N a n M o a S c i e n c e p t e o r a n d r i o a l u s s E n g i n e e r i n g edited by G Q Lu University of Queensland, Australia X S Z h a o National University of Singapore, Singapore Imperial College Press Published by Imperial College Press 57 Shelton Street Covent Garden London WC2H 9HE Distributed by World Scientific Publishing Co Pte Ltd Toh Tuck Link, Singapore 596224 USA office: 27 Warren Street, Suite 401^02, Hackensack, NJ 07601 UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library NANOPOROUS MATERIALS: SCIENCE AND ENGINEERING Series on Chemical Engineering Copyright © 2004 by Imperial College Press All rights reserved This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the Publisher For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA In this case permission to photocopy is not required from the publisher ISBN ISBN 1-86094-210-5 1-86094-211-3 (pbk) Editor: Tjan Kwang Wei Printed in Singapore by World Scientific Printers (S) Pte Ltd Preface In the last decade, we have witnessed a rapid growth in research and development of nanotechnology, especially nanostructured materials Nanoporous materials as an important class of nanostructured materials possess high specific surface area, large pore volume, uniform pore size, and rich surface chemistry These materials present great promises and opportunities for a new generation of functional materials with improved and tailorable properties for applications in adsorption, membranes, sensors, energy storage, catalysis and photocatalysis, and biotechnology, etc Interest in making materials from nanoscale building blocks arose from discoveries that by controlling the size in the range of 1-100 nm and the assembly of such constituents, one could alter and prescribe the properties of the assembled nanostructures Nanoscale phenomena and objects have been around for some time Catalysts, for example, are mostly nanoscale particles, and catalysis is a nanoscale phenomenon What is new and different now is the degree of understanding and deliberate control and precision that the new nanoscale techniques afford Instead of discovering new materials by random search (trial-and-error), we can now design them systematically Nanoporous materials can have long-range structural order or disordered structure and contain pores of the dimension of a few nanometers to tens of nanometers Some applications such as catalysis take advantage of high surface area and pore confinement effects Synthesis and processing of nanoporous materials with controllable structures and properties require new approaches such as molecular templating and intercalation in a bottom-up manner From a practical standpoint, a large specific surface for nanoparticles is most desired for catalysis However, fine powder catalysts can cause serious operational problems such as agglomeration, difficulties in loading, pressure drop, and separation of catalyst from the reaction products A feasible approach to generating a large and accessible surface area of catalyst but avoiding the morphology of fine powder is to create a composite or immobilized structure One can disperse nanoparticles of metals or oxides in an inorganic support to stabilize the discrete nanoparticles, meanwhile maintaining most of their surface accessible to reactant molecules However, the conventional methods of preparing the catalysts such as impregnation often result in agglomerated catalyst particles in the support, thus decreasing the active surface area, and uniformity of the active centers With nanostructuring techniques, active metal or oxide precursors can be incorporated or grafted on the nanoporous support during synthesis thus not only increase the control in catalyst particle size, surface area and dispersion, but also eliminating the cost and problems associated with impregnation Since the early 1990s, a large number of microporous and mesoporous materials have found wide applications in catalysis Major breakthroughs in materials synthesis such as the templated synthesis of mesoporous molecular sieves M41S and porous clay heterostructures have opened exciting avenues for designing new classes of nanoporous materials based on molecular templating and self-assembly principle (with pore dimensions between to 10 nm) These materials offer great potential for applications in separation and catalysis, particularly reactions involving large and bulky molecules We are excited at the prospect of an explosion of revolutionary discoveries at nanoscale The new millennium presents opportunities as well as challenges to scientists and engineers working in this dynamic field of nanoporous materials in terms of the tailor-design, synthesis and characterization for specific functionalities and applications The main objectives of this book are to provide the readers with an overview of the field of nanoporous materials and to present the latest advances in various areas from synthesis, characterization, surface modification to adsorption and separation processes, and biological and catalytic applications Fundamentally, this book contains chapters dealing with important issues in synthesis of nanoporous materials of various compositions, characterization techniques, surface modification/ functionalization, catalyst design and nanostructure tailoring, and adsorption/separation application including bioseparation This book presents 28 comprehensive chapters reviewing the state of the art in the field of nanoporous materials contributed by some of the finest scientists in the world in this field With an overview of nanoporous materials in chapter 1, chapters 2-10 describe some general strategies for the synthesis of nanoporous materials such as the nonionic block copolymer template method, the synthesis of composite materials with a zeolite framework, preparation of hydrophobic membranes using sol-gel technique, macroporous materials templated by colloidal crystals, and carbon nanotubes The advances in characterization of nanoporous materials by physical adsorption in combination with simulation, and modification and functionalization of nanoporous materials are covered in chapters 11-16 In addition to traditional pore evaluation methods such as the BJH method based on Kelvin equation for pore size determination, the development of microscopic methods, such as the non-local-density functional theory (NLDFT) or computer simulation methods (e.g monte-carlo and molecular-dynamic simulations), which allow the description of the configuration of adsorbed molecules in pores on a molecular level (elaborated in chapters 11 and 12) Surface functionalization of nanoporous materials by grafting, co-condensation routes, and molecularly designed dispersion methods, surface alumination to alter acidity, as well as measurement of surface acidity can be found in chapters 13-16 Recent developments in the catalytic applications of nanoporous materials, ranging from acidic catalysis to base catalysis, from shape-selective catalysis to environmentally friendly catalysis, are presented in chapters 17-21 Adsorption- and separation processes involving nanoporous materials are subjects of chapters 22-28 Nanoporous materials for the removal of pollutants in gas or liquid phase are elaborated Separation and immobilization of enzymes are reviewed in chapters 26 and 27 We would like to thank the authors of the chapters for their valuable and timely contributions, and for their patience and cooperation in the editing process We hope that this book would be a useful reference for senior students, graduate students and researchers in materials chemistry, physical and colloid chemistry, chemical engineering, materials science, biotechnology and nanotechnology Finally, we would like to express our sincere thanks to Professor Ralph T Yang, University of Michigan, the Series Editor of Chemical Engineering for Imperial College Press for his kind invitation to contribute this volume We would also like to thank the Editor in Imperial College Press, Tjan Kwang Wei for his great assistance We are very grateful to Sharon Mathiesen for her wonderful help with manuscript management and editing Last but not the least, to our respective families for their love, understanding and support in this endeavor G.Q (Max ) Lu Brisbane, Australia November, 2003 George X S Zhao Singapore Contents Preface v Nanoporous Materials-an Overview 1.1 Introduction 1.2 Classification of Nanoporous Materials 1.3 Properties and Characterization of Nanoporous Materials 1.4 Major Opportunities in Applications 1.5 Concluding Remarks 11 References 13 Advances in Mesoporous Materials Templated by Nonionic Block Copolymers 14 2.1 Introduction 14 2.2 Siliceous Mesoporous Materials 16 2.3 Wall Structures of Mesoporous Materials Templated by Amphiphilic Block Copolymers 22 Morphology of Mesoporous Materials Templated by Block Copolymers 24 2.5 Non-siliceous Structures 28 2.6 Applications 33 2.7 Conclusion Remarks 38 2.8 Acknowledgements 38 References 39 Zeolite/Mesoporous Molecular Sieve Composite Materials 47 3.1 Introduction 47 3.2 Mechanisms of Zeolite Germination 48 2.4 This page has been reformatted by Knovel to provide easier navigation ix x Contents 3.3 51 3.4 Catalytic Properties 84 3.5 Future Challenges 90 3.6 Conclusion 93 3.7 Acknowledgements 93 References Synthesis Strategies for Zeolite/MMS Composites 93 Chromium-containing Ordered Nanoporous Materials 101 4.1 101 4.2 Materials and Methods 103 4.3 Results and Discussion 106 4.4 Conclusion 118 4.5 Acknowledgements 119 References Introduction 119 Surfactant-templated Mesostructured Materials: Synthesis and Compositional Control 125 5.1 125 5.2 Synthesis Routes 126 5.3 Compositions of Mesostructured and Mesoporous Materials 140 5.4 Conclusions and Outlook 151 5.5 Acknowledgments 152 References Introduction 152 Organic Host-guest Structures in the Solid State 165 6.1 Introduction 166 6.2 Host Design Principles 168 6.3 C3 Symmetry and Halogen Halogen Interaction in Host Design 170 6.4 Wheel-axle Host Lattice 177 6.5 Design of Layered Host: Crystal Engineering 179 6.6 Gas Storage in Interstitial Voids 182 6.7 Guest Selectivity in Inclusion 184 This page has been reformatted by Knovel to provide easier navigation Contents xi 6.8 185 6.9 Acknowledgement 185 References Conclusions 185 Nonsurfactant Route to Nanoporous Phenyl-modified Hybrid Silica Materials 188 7.1 188 7.2 Methods 191 7.3 Results and Discussion 192 7.4 Conclusions 202 7.5 Acknowledgements 202 References Introduction 202 3D Macroporous Photonic Materials Templated by Self Assembled Colloidal Spheres 206 8.1 Introduction 206 8.2 A Survey of Photonic Bandgap 207 8.3 Nanolithography for Photonic Crystals 211 8.4 Self-assembly Approaches to 3D Photonic Crystals 212 8.5 Fabrication of Intentional Defects in 3D Photonic Crystals 226 Acknowledgements 228 References 228 8.6 Hydrophobic Microporous Silica Membranes for Gas Separation and Membrane Reactors 237 9.1 Introduction 237 9.2 Inorganic Membranes 238 9.3 Hydrothermal Stability and Hydrophobicity-key Areas of Improvement 243 9.4 Membrane Reactors 251 9.5 Perspective and Concluding Remarks 256 9.6 Acknowledgement 257 References 257 This page has been reformatted by Knovel to provide easier navigation xii Contents 10 Synthesis and Characterization of Carbon Nanotubes for Hydrogen Storage 263 10.1 Introduction 264 10.2 Construction, Structure and Unique Properties of Carbon Nanotubes 266 10.3 Synthesis of Carbon Nanotubes 271 10.4 Surface and Pore Structure of Carbon Nanotubes 279 10.5 Experimental Investigations on Hydrogen Uptake in Carbon Nanotubes 286 Theoretical Predictions and Simulations of Hydrogen Uptake in Carbon Nanotubes 295 Possible Hydrogen Adsorption Sites in Carbon Nanotubes 303 10.8 Future Research Topics and Remarks 308 10.9 Acknowledgement 309 References 309 10.6 10.7 11 Physical Adsorption Characterization of Ordered and Amorphous Mesoporous Materials 317 11.1 Introduction 317 11.2 Surface and Pore Size Analysis by Physisorption: General Aspects 322 11.3 Pore Condensation and Adsorption Hysteresis 328 11.4 Pore Size Analysis of Mesoporous Solids 345 11.5 Concluding Remarks 355 11.6 Acknowledgements 356 11.7 References 356 12 Molecular Simulation of Adsorption in Porous Materials 365 12.1 Introduction 366 12.2 Simulation Techniques 366 12.3 Thermodynamics 369 12.4 Adsorption in Spaces with Simple Geometries 372 12.5 Adsorption Heterogeneity 380 This page has been reformatted by Knovel to provide easier navigation materials for potential biocatalysis, biosensor, bioreactor and pharmaceutical applications Various enzymes including phosphatases, horseradish peroxidase, glucose oxidase, and organophosphorus acid anhydrolyse in mesoporous host matrices exhibit significantly enhanced catalytic activities over those in microporous hosts Observation of enhanced stability of encapsulated enzymes prompted us to study the protein unfolding and refolding in confined space as determined by the pore sizes in the host matrix The extent of refolding of cytochrome c in the mesoporous host was found to increase with the pore sizes With further research this method could be established as a unique tool for studying the protein folding pathway, folding intermediates, conformation change, and probably single molecule activity as well as the proteinprotein interactions Acknowledgements This work has been supported in part by the National Institutes of Health (Grant No DE09848), the Commonwealth of Pennsylvania through a grant to the Nanotechnology Institute of Southeastern Pennsylvania, the US Army Research Office, the US Army Research Laboratory, the US Department of Energy, and the National Natural Science Foundation of China (NSFC Nos 29874002, 19810760343 and 29825504) The authors wishes to thank a cadre of students, associates and collaborators for their contributions to the work described in this article References L Kresge C, T., Leonowicz M E., Roth W J., Vartuli J C and Beck J S., Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism, Nature 359 (1992) pp 710-12 Beck J S., Vartuli J C , Roth W J., Leonowicz M E., Kresge C T., Schmitt K D., Chu C T W., Olson D H and Sheppard E W., A new family of mesoporous molecular sieves prepared with liquid crystal templates, J Am Chem Soc 114 (1992) pp 10834-43 Ying J.Y., Mehnert C P and Wong M.S., Synthesis and applications of supramolecular-templated mesoporous materials, Angew Chem Int Ed 38 (1999) pp 56-77 Carati A., Ferraris 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G., Rigid matrix artificial chaperone (RMAC)-mediated refolding of heme proteins, Polym Mater ScL Eng 87 (2002) pp 252-253 68 Avnir D., Braun S., Lev O,, and Ottolenghi M., Enzymes and other proteins entrapped in sol-gel materials, Chem Mater (1994) pp 1605-14 69 Dave B.C., Dunn B., Valentine J.S., and Zink J.I., Sol-gel encapsulation methods for biosensors, Anal Chem 66 (1994) pp 1120A-1127A 70 Xie S., Single-molecule approach to enzymology, Single Molecules (2001) pp 229236 71 Wei Y., Sun Z.F., Spiro T., Yuan J.M et al Using resonance Raman spectroscopy to monitor the folding states of cytochrome c encapsulated in mesoporous matrices, Manuscript in preparation 72 Onuchic J N., Wolynes P G., Luthey-Schulten Z and Socci N D., Toward an outline of the topography of a realistic protein-folding funnel, Proc Nat Acad ScL USA 92 (1995) pp 3626-30 73 Sun Z and Wei Y., Unpublished results Author Index A Ahn W.S 649 B Baltes M Burleigh M.C 487 756 C Cheng H-M ChongA.S.M Choudhary V.R Cool P 263 393 596 487 D Daehler A Dai S Denoyel R Diniz da Costa J.C Dong H 812 756 727 237 188 F Fan J Fang H-T Feng Q 14 263 188 G Giessler S 237 H Han Y J Jansen S A 519 188 K Kaliaguine S Kim GJ Knowles W.V L Le Cloirec P LiF LiZ-C Liu C Liu X Lu G.Q 47 649 125 772 263 188 263 14 1,237,393 M Macquarrie DJ Mokaya R MotaJ.P.B 553 427 694 N Nangia A Nicholson D 165 365 O O'Connor AJ On Do Trong 812 47 Q QiuK-Y 188, 873 S Selvam P SeoG Shen J-P Song C Stevens G.W 101 649 623 464, 623 812 T Thommes M TianB Turaga U.T 317 14 464 U Uphade B.S 596 V Vansant E.F 487 W Wang CE Wei Y Wong M.S Wright P.A 188 188,873 125 849 X Xiao F-S XuJ XuX 519 188 464 Y Yang H Yang Q-H Yiu H.H.P YuC 14 263 849 14 Z Zhao D.Y Zhao X.S Zheng J Zhou Z.C 14 1,206,393,464 464 206 Index Index terms Links A acid catalysis 74 acid-base pairs 31 acidity 85 651 536 557 439 653 519 633 645 acidity Brönsted 479 Lewis 480 adsorbent – environmental remediation 757 767 capacity 812 815 physical 383 equilibria 781 kinetics 775 thermodynamics 380 adsorption alkylation 628 820 630 B base catalysis 575 basity 657 BET 324 bioadsorption 812 biocompatible nonsurfactant template 874 bioadsorption 812 BJH 329 breakthrough curve 791 659 This page has been reformatted by Knovel to provide easier navigation 895 896 Index terms Links C calorimetry 468 canonical Monte Carlo (GCMC) 367 capillary condensation 331 carbon nanotubes 266 catalysis 102 catalyst 487 chiral catalyst 668 chromium catalyst 102 clathrate 168 co-condensation 188 861 colloidal microspheres 214 composite materials 427 519 407 555 51 corona 369 22 cracking 435 crystal engineering 179 crystallization 436 48 D density function theory 729 diffusion 731 697 E encapsulation of enzyme 880 environmental catalysts 596 enzyme 815 enzyme immobilization 851 EPR 481 817 F Friedel-Crafts alkylation 562 FTIR 473 This page has been reformatted by Knovel to provide easier navigation 556 761 897 Index terms functionalization Links 394 573 760 861 863 gas separation 237 241 gas storage 182 293 grafting 403 446 555 663 664 248 395 418 78 394 405 317 322 immobilization 649 668 isopropylation 632 G 760 graphite 269 H host-guest compounds 165 hydrogen bonding 169 energy 308 hydrophobicity hydrothermal stability hysteresis I K Kelvin equation 328 329 L Langmuir isotherm 748 Lewis acid 561 Lewis base 598 linear driving force (LDF) 722 liquid-phase adsorption 742 563 598 This page has been reformatted by Knovel to provide easier navigation 898 Index terms Links M macroporous materials 225 membrane reactor 251 membranes 237 mesoporous carbons 147 materials 126 metal oxides 144 silica spheres 879 metal oxides 499 microporosity 22 23 molecular-dynamic (MD) simulations 321 368 molecularly designed dispersion 488 monolayer 487 Monte-carlo (MC) simulation 317 488 N nanocatalysts 499 nanosized zeolite 537 NMR 477 non-ionic block copolymer 14 16 non-local-density-functional theory (NLDFT) 317 321 non-silicate mesoporous materials 129 nonsurfactant fructose template 190 355 O oxidation 113 P particle uptake rate equation 713 phenyl groups 193 physical adsorption 322 PMO 762 This page has been reformatted by Knovel to provide easier navigation 899 Index terms Links positron annihilation spectroscopy (PAS) 481 post-alumination 429 post-treatment 527 protein refolding and unfolding 882 proteins 812 528 814 816 522 523 R redox catalysis 660 S self assembly 207 SEM 220 separation 816 shape selective catalysis 635 silylation 398 size exclusion 827 sol-gel 238 structural stability 125 superacid 521 supported catalysts 599 surface chemistry 727 729 modification 499 500 structure 271 surfactant-templating routes 127 synthesis 126 3D photonic crystals 211 T template 207 templating mechanism titration 466 TPD 470 Transport 694 This page has been reformatted by Knovel to provide easier navigation 849 900 Index terms Links V volumetric adsorption 323 Z zeolite 48 366 630 This page has been reformatted by Knovel to provide easier navigation 632 ... characterization of nanoporous materials by physical adsorption in combination with simulation, and modification and functionalization of nanoporous materials are covered in chapters 11-16 In addition to... nanotechnology, and the importance of nanomaterials The basic concepts and definitions in relation to porous materials and nanoporous materials will be given to understand the context of nanoporous materials. .. catalysis has had a major impact on chemical and fuel production, environmental protection and remediation, and processing of consumer products and advanced materials [8] A survey of U.S industries