Modern inorganic synthetic chemistry

MODERN INORGANIC SYNTHETIC CHEMISTRY Edited by RUREN XU, WENQIN PANG, QISHENG HUO AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands Linacre House, Jordan Hill, Oxford OX2 8DP, UK Copyright Ó 2011 Elsevier B.V All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone: (+44) 1865 843830, fax: (+44) 1865 853333, E-mail: permissions@elsevier.com You may also complete your request online via the Elsevier homepage (http://elsevier.com), by selecting “Support & Contact” then “Copyright and Permission” and then “Obtaining Permissions.” Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-444-53599-3 For information on all Elsevier Publications visit our Web site at elsevierdirect.com 11 12 13 10 Printed and bound in the Netherland Foreword I have great pleasure in writing the Foreword for this fine book on Modern Inorganic Synthetic Chemistry written and edited by Professors Xu, Pang, and Huo The book consisting of 24 chapters covers a variety of aspects of present-day synthetic inorganic chemistry Inorganic chemistry itself has undergone great change in the last two decades or so wherein it has absorbed various aspects of materials science as well as chemical biology The uniqueness of this present book is that it covers most of the recent developments in inorganic synthetic chemistry It is refreshing to see that the book has chapters on hightemperature as well as low-temperature synthesis, hydrothermal and solvothermal synthesis, high-pressure synthesis, and photochemical synthesis The book covers preparation of a large variety of inorganic materials under different conditions which include the use of microwaves The book has a chapter on coordination compounds and coordination polymers as well as cluster compounds Organometallic chemistry has not been ignored and is suitably covered along with inorganic polymers Special mention must be made of the fine coverage on porous materials, hosteguest materials, ceramics, and amorphous materials as well as nanomaterials and membranes In addition, there is also a chapter on crystal growth Inorganic synthesis related to biomimetic synthesis constitutes a chapter The book concludes with a discussion of synthetic design All in all, I consider this book to be a very valuable reference book for students, teachers, and practitioners of modern inorganic chemistry in the broadest sense, and materials chemistry in particular I have great pleasure in recommending this book to the chemical community I wish the book great success C.N.R Rao National Research Professor and Linus Pauling Research Professor, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India xv Preface In 1998, Stephen J Lippard of MIT made an insightful remark about the future development of chemistry over the next 25-years: “What is most important about chemistry is that we make new things We don’t just study the natural world; we make new molecules, new catalysts, and new compounds of uncommon reactivity Part of our subject allows us to be creatively artistic through the synthesis of beautiful and symmetric molecules Our ability to rearrange atoms in new ways allows us a tremendous opportunity for creation that other sciences don’t have.” (Chemistry’s Golden Age in C&EN News, Jan 12, 1998) Ryoji Noyori, a Nobel laureate in 2001, further emphasized in his feature article “Synthesizing our future” (Nature Chemistry 2009, April) that “Chemistry has a central role in science, and synthesis has a central role in chemistry To begin, the central place of synthesis in chemistry is emphasized and extended to chemistry place in science.” Indeed, synthetic chemistry is undoubtedly the core of chemistry, and it provides the most powerful tool for chemists to shape the world and thus the future of our society Chemists have not only discovered and synthesized a large number of substances that exist in nature but also created many new compounds, phases, and states of matter According to the latest information from the CAS, over 50 million organic and inorganic compounds have been registered Many of these have become indispensable in our daily life and in industrial productions, providing a continuous driving force for the further advances of science and technology With the advent of the 21st century and the rapid development of new technologies, there is greater demand for synthetic chemists to create increasingly more compounds and materials with novel structures and functions In the mean-time, greater attentions have been made to the basic studies in areas relevant to green synthetic routes, biomimetic syntheses, inorganic syntheses under extreme conditions, molecular engineering, and rational tectonics, gearing toward syntheses of new matters in more efficient, focused, and economical manners These are important for the sustainable and rapid advancement in both science and technology in the new century Examples of the role played by synthetic chemistry in driving industrial revolution and development of new sciences are numerous In the early 20th century, Fritz Haber used nitrogen from the air and hydrogen from water gas as raw materials to produce ammonia, the main ingredient of fertilizers, which greatly helped to accelerate the growth of food production to feed the world’s rapidly increasing population Since the mid20th century, the successful synthesis of a large number of new drugs has significantly curbed infectious diseases and improved the health conditions of mankind The creation of three major synthetic materials, namely the synthetic fiber, plastic, and synthetic rubber, has formed an important basis for modern industrial and agricultural developments around the world These are all powerful evidences of the contribution of chemistry, especially synthetic chemistry, in improving the overall well-being of mankind Advances in synthetic chemistry have led to continuous creation and development of new compounds and materials and provided the basis for studying their structures, functions, and reactions This has become a major driving force for the progress of chemistry and related disciplines In fact, what lies beneath the most significant technological advancements of the 20th century, such as information technology, nuclear technology, laser, nanotechnology, and aerospace technology, is the chemical synthesis of new and advanced materials Without the efforts of generations of synthetic chemists and their achievements in synthesizing new matter and materials, these advancements would not have been possible Thus, the related scientific areas such as semiconductor, superconductor, cluster, and nanoscience could not have come into being As a crucial part of synthetic chemistry, modern inorganic synthesis has become a key branch of inorganic chemistry Its scope encompasses both traditional synthesis and the new science of material preparation and assembly With the synthesis and preparation of a large number of new compounds, phases, and materials each year, inorganic synthesis has quickly become a key area in the recent development of inorganic chemistry and related disciplines The vibrant growth of emerging sciences and technologies in the 21st century has placed increased demands on the development of new inorganic materials In addition, these new materials have fueled the developments of new industries and scientific disciplines With the development of synthetic chemistry, special synthesis techniques, structural chemistry, and theoretical chemistry, as well as their interplays with related disciplines such as life science, materials science, and xvii xviii PREFACE computer science, the science of inorganic synthesis has expanded from conventional synthesis to synthesis under extreme conditions, rationally designed synthesis, and biomimetic synthesis focused on inorganic materials with specifically designed structures and functions In view of its broad scope of research and its close relationship with other disciplines, we believe that it is necessary to present to our readers the science of inorganic synthesis chemistry in the context of modern synthetic and preparative chemistry in a systematic manner Currently, there are a number of books and monographs focused on this discipline, but generally speaking, they tend to be manuals or specialized works This prompts us to have devoted considerable effort to the writing of this book by experts in relevant fields to provide both a broad coverage and an in-depth discussion of the synthesis and preparative inorganic chemistry We name this book Modern Inorganic Synthetic Chemistry The 24 chapters of the book are grouped into four parts The first part consists of Chapters 2-8 The discussion centers on inorganic synthesis and preparation routes under specific conditions, dealing with inorganic synthesis and preparative chemistry under specific conditions such as high temperature, low temperature and cryogenic condition, hydrothermal and solvothermal condition, high and superhigh pressure, photochemical, microwave irradiation, and plasma conditions The second part consists of Chapters 9-14, focused on the synthesis, preparation, and assembly of six important categories of compounds, with wide coverage of distinct synthetic chemistry systems, namely coordination compounds, coordination polymers, clusters, organometallic compounds, nonstoichiometric compounds, and inorganic polymers The third part consists of Chapters 15-22 Seven important representative inorganic materials are selected for discussion of their chemistry of preparation and assembly, including porous materials, advanced ceramic, amorphous and nanomaterials, inorganic membrane, and assembly of two types of advanced functional materials The last part, unique to this book, is composed of two chapters that bring the reader to the frontiers of inorganic synthesis and preparative chemistry, with Chapter 23 on biomimetic synthesis and Chapter 24 on rationally designed synthesis With the inclusion of these two chapters, we aim to introduce to the reader the two emerging areas in synthetic chemistry Also worth mentioning is that this book has a collection of more than 3000 references, the majority of which are from the last decade It is hoped that these references provide a comprehensive list of the relevant literature on the recent development and new directions in the field of modern synthetic inorganic chemistry To provide a comprehensive and an in-depth coverage of this rapidly evolving field, particularly about the frontiers of related research, we invited a group of scientists, who work at the forefront of their respective research areas, to write chapters in their areas of expertise In this book, we have tried to present to the reader both mature achievements and recent developments in the field when making the high-level design of the book We recognize that we might not necessarily have the best balance between the two even with our best efforts We also recognize that there could be some overlaps among different chapters written by different authors We tried our best to minimize this issue, but overlaps at some level might still exist in the book We sincerely hope that the reader can understand and would be willing to provide us feedbacks and comments This book not only highlights the core science, frontiers, and possible directions of different branches of inorganic synthesis chemistry but also touches on structural chemistry and functional features of synthesized materials Therefore, it can serve as a textbook as well as a key reference book for university senior undergraduate students and graduate students in chemistry, chemical engineering, and materials science It can also be used as a specialized reference book for researchers and technicians who work in synthetic chemistry and related fields We, the editors, would like to take this opportunity to thank all the authors whose hard work made possible the completion of this book in a timely fashion We also want to thank Professor Raj Pal Sharma of Panjab University for his careful work in fixing grammar throughout this book Special thanks go to colleagues and students in the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry at Jilin University, who did almost all the preparation work for this book, including paperwork, figure design, reference checks, and much more Ruren Xu, Professor State Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin University, Changchun, China Contributors Julia K.C Abbott Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996, USA Jiesheng Chen School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China Xiao-Ming Chen MOE Key Laboratory of Bioinorganic and Synthetic Chemistry School of Chemistry & Chemical Engineering Sun Yat-Sen University Guangzhou 510275, China Shun-Liu Deng Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China Brenda A Dougan Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996, USA Xue Duan State Key Laboratory of Chemical Resource Engineering, Box 98, Beijing University of Chemical Technology, Beijing 100029, P R China David G Evans State Key Laboratory of Chemical Resource Engineering, Box 98, Beijing University of Chemical Technology, Beijing 100029, P R China Shouhua Feng State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Jingkun Guo State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China Guangyan Hong State Key Laboratory of Rare Earth Resources Utilization, 5625 Renmin Street, Changchun 130022, China Zhuang-Qi Hu Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China Xiaobin Huang School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China Qisheng Huo State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Lei Jiang Research Center for Biomimetic Smart Science and Technology, College of Chemistry and Environment, Beijing University of Aeronautics and Astronautics, Beijing 100191, China, Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China Huamin Kou State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China Guanghua Li State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Jiang Li State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China Jerry Y.S Lin Chemical Engineering School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85260, USA Xiaoyang Liu State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Xinsheng Liu BASF Corporation, R&D Center, Middlesex-Essex Turnpike, Iselin, NJ 08830, USA 25 Jian Liu ARC Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia Kesong Liu Research Center for Biomimetic Smart Science and Technology, College of Chemistry and Environment, Beijing University of Aeronautics and Astronautics, Beijing 100191, China Jun Lu State Key Laboratory of Chemical Resource Engineering, Box 98, Beijing University of Chemical Technology, Beijing 100029, P R China Changsheng Lu State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, 22 Hankou Road, Nanjing 210093, China Qingjin Meng State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, 22 Hankou Road, Nanjing 210093, China Wenqin Pang State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Shi Zhang Qiao ARC Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia xix xx CONTRIBUTORS Gao Qing (Max) Lu ARC Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia Shriya K Seshadri Chemical Engineering School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85260, USA Qiang Su School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China Ruren Xu State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Zi-Ling Xue Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996, USA Wenfu Yan State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Yuan-Zhi Tan Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China Guo-Yu Yang State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 West Yangqiao Road, Fuzhou 350002, China Xiaozhen Tang School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China Jihong Yu State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China Ji-Tao Wang Department of Microelectronics, University, Shanghai 200433, China Fudan Jilin Zhang State Key Laboratory of Rare Earth Resources Utilization, 5625 Renmin Street, Changchun 130022, China Su-Yuan Xie Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China Jingping Zhao State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China C H A P T E R Introduction - Frontiers in Modern Inorganic Synthetic Chemistry Ruren Xu Jilin University, China from the abundantly available H2 and N2 using osmium as the catalyst Twenty years later, C Bosch improved the technique by using inexpensive iron instead of expensive osmium as the catalyst, which laid a solid foundation for the human society to maintain a continued increase in food production to keep up with the human population increase; a major challenge that we have been facing since the past century Because of their profound contributions to science as well as to the human society, Haber and Bosch received Nobel prizes in chemistry in 1918 and 1931, respectively Health industry is another area where synthetic chemistry has been playing pivotal roles Outstanding examples since the mid-twentieth century include the successful syntheses of SAS drug, penicillin, a variety of antibiotics and other medicines, which have substantially improved and continue to improve our overall abilities in treating human diseases and fighting against them Our ability in producing the three major classes of synthetic materials, namely synthetic fiber, synthetic plastic, and synthetic rubber, has paved the way for many of the recent industrial and agricultural advances There is no doubt that chemistry, especially synthetic chemistry, has been making considerable contributions to improve the living conditions of the human society From a scientific perspective, a pool of very large number of new materials created by synthetic chemistry has provided plenty of samples for studying the structureefunction (property) relationships of materials as well as their syntheses, facilitating scientists to study the fundamental chemistry of these materials, which has become a driving force in the recent developments of chemistry and related sciences For example, the successful preparation of single crystalline silicon and Synthetic chemistry is at the core of modern chemistry; it provides the most powerful means for chemists to create the material foundation for our envisioned world Its main objective is to create a large variety of compounds, phases, materials, and ordered chemical systems needed by our rapidly advancing society, going considerably beyond just finding and synthesizing naturally existing compounds According to recently published studies, over 50 million compounds, naturally existing or not, have been discovered or synthesized, some of which have become indispensable to our daily life These compounds have provided the basis for many scientific and technological advances in the recent history In turn, these advances have created rapidly increasing needs for new materials with specific structures and functions, posing challenges to, as well as creating opportunities for synthetic chemists Specifically, we see increasing needs in this new century, for novel synthesis strategies and techniques, as well as for the related scientific understanding, gearing toward green synthesis, biomimetic synthesis, inorganic synthesis under extreme conditions, and molecular and tectonic engineering of inorganic materials, in efficient, rationally designed and economic manners We believe that these are among the most essential key elements for the continuing and rapid advancement of science and technology in this new century [1,2] In the past century, advances in synthetic chemistry have often been the key driving force for the industrial revolutions and birth of new science and technologies; examples of this sort have been numerous [2] For instance, F Haber, in the early twentieth century, invented a high-pressure technique to synthesize ammonia, the key ingredient of chemical fertilizers, Modern Inorganic Synthetic Chemistry, DOI: 10.1016/B978-0-444-53599-3.10001-0 Copyright Ó 2011 Elsevier B.V All rights reserved INTRODUCTION - FRONTIERS IN MODERN INORGANIC SYNTHETIC CHEMISTRY numerous semiconductive materials has fueled the emergence of information technology; the production and posttreatment of nuclear fuel of uranium and plutonium, the key to the nuclear technology and safe application, have all been built on chemical technologies with roots in synthetic chemistry Similar can be said about other high technologies such as laser, nanotech, aviation, and space technology Without a doubt, the so-called six great technology inventions in the twentieth century would have never materialized without the foundational work by generations of synthetic chemists in the past The same is true about other technological breakthroughs and growth points in related sciences such as semiconductor, super conduction, cluster, and nanotechnology Modern inorganic synthetic chemistry, an important branch of synthetic chemistry, has evolved considerably from the traditional synthesis and preparation of inorganic compounds, which now includes the synthesis, assembly, and preparation of supramolecular and highlevel ordered structures in its studies In recent years, we have been witnessing that an increasingly large number of new inorganic compounds, phases, and complex materials are being synthesized and assembled, having made inorganic synthetic chemistry a key driver for many new scientific and technological developments and advancements We anticipate that inorganic synthetic chemistry will continue to play equally or more important roles in science as well as in our upcoming life 1.1 DEVELOPMENT OF NEW SYNTHETIC REACTIONS, SYNTHETIC ROUTES, TECHNOLOGIES AND ASSOCIATED BASIC SCIENTIFIC STUDIES 1.1.1 The Basic Inorganic Compounds This basic class includes covalently bonded molecular compounds, coordination compounds, cluster compounds, metal organic compounds, nonstoichiometric compounds and inorganic polymer, among others 1.1.2 Inorganics and Materials with Specific Structures Study of inorganic compounds and phases with specific structures is becoming increasingly important as the need for materials with specific properties and functions continues to rise It is well accepted that the properties and functions of materials are determined by their structures and compositions More specifically, such properties and functions are often determined by the characteristics of high-level molecular structures such as those of molecular aggregates, ordered molecular assemblies, and structures in condensed states instead of single molecular structures Take defects for example, the properties and functions of materials often result from various forms of structural defects in their component compounds or phases in condensed state A key reason that many complex oxides are being used as popular substrates for functional materials is that they can form many types of structural defects in addition to their many adjustable component elements Hence, it has become a major topic at the forefront of inorganic chemistry research to study the preparation of solid-state matters with specific structural defects and the associated principles as well as related detection techniques In addition, the key research topics in today’s inorganic chemistry also include preparation of surfaces and interfaces with specific structures and properties, stacking of layered compounds, preparation of specific polytypes and their intergrowths as well as intercalation structures and low-dimensional structures of inorganic compounds, synthesis and preparation of inorganic compounds with mixed valence complexes and clustered compounds with specific structures, as well as the rapidly emerging and increasingly useful porous compounds with specific channel structures such as microporous crystals, meso- and hierarchical porous materials Also particularly interesting is the preparation of phases that tend to form distinct structures and are able to form large varieties of distinct structures under extreme synthetic conditions like high or ultrahigh pressures While a few synthesis examples with the aforementioned characteristics have been reported in the literature, such studies have generally been done in rather ad hoc manners, often accomplished through utilizing the particularity of specific reactions or specific synthesis techniques rather than based on new understanding of a general class of synthesis problems and new synthesis technologies The latter is clearly more important for the future development of synthetic chemistry 1.1.3 Inorganics and Materials in Special Aggregate States Another important class of materials are the compounds in special aggregate state, such as in nano state, ultrafine particles, clusters, noncrystalline state, glass state, ceramic, single crystal, and other matters with varying crystalline morphologies such as whisker and fiber The rapid emergence of nanoscience and technology strongly suggests that different aggregate states of the same matter could exhibit different properties and have different functions The understanding of this could have substantial implications to the future development of science as well as new functional materials BASIC RESEARCH IN SUPPORT OF GREEN SYNTHESIS 1.1.4 Assembly of High-level Ordered Structures There is an emerging class of functional inorganic materials, commonly characterized as being highly ordered supramolecular systems, formed via selfassembly among molecules or molecular aggregates through molecular recognition The key interaction forces in the formation of such large molecular assemblies are intermolecular non- or weak-bond interactions (van der Waals and hydrogen bond) Examples of such materials include coordination polymers, inorganic polymers, and molecular systems with specific structural features such as nanosystems, capsula, ultrathin membrane (monolayer membrane, multilayer composited membrane), interfaces, two-dimensional layered structures, and three-dimensional biological systems; many of which have been widely used for fabricating high-tech microdevices Self-assembly is increasingly becoming a key and practical technique in the synthesis and preparation of complex functional systems It has even been suggested that the introduction of self-assembly-based synthesis techniques could fundamentally advance the chemical production processes that are being widely used in the current industries [2] 1.1.5 Composition, Assembly, and Hybridization of Inorganic Functional Materials The following areas have received considerable attention in recent years: (1) multi-phase composition of materials including enhanced or reinforced fiber- (or whisker-)based materials, the second-phase particle dispersion materials, two- or multi-phase composite materials, inorganic and organic materials, inorganics and metals, and functional gradient materials as well as nanomaterials; and (2) composite material-related hosteguest chemistry, which represents a highly interesting and a very challenging research area The research focuses include, for example, the assembly of different types of chemical entities in hosts with microporous or mesoporous frameworks such as quantum dot or super lattice-forming semiconductive clusters, nonlinear optical molecules, molecular conductors made of linear conductive polymers and electron transfer chains as well as DeA transfer pairs All these complex composites could be assembled through synthetic routes consisting of ion exchanges, CVDs, “ships in bottle” and microwave dispersion; (3) nanohybridization of inorganics and organics, which represents a rapidly emerging interdisciplinary field It studies the formation of new hybrid materials through combining polymerization and solegel processes These hybrid materials possess those properties which are generally absent in pure inorganics or pure organics, and are increasingly being used in fiber optics, wave propagation, and nonlinear materials It is worth noting that the first survey about this emerging field was published in 1996 by P Judeinstein [3] As outlined above, a key task in today’s inorganic synthetic chemistry is to develop novel synthetic reactions, synthetic routes, and associated techniques aiming to create new functional materials with specifically desired multilevel structures in condensed states As per the past experience, the discovery of a novel and effective synthetic route or technique has typically led to the creation of a large class of new matters and materials For example, the advent of solegel synthetic route has been a key reason for the development and emergence of nano-states and nanocomposite materials, glass states and glass composites, ceramic and ceramic-based composites, fibers and related composites, inorganic membranes and composite membranes, and hybrid materials The core chemistry of this synthetic route is hydrolysis and polymerization of starting reactant molecules (or ions) in aqueous solution, i.e., from molecular / polymeric state / sol / gel / crystalline state (or noncrystalline state) This synthetic process could possibly be regulated differently at each individual reaction step so as to create solid-state compounds or materials with different structures or in different aggregate states While highly promising, we are clearly not there yet due to the complexity as well as our limited understanding of polymerization processes of inorganic molecules in both theoretical and experimental executions Thus, fundamental studies of these issues represent key areas of focus in today’s inorganic synthetic chemistry In summary, the near and intermediate-term objectives for today’s inorganic synthetic chemists are to develop novel and more effective synthetic technologies and to carry out related theoretical studies aiming to gain better understanding of the desired new synthesis capabilities which are both economical and environmentfriendly 1.2 BASIC RESEARCH IN SUPPORT OF GREEN SYNTHESIS The vast majority of known synthetic reactions, especially those used in the preparation of a large variety of rare elements from their ores or raw materials, in the production of fine chemicals as well as in medical and pharmaceutical industries, produce large amounts of by-products, which, along with the used chemicals, solvents, additives, and catalysts, often add major pollutants to our environment and have created considerable environmental issues in the past Thus, it has 576 24 FRONTIER OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY (II) TABLE 24.4 Calculated charge density (CDguest) and occupied volume (Vocc) of several organic amines, and the interaction energy (Einter, kcal/mol) and H-bonding interaction energy (EH-bonds, kcal/mol) of the hosteguest Code Organic aminea ˚ 3)c Vocc (A CDguest Einter n-Butylamine 773.44 0.2 À77.92 39.87 n-Propylamine 665.68 0.25 À82.19 À41.83 Cyclohexanamine 852.16 0.14 À71.14 À41.80 Cyclopentylamine 813.44 0.17 À70.75 À44.69 1,6-Diaminohexane 561.8 0.25 À42.08 À17.81 1,8-Diaminooctane 726.76 0.2 À37.03 À19.09 1,9-Diaminononane 854.72 0.18 À43.42 À27.26 1,10-Diaminodecane 860.04 0.17 À17.07 À8.26 Diethylenetriamine b 501.08 0.29 À43.46 À23.52 10 Diaminobicyclooctane 486.52 0.25 À26.81 À3.51 EH-bonds a Bold: experimental template; Italic: predicted templates Diethylenetriamine is diprotonated Occupied volumes of all templates in one unit cell are considered, and number of template molecules is determined based on the charge balance Reprinted with permission from [61] Copyright 2008 American Chemical Society b c The ratios of framework charge/framework T number and template charge/template non-H number were calculated as the charge densities of host framework and organic template, respectively Materials Studio software was used to calculate the “free volume” of the ZnHPO-CJ1 and the “occupied volume” of guest organic molecules in free status Cerius2 package was used to calculate the nonbonding interactions between the host framework and the guest molecules based on the Burchart 1.01eDreiding 2.21 force field More detailed information about the calculation could be found in Ref [60] The suitable template molecules should first meet the space matching and charge matching with the host framework Furthermore, they should have lower interaction energies with the host framework On the basis of the above criteria, some suitable templates that could potentially direct the formation of the extra-large pore structure of ZnHPO-CJ1 were predicted For example, cyclohexylamine (CHA), cyclopentylamine (CPA), and n-propylamine were predicted as favorable templates Experimentally, utilizing these amines as the templates, (C5H12N)2[Zn3 (C6H14N)2[Zn3(HPO3)4](ZnHPO-CJ2), (HPO3)4] (ZnHPO-CJ3), and (C3H10N)2[Zn3(HPO3)4] (ZnHPO-CJ4) were successfully hydrothermally prepared with target extra-large 24-ring channels analogous to (C4NH12)2[Zn3(HPO3)4] (ZnHPO-CJ1) [61] Their structures were characterized by powder X-ray diffraction analysis as well as single-crystal crystal structure analysis Figure 24.25 shows the frameworks of ZnHPOCJ2 and ZnHPO-CJ3 Each 24-ring channel accommodates multiple protonated cyclohexylamine CH2 ị5 ỵ CHNHỵ cations and cyclopentylamine CH2 ị4 CHNH3 cations, respectively FIGURE 24.25 Crystal structures of (a) ZnHPO-CJ2 and (b) ZnHPO-CJ3 viewed along the [001] direction Reprinted with permission from [61] Copyright 2008 American Chemical Society ATTEMPTS TO THE RATIONAL SYNTHESIS OF INORGANIC POROUS CRYSTALLINE MATERIALS 24.3.1.2.4 CO-TEMPLATING SYNTHESIS OF SILICOALUMINOPHOSPHATES WITH THE SAV AND KFI FRAMEWORK TOPOLOGIES Castro et al [62] investigated a co-templating strategy assisted by molecular modeling for the synthesis of silicoaluminophosphates with SAV and KFI zeotype frameworks STA-7 (SAV) has a three-dimensional 8-ring channel system Its structure is composed of D6Rs and possesses two types of cages (Fig 24.26) The cyclam and tetraethylammonium cations (TEAỵ) were used for the synthesis of SAPO STA-7 Single-crystal diffraction analysis showed that the TEAỵ cations fit nicely in the smaller cages, and indicated that the cyclam molecules reside in the larger cage disorderedly If n-proplyamine (DPA) and diisopropylamine (DIPA) were used instead of TEAỵ in the synthesis, the product was mainly STA-6 (SAS) with minor admixed STA-7 Modeling of their lowest energy configurations in the smaller cage of STA-7 provided some idea of the role of TEAỵ The binding energies of DPA, DIPA, and TEAỵ in the smaller cage are À83.6, À124.9, and À125.6 kJ molÀ1, respectively The modeled position of TEAỵ is close to the position measured experimentally but the DPA protrudes from the smaller cage The higher selectivity of TEAỵ over DIPA is attributed to its better fit to the geometry of the cage of STA-7 KFI was previously reported as an aluminosilicate zeolite ZK-5 [63] Like the SAV framework, it is built up from D6Rs only, but with a different stacking 577 arrangement (Fig 24.27) The (001) surface of SAV is topologically identical to the surface of KFI As with SAV, KFI also has two types of cages, i.e., the a-cage found in AlPO4-42 (LTA) and a smaller cage found in zeolite merlinoite (MER) A co-templating strategy as the synthesis of SAPO SAV was therefore employed It was believed that the azaoxacryptand 4,7,13,16,21, 24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (K222) which was a good template for AlPO4-42 [64] would fit the a-cage, and some smaller organic amine or ammonium cations might fit the smaller mer cage of KFI A few readily available amines and alkylammonium cations were screened computationally for their fit within the mer cages of KFI with an AlPO4 composition, including tetramethylammonium (TMAỵ), TEA and tetraproplyammonium (TPAỵ) cations, methylamine (MA), ethylamine (EA), propylamine (PA), dimethylamine (DMA), diethylamine (DEA), DPA, DIPA, triethylamine (TREA), and diisopropylethylamine (DIPEA) The nonbonding energies are shown in FIGURE 24.27 Above: The structures of SAV (left) and KFI (right) FIGURE 24.26 The structure of STA-7 with two different types of cages, A and B (aluminum atoms are gray, phosphorus black, and oxygen white) Images reproduced with permission from [62] Both are made up entirely of D6Rs (in blue), which can be distinguished when viewed along the a-axis In SAV, layers are stacked along the c-axis by a simple translation, whereas in KFI adjacent layers are related by a mirror plane perpendicular to the c-axis Below: The KFI structure and with a- and mer cages outlined in grey, respectively Images reproduced with permission from [62] 578 24 FRONTIER OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY (II) FIGURE 24.28 Above: A histogram of the nonbonding energies of potential co-templates for the mer cages of the AlPO4-KFI structure, indicating that TEAỵ ions have most favorable binding energies Below: The modeled position of the TEAỵ cations within the mer cages of the AlPO4-KFI structure (left) and that observed experimentally (right) In the latter, one of two symmetry-related positions is shown Images reproduced with permission from [62] Fig 24.28 As can be seen, the most favorable binding energy is 177.8 kJ mol1 for the TEAỵ cation Experimentally, TEAỵ was used a co-template with K222 in the synthesis from a magnesioaluminophosphate gel system, and gave the desired AlPO4-based KFI product Single-crystal structure analysis of MgAPO KFI revealed that the TEAỵ cations were located within the MER cages in the configuration predicted by modeling Using the K222/TEAỵ combination, CoAPO and SAPO compositional variants of KFI were also successfully synthesized 24.3.2 Synthesis Guided by Substituent Element Effects 24.3.2.1 Synthesis of D4R-containing Zeolites by using Ge as a Silica Substituent Some elements have been found to have a potential ability to direct the formation of a particular building unit For example, Be and Zn atoms tend to direct the formation of 3-rings in zeolite structures A series of germanates with D4R structures have been reported [65] Recently, employing Ge as a silica substituent combined with the use of novel template molecules, Corma’s group has successfully synthesized a number of novel D4R-containing germanosilicate zeolites Ge preferentially occupies positions at the D4R units [66] The structure-directing effect of Ge towards the formation of D4R-containing zeolites is due to the fact that the smaller GeeOeGe angles than the SieOeSi angles can relax the geometric constraints in the D4R units and thus stabilize the resulting structures For example, zeolite ITQ-21 was synthesized in the gel with molar composition 0.33GeO2:0.67SiO2:0.50 MSPTOH:0.5HF:20H2O at 175  C for days using N-methylsparteinium hydroxide (MSPTOH) as SDA [67] In the absence of Ge in the reaction mixture CIT-5 (CFI) was formed which did not have D4Rs in the structure The structure-directing role of Ge in the D4Rcontaining zeolites has been also clearly shown by the synthesis of polymorph C of zeolite beta (BEC) with a variety of organic template molecules [68] The syntheses were carried out in the gels with molar compositions (1 À x)SiO2:xGeO2:(0.5e0.25)SDAOH:0.5HF:wH2O at 135e175  C for 15e120 h Notably, when Ge was introduced into the reaction system, only the D4R-containing BEC structure was obtained irrespective of the type of the template used In the absence of Ge, different zeolite phases including ITQ-4, beta, and ZSM-12 were obtained depending on the template used Remarkably, novel zeolites with extra-large pore structures have been prepared by using Ge as a silica substituent Notable examples, as shown in Figs 24.29e 24.31 (framework structures and three templates used), are ITQ-15 [69] with two-dimensional 14 Â 12-ring channels (FD: 15.6), ITQ-33 [70] with three-dimensional 18 Â 10 Â 10-ring channels (FD: 12.3), and ITQ-37 [71] with three-dimensional 30-ring channels (FD: 10.3) Interestingly, ITQ-37 represents an interrupted zeotype structure that contains extra-large mesoporous 30-ring gyroidal channel with the pore dimension of 7.05 Â ˚ and the lowest framework density among all 22.04 A the known four-connected zeolite structures It was synthesized using the bulky diammonium ion, which contains chiral centers, as the organic SDA More recently, Jiang et al [72] reported a new silicogermanate ITQ-44 with three-dimensional 18 Â 12 Â 12-ring channels by using (20 R, 60 S)-20 , 60 -dimethylspiro[isoindole2,10 -piperidin-10 -ium] as an SDA Interestingly, ITQ-44 is featured by novel D3Rs along with D4Rs There is also a preferential Ge occupancy of the D3Rs The structure of ITQ-44 is closely related to that of ITQ-33 The 12-ring channels in ITQ-44 can be viewed as expansion of the 10-ring channels through D3Rs (Fig 24.32) 24.3.2.2 Heteroatom-stabilized Chiral Framework of Aluminophosphate Molecular Sieves Heteroatoms have also demonstrated their effect on stabilization the chiral zeolite frameworks as demonstrated by the work of Song et al [73] Li et al have developed a method for the design of chiral zeolite frameworks with specified pore geometries through ATTEMPTS TO THE RATIONAL SYNTHESIS OF INORGANIC POROUS CRYSTALLINE MATERIALS 579 FIGURE 24.29 (a) The 14-ring view along c-axis (b) The 12-ring view along the b-axis (c) The SDA cation used in ITQ-15 synthesis Only the TeT connections are shown FIGURE 24.30 (a) Lateral view of the ITQ-33 structure, showing the 10-ring and (b) The SDA cation used in ITQ-33 constrained assembly of atoms (see Section 2.1.1) According to the theoretical results, most four-connected frameworks generated with chiral channels are energetically unfavorable for the SiO2 composition because of the special geometric strains in such structures This suggests that introducing other elements such as Be, B, Ge, and transition metals, instead of Si, might be a promising strategy for stabilizing such frameworks, as they could offer a more reasonable bonding geometry, like bond distances and bond angles than an SiO2 composition does By the incorporation of metal ions (Co2ỵ, Mg2ỵ, Fe2ỵ, etc.) into the aluminophosphate framework, novel heteroatom-containing chiral aluminophosphate MAPO-CJ40 (M ẳ Co2ỵ, Mg2ỵ, Fe2ỵ, etc.) has been synthesized with one-dimensional helical 10-ring channels Figure 24.33 shows the structure of CoAPO-CJ40 Its structure is based on the strict alternation of MO4 (M ¼ Al, Co) and PO4 tetrahedra forming an anionic [Co2Al10P12O48]2À framework Charge neutrality is achieved by protonated diethylamine cations The helical 10-ring channels are enclosed by double helical ribbons of the same handedness made of the edge sharing of 6-rings along the 21 screw axis The Co atoms, which substitute one of the three unique Al sites, adopt a helical arrangement along the channel The framework of CoAPO-CJ40 is intrinsically chiral with underlying symmetry of I212121 and exhibits a new zeotype structure which has been assigned as JRY It was noted that pure aluminophosphate AlPO-CJ40 could not be successfully prepared in the absence of Co or Zn ions In CoAPO-CJ40, the Co atoms exclusively occupy the Al(1) position among the three unique Al sites, with a probability of 50% This could be explained by a molecular mechanics computation and geometric calculation A structure model with a pure AlPO4 composition was built by replacing all the Co atoms by Al atoms The bond angle variance for each AlO4/PO4 tetrahedron was calculated after the geometry of this structure model was fully optimized The results showed that there is a large bond angle variance on the Al(1) site (Table 24.5) which indicates that the Al(1)-centered tetrahedron may suffer from high distortion from the ideal tetrahedron The incorporation of Co atoms might be necessary for the framework to relax the high distortion, thus stabilizing the whole structure Three other structure models were built by replacing Al(1), Al(2), and Al(3) with Co atoms, respectively The calculated framework energies of the three optimized models are À9401.35, À9374.83, and À9372.36 kcal molÀ1 per unit cell, respectively Therefore the first structure model in which cobalt atoms occupy the Al (1) position should be the most reasonable one This result agrees with the single-crystal structure analysis In summary, molecular simulations and geometric 580 24 FRONTIER OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY (II) ˚ thick) viewed down the [111] direction All double 4-rings have the same orientation (b) The 30-ring built (a) A slice (15.3 A from 10 tertiary building units The centers of the tertiary building units fall on the nodes of one srs net (c, d) The large cavity defined by three 30-rings in the topological and tiling methods (e) Structure of SDA cation used for synthesizing the ITQ-37 zeolite SDA contains four chiral centers (marked with asterisks) in a mesoconformation, making the overall molecule achiral Reprinted with permission from Macmillan Publishers Ltd: Nature [71], Copyright (2009) FIGURE 24.31 calculations demonstrated that Co2ỵ ions play an important role in stabilizing the chiral framework 24.3.3 Synthesis Guided by Data Mining The difficulty towards the rational synthesis of zeolitic inorganic porous crystalline materials lies in the unclear relationship of the synthetic factors and resulting structural characters In order to establish such a relationship, Yan et al [74] established a Zeobank, which contains a database of AlPO synthesis, and a database of AlPO structures The databases are available at the Website http://izasc.ethz.ch/fmi/xsl/IZA-SC/ol htm [75] The Zeobank will allow to apply computational techniques to study complex relationships between the synthetic parameters and the corresponding zeolite structures in a systematic manner An SVM-based computational study on microporous aluminophosphates has demonstrated the general feasibility in establishing a relationship between the synthetic parameters and the structural features of the zeolite materials This provides a useful strategy to the rational synthesis of zeolitic inorganic crystalline materials [76] The AlPO synthesis database contains over 1600 reaction data for ca 230 AlPO structures The data were mostly collected from the literature Each entry in the database consists of four pieces of synthesis information: the source materials, the template, the synthesis conditions, and the structural characteristics of the product The channel systems of microporous AlPOs can be divided into 17 types according to the sizes of their pore rings Among them, AlPOs with (6,12)-rings represent a major class, and 396 synthetic records in the database are associated with this channel system An SVM-based computational study has been performed for predicting the formation of (6,12)-ring-containing microporous aluminophosphates For a specified classification problem, an SVM is trained (or supervised) to learn to optimally distinguish the data elements in a positive data set from the data elements in a negative data set, together forming the training data set, based on their respective feature values ATTEMPTS TO THE RATIONAL SYNTHESIS OF INORGANIC POROUS CRYSTALLINE MATERIALS 581 FIGURE 24.32 (a) The ternary building unit of both ITQ-33 and ITQ-44 (b) Condensation of the tertiary units in columns through the 3-ring for ITQ-33 (indicated by the cycle) (c) Condensation of the tertiary building unit in columns through the double 3-ring (D3R) for ITQ-44 (indicated by the cycle) (d) The 18-ring pore view down along the c-axis for both ITQ-33 and ITQ-44 [77] During the training, an SVM continues to adjust two parallel (separating) hyperplanes in the feature space, attempting to keep as many positive data elements on one side of a hyperplane and the negative points on the other side of the parallel hyperplane as possible, and the two hyperplanes have the largest distance possible Distinguishing between the (6,12)-ring-containing AlPOs and the other AlPOs in the AlPO synthesis database is essentially a binary classification problem Feature selection is crucial for the successful classification by an SVM-based classifier Through analyses of a database of AlPO synthesis with ca 1600 reaction data, a number of synthetic parameters are identified as the features (F) such as three gel molar ratios of Al2O3 (F1), P2O5 (F2), and the organic amine template (F4), as well as a number of parameters associated with the geometric and electronic characteristics of the templates as the input (Table 24.6) Eleven template parameters are considered that are believed to cover the most important features of a template, including the longest distance (F11), the second longest distance (F12), and the shortest distance (F13) associated with the template geometry, the van der Waals (VDW) volume (F14), the dipole moment (F15), the ratio of C/N (F16), the ratio of N/(C ỵ N) (F17), and the ratio of N/VDW volume (F18) in the template, the Sanderson electronegativity (F19), the number of freely rotated single bond (F20), and the max Hỵ number (F21) Using these parameters, an SVM-based classifier has been trained on a training data set containing 363 (6,12)ring-containing AlPOs and 1069 AlPOs without such rings Three important features related to the molar concentrations of Al2O3, P2O5, and the organic template in the starting gel and the 11 template parameters are used as the input parameters for training the classifier The output of the trained classifier is either or 1, 582 24 FRONTIER OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY (II) FIGURE 24.33 Framework structure of CoAPO-CJ40 (a) Viewed along the [010] direction; (b) the helical 10-ring channel and helical arrangement of cobalt atoms (white color for Co); (c) the 10-ring channel enclosed by double helical ribbons made up of the edge sharing of 6-rings representing a resulting structure containing a (6,12)ring or not, respectively Each synthetic parameter has been tested individually as well as some of them in combinations in order to know which ones may have the predictive power in distinguishing the two classes of AlPOs For example, it is found that a classifier using only three synthetic parameters involving the molar concentrations of Al2O3 (F1), P2O5 (F2), and template (F4) cannot predict TABLE 24.5 The bond angle variance for each AlO4/PO4 tetrahedron for CoAPO-CJ40 Al0 Co1 Co2 Co3 Si Al1 4.62290 0.48070 6.48750 8.80290 3.07350 Al2 1.76090 6.11130 19.32990 17.14490 1.85990 Al3 3.18480 2.82550 8.67860 20.04860 0.77040 P1 1.04380 0.08400 15.06540 2.93800 1.22310 P2 1.54060 0.70720 3.60340 12.34910 2.45710 P3 0.71630 0.11130 1.28080 2.57930 2.79310 SUM 12.86930 10.32000 54.44560 63.86280 12.17710 AVR 2.14488 1.72000 9.07427 10.64380 2.02952 X Song, Y Li, L Gan, Z Wang, J Yu, R Xu: Heteroatom-stabilized chiral framework of the aluminophosphate molecular sieves Angewandte Chemie International Edition 2009 Volume 48, Page 314 Copyright Wiley-VCH Verlag GmbH & Co KGaA Reproduced with permission [73] if an AlPO contains (6,12)-rings or not Further introducing the 11 aforementioned template parameters along with the three synthetic parameters, individually or grouping combinations, as the classification features, gave substantially different levels of classification performance This suggested that the choice of suitable template parameters was important to the classification performance The highest and the lowest predicting accuracies among different combinations are shown in Fig 24.34 In view of the highest accuracy as a function of the number (N) of the used template parameters, it was found that adding two or more template parameters generally gave better performance in the classification than individual parameter-based classifiers By analyzing the classification performances based on different combinations of the template parameters with Al2O3 (F1), P2O5 (F2), and template (F4), the most relevant template parameters could be identified to the classification problem Notably, it was found that the second longest distance within each template (F12) has the best prediction performance among all individual parameters, giving a training accuracy of 80.54% and a testing accuracy of 78.08% by itself (Fig 24.35) Further combination of F12 with another electronic parameter of the template such as F16 (the ratio of C/N) or F18 (the ratio of N/VDW volume), gave the training accuracy 83.66À84.31%, and the testing accuracy 81.61À81.75% (Table 24.7) ATTEMPTS TO THE RATIONAL SYNTHESIS OF INORGANIC POROUS CRYSTALLINE MATERIALS TABLE 24.6 Gel composition Organic template 583 Description of the input synthetic parameters Codea Description of parameters F1 The molar amount of Al2O3 in the gel composition F2 The molar amount of P2O5 in the gel composition F4 The molar amount of template in the gel composition F11 The longest distance of organic template F12 The second longest distance of organic template F13 The shortest distance of organic template F14 The Van der Waals volume F15 The dipole moment F16 The ratio of C/N F17 The ratio of N/(C ỵ N) F18 The ratio of N/Van der Waals volume F19 The Sanderson electronegativity F20 The number of free rotated single bond F21 The maximal number of protonated H atoms FIGURE 24.34 Highest and lowest prediction accuracies of Nparameter combinations along with the molar concentrations of F1, F2, and F4 by using a Gaussian RBF kernel function Reprinted from Microporous and Mesoporous Materials, Jiyang Li, Miao Qi, Jun Kong, Jianzhong Wang, Yan Yan, Weifeng Huo, Jihong Yu, Ruren Xu, Ying Xu, Computational prediction of the formation of microporous aluminophosphates with desired structural features, Copyright (2010), with permission from Elsevier [76] a [F3], [F5]e[F10] refer to other synthetic parameters such as the crystallization temperature and time, and the feature of the solvent which are ignored in this study Molecular dimensions of the organic template are calculated based on the optimized model by using PM3 method in MOPAC 2000 The longest, the second longest, and the shortest distances are defined as the three largest lengths of an organic template in three perpendicular directions of space Reprinted from Microporous and Mesoporous Materials, Jiyang Li, Miao Qi, Jun Kong, Jianzhong Wang, Yan Yan, Weifeng Huo, Jihong Yu, Ruren Xu, Ying Xu, Computational prediction of the formation of microporous aluminophosphates with desired structural features, Copyright (2010), with permission from Elsevier [76] Computational data mining techniques showed a great promise in guiding the rational synthesis of zeolitic materials Currently various computation techniques have been used to retrieve information from the data analysis [78] such as neural networks, support vector machines, classification trees, clustering analysis, principal component analysis, and control theory However, it is worth mentioning that many factors influence the prediction results such as the number and the quality of the data set in the Zeobank database, the feature selection of the input synthetic parameters and the output structural parameters in the classification, and the data mining techniques Moreover, the successful prediction of the formation of microporous materials with specified structural features will heavily rely on the deep understanding of zeolite synthetic chemistry FIGURE 24.35 Effect of single template parameter along with F1, F2, and F4 on the classification result Reprinted from Microporous and Mesoporous Materials, Jiyang Li, Miao Qi, Jun Kong, Jianzhong Wang, Yan Yan, Weifeng Huo, Jihong Yu, Ruren Xu, Ying Xu, Computational prediction of the formation of microporous aluminophosphates with desired structural features, Copyright (2010), with permission from Elsevier [76] 584 24 FRONTIER OF INORGANIC SYNTHESIS AND PREPARATIVE CHEMISTRY (II) TABLE 24.7 Sets of input template parameters exhibiting highest accuracy Na Template parameters Training accuracy (%) Testing accuracy (%) F12 80.54 78.08 F12 F16 84.31 81.75 F12 F16 F21 85.74 82.06 F12 F15 F16 F17 86.94 82.31 F12 F15 F16 F17 F18 87.51 82.44 F12 F13 F14 F15 F18 F19 87.86 82.36 F12 F13 F14 F15 F17 F19 F21 87.94 82.36 F12 F13 F14 F15 F17 F18 F19 F21 87.97 82.17 F12 F13 F14 F15 F16 F17 F18 F19 F21 87.97 82.08 10 F12 F13 F14 F15 F16 F17 F18 F19 F20 F21 87.99 81.97 11 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 F21 87.98 81.64 a N is the number of input template parameters Reprinted from Microporous and Mesoporous Materials, Jiyang Li, Miao Qi, Jun Kong, Jianzhong Wang, Yan Yan, Weifeng Huo, Jihong Yu, Ruren Xu, Ying Xu, Computational prediction of the formation of microporous aluminophosphates with desired structural features, Copyright (2010), with permission from Elsevier [76] 24.4 FUTURE PERSPECTIVE ON THE TAILOR-MADE SYNTHESIS OF DESIRED INORGANIC POROUS CRYSTALLINE MATERIALS Zeolitic inorganic porous crystalline materials are of importance in many technological processes such as catalysis, adsorption, and separation because of their unique pore architectures coupled with the active reaction sites Especially, zeolites are very successful catalysts in shape-selective catalysis that have found many industrial applications Fine-tuning zeolites with controlled pore architectures, such as the pore system, pore dimension, and pore shape, will improve their performance for applications Clearly, this represents a formidable challenge and will call for a capability to tailor-made synthesis of inorganic porous crystalline materials with desired structures and functionalities [79] Currently, computational approaches, combined with increasing knowledge and understanding of the propertyestructureesynthesis have greatly facilitated the designed synthesis of zeolitic inorganic crystalline porous materials Figure 24.36 depicts the future blueprint for the tailor-made synthesis of desired zeolitic materials The engineering to access the target functional inorganic porous crystalline materials can be described as following: (i) A practical application, e.g., a specific catalytic reaction, raises detailed requirements for the structures with defined pore dimension, pore system, pore shape, active sites, etc (ii) The desired porous structures are then designed by computational methods (iii) By using computational modeling, the candidate SDA molecules are predicted for the given structures Further data-mining techniques will predict the synthesis conditions for the target structures (iv) The synthesis is achieved by using various synthetic techniques under hydrothermal or solvothermal conditions Especially, the combinatorial techniques will allow exploring in a large experimental space by means of the appropriate experimental design (v) The structures of as-made materials are identified by comparing the experimental X-ray diffraction patterns with the simulated ones derived from the theoretical structures (vi) The application is eventually accessible by such a rational design and synthesis approach It is worth underscoring here that toward the rational synthesis of inorganic porous crystalline materials, there still remain a number of challenges ahead to achieve such a goal Although great strides have been made in CONCLUDING REMARKS 585 methods to the rational design philosophy Our dream is to control chemically the self-assembly process of inorganic materials with predictable compositions, structures and functionalities, and eventually to replace the classical trial-and-error strategy This is, in fact, a long journey from possibility to reality Despite the difficulties, this is the way where the synthetic chemists should concentrate More research as well as untiring efforts should be driven along these directions References FIGURE 24.36 Future blueprint for engineering the rational synthesis of zeolitic materials with desired functionalities and structures Copyright 2010 American Chemical Society Reprinted with permission from [79] Copyright 2003 American Chemical Society this area, future advances in understanding the formation mechanism at the molecular level are needed before the promise is fulfilled 24.5 CONCLUDING REMARKS Nowadays, the search for new inorganic materials has been changing from the past empirical, trial-and-error [1] R Noyori, Nat Chem (2009) 5e6 [2] Ch Baerlocher, L.B McCusker, [3] R Xu, W Pang, J Yu, Q Huo, J Chen, Chemistry of Zeolites and Related Porous Materials: Synthesis and Structure, Wiley, 2007 [4] S Kulprathipanja, Zeolites in Industrial Separation and 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activated low-pressure CVD diamond synthesis, 152 additive effect, 219 adiabatic combustion temperature, 25 adsorption - desorption, 339 advanced ceramic, 429 alkali metal clusters, 406, 407 alkali metals, 406, 407, 408 alkyls, 270 allylic and polyene complexes, 288 AlON transparent ceramics, 446 AlPO4-5, 349, 410, 411, 412, 415, 417, 418, 424 alumina transparent ceramics, 443-444 aluminoborates, 240 aluminophosphate, 178, 405, 413, 424 amorphous materials, 455 amorphous microporous membranes, 508 anhydrous RE chlorides, 34 anion interstitialcy, 323 anion vacancy, 324 anisotropic, 543 antifogging, 543 antireflection, 543 arc melting furnace, 10 arc-discharge, 249 arene complexes, 288 AsF5, 52 assembly, 2, 228 atomic layer chemical vapor deposition (ALCVD or ALD), 152 automated assembly, 566 B bacteria, 525 basic structural unit, 340 beetle, 543 berthollide, 321 bio-inspired, 525 biomedical phosphazene, 301 biomimetic Synthesis, biomimetics, 525 biomineralization, 525 biotemplates, 525 borates, 238, 239 borogermanates, 241 bottom-up, 479 Buckminsterfullerene C60, 249 building units design, 562 building units, 341 butterfly wings, 543 C cage structure, 251 carbene complexes, 282 carbon cluster, 249 carbon matters, 413 carbon nanotube/AlPO4-5, 415 carbon nanotube (CNT), 153, 405, 414, 415, 548 carbon, 251 carbonyl complexes, 271 carbyne complexes, 282, 284, 286 cation interstitialcy, 323 cation vacancy, 337 ceramic matrix composites (CMCs), 435 ceramic nanocomposites, 442 ceramic scintillators, 449-454 ceramics, 176, 185, 186, 187, 189, 193 ceria, 334 Cf/C Composites, 436 Cf/SiC Composites, 437 Cf/SiO2 Composites, 436 chabazite, 409, 413 chalcogenide clusters, 227, 243 chalcogenides, 16, 347 chemical etching, 482 chemical mass transportation, 154 chemical precipitation, 430 chemical preparation, 429 chemical vapor deposition (CVD), 151, 429 chimie douce, 387 chiral materials, 539 chiral molecular recognition, 241 chirality and symmetry, 241 chlorine gas, 137 cinnabar, 151 cluster-organic frameworks, 234 cluster, 227 CMK-1, 367 CNTs/BaTiO3 composites, 443 CNTs/SiO2 composites, 442 cocondensation, 60 cold baths, 39 cold trap, 45 colloid chemical, 487 color center, 324 combustion synthesis, 22 complex fluorides, 75 p complexes, 279 component exchange, 199 composite, 405, 407 composition, 587 computer simulations, 565 configurational entropy, 325 confinement technique, 520 cooperative self-assembly, 352 coordination compounds, 197 coprecipitation method, sol-gel techniques, 329 core-shell, 480 counter diffusion self-assembly (CDSA), 520 counter-ion effect, 221 cryosynthesis, 27, 198 cryosynthetic reactions, 60 crystal grower equipment, crystal growth, 68 crystallization, 176, 177, 178, 182, 183, 190, 343 Cu-BTC, 512 cycloaddition, 255 cyclomatrix polymers, 296 cyclopentadienyl complexes, 288 cyclophosphazene, 296 D DAC, 98, 100, 101, 102, 103, 104, 105, 106, 114 Daltonides, 321 data mining, 571 DDR, 510 deep eutectic solvent, 89 degree of fill, 66 dense membranes, 507 designed synthesis, 234 desired structures, 555 diamond anvil cell (DAC), 100, 123 diamond anvil cell, 101, 107, 114 diamonds, 98, 100, 101, 102, 104, 105, 106, 110, 112, 113, 114, 119, 120, 121, 122, 123 diatom, 525 dip coating, 516 direct synthesis, 197 directed assembly, 234, 235 directed substitution, 230, 231 directed-combination, 235 divalent rare earth ions, 15 DNA, 525 double hydrophilic block copolymers (DHBCs), 531 dye molecules, 405, 410, 411, 412 E E-factor, EELS, 336 electrochemical synthesis in situ oxidation, 387 electrochemical synthesis, 201 588 electronic structure, 111, 114, 115, 118 electrophilic abstraction, 278 electrophilic addition, 278 electrospinning, 546 electrostatic layer-by-layer (LBL) assembly, 392 elimination, 273 emulsion, 487 encapsulation, 407, 408, 410, 419, 422, 423, 424 endofullerene, 253 epitaxial growth, 156 epitaxy, 156 EPR, 337 equation of state, 103, 104, 115 evaporation-induced self-assembly (EISA), 359, 517 evolutionary tree, 78 exohedral derivatization, 253 extended carnot theorem, 166 extreme conditions, F Fe3O4, 333 FeO, 332 film deposition, 156 fish scales, 543 flames, 250 formation criteria, 455 formation mechanism, 343 framework density (FD), 341 framework generation, 560 framework, 340 free energy, 322 Frenkel defects, 323 FSM-16, 354 fullerenes, 249 fused pentagons, 253 G gas permeation, 510 gas separation, 512 gas-solid synthesis, 328 gecko feet, 543 gecko, 525 germanates, 241 glass, 174, 185, 188, 189, 193 glass-ceramics, 189 glove box, 290, 292 gmelinite, 342 gradient, 103, 104, 105 graphite evaporation, 249 graphite, 249 green synthesis, H H2 production, 143 halides, 15 halogenation reactions, 255 helical tubes, 236 heteroepitaxy, 156 hexadecafluorophthalocyanine, 423 hierarchical, 350 high oxidation state transition metal oxides, 120 SUBJECT INDEX high oxidation state, 107, 109, 125 high pressure and high temperature, 98, 112, 113, 120, 121, 122, 123 high pressure apparatus, 98, 99, 100, 104, 105, 106 high pressure inorganic synthesis, 110, 125 high pressure, 97, 98, 99, 100, 101, 102, 103, 104, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 128 high temperature superconductor, 117, 124, 125 high temperature, 98, 99, 101, 104, 105, 106, 107, 112, 113, 117, 118, 119, 120, 121, 122, 123, 124, 125 high-pressure apparatuses, diamond anvil cells (DACs), 98 high-pressure autoclave, 63 high-temperature species, 27 high-valent metals, 201 homoepitaxy, 156 host-guest composite, 408, 410, 411, 412, 413, 414, 418, 419, 420, 425 host-guest material, 405, 407, 410, 411, 412, 414, 416, 418, 423, 425 host-guest nanocomposite materials, 424 host-guest symmetry and charge matching, 242 host-guest, 405, 407, 408, 409, 410, 411, 418 hot spots, 175, 176 HPLC, 253 HRTEM, 336 HXY molecules, 54 hybrid zeolite, 347 hybrid, 145 hybridization, hydrides, 270 hydro(solvo)thermal conditions, 239 hydrolysis and condensation, 19 hydrothermal biochemistry, 78 Hydrothermal synthesis, 63, 176, 387, 389, 397 Hydrothermal/solvothermal Method, 342, 432 I ice-templated, 547 ideal synthesis, in situ growth ceramic matrix composites, 441 in situ growth method, 392 in situ growth particle-reinforced ceramic composites, 441, 442 in situ high pressure, 100, 102, 116, 124 in situ ligand formation, 222, 225 in situ ligand reactions, 73 in situ metal/ligand reactions, 221 in situ template method, 296 in situ ultrahigh pressure, 125 inclusion complexation, 203 induced congregation, 243 induced synthesis, 236 inorganic materials, 97, 120, 125 inorganic membranes, 507 inorganic polymers, 295 inorganic synthesis, ultrahigh pressure, 97 inorganic synthesis, 97, 98, 106, 110, 117, 125 insect, 525 insertion, 273 integration of structures and functions, 442 intergrowths, 342 intermediate oxidation states, 119 intermolecular and intramolecular deamination coupling reactions, 229 interpenetration, 216, 219, 220 intramolecular decoration or intermolecular linkage, 232 intrinsic defect, 324 iodine tungsten lamp, 154 ionic conductors, 74 ionic liquids, 89 ionothermal synthesis, 89, 349 iron(II) oxide, 332 g-irradiation Synthesis, 335 isolated pentagon rule (IPR), 252 K kinetic model, 159 KrF2, 53 L laboratory cryogenic systems, 39 lacunary directing synthesis, 229 lacunary sites, 229, 230 Langmuire Blodgett technology, 395 lanthanide germanate clusters, 243 large volume apparatus, 98, 103 large volume press, 100, 101, 102, 104, 106 large volume, 98, 104, 125 laser ceramics, 446 laser materials, 411 laser vaporization, 250 laser, 411, 412 layer-by-layer assembly, 484, 547 layered double hydroxides, 375, 376, 384, 386 layered inclusion compounds, 203 ligand substitution, 200 ligands, 197 light absorption, 130 light element, 114, 119 light emission devices (LED), 152 liquid crystal template, 352 lithography, 481 Ln germanate cluster organic frameworks, 243 long-range cation order, 377, 378 lotus leaves, 543 low temperature chemical separation, 46 low temperature fractional condensation, 46 low temperature fractional distillation, 46 low temperature selective adsorption, 46 low-pressure chemical vapor deposition (LPCVD), 152 low-valent Metals, 201 LRS, 337 M macrocyclic template, 204 macroporous, 368 589 SUBJECT INDEX magnetite, 332 material, 405, 408, 409, 410, 411, 412, 413, 414, 416, 417, 418, 420, 422, 425 matrix isolation, 198 matrix photogeneration, 55 MCM-41, 353, 408, 413, 414, 416, 417, 418, 419, 420, 422, 423, 425 MCM-48, 355 mechanism, 274 membranes, 180 mercury lamps, 131 mesoporous carbon materials, 366 mesoporous host-guest materials, 411 mesoporous material, 176, 178, 410, 411, 417, 418, 423 mesoporous membrane, 507 mesoporous silica, 411, 425 mesoporous, 350, 353, 408, 409, 411, 412, 413, 414, 416, 417, 418, 419, 423, 424, 425 metal cluster, 203, 406, 407 metal complex, 405, 419, 423 metal exchange, 199 metal films, 140 metal fluorides, 137 metal oxide films, 142 metal vapor synthesis, 198 metal-cluster nodes, 211 metal-deficient, 326 metal-organic chemical vapor deposition (MOCVD), 154 metal-organic framework (MOF), 72, 346 metal-rich, 326 metalemetal bond cleavage, 136 metal-schiff base, 421 MFI, 510 MgAl2O4 transparent ceramics, 445 MgCl2$6NH3, 57 microemulsions, 431 microlaser material, 411 microlaser, 411 microporous aluminophosphate, 339, 425 microporous carbons, 366 microporous inorganic membranes, 507 microporous, 339, 410, 411, 412, 413, 414, 416, 419, 422, 423, 424, 425, 427 microwave heating, 173, 174, 175, 176, 177, 178, 180, 181, 182, 183, 185, 186, 187, 189, 190, 192, 193 microwave or ultrasound aging methods, 387 microwave radiation, 173, 174, 175, 176, 189 middle-valent metals, 201 mineralizer, 350 mixing valence, 119 modern thermodynamics, 166 MOFs, 512 molecular design, 209 molecular reactors, 395, 397, 398 molecular sieves, 346, 525 molecular vessel, 395, 396, 398 molten salt electrolysis, 31 Morey autoclave, 85 mosquito eyes, 543 multi-anvil, 99, 100 olefin complexes, 287 Oparin’s hypothesis, 78 open-framework materials, 70 optical ceramic for windows, 443 ordered mesoporous membranes, 508 organiceinorganic hybrid materials, 71 organometallic complex, 132, 259 organometallic coordination, 129 organometallic, 269 oxidative addition, 271 oxides and complex oxides, 14 oxo boron clusters, 239 oxo clusters, 227 oxo lanthanide clusters, 236 oxo main group clusters, 238 oxo metal clusters, 227 oxygen partial pressure, 328 oxygen-deficient, 326 oxyhalide, 16 phase transition, 97, 98, 101, 103, 104, 106, 114, 115, 116, 123 photo-induced electron transfer, 136 photo-isomerization, 134 photocatalytic water splitting, 143 photochemical synthesis, 129 photoluminescence, 318, 414, 418 photolysis, 54 photon energy, 130 photosensitization, 136 photosubstitution, 132 phthalocyanine metal complexes, 422 phthalocyanine, 422, 423 physical vapor deposition (PVD), 151 pillared-layer, 213 piston-cylinder, 98, 99, 100, 101, 103, 104, 105, 106 plasma reaction, 251 plasma-enhanced chemical vapor deposition (PECVD or PCVD), 151 plasma, 190, 192 platinum, 408, 413 pnictides and oxypnictides, 17 point defects, 323 polycyclic aromatic hydrocarbons, 251 polyelectrolytes, 529 polymer host-guest, 413 polymer, 405, 409, 412, 413 polymeric membranes, 507 polyoxometalate, 228 polyphosphazenes, 295 polysilaethers, 295 polysilanes, 315 polyurethane, 310 pore geometries, 556 pore narrowing, 508 pore orientations, 517 pore size control, 358 porous inorganic membranes, 507 porous material, 339, 555 porphyrin, 422 postsynthesis hydrothermal treatment, 358 pre-intercalation method, 387 pre-pillaring Method, 387 precursor-induced complexation, 198 pressure affects, 110, 115 pressure calibration, 102, 104 pressure sintering, 433, 434 pressure transmitting media, 98, 100, 101, 102, 103, 104, 105 Prussian blue film, 142 pyrolysis, 251 P Q paramagnetic property, 419 particle dispersion-strengthened ceramic matrix composites, 440 particles, 405 periodic mesoporous organosilicas (PMOs), 360 peripheral substitution, 234 permeation, 507 perovskite, 74, 113, 114, 115, 118 pH effect, 218 quantum yield, 130 a-quartz, 68 multianvil high-temperature high-pressure devices, 121 multianvil, 99, 101 multichannel, 546 multinuclear compound, 203 multiscale, 525 N nacre, 525 nano-building units, 484 nano-sized materials, 142 nanocasting, 360 nanoceramics, 432 nanochemistry, 479 nanocrystal, 349, 480 nanofabrication, 480 nanomaterials, 76, 183, 479 nanoscaled powders, 429 nanowires, 153 Ni/Al2O3 (Co/Al2O3) composites, 440 non-equilibrium aging method, 384 non-IPR fullerenes, 252 nonaqueous, 349 nonequilibrium nondissipative thermodynamics, 152 nonequilibrium phase diagrams, 152 nonlinear optical, 239, 307 nonspontaneous reaction, 152 nonstoichiometric compounds, 321 nucleation, 343 nucleophilic abstraction, 277 nucleophilic addition, 276 O R R3SiCo(CO)4 type compounds, 52 Raman diffraction, 101 Raman spectrum, 105, 116 rare earth-containing materials, 14 rational approaches, 555 redox interaction, 200 590 reductive elimination, 271 resistance furnaces, rice leaves, 543 S sandwich-type cluster, 231 SBA-15, 354, 408, 409 SBA-16, 356 SBA-2, 356 scale chemistry, 563 schiff base, 421, 422 Schlenk techniques, 289 Schottky defects, 324 secondary assembly method, 387 secondary growth, 513 self-assembly, 3, 532 self-cleaning, 543 self-polymerization, 240, 243 self-propagating high-temperature synthesis (SHS), 189, 193 semiconductor films, 129 semiconductor particles, 415, 417 semiconductor, 153, 405 separate nucleation and aging steps (SNAS), 384 separation membranes, 308 sesquioxide transparent ceramics, 448 shape preservation, 153 shell membranes, 525 short-range cation order, 379 SHS Process, 24, 25, 186, 189 SiCf/CMCs, 438 SiCp/Si3N4 Composites, 441 SiCw/Al2O3 Composites, 439 SiCw/Si3N4 Composites, 440 siliceous mesostructured cellular foams (MCFs), 356 silicon, 416, 418 silicones, 295 silver sulfide, 417 silver, 407, 408, 417 simulation model, 161 single metal nodes, 209 SiO2, 424, 525 skeleton convert technique, 297 skew coordination orientation, 236 SNAS, 384 solar energy cell electrolysis, 145, 148, 150 solar generation, 250 sol-gel method, 22, 181, 387, 430, 488, 490, 492, 494, 496, 498, 500, 502, 504, 506 solid polymer electrolytes, 311 solid-state chemistry, 322 solid-state reaction method, 447 solid-state reactions, thermal decomposition, 328 solid-state synthesis, 186, 193, 202 solid-gas, 186, 189, 190, 193 SUBJECT INDEX solution photochemical deposition, 141 solvent effect, 220 solvent evaporation method, 390 solvothermal synthesis, 63, 349 solvothermal/hydrothermal technique, 335 spark plasma sintering, 10, 435 spatial effects, 235 spider silk, 543 spin coating, 395, 516 spontaneous reaction, 152 staged structures, 382 step coverage, 153 stereospecificity, 241 steric hindrance, 236 stoichiometric compounds, 321 structural memory effect, 386 subcomponent exchange, 200 substituent element effects, 571 substituted synthesis, 228 substitution, 270 sulfide, 416, 417 sulfur, 409 super-hard materials, 114 superconductor, 117, 119, 124, 125, 329 Supercritical water oxidation, 83 Supercritical water, 81 superheating, hot spots, 176 superheating, 175, 176, 192 superhydrophobic, 301 superhydrophobicity, 525 superoleophobicity, 525 supramolecular isomerism, 219 surface polymerization, 299 surfactant packing parameter, 353 synergetic effects, 234 synergistic combination, 240 Synergistic coordination, 237, 238 synergistic directing agents, 231 synergistic directing synthesis, 231 synthesis through acid-base pair, 359 synthetic strategies, 228 T tailor-made Synthesis, 584 TEM, 337 temperature effect, 215 temperature measurement, 98 template, 238, 240, 344, 387, 485, 571 tetrahedral clusters, 243, 245, 247 constant pH method, 383, 389 salteoxide (or saltehydroxide) method, 387 structure-directing effect, 571 variable pH method, 384, 388, 389 thermodynamic coupling, 152, 163 thermometry, 40 thin films, 138 TiO2, 330 top-down, 479 transition metal oxides, 108 transparent ceramics, 443 trisulfur, 409 U ultrahigh pressure inorganic synthesis, 97, 125 ultrahigh pressure, 97, 115, 125 ultrathin films, 138-139 UO2, 332 upconversion luminescent materials, 448 uranium oxides, 331 urea hydrolysis method, 384, 385, 389 V vacuum degree, 40 vacuum pump, 59 vacuum sintering, 447 W warmup reactions, 60 water strider, 543 wettability, 525 Whisker-reinforced ceramic matrix composites, 439 Wustite, 332 X X-ray diffraction, 101, 103, 114, 123 XANES, 337 Xe[PtF6], 53 Y YAG Transparent Ceramics, 446 Z zeolite A, 340, 407, 409, 410, 417, 418 zeolite coatings, 91 zeolite L, 410, 411 zeolite membranes, 507 zeolite X, 340, 420, 422, 423 zeolite Y, 340, 406, 407, 408, 410, 412, 413, 415, 416, 417, 418, 419, 420, 421, 422, 423, 424, 425 zeolite-like, 346 zeolite, 64, 176, 177, 178, 339, 405, 406, 407, 408, 409, 410, 411, 412, 413, 414, 415, 416, 417, 418, 419, 420, 421, 422, 423, 424, 425 zeolites, microwave heating, 178 Zeotype, 346 ZIF-7, 512 ZIF-8, 512 zinc phthalocyanine, 423 zinc, 409, 417, 422, 428 ZSM-5, 349 ... fertilizers, Modern Inorganic Synthetic Chemistry, DOI: 10.1016/B978-0-444-53599-3.10001-0 Copyright Ó 2011 Elsevier B.V All rights reserved 2 INTRODUCTION - FRONTIERS IN MODERN INORGANIC SYNTHETIC CHEMISTRY. .. on Modern Inorganic Synthetic Chemistry written and edited by Professors Xu, Pang, and Huo The book consisting of 24 chapters covers a variety of aspects of present-day synthetic inorganic chemistry. .. and nanotechnology Modern inorganic synthetic chemistry, an important branch of synthetic chemistry, has evolved considerably from the traditional synthesis and preparation of inorganic compounds,