Selective Nanocatalysts and Nanoscience E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 540

Veröffentlichungsjahr: 2011

Beschreibung

Filling a gap in the catalysis and nano literature, this monograph is unique in focusing on both nanostructured heterogeneous and homogeneous catalysis. As such, it describes a selection of heterogeneous catalysts in use, showing that the dimension of the relevant portions of the catalysts are always in the 1-100 nm range, and so may be properly understood as nanomachines for the chemical manipulation of molecules to perform high precision selective synthesis. The prominent international authors then go on to show that the concept of nanoscience can be equally applied to artificial homogeneous catalysts whose active sites are generally considered as "single-sites" having a "molecular" dimension. The result is an excellent overview of such hot topics as nanoparticles, MOFs and more, making this indispensable reading for catalytic and organic chemists, as well as those working on organometallics.

Leseprobe

Table of Contents

Cover

Series page

Title page

Copyright page

Preface

List of Contributors

1 The Structure and Reactivity of Single and Multiple Sites on Heterogeneous and Homogeneous Catalysts: Analogies, Differences, and Challenges for Characterization Methods

1.1 Introduction

1.2 Definition of Multiple- and Single-Site Centers in Homogeneous and Heterogeneous Catalysis

1.3 The Characterization Methods in Heterogeneous Catalysis (Including Operando Methods)

1.4 Conclusions

2 Supported Nanoparticles and Selective Catalysis: A Surface Science Approach

2.1 General Introduction

2.2 Synthesis of Supported Metal Nanoparticles: Size and Shape Control

2.3 Selective Catalysis of Supported Metal Nanoparticles

2.4 Summary

3 When Does Catalysis with Transition Metal Complexes Turn into Catalysis by Nanoparticles?

3.1 Introduction

3.2 Nanoparticles vs. Homogeneous Catalysts in C–C Bond-Forming Reactions

3.3 Nanoparticles vs. Homogeneous Catalysts in Hydrogenation Reactions

3.4 Platinum-Catalyzed Hydrosilylation

3.5 Conclusions

4 Capsules and Cavitands: Synthetic Catalysts of Nanometric Dimension

4.1 Introduction on Supramolecular Catalysis

4.2 Compartmentalization of Reactive Species in Synthetic Hosts as Supramolecular Catalysts

4.3 Conclusions

4.4 Outlook

Acknowledgments

5 Photocatalysts: Nanostructured Photocatalytic Materials for Solar Energy Conversion

5.1 Principles of Overall Water Splitting Using Nanostructured Particulate Photocatalysts

5.2 Oxide Photocatalysts for Overall Water Splitting

5.3 Visible Light-Responsive Photocatalysts for Overall Water Splitting

5.4 Conclusions

6 Chiral Catalysts

6.1 The Origin of Enantioselectivity in Catalytic Processes: the Nanoscale of Enantioselective Catalysis

6.2 Parameters Affecting the Geometry of the Metal Environment

6.3 Case of Study (1): Bis(oxazoline)–Cu Catalysts for Cyclopropanation

6.4 Case of Study (2): Catalysts for Diels–Alder Reactions

6.5 Case of Study (3): Salen-Based Catalysts

6.6 Case of Study (4): Multifunctional Catalysis

6.7 Conclusions

7 Selective Catalysts for Petrochemical Industry

7.1 Overview of Petrochemical Industry and Refinery Processes

7.2 Catalysis in the Petrochemical Industry

7.3 Microporous Materials and Shape Selectivity

7.4 Selected Examples of Shape-Selective Catalysis by Zeolites/Zeotypes

7.5 Summary and Outlook

8 Crystal Engineering of Metal-Organic Frameworks for Heterogeneous Catalysis

8.1 Introduction

8.2 Volatile Molecules Coordinated Metal Nodes Acted as Catalytic Centers

8.3 Coordinatively Unsaturated Metal Nodes Acted as Catalytic Centers

8.4 Coordinatively Unsaturated Catalytic Metal Ions Exposed in the Pores of MOFs

8.5 Guest-Accessible Catalytically Functionalized Organic Sites in Porous MOF

8.6 Nanochannel-Promoted Polymerization of Organic Substrates in Porous MOFs

8.7 Homochiral MOFs Used as Enantioselective Catalysts

8.8 Conclusions and Outlook

Acknowledgments

9 Mechanism of Stereospecific Propene Polymerization Promoted by Metallocene and Nonmetallocene Catalysts

9.1 Introduction

9.2 Mechanism of Polymerization

9.3 Elements of Chirality

9.4 Chiral-Site Stereocontrol: Isotactic Polypropylene by Primary Propene Insertion

9.5 Chiral-Site Stereocontrol: Syndiotactic Polypropylene by Primary Propene Insertion

9.6 Chain-End Stereocontrol: Syndiotactic Polypropylene by Secondary Propene Insertion

9.7 Conclusions

Index

Further Reading

Zhou, Q.-L. (Ed.)

Privileged Chiral Ligands and Catalysts

2011

Hardcover

ISBN: 978-3-527-32704-1

Guo, J. (Ed.)

X-Rays in Nanoscience

Spectroscopy, Spectromicroscopy, and Scattering Techniques

2011

Hardcover

ISBN: 978-3-527-32288-6

Cybulski, A., Moulijn, J. A., Stankiewicz, A. (Eds.)

Novel Concepts in Catalysis and Chemical Reactors

Improving the Efficiency for the Future

2010

Hardcover

ISBN: 978-3-527-32469-9

Cejka, J., Corma, A., Zones, S. (Eds.)

Zeolites and Catalysis

Synthesis, Reactions and Applications

2010

Hardcover

ISBN: 978-3-527-32514-6

de Jong, K. P. (Ed.)

Synthesis of Solid Catalysts

2009

Hardcover

ISBN: 978-3-527-32040-0

Astruc, D. (Ed.)

Nanoparticles and Catalysis

2008

Hardcover

ISBN: 978-3-527-31572-7

Ertl, G., Knözinger, H., Schüth, F., Weitkamp, J. (Eds.)

Handbook of Heterogeneous Catalysis

8 Volumes

Second completely revised and enlarged edition

2008

Hardcover

ISBN: 978-3-527-31241-2

The Editors

Prof. Adriano Zecchina

Dipto. di Chimica IFM

Università di Torino

Via Pietro Giuria 7

10125 Torino

Italy

Prof. Dr. Silvia Bordiga

University of Turin

NIS Centre of Excellence

via P. Giuria 7

10125 Torino

Italy

Dr. Elena Groppo

University of Turin

NIS Centre of Excellence

via P. Giuria 7

10125 Torino

Italy

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British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2011 Wiley-VCH Verlag & Co. KGaA,

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ISBN: 978-3-527-32271-8

ePDF ISBN: 978-3-527-63570-2

ePub ISBN: 978-3-527-63569-6

Mobi ISBN: 978-3-527-63571-9

oBook ISBN: 978-3-527-63568-9

Preface

Catalysis and selective catalysis are at the core of synthetic chemistry. In the last century, the development of catalysis has followed two distinct paths, heterogeneous and homogeneous, initially separated and then intimately interconnected. In the first part of the 20th century, heterogeneous catalysis obtained important results, as evidenced by the six Nobel Prizes awarded in just 50 years, beginning with W. Ostwald (1909), followed by P. Sabatier (1912), F. Haber (1918), K. Bosh (1931), up to K. Ziegler, and G. Natta (1956). These results led quickly to important industrial applications, ranging from nitric acid production from ammonia oxidation, to ammonia synthesis, to hydrogenation reactions, and finally to olefin polymerization. Although the majority of these reactions, occurring on transition metal surfaces or on isolated transition metal sites, are relatively simple, at that time little was known about the reaction mechanism and only the development of surface science and computational methods, with the contribution of the Nobel laureates I. Langmuir (1932), C. Inshelwood (1933), and G. Ertl (2007), led to a progressively accurate understanding of the surface structures involved in the catalytic events. The research in heterogeneous catalysis gradually stimulated both the synthesis and the study of finely divided materials (metal oxides, metals, and supported metals), exhibiting a high surface area. These studies certainly contributed to open the era of nanoscience. Similarly, the need of surface characterization has stimulated the development of increasingly surface-sensitive methods.

Although the problem of selectivity in heterogeneous catalysis had not been neglected until then, it is certainly true that this started to become critical with the advent of Ziegler–Natta catalysts and the related synthesis of isotactic polypropylene and since then, the problem of selectivity has started to attract the attention of an increasing number of researchers involved in the construction and characterization of catalytic centers, having the desired selectivity properties. The results in this research area were remarkable, although prevalently obtained through an empirical approach, more than as a result of a rational ab initio design. However, an overall achievement has emerged from such studies, namely the selectivity is the result of a complex design of surface active sites, through the fine tuning of the ligands.

Approximately at the same time, chemists started to develop homogeneous catalysts showing increasingly better defined structures; the list of Nobel Prizes awarded in this field, starting with G. Wilkinson (1973), and followed by W.S. Kowles, R. Noyori, and B. Sharpless (2001), and Y. Chauvin, R. Grubbs, and R. Schrock (2005), fully testifies to these contributions. One of the most remarkable examples of construction of a class of homogeneous catalysts based on a rational design of the active centers is that of Zr-based metallocenes for selective olefin polymerization, for which the steroselective properties were obtained by appropriate design of the ligands sphere.

After about a century since the first Nobel Prize was awarded to catalysis, we can state that both heterogeneous and homogeneous approaches lead to the same general conclusion: a selective catalyst can be considered a nanomachine obtained through a precise control of the structure of the active sites, of the three-dimensional environment and of their relationship. For homogeneous and heterogeneous selective catalysts, the three-dimensional environment around the active sites resembles the tunable structure of enzymes, which are the most efficient catalysts optimized by nature over billions of years. In this regard, a point that merits a specific comment is the fact that, while in the past heterogeneous and homogeneous catalysis mainly followed separate development dynamics, today it is becoming increasingly clear that they are strongly interconnected and that the achievements obtained in one area have influence on the other one. In other words, selective catalysis is a single chapter of science, whatever it is, homogeneous, heterogeneous, or even enzymatic. The chapters of this book, devoted to both heterogeneous and homogeneous catalysts, have been selected following this basic approach:

1. The Structure and Reactivity of Single and Multiple Sites on Heterogeneous and Homogeneous Catalysts: Analogies, Differences, and Challenges for Characterization Methods by A. Zecchina, S. Bordiga, and E. Groppo.

2. Supported Nanoparticles and Selective Catalysis: A Surface Science Approach by W. Zhang.

3. When Does Catalysis with Transition Metal Complexes Turn into Catalysis by Nanoparticles? by J. DeVries.

4. Capsules and Cavitands: Synthetic Catalysts of Nanometric Dimension by G. Borsato, J. Rebek Jr., and A. Scarso.

5. Photocatalysts: Nanostructured Photocatalytic Materials for Solar Energy Conversion by K. Domen.

6. Chiral Catalysts by J.M. Fraile, J.I. García, and J.A. Mayoral.

7. Selective Catalysts for Petrochemical Industry: Shape Selectivity in Microporous Materials by S. Svelle and M. Bjørgen.

8. Crystal Engineering of Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis by Chuan-De Wu.

9. Mechanism of Stereospecific Propene Polymerization Promoted by Metallocene and Nonmetallocene Catalysts by A. Correa and L. Cavallo.

From the above-mentioned titles, the effort to mix both homogeneous and heterogeneous catalysts in a single book is evident.

Elena Groppo

Silvia Bordiga

Adriano Zecchina

List of Contributors

Morten Bjørgen

Norwegian University of Science and Technology

Department of Chemistry

Trondheim N-7491

Norway

Silvia Bordiga

Department of Inorganic, Physical and Material Chemistry (IFM)

NIS Centre of Excellence Nanostructured Interfaces and Surfaces

University of Torino

Via P. Giuria 7

10125 Torino

Italy

Giuseppe Borsato

Università Ca’ Foscari di Venezia

Dipartimento di Scienze Molecolari e Nanosistemi

Calle Larga S. Marta 2137

30123 Venice

Italy

Luigi Cavallo

Università di Salerno

Dipartimento di Chimica

Via ponte don Melillo

84084 Fisciano, SA

Italy

Andrea Correa

Università di Salerno

Dipartimento di Chimica

Via ponte don Melillo

84084 Fisciano, SA

Italy

Kazunari Domen

The University of Tokyo

School of Engineering

Department of Chemical System Engineering

Tokyo 113-8656

Japan

José M. Fraile

Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)

Departamento de Química Orgánica

Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C. C/ Pedro Cerbuna s/n

50009 Zaragoza

Spain

José I. García

Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)

Departamento de Química Orgánica

Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C. C/ Pedro Cerbuna s/n

50009 Zaragoza

Spain

Elena Groppo

Department of Inorganic, Physical and Material Chemistry (IFM)

NIS Centre of Excellence Nanostructured Interfaces and Surfaces

University of Torino

Via P. Giuria 7

10125 Torino

Italy

José A. Mayoral

Instituto de Síntesis Química y Cattálisis Homogénea (ISQCH)

Departamento de Química Orgtánica

Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C. C/ Pedro Cerbuna s/n

50009 Zaragoza

Spain

Julius Rebek Jr.

The Scripps Research Institute

The Skaggs Institute for Chemical Biology

La Jolla, CA 92037

USA

Alessandro Scarso

Università Ca’ Foscari di Venezia

Dipartimento di Scienze Molecolari e Nanosistema

Calle Larga S. Marta 2137

30123 Venice

Italy

Stian Svelle

University of Oslo

Innovative Natural Gas Processes and Products (inGAP), Department of Chemistry

Oslo N-0315

Norway

Johannes G. de Vries

DSM Innovative Synthesis BV

A Unit of DSM Pharma Chemicals

P.O. Box 18

6160 MD Geleen

The Netherlands

Da Wang

Nankai University

Institute of Polymer Chemistry, Key Laboratory of Functional Polymer Materials of Ministry of Education

Tianjin 300071

China

Chuan-De Wu

Zhejiang University

Department of Chemistry

Hangzhou 310027

China

Rui Yan

Nankai University

Institute of Polymer Chemistry, Key Laboratory of Functional Polymer Materials of Ministry of Education

Tianjin 300071

China

Adriano Zecchina

Department of Inorganic, Physical and Material Chemistry (IFM)

NIS Centre of Excellence Nanostructured Interfaces and Surfaces

University of Torino

Via P. Giuria 7

10125 Torino

Italy

Wangqing Zhang

Nankai University

Institute of Polymer Chemistry, Key Laboratory of Functional Polymer Materials of Ministry of Education

Tianjin 300071

China