Sets the stage for environmentally friendly industrial organic syntheses

From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability.

Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an international team of leading chemists representing both industry and academia. The book begins with a chapter on environmentally benign oxidants and then covers:

• Selective oxidations catalyzed by TS-1 and other metal-substituted zeolites
• Selective catalytic oxidation over ordered nanoporous metallo-aluminophosphates
• Selective oxidations catalyzed by mesoporous metal-silicates
• Liquid phase oxidation of organic compounds by supported metal-based catalysts
• Selective liquid phase oxidations in the presence of supported polyoxometalates
• Selective oxidations catalyzed by supported metal complexes
• Liquid phase oxidation of organic compounds by metal-organic frameworks
• Heterogeneous photocatalysis for selective oxidations with molecular oxygen

All the chapters dedicated to specific types of catalysts follow a similar organization and structure, making it easy to compare the advantages and disadvantages of different catalysts. The final chapter examines the latest industrial applications, such as the production of catechol and hydroquinone, cyclohexanone oxime, and propylene oxide.

With its unique focus on liquid phase heterogeneous oxidation catalysis, this book enables researchers in organic synthesis and oxidation catalysis to explore and develop promising new catalytic materials and synthetic routes for a broad range of industrial applications.

MARIO G. CLERICI, Laurea in Chemistry, has over thirty-five years of industry experience working with organic synthesis and homogeneous and heterogeneous catalysis in the ENI group. He also taught courses in the Department of Industrial Chemistry at the University of Turin, Italy, for eight years and served as a scientific expert on clean catalytic technologies at the International Centre for Science and High Technology, Trieste. A recipient of the Donald W. Breck Award, Dr. Clerici holds more than forty patents.

OXANA A. KHOLDEEVA, PhD, is Head of the Research Group for Heterogeneous Catalysis for Liquid-Phase Selective Oxidations at the Boreskov Institute of Catalysis, Russia, and a visiting professor at several universities in Europe and the United States. As the author of over 100 articles and nine patents, she participated in the expert panel of the sixth World Congress on Oxidation Catalysis and is a member of the International Advisory Board for the International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation (ADHOC).

Preface

List of contributors

1Environmentally Benign Oxidants
Giorgio Strukul and Alessandro Scarso

1.1 Introduction

1.2 Oxygen (Air)

1.3 Alkylhydroperoxides

1.4 Hydrogen Peroxide

1.5 Conclusions

References

2Oxidation Reactions Catalyzed by Transition Metal-Substituted Zeolites
Mario G. Clerici and Marcelo E. Domine

2.1 Introduction

2.2 Synthesis and Characterization of Zeolites

2.3 Catalytic Properties

2.4 Mechanistic Aspects

2.5 Stability of Metal-Substituted Zeolites to Reaction Conditions

2.6 Conclusions

References

3 Selective Catalytic Oxidation over Ordered Nanoporous Metallo-Aluminophosphates
Parasuraman Selvam and Ayyamperumal Sakthivel

3.1 Introduction

3.2 Synthesis

3.3 Characterization

3.4 Catalytic Properties

3.5 Mechanistic Aspects

3.6 Catalysts Stability

3.7 Conclusion

References

4 Selective Oxidations Catalyzed by Mesoporous Metal-Silicates
Oxana A. Kholdeeva

4.1 Introduction

4.2 Synthesis and Characterization

4.3 Catalytic Properties

4.4 Mechanistic Aspects 4.5 Stability

4.5.1 Mechanisms of Deactivation 4.5.2 Solving Problem of Hydrothermal Stability 4.5.3 Hydrothermally Stable Catalysts: Scope and Limitations 4.6 Conclusion and Outlook

References

5 Liquid phase oxidation of organic compounds by supported metal-based catalysts with a focus on gold
Cristina Della Pina, Ermelinda Falletta and Michele Rossi

5.1 Introduction

5.2 Catalyst Preparation and Characterization

5.3 Catalytic Properties

5.3.3 Oxidation of Carbohydrates: the Case of Glucose

5.4 Reaction Mechanisms

5.5 Catalyst Stability

5.6 Conclusions

References

6 Selective Liquid Phase Oxidations in the Presence of Supported Polyoxometalates
Craig L. Hill and Oxana A. Kholdeeva

6.1 Introduction

6.2 Synthesis and Characterization

6.3 Catalytic Properties

6.4 Mechanistic Aspects

6.5 Stability

6.6 Conclusion

References

7 Selective Oxidations Catalyzed by Supported Metal Complexes
Alexander Sorokin

7.1 Introduction

7.2 Synthesis and Characterization

7.2.1 General Synthetic Strategies 7.2.1.1 Grafting

7.3 Catalytic Properties and Stability

7.4 General Remarks on Stability

7.5 Conclusion

References

8 Liquid Phase Oxidation of Organic Compounds by Metal-Organic Frameworks
YoungKyu Hwang, Gérard Férey, U-Hwang Lee and Jong-San Chang

8.1 Introduction 8.2 Characteristics and Active Sites

8.2.1 Characteristics

8.3 Catalytic Properties

8.4 Mechanistic Aspects

8.5 Stability

8.6 Conclusion

References

9 Heterogeneous Photocatalysis for Selective Oxidations with Molecular Oxygen
Andrea Maldotti, Rossano Amadelli and Alessandra Molinari

9.1 Introduction

9.2 Catalysts Preparation and Mechanistic Aspects

9.3 Catalytic Properties

9.4 Stability

9.5 Conclusions

References

10 Industrial Applications

10.1 The Hydroxylation of Phenol to Hydroquinone and Catechol
Ugo Romano and Marco Ricci

References

10.2 The Greening of Nylon: the Ammoximation Process
Franco Rivetti and Roberto Buzzoni

References

10.3 Production of Propylene Oxide
Anna Forlin, Massimo Bergamo and Joerg Lindner

References

10.4 Engineering Aspects of Liquid Phase Oxidations
Bruce D. Hook

Reactor.

References