent with known AI, Si substitution in tectosilicates is presented in detail with a suggestion that the theory could be extended to other tetrahedral framework elements. Reports of other such framework substitutions, including Ga, Ge, Be, B, Mg, Fe, Cr and P, are thoroughly reviewed and critically evaluated. Barrer concludes that the evidence for substitution in Zeolite frameworks is conclusive for Ga and Ge, incomplete and ambiguous for B Ill, Fe III, Cr III, Zr IV or Ti TM, and requires further substantiation in the case of pV. The ceramic literature is briefly reviewed to exemplify the substitution of N for O in tetrahedral frameworks in the known silicon and aluminum nitrides and oxynitrides, and the suggestion made that nitride-con-
Reviews
taining zeolite frameworks might be synthesized 'ammonothermally' using ammonia or hydrazine as solvent in place of water. As a bonus to the reader the section in this chapter on Lowenstein's avoidance rule and A], Si ordering contains an up-to-date compendium of the recent large volume of literature on 29Si NMR studies on zeolite frameworks. The final chapter on salt-bearing tectosilicates (43 pp) in which salt instead of water fills the lattice rounds out the discussion of porous tectosilicates. Synthesis can be achieved in the absence (dry) or presence of water (hydrothermal). Sub-headings include the structure of zeolite-salt solid solutions, salt up-take from aqueous solution, and salt storage, release and decomposition. There is no doubt that Barrer's latest monograph will become an invaluable reference for scientists active in the field of hydrothermal, silicate, and zeolite synthesis. It brings together in one volume relevant information scattered throughout various segments of the literature. Barrer's approach of positioning zeolite synthesis in the broader context of hydrothermal and inorganic chemistry adds a richness and perspective to the treatment of the subject, and expands the reader's horizons beyond the confines of zeolite synthesis. The reader is reminded that the volume by intent covers only a selected portions of the extensive literature on silicate and zeolite synthesis. References to many useful contributions have been omitted. For a more comprehensive review, the reader should supplement the volume with other reference texts and review articles presently in the literature, such as D. W. Breck's Zeolite monograph.* Some minor errors and incompleteness in references were noted during the course of the review. The book is pleasantly readable, of high publication quality, and attractively packaged in a bright lavender cover.
Edith M. Flanigen Union Carbide Corporation Tarrytown, New York, USA
* D. W. Breck, 'Zeolite Molecular Sieves,Structure, Chemistry and Uses', Wiley-lntersciance,New York, 1974, Ch. 4, pp. 245-347
LITERATURE A N N O U N C E M E N T Size and Shape Characterization of Fibrous Zeolites by Electron Microscopy Kim B. Shedd, Robert L. Virta and Ann G. Wylie RI 8674: Bureau of Mines Report of Investigations/1982 This publication may be of interest to readers of ZEOLITES who are concerned with fibrous minerals and health. The objective of the research reported in RI 8674 was to compare the size and shape of fibrous zeolites to amphibole cleavage fragments and asbestos.
Free copies of this publication are available from: Kim B. Shedd, United States Department of the Interior, Bureau of Mines, 4900 Lasalle Road, Avondale, Maryland 20782, USA.
ZEOLITES, 1983, Vol 3, July 279
genides (Halbert); hydrogen containing materials (Buschow and van Mal); intercalation in biological systems (Wilson and Jones); reactions in crystallographic sheet structures (Anderson); oxide insertion compounds (Dickens and Pye); lithium intercalation compounds of vanadium chalcogenides (Murphy); and physical properties of intercalation compounds of transition metal chalcogenides (Thompson and Di Salvo). It will be seen from the above headings that the main thrust is in the direction of the layered chalcogenides to which seven of the 18 chapters are devoted. Nevertheless, graphite, layer silicates, zeolites, ~-alumina and certain other oxides, acid salts and metals all receive attention as host crystals. Biological intercalates introduce a novel theme, and, while not closely connected with intercalation, the chapter on crystallographic shear structures makes interesting reading. Chemical and structural aspects have been emphasized more than actual and potential applications. The book is well produced and relatively few printing errors have been observed by this Reviewer. Authors, editors and publishers have produced an up-to-date survey of an important area of chemical endeavour.
R. M. Barfer
Hydrothermal Chemistry of Zeolites R. M. Barrer, FRS Academic Press, London 1982, ISBN 0-12-079360-1,360 pp, price £31.00/US ~57.50 The Zeolite scientific community again profits from the continuing contributions of Professor Barrer to zeolite chemistry. The monograph covers hydrothermal synthesis with emphasis on the formation and transformation of zeolites. It includes a comprehensive compilation and collation of the life-long work of Professor Barrer and associates in hydrothermal silicate chemistry and zeolite synthesis, highlighted by his latest insights and suggestions for future directions. The volume begins with a concise review of the occurrence, structure and classification, and properties of zeolites (42 pp). The next chapter on Introduction to the Hydrothermal Chemistry of Silicates (57 pp) develops basic principles and convincingly illustrates the immense scope and power of hydrothermal reactions of silicates and oxides. Subjects covered include phase equilibria, stabilization of porous crystals by guest molecules, solubility and alkalinity. Examples of hydrothermal reactions broadly span the structural classes from clays to dense tectosilicates and oxides such as corundum (e-AI203).
278 ZEOLITES, 1983, Vol 3, July
The next several chapters (145 pp) cover zeolite synthesis. The concept of metastability in zeolite formation is introduced as typified by reactant effects, heterogeneous reaction mixtures, kinetic rather than thermodynamic control of nucleation, and Ostwald's rule of successive transformations. The stages of pre-nucleation, nucleation, cyrstallization and transformations are systematically developed. The discussion of reactant and synthesis variables focuses on the need for information about precursor states and species. It includes sections on aluminate and silicate solution species and techniques for their determination including recent 29Si NMR methods. Barrer then reviews nucleation theory, the kinetics of zeolite nucleation and crystal growth, and the effect of reaction variables. The structure-directing roles of cations, organic bases, and cation templates, are developed in detail. An assessment of the present best mechanistic picture of zeolite formation supports the view that nucleation occurs from dissolved precursor species, that crystal growth involves condensa-
Book
tion-polymerization of dissolved species on the growing surface, and that crystal growth primarily involves deposition of dissolved species on the crystals. The last chapter (5) on zeolite synthesis covers the mapping of crystallization fields, comparison of different source materials for zeolite production, and transformation reactions involving zeolites. It includes a systematic review of synthesis in various cations and mixed cation-aluminosilicate systems, at higher and lower synthesis temperatures, and synthesis from layer silicates, glasses,and other non-gel reactant systems. The next chapter (6, 54 pp) on isomorphous substitution is, in this reviewer's opinion, one of the highlights of the monograph and a much needed contribution in hydrothermal silicate and zeolite synthesis literature. The scope of isomorphous replacements covered includes cation exchange, replacement of Si in anionic frameworks by a wide variety of other elements, replacement of framework oxygen, and replacement of intracrystalline salts or molecular water by other species. The literature on isomorphous substitution of AI for Si is reviewed and classified. A statistical thermodynamic formulation consistent with known AI, Si substitution in tectosilicates is presented in detail with a suggestion that the theory could be extended to other tetrahedral framework elements. Reports of other such framework substitutions, including Ga, Ge, Be, B, Mg, Fe, Cr and P, are thoroughly reviewed and critically evaluated. Barrer concludes that the evidence for substitution in Zeolite frameworks is conclusive for Ga and Ge, incomplete and ambiguous for B Ill, Fe III, Cr III, Zr IV or Ti TM, and requires further substantiation in the case of pV. The ceramic literature is briefly reviewed to exemplify the substitution of N for O in tetrahedral frameworks in the known silicon and aluminum nitrides and oxynitrides, and the suggestion made that nitride-con-
Reviews
taining zeolite frameworks might be synthesized 'ammonothermally' using ammonia or hydrazine as solvent in place of water. As a bonus to the reader the section in this chapter on Lowenstein's avoidance rule and A], Si ordering contains an up-to-date compendium of the recent large volume of literature on 29Si NMR studies on zeolite frameworks. The final chapter on salt-bearing tectosilicates (43 pp) in which salt instead of water fills the lattice rounds out the discussion of porous tectosilicates. Synthesis can be achieved in the absence (dry) or presence of water (hydrothermal). Sub-headings include the structure of zeolite-salt solid solutions, salt up-take from aqueous solution, and salt storage, release and decomposition. There is no doubt that Barrer's latest monograph will become an invaluable reference for scientists active in the field of hydrothermal, silicate, and zeolite synthesis. It brings together in one volume relevant information scattered throughout various segments of the literature. Barrer's approach of positioning zeolite synthesis in the broader context of hydrothermal and inorganic chemistry adds a richness and perspective to the treatment of the subject, and expands the reader's horizons beyond the confines of zeolite synthesis. The reader is reminded that the volume by intent covers only a selected portions of the extensive literature on silicate and zeolite synthesis. References to many useful contributions have been omitted. For a more comprehensive review, the reader should supplement the volume with other reference texts and review articles presently in the literature, such as D. W. Breck's Zeolite monograph.* Some minor errors and incompleteness in references were noted during the course of the review. The book is pleasantly readable, of high publication quality, and attractively packaged in a bright lavender cover.
Edith M. Flanigen Union Carbide Corporation Tarrytown, New York, USA
* D. W. Breck, 'Zeolite Molecular Sieves,Structure, Chemistry and Uses', Wiley-lntersciance,New York, 1974, Ch. 4, pp. 245-347
LITERATURE A N N O U N C E M E N T Size and Shape Characterization of Fibrous Zeolites by Electron Microscopy Kim B. Shedd, Robert L. Virta and Ann G. Wylie RI 8674: Bureau of Mines Report of Investigations/1982 This publication may be of interest to readers of ZEOLITES who are concerned with fibrous minerals and health. The objective of the research reported in RI 8674 was to compare the size and shape of fibrous zeolites to amphibole cleavage fragments and asbestos.
Free copies of this publication are available from: Kim B. Shedd, United States Department of the Interior, Bureau of Mines, 4900 Lasalle Road, Avondale, Maryland 20782, USA.
ZEOLITES, 1983, Vol 3, July 279