Molecular Water Oxidation Catalysis E-Book

Antoni Llobet

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 522

Veröffentlichungsjahr: 2014

Beschreibung

Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting.

Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evolving system of photosystem II and the heme chlorite-dismutase.

This book is a valuable resource for researchers working on water oxidation catalysis, solar energy conversion and artificial photosynthesis, as well as for chemists and materials scientists with a broad interest in new sustainable energy conversion schemes.

Leseprobe

Table of Contents

Cover

Title Page

Copyright

List of Contributors

Preface

Chapter 1: Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis

1.1 Introduction

1.2 Structural Studies of the OEC

1.3 The Dark-Stable State of the OEC

1.4 Biomimetic Oxomanganese Complexes

1.5 Base-Assisted O–O Bond Formation

1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis

1.7 Conclusion

Acknowledgments

References

Chapter 2: O–O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase

2.1 Introduction

2.2 Origins of O

2

-Evolving Chlorite Dismutases (Clds)

2.3 Major Structural Features of the Proteins and their Active Sites

2.4 Efficiency, Specificity, and Stability

2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide

2.6 Possible Mechanisms

2.7 Conclusion

Acknowledgements

References

Chapter 3: Ru-Based Water Oxidation Catalysts

3.1 Introduction

3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics

3.3 O–O Bond Formation Mechanisms

3.4 Polynuclear Ru Water Oxidation Catalysts

3.5 Mononuclear Ru WOCs

3.6 Anchored Molecular Ru WOCs

3.7 Light-Induced Ru WOCs

3.8 Conclusion

Acknowledgments

References

Chapter 4: Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands

4.1 Introduction

4.2 Binuclear Ru Complexes

4.3 Mononuclear Ru Complexes

4.4 Homogeneous Light-Driven Water Oxidation

4.5 Water Oxidation Device

4.6 Conclusion

References

Chapter 5: Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands

5.1 Introduction

5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs

5.3 Water Oxidation by Intramolecular O–O Coupling with [Ru

II

2

(

μ

-Cl)(bpy)

2

(btpyan)]

3+

5.4 Mononuclear Ru–Aqua Complexes with a Dioxolene Ligand

5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates

References

Chapter 6: Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation

6.1 Introduction

6.2

Bernhard 2008

[11]

6.3

Crabtree 2009

[12]

6.4

Crabtree 2010

[13]

6.5

Macchioni 2010

[14]

6.6 Albrecht/Bernhard 2010 [15]

6.7 Hetterscheid/Reek 2011 [16, 17]

6.8 Crabtree 2011 [18]

6.9 Crabtree 2011 [19]

6.10 Lin 2011 [20]

6.11 Macchioni 2011 [21]

6.12 Grotjahn 2011 [22]

6.13 Fukuzumi 2011 [23]

6.14 Lin 2012 [24]

6.15 Crabtree 2012 [25–27]

6.16 Albrecht/Bernhard 2012 [28]

6.17 Crabtree 2012 [29]

6.18 Beller 2012 [30]

6.19 Lin 2012 [31]

6.20 Lloblet and Macchioni 2012 [33]

6.21 Analysis

References

Chapter 7: Complexes of First Row d-Block Metals: Manganese

7.1 Background

7.2 Oxidation States of Manganese in an Aqueous Environment

7.3 Dinuclear Manganese Complexes: Syntheses and Structures

7.4 Redox and Acid–Base Chemistry of Mn

2

-μ-WDL Systems

7.5 Mn

2

Systems: Oxygen Evolution (but not Water Oxidation) Catalysis

7.6 Mn

2

Complexes/the OEC/Ru

2

Catalysts: A Comparison

7.7 Heterogeneous Water Oxidation Catalysis by Mn

>2

Systems

7.8 Conclusion

Acknowledgements

References

Chapter 8: Molecular Water Oxidation Catalysts from Iron

8.1 Introduction

8.2 Fe-Tetrasulfophthalocyanine

8.3 Fe-TAML

8.4 Fe-mcp

8.5 as a Microheterogeneous Catalyst

8.6 Conclusion

References

Chapter 9: Water Oxidation by Co-Based Oxides with Molecular Properties

9.1 Introduction

9.2 CoCat Formation

9.3 Structure and Structure–Function Relations

9.4 Functional Characterization

9.5 Directly Light-Driven Water Oxidation

References

Chapter 10: Developing Molecular Copper Complexes for Water Oxidation

10.1 Introduction

10.2 A Biomimetic Approach

10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes

10.4 Conclusion

Acknowledgement

References

Chapter 11: Polyoxometalate Water Oxidation Catalytic Systems

11.1 Introduction

11.2 Recent POM WOCs

11.3 Assessing POM WOC Reactivity

11.4 The System

11.5 as an Oxidant for POM WOCs

11.6 Additional Aspects of WOC System Stability

11.7 Techniques for Assessing POM WOC Stability

11.8 Conclusion

Acknowledgments

References

Chapter 12: Quantum Chemical Characterization of Water Oxidation Catalysts

12.1 Introduction

12.2 Computational Details

12.3 Methodology

12.4 Water Oxidation Catalysts

12.5 Conclusion

References

Index

End User License Agreement

Pages

xi

xii

xiii

xv

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

22

21

23

24

25

26

27

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

135

136

137

138

140

139

141

142

143

144

145

146

147

148

149

150

151

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

254

255

257

260

258

259

261

262

263

264

265

Guide

Table of Contents

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Scheme 2.1

Scheme 2.2

Figure 3.1

Figure 3.2

Figure 3.5

Figure 3.3

Scheme 3.1

Figure 3.4

Scheme 3.2

Scheme 3.3

Scheme 3.4

Scheme 3.5

Figure 3.6

Scheme 3.6

Figure 3.7

Figure 3.8

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 4.15

Figure 4.16

Figure 4.17

Figure 4.18

Figure 4.19

Figure 4.20

Figure 4.21

Scheme 5.1

Scheme 5.2

Figure 5.1

Scheme 5.3

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Scheme 5.4

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Scheme 5.5

Figure 5.12

Figure 5.13

Figure 5.14

Figure 5.15

Figure 5.16

Figure 5.17

Figure 5.18

Figure 5.19

Figure 5.20

Scheme 5.6

Figure 5.21

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 6.10

Figure 6.11

Figure 6.12

Figure 6.13

Figure 6.14

Figure 6.15

Figure 7.1

Scheme 7.1

Scheme 7.2

Figure 7.2

Scheme 7.3

Scheme 7.4

Figure 7.3

Figure 7.4

Figure 8.1

Figure 8.2

Figure 8.3

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.9

Figure 9.10

Scheme 10.1

Figure 10.1

Scheme 10.2

Scheme 10.3

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 11.1

Scheme 11.1

Figure 12.1

Figure 12.2

Figure 12.3

Figure 12.4

Figure 12.5

Figure 12.6

Figure 12.7

Figure 12.8

Figure 12.9

Figure 12.10

Figure 12.11

List of Tables

Table 1.1

Table 4.1

Table 4.2

Table 4.3

Table 5.1

Table 5.2

Table 5.3

Table 5.4

Table 8.1

Table 8.2

Table 8.3

Table 9.1

Table 10.1

Table 11.1

Molecular Water Oxidation Catalysts

A Key Topic for New Sustainable Energy Conversion Schemes

Edited by

ANTONI LLOBET

Institute of Chemical Research of Catalonia, Tarragona, Spain

This edition first published 2014

© 2014 John Wiley & Sons, Ltd

Registered office

John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom

For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com.

The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.

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, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books.

Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. It is sold on the understanding that the publisher is not engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom. If professional advice or other expert assistance is required, the services of a competent professional should be sought

The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom.

Library of Congress Cataloging-in-Publication Data

Molecular water oxidation catalysis : a key topic for new sustainable energy conversion schemes / editor, Antoni Llobet.

pages cm

Includes bibliographical references and index.

ISBN 978-1-118-41337-1 (cloth)

1. Energy harvesting. 2. Water– Purification– Oxidation– By-products. 3. Renewable energy sources. 4. Electric power production from chemical action. I. Llobet, Antoni, 1960- editor of compilation.

TJ808.M65 2014

621.31′242— dc23

2014004158

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

ISBN: 9781118413371

1 2014

List of Contributors

Martin Albrecht

, School of Chemistry & Chemical Biology, University College Dublin, Dublin, Ireland

Shoshanna M. Barnett

, Department of Chemistry, University of Washington, Seattle, WA, USA

Victor S. Batista

, Department of Chemistry, Yale University, New Haven, CT, USA

Stefan Bernhard

, Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA

Roger Bofill

, Department of Chemistry, Autonomous University of Barcelona, Barcelona, Spain

Gary W. Brudvig

, Department of Chemistry, Yale University, New Haven, CT, USA

Christopher J. Cramer

, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA

Holger Dau

, Department of Physics, Free University of Berlin, Berlin, Germany

Lele Duan

, Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm, Sweden

Jennifer L. DuBois

, Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA

W. Chadwick Ellis

, Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY, USA

Mehmed Z. Ertem

, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA

Lluis Escriche

, Department of Chemistry, Autonomous University of Barcelona, Barcelona, Spain

Laia Francàs

, Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain

Etsuko Fujita

, Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA

Laura Gagliardi

, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA

Jordi García-Antón

, Department of Chemistry, Autonomous University of Barcelona, Barcelona, Spain

Yurii V. Geletii

, Department of Chemistry, Emory University, Atlanta, GA, USA

Karen Goldberg

, Department of Chemistry, University of Washington, Seattle, WA, USA

Craig L. Hill

, Department of Chemistry, Emory University, Atlanta, GA, USA

Katharina Klingan

, Department of Physics, Free University of Berlin, Berlin, Germany

Philipp Kurz

, Institute for Inorganic and Analytical Chemistry, Albert-Ludwigs-University of Freiburg, Freiburg, Germany

Antoni Llobet

, Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain; Department of Chemistry, Autonomous University of Barcelona, Barcelona, Spain

Hongjin Lv

, Department of Chemistry, Emory University, Atlanta, GA, USA

James M. Mayer

, Department of Chemistry, University of Washington, Seattle, WA, USA

Neal D. McDaniel

, Phillips 66, Bartlesville, OK, USA

Pere Miró

, Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA

James T. Muckerman

, Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA

Jared C. Nesvet

, Department of Chemistry, University of Washington, Seattle, WA, USA

Marcel Risch

, Department of Physics, Free University of Berlin, Berlin, Germany; Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge, MA, USA

Ivan Rivalta

, Department of Chemistry, Yale University, New Haven, CT, USA

Xavier Sala

, Department of Chemistry, Autonomous University of Barcelona, Barcelona, Spain

Margaret L. Scheuermann

, Department of Chemistry, University of Washington, Seattle, WA, USA

Jordan M. Sumliner

, Department of Chemistry, Emory University, Atlanta, GA, USA

Licheng Sun

, Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm, Sweden; State Key Lab of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology, Dalian, China

Koji Tanaka

, Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto, Japan

Lianpeng Tong

, Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm, Sweden

James W. Vickers

, Department of Chemistry, Emory University, Atlanta, GA, USA

Tohru Wada

, Department of Chemistry, College of Science and Research Center for Smart Molecules, Rikkyo University, Toshima, Tokyo, Japan

Christopher R. Waidmann

, Department of Chemistry, University of Washington, Seattle, WA, USA

James A. Woods

, Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA

Ivelina Zaharieva

, Department of Physics, Free University of Berlin, Berlin, Germany

Preface

The evolution of humanity is directly linked to our access to energy resources. In the last few decades, the importance of oil access and processing to modern society has become clear, basically dictating world economic politics and countries' welfare. The extraordinarily high rate of fossil fuel consumption, the realization that these fossil fuel resources are not limitless, and the consequences of substantially increasing the CO2 concentration in the atmosphere clearly advocate for a change of energy source. Sunlight is a highly desirable one as it is the only one that is truly sustainable in the long term.

Nature has been harvesting sunlight as a source of energy for a few billion years through photosynthetic processes like the ones carried out by green plants and algae. Nature's strategy consists in the oxidation of H2O to dioxygen and the reduction of CO2 and generation of carbohydrates. Water splitting is a promising strategy for capturing the sun's energy. It involves coupling light harvesting to the oxidation of water to dioxygen, in the same manner as in the natural system, and the reduction of protons to hydrogen. The design of devices aimed at energy harvesting, based on sunlight and water splitting, requires efficient water oxidation catalysts (WOCs). Thus special attention needs to be paid to understanding this reaction in order to come up with technologically useful WOCs. In addition, the knowledge gained from molecular WOCs is also very useful in shedding light on how complex systems such as the oxygen evolving complex (OEC) of photosystem II (PSII) work and how heterogeneous systems used as intermediates are much more difficult to characterize.

This book is exclusively dedicated to the field of molecular water oxidation catalysis in the homogeneous phase, which has experienced spectacular development in the last 5 years. The first chapter, by Rivalta, Brudvig, and Batista, is dedicated to the OEC-PSII of the natural system, to some Mn complexes that act as mimics of the OEC-PSII, and to the theoretical description of these systems based on density functional theory (DFT). Chapter 2, by DuBois, looks at chlorite dismutase, a heme protein that is capable of making O–O bonds, one of the crucial reactions in producing molecular oxygen. Chapters 3 and 4 concern low-molecular-weight second-row transition-metal complexes, which have been reported to be able carry out water oxidation; these chapters are written by two teams: Chapter 3 by Francàs, Bofill, García-Antón, Escriche, Sala, and Llobet and Chapter 4 by Duan, Tong, and Sun. Chapter 5 reports a WOC based on Ru but containing non-redox-innocent ligands; it is authored by Wada, Tanaka, Muckerman, and Fujita. Chapter 6, by Woods, Bernhard, and Albrecht, focuses on Ir complexes that act as WOCs. The next four chapters are dedicated to first-row WOCs. Kurz reports on Mn, Ellis, McDaniel, and Bernhard on Fe, Risch, Klingan, Zaharieva, and Dau on Co, and Barnett, Waidmann, Scheuermann, Nesvet, Goldberg, and Mayer on Cu. Chapter 11, by Sumliner, Vickers, Lv, Geletii, and Hill, is dedicated to polyoxometalates, which can be considered low–molecular-weight models of surfaces. Finally, the book closes with a theoretical DFT description of a variety of Ru, Co, and Fe complexes, presented by Miró, Ertem, Gagliardi, and Cramer.

Chapter 1Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis

Ivan Rivalta, Gary W. Brudvig and Victor S. Batista

Department of Chemistry, Yale University, New Haven, CT, USA

1.1 Introduction

Photosystem II (PSII) is a 650 kDa protein complex embedded in the thylakoid membrane of green plant chloroplasts and the internal membranes of cyanobacteria. It is responsible for catalyzing oxygen evolution by water splitting into oxygen, protons and electrons. The catalytic site is the oxygen-evolving complex (OEC) embedded in the protein subunit D1, an oxomaganese cuboidal core comprising earth-abundant metals ( and ) linked by bridges. The reaction is initiated upon light absorption by an antenna complex, in a process that oxidizes the chlorophyll a species P680 and forms the radical cation a strong oxidizing species that in turns oxidizes tyrosine YZ, a redox-active amino acid residue located in close proximity to the oxomanganese cluster. The oxidized YZ is able to oxidize Mn, storing oxidizing equivalents in the inorganic core of the OEC. This photocatalytic process is repeated multiple times while evolving the OEC through five oxidation storage states (S0–S4) along the catalytic cycle (the so-called Kok cycle) [1, 2]. In the fully oxidized S4 state, the Mn cluster catalyzes oxygen evolution, completing the four-electron water oxidation reaction that splits water into molecular oxygen, protons and electrons, as follows:

1.1

The characterization of the OEC structure and overall structural rearrangement during the multistep photocatalytic cycle is crucial for understanding the reaction mechanism and for the design of biomimetic catalytic systems. X-ray spectroscopy has been largely used to reveal the atomistic details of the OEC structure, with several X-ray crystal models proposed in the past decade [3–6]. The most recent breakthroughs in the field have resolved the OEC structure at resolution [7], including the complete coordination of metal centers by water ligands and proteinaceous side chains. However, the high doses of X-ray radiation necessary for data collection are thought to have reduced the Mn centers, changing the geometry of the OEC and leaving uncertain the actual geometry of the oxomanganese complex in its dark-adapted (S1) state [8–11]. A model of the OEC in the S1