CO2 Hydrogenation Catalysis

1 Cover

2 Title Page CO 2 Hydrogenation Catalysis Edited by Yuichiro Himeda

3 Copyright Editor Dr. Yuichiro Himeda National Institute of Advanced Industrial Science and Technology AIST Tsukuba West, 16‐1 Onogawa 305‐8569 Tsukuba, Ibaraki Japan Cover Cover Design: Wiley Cover Image: Courtesy of Yuichiro Himeda All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for 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 >. © 2021 WILEY‐VCH, GmbH, Boschstr. 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Print ISBN: 978‐3‐527‐34663‐9 ePDF ISBN: 978‐3‐527‐82409‐0 ePub ISBN: 978‐3‐527‐82410‐6 oBook ISBN: 978‐3‐527‐82411‐3

4 Preface Preface Carbon dioxide is widely considered to be primarily responsible for global climatic changes. Presently, scientists are facing enormous challenges in mitigating the global CO 2 emissions. Significant progress has recently been achieved in the research topic of the catalysis of CO 2 hydrogenation, as one of the most important subjects in chemistry. In addition, the paradigm shift from fossil fuels to low‐carbon renewable energy (solar photovoltaics and wind) in recent years will allow for the competition between the CO 2 emission by energy consumption and its fixation by CO 2 conversion. In future, advancement in the fields of carbon capture and utilization is expected. I would like to thank all the authors, who are all acknowledged as world expert in their area of CO 2 hydrogenation, for their enthusiastic efforts to present recent advances in CO 2 hydrogenation. Their state‐of‐the‐art research gives exceptionally beneficial information to the researchers, teachers, and students who are interested in the research field of CO 2 hydrogenation. I anticipate that their contributions will stimulate further study in CO 2 utilization as well as CO 2 hydrogenation. I would also like to thank the Wiley‐VCH team for their continuous support. Finally, I deeply appreciate the members of my research group for their valuable assistance, especially Dr. Ryoichi Kanega for the cover design, and Dr. Hide Kambayashi for data survey. In the spring and summer of 2020, the world has been hit by the COVID‐19 pandemic. Despite these difficult times, I am delighted that this book could be completed. July 2020 Yuichiro Himeda National Institute of Advanced Industrial Science and Technology, Global Zero Emission Research Center, Tsukuba, Japan

5 1 Introduction 1.1 Direct Use of CO2 1.2 Chemicals from CO 2as a Feedstock 1.3 Application and Market Studies of CO 2Hydrogenation Products 1.4 Supply of Materials 1.5 Political Aspect: Tax 1.6 Conclusion and Perspectives References

6 2 Homogeneously Catalyzed CO 2Hydrogenation to Formic Acid/Formate by Using Precious Metal Catalysts 2.1 Introduction 2.2 Ir Complexes 2.3 Ru Complexes 2.4 Rh Complexes 2.5 Summary and Conclusions References

7 3 Homogeneously Catalyzed CO 2Hydrogenation to Formic Acid/Formate with Non‐precious Metal Catalysts 3.1 Introduction 3.2 Iron‐Catalyzed CO2 Hydrogenation 3.3 Cobalt‐Catalyzed CO2 Hydrogenation 3.4 Nickel‐Catalyzed CO2 Hydrogenation 3.5 Copper‐Catalyzed CO2 Hydrogenation 3.6 Manganese‐Catalyzed CO2 Hydrogenation 3.7 Other Non‐precious Metals for CO2 Functionalization 3.8 Conclusions and Perspectives References

8 4 Catalytic Homogeneous Hydrogenation of CO 2to Methanol 4.1 Carbon Recycling and Methanol in the Early Twenty‐First Century 4.2 Heterogeneous Catalysis for CO2 to Methanol 4.3 Homogeneous Catalysis – An Alternative for CO2 to Methanol 4.4 Conclusion References

9 5 Theoretical Studies of Homogeneously Catalytic Hydrogenation of Carbon Dioxide and Bioinspired Computational Design of Base‐Metal Catalysts 5.1 Introduction 5.2 H 2 Activation and CO2 Insertion Mechanisms 5.3 Hydrogenation of CO2 to Formic Acid/Formate 5.4 Hydrogenation of CO2 to Methanol 5.5 Summary and Conclusions References

10 6 Heterogenized Catalyst for the Hydrogenation of CO 2to Formic Acid or Its Derivatives 6.1 Introduction 6.2 Molecular Catalysts Heterogenized on the Surface of Grafted Supports 6.3 Molecular Catalysts Heterogenized on Coordination Polymers 6.4 Molecular Catalysts Heterogenized on Porous Organic Polymers 6.5 Concluding Remarks and Future Directions References

11 7 Design and Architecture of Nanostructured Heterogeneous Catalysts for CO 2Hydrogenation to Formic Acid/Formate 7.1 Introduction 7.2 Unsupported Bulk Metal Catalysts 7.3 Unsupported Metal Nanoparticle Catalysts 7.4 Supported Metal Nanoparticle Catalysts 7.5 Embedded Single‐Atom Catalysts 7.6 Summary and Conclusions References

12 8 Heterogeneously Catalyzed CO 2Hydrogenation to Alcohols 8.1 Introduction 8.2 CO 2 Hydrogenation to Methanol – Past to Present 8.3 CO 2 Hydrogenation to Ethanol and Higher Alcohols – Past to Present 8.4 Summary References

13 9 Homogeneous Electrocatalytic CO 2Hydrogenation 9.1 CO 2 Reduction to C─H Bond‐Containing Compounds: Formate or Formic Acid 9.2 Prospects in Electrocatalysis: CO2 Reduction Beyond Formation of One C─H Bond References

14 10 Recent Advances in Homogeneous Catalysts for Hydrogen Production from Formic Acid and Methanol 10.1 Introduction 10.2 Formic Acid Dehydrogenation 10.3 Aqueous‐phase Methanol Dehydrogenation 10.4 Conclusion References

15 Index

16 End User License Agreement

1 Chapter 1 Table 1.1 Chemicals produced commercially from CO 2. Table 1.2 Characteristics of various energy vectors. Table 1.3 Concentration of CO 2and contaminants from various sources. Table 1.4 CO 2capture technologies.

2 Chapter 2 Table 2.1 Hydrogenation of CO 2to formic acid/formate with precious metals. Table 2.2 p K avalues of functional OH groups in complexes. Table 2.3 p K avalues of functional NH groups in complexes. Table 2.4 Catalytic performance of complexes with NH and NMe moieties. a Table 2.5 p K avalues of OH and/or NH groups in functional complexes.

3 Chapter 6Table 6.1 Summary of catalytic conditions for CO 2hydrogenation to formate by...

4 Chapter 8Table 8.1 Catalytic performances of selected catalysts for gas‐phase CO 2hydr...Table 8.2 Catalytic performances of selected catalysts for gas‐phase CO 2hydr...

5 Chapter 9Table 9.1 Group 9 metal complexes as electrocatalysts for CO 2to formate conv...Table 9.2 Group 8 metal complexes as electrocatalysts for CO 2to formate conv...Table 9.3 Nickel complexes as electrocatalysts for CO 2to formate conversion....Table 9.4 Iron and iron/molybdenum clusters as electrocatalysts for CO 2to fo...