Interfacial Catalysis

INTERFACIAL 

C ATALYS I s 

EDITED BY 

ALEXANDER G. VOLKOV 

Oakwood College 

Huntsville, Alabama, U.S.A. 

a% 

MARCEL 

DEKKER 

MARCEL DEKKER, INC. 

NEW YORK BASEL 

Copyright © 2003 by Taylor & Francis Group, LLC

ISBN: 0-8247-0839-3 

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Preface 

Interfacial catalysis plays a key role in many chemical, physical, and biological processes. 

The past decade has witnessed a huge increase of research interest in the study of interfacial 

catalysis at liquid interfaces. Processes taking place at the interface between two 

immiscible liquid phases are fundamental to life since virtually all energy conversion 

processes in living organisms occur at liquid interfaces. The properties of liquid–liquid 

interfaces are very important for a variety of industries, including biotechnology, organic 

synthesis, nanochemistry, catalysis, pharmaceuticals, cosmetics, paints, detergents, oil 

extraction processes, and mining. 

The interface between two immiscible liquids with immobilized photosynthetic pigments 

serves as a convenient model for investigating photoprocesses that are accompanied 

by spatial separation of charges. The efficiency of charge separation is defined by the 

quantum yield of any photochemical reaction. Heterogeneous systems in which the oxidants 

and the reductants are either in different phases or sterically separated are the most 

effective in this regard. Different solubilities of the substrates and reaction products in the 

two phases of heterogeneous systems can alter the redox potential of reactants, making it 

possible to carry out reactions that cannot be performed in a homogeneous phase. 

The book is organized into five parts. Part I consists of seven chapters and deals with 

fundamental aspects of interfacial phenomena such as catalytic properties of liquid interfaces, 

electrochemistry at polarized interfaces, ion solvation and resolvation, interfacial 

potentials, separations, and interfacial catalysis in metal complexation and in enhanced oil 

recovery. 

Part II contains four chapters about history, theory, molecular mechanisms, synthesis, 

and experimental systems in phase transfer catalysis. 

Part III deals with micellar catalysis, enzymology, and photochemical reactions in 

reversed micelles. 

The chapters in Part IV discuss biological aspects of interfacial and membrane 

catalysis including bioelectrocatalysis, ion channels, mechanisms of respiration and photosynthesis, 

membrane catalysis, and ion transport processes. 

Part V, which is about interfacial photocatalysis, includes such topics as nanochemistry, 

nanoparticles, self-organized microheterogeneous structures, photosensitizers, 


and photocatalytic oxygen evolution. The experimental systems and theoretical analysis of 

interfacial photocatalytic systems are also discussed in Chapters 14, 15, and 18. 

I would like to extend my thanks to the authors for the time they spent on this 

project and for teaching us about their work on nanochemistry and interfacial catalysis. I 

also thank our Acquisitions Editor, Anita Lekhwani, and our Production Editor, Joseph 

Stubenrauch, for their friendly and courteous assistance. 

Alexander G. Volkov 


Contents 

Preface 

Contributors 

Part I. Interfacial Phenomena 

1. Interfacial Catalysis at Oil/Water Interfaces 


2. Electrochemistry of Chemical Reactions at Polarized Liquid–Liquid Interfaces 

Takashi Kakiuchi 

3. Interfacial Catalysis in Metal Complexation 

Hitoshi Watarai 

4. The Role of Water Molecules in Ion Transfer at the Oil/Water Interface 

Toshiyuki Osakai 

5. Interfacial Potential and Distribution Equilibria Between Two Immiscible 

Electrolyte Solutions 

Le Quoc Hung 

6. Use of Cyclodextrins or Porous Inorganic Supports to Improve Organic/ 

Aqueous Interfacial Transfers 

Martine Urrutigoïty and Philippe Kalck 

7. Ultrathin Films: Their Use in Enhanced Oil Recovery and in Interfacial 

Catalysis 

Lu Zhang, Sui Zhao, Jia-Yong Yu, Angelica L. Ottova´, and H. Ti Tien 

Part II. 

Phase Transfer Catalysis 

8. Phase Transfer Catalysis 

Mieczysiaw Mąkosza and Michai Fedoryn´ski 

9. Liquid–Liquid Phase Transfer Catalysis: Basic Principles and Synthetic 

Applications 

Domenico Albanese 

10. Phase Transfer Catalysis: Fundamentals and Selected Systems 

Jing-Jer Jwo 


11. Interfacial Mechanism and Kinetics of Phase-Transfer Catalysis 

Hung-Ming Yang and Ho-Shing Wu 

Part III. 

Micellar Catalysis 

12. Enzymes in Reverse Micelles (Microemulsions): Theory and Practice 

Andrey V. Levashov and Natalia L. Klyachko 

13. Micellar Catalysis 

Vincent C. Reinsborough 

14. Multiple Effects of Water Pools and Their Interfaces Formed by Reversed 

Micelles on Enzymic Reactions and Photochemistry 

Ayako Goto, Yuko Ibuki, and Rensuke Goto 

Part IV. 

Interfacial Biocatalysis and Membrane Catalysis 

15. Supported Planar BLMs (Lipid Bilayers): Formation, Methods of Study, 

and Applications 

Angelica L. Ottova´ and H. Ti Tien 

16. Bioelectrocatalysis 

Kenji Kano and Tokuji Ikeda 

17. Energetics and Gating of Narrow Ionic Channels: The Influence of Channel 

Architecture and Lipid–Channel Interactions 

Peter C. Jordan, Gennady V. Miloshevsky, and Michael B. Partenskii 

18. Biocatalysis: Electrochemical Mechanisms of Respiration and Photosynthesis 


19. New Types of Membrane Reactions Mimicking Biological Processes 

Sorin Kihara 

20. Ion-Transport Processes Through Membranes of Various Types: Liquid 

Membrane, Thin Supported Liquid Membrane, and Bilayer Lipid Membrane 

Osamu Shirai and Sorin Kihara 

Part V. 

Interfacial Photocatalysis 

21. Development of Structurally Organized Photocatalytic Systems for 

Photocatalytic Hydrogen Evolution on the Basis of Lipid Vesicles with 

Semiconductor Nanoparticles Fixed on Lipid Membranes 

Oxana V. Vassiltsova and Valentin N. Parmon 

22. Catalysis and Photocatalysis at Polarized Molecular Interfaces: An 

Electrochemical Approach to Catalytic Processes Based on Two-Phase 

Systems, Self-Organized Microheterogeneous Structures, and 

Unsupported Nanoparticles 

Riikka Lahtinen, Henrik Jensen, and David J. Fermı´n 

23. Photosensitizers at Interfaces of Model Membranes 

Sarah A. Gerhardt and Jin Z. Zhang 


Contributors 

Domenico Albanese Dipartimento di Chimica Organica e Industriale, Universita` degli 

Studi di Milano, Milan, Italy 

Michał Fedoryn´ski 

Poland 

Faculty of Chemistry, Warsaw University of Technology, Warsaw, 

David J. Fermı´n Laboratoire d’Electrochimie Physique et Analytique, Ecole 

Polytechnique Fe´ de´ rale de Lausanne, Lausanne, Switzerland 

Sarah A. Gerhardt Department of Chemistry, University of California at Santa Cruz, 

Santa Cruz, California, U.S.A. 

Ayako Goto 

Rensuke Goto 

Japan 

School of Informatics, University of Shizuoka, Shizuoka, Japan 

Institute for Environmental Sciences, University of Shizuoka, Shizuoka, 

Le Quoc Hung Institute of Chemistry, National Center for Natural Science and 

Technology, Hanoi, Vietnam 

Yuko Ibuki 

Japan 

Institute for Environmental Sciences, University of Shizuoka, Shizuoka, 

Tokuji Ikeda Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto 

University, Kyoto, Japan 

Henrik Jensen Laboratoire d’Electrochimie Physique et Analytique, Ecole Polytechnique 

Fe´ de´ rale de Lausanne, Lausanne, Switzerland 

Peter C. Jordan Department of Chemistry, Brandeis University, Waltham, 

Massachusetts, U.S.A. 


Jing-Jer Jwo Department of Chemistry, National Cheng Kung University, Tainan, 

Taiwan, Republic of China 

Takashi Kakiuchi Department of Energy and Hydrocarbon Chemistry, Kyoto 


Philippe Kalck Laboratoire de Catalyse, Chimie Fine et Polyme` res, Ecole Nationale 

Supe´ rieure des Inge´ nieurs en Arts Chimiques et Technologiques, Toulouse, France 

Kenji Kano Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto 


Sorin Kihara 

Department of Chemistry, Kyoto Institute of Technology, Kyoto, Japan 

Natalia L. Klyachko Department of Chemical Enzymology, Faculty of Chemistry, 

Moscow State University, Moscow, Russia 

Riikka Lahtinen 

Kingdom 

Department of Chemistry, University of Liverpool, Liverpool, United 

Andrey V. Levashov 

Moscow, Russia 

Mieczysław Mąkosza 

Warsaw, Poland 

Department of Chemical Enzymology, Moscow State University, 

Institute of Organic Chemistry, Polish Academy of Sciences, 

Gennady V. Miloshevsky 


Department of Chemistry, Brandeis University, Waltham, 

Toshiyuki Osakai 

Japan 

Angelica L. Ottova´ 

Michigan, U.S.A. 

Department of Chemistry, Faculty of Science, Kobe University, Kobe, 

Department of Physiology, Michigan State University, East Lansing, 

Valentin N. Parmon 

Boreskov Institute of Catalysis, Novosibirsk, Russia 

Michael B. Partenskii Department of Chemistry, Brandeis University, Waltham, 


Vincent C. Reinsborough Department of Chemistry, Mount Allison University, 

Sackville, New Brunswick, Canada 

Osamu Shirai Department of Nuclear Energy System, Japan Atomic Energy Research 

Institute, Ibaraki, Japan 

H. Ti Tien Department of Physiology, Michigan State University, East Lansing, 

Michigan, U.S.A. 


Martine Urrutigoı¨ty Laboratoire de Catalyse, Chimie Fine et Polyme` res, Ecole 

Nationale Supe´ rieure des Ingénieurs en Arts Chimiques et Technologiques, Toulouse, 

France 

Oxana V. Vassiltsova 

Boreskov Institute of Catalysis, Novosibirsk, Russia 

Alexander G. Volkov Department of Chemistry, Oakwood College, Huntsville, 

Alabama, U.S.A. 

Hitoshi Watarai Department of Chemistry, Graduate School of Science, Osaka 

University, Osaka, Japan 

Ho-Shing Wu Department of Chemical Engineering, Yuan-Ze University, Taoyuan, 

Taiwan, Republic of China 

Hung-Ming Yang Department of Chemical Engineering, National Chung Hsing 

University, Taichung, Taiwan, Republic of China 

Jia-Yong Yu Research Center for Enhanced Oil Recovery, Technical Institute of Physics 

and Chemistry, Chinese Academy of Sciences, Beijing, People’s Republic of China 

Jin Z. Zhang Department of Chemistry and Biochemistry, University of California at 

Santa Cruz, Santa Cruz, California, U.S.A. 

Lu Zhang Research Center for Enhanced Oil Recovery, Technical Institute of Physics 


Sui Zhao Research Center for Enhanced Oil Recovery, Technical Institute of Physics

Interfacial Catalysis

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