Carbon Dioxide Reduction through Advanced Conversion and Utilization Technologies K34880_Title Page.indd 1 03/01/19 6:32:47 AM Electrochemical Energy Storage and Conversion Series Editor: Jiujun Zhang National Research Council Institute for Fuel Cell Innovation Vancouver, British Columbia, Canada Recently Published Titles Graphene: Energy Storage and Conversion Applications Zhaoping Liu and Xufeng Zhou Lithium-Ion Batteries: Fundamentals and Applications Yuping Wu Lead-Acid Battery Technologies: Fundamentals, Materials, and Applications Joey Jung, Lei Zhang, and Jiujun Zhang Solar Energy Conversion and Storage: Photochemical Modes Suresh C. 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Wilkinson, Jiujun Zhang Carbon Dioxide Reduction through Advanced Conversion and Utilization Technologies Yun Zheng, Bo Yu, Jianchen Wang, Jiujun Zhang https://www.crcpress.com/Electrochemical-Energy-Storage-and-Conversion/book-series/ CRCELEENESTO Carbon Dioxide Reduction through Advanced Conversion and Utilization Technologies Yun Zheng Bo Yu Jianchen Wang Jiujun Zhang K34880_Title Page.indd 2 03/01/19 6:32:58 AM CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2019 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed on acid-free paper International Standard Book Number-13: 978-1-138-09529-8 (Hardback) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright. com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Names: Zheng, Yun (Chemical engineer), author. Title: Carbon dioxide reduction through advanced conversion and utilization technologies / Yun Zheng, Bo Yu, Jianchen Wang, Jiujun Zhang. Description: Boca Raton : Taylor & Francis, CRC Press, 2019. | Series: Electrochemical energy storage and conversion | Includes bibliographical references and index. Identifiers: LCCN 2018057440| ISBN 9781138095298 (hardback : alk. paper) | ISBN 9781315104171 (ebook) Subjects: LCSH: Carbon dioxide--Separation. | Electrolytic reduction. | Carbon dioxide--Recycling. Classification: LCC TP244.C1 Z44 2019 | DDC 660.028/6--dc23 LC record available at https://lccn.loc.gov/2018057440 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface.......................................................................................................................xi CRC Press Acknowledgments ..................................................................................................xiii Taylor & Francis Group Authors .....................................................................................................................xv 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Chapter 1 Introduction to CO Reduction through Advanced Conversion © 2019 by Taylor & Francis Group, LLC 2 CRC Press is an imprint of Taylor & Francis Group, an Informa business and Utilization Technologies ................................................................1 No claim to original U.S. Government works 1.1 Globe Energy Status, Challenges, and Perspectives ...................1 1.2 CO Emission and Reducing .......................................................2 Printed on acid-free paper 2 1.3 Main Approaches of CO Conversion and Utilization ................4 2 International Standard Book Number-13: 978-1-138-09529-8 (Hardback) References ............................................................................................6 This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume Chapter 2 Fundamentals of CO Structure, Thermodynamics, and Kinetics .......9 responsibility for the validity of all materials or the consequences of their use. The authors and publishers 2 have attempted to trace the copyright holders of all material reproduced in this publication and apologize 2.1 Molecular Structure of CO ........................................................9 to copyright holders if permission to publish in this form has not been obtained. If any copyright material 2 has not been acknowledged please write and let us know so we may rectify in any future reprint. 2.2 Thermodynamics of CO ............................................................9 2 2.3 Kinetics of CO Conversion ......................................................14 Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, 2 2.4 Summary ...................................................................................16 transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval References ..........................................................................................16 system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright. Chapter 3 Enzymatic and Mineralized Conversion Process of CO com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood 2 Conversion ......................................................................................19 Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the 3.1 Enzymatic Conversion of CO ..................................................19 CCC, a separate system of payment has been arranged. 2 3.2 Mineralization Process of CO Conversion ..............................22 2 Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are 3.3 Summary ...................................................................................26 used only for identification and explanation without intent to infringe. References ..........................................................................................27 Library of Congress Cataloging-in-Publication Data Chapter 4 Thermochemical and Photochemical/Photoelectrochemical Names: Zheng, Yun (Chemical engineer), author. Conversion Process of CO Conversion .............................................31 Title: Carbon dioxide reduction through advanced conversion and utilization 2 technologies / Yun Zheng, Bo Yu, Jianchen Wang, Jiujun Zhang. 4.1 Thermochemical Process of CO Conversion ...........................31 Description: Boca Raton : Taylor & Francis, CRC Press, 2019. | Series: 2 Electrochemical energy storage and conversion | Includes bibliographical 4.1.1 CO Hydrogenation to CH OH .....................................31 2 3 references and index. 4.1.2 CO Hydrogenation to HCOOH ....................................33 Identifiers: LCCN 2018057440| ISBN 9781138095298 (hardback : alk. paper) | 2 4.1.3 CO (Dry) Reforming of Methane (DRM) ...................35 ISBN 9781315104171 (ebook) 2 Subjects: LCSH: Carbon dioxide--Separation. | Electrolytic reduction. | 4.2 Photocatalytic and Photoelectrochemical Processes of Carbon dioxide--Recycling. CO Conversion .........................................................................38 Classification: LCC TP244.C1 Z44 2019 | DDC 660.028/6--dc23 2 4.3 Summary ...................................................................................42 LC record available at https://lccn.loc.gov/2018057440 References ..........................................................................................42 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com v vi Contents Chapter 5 Low-Temperature Electrochemical Process of CO Conversion ........49 2 5.1 Brief Introduction to the Electrochemical Process of CO  Conversion .........................................................................49 2 5.2 Thermodynamics of Low-Temperature Electrochemical Process ......................................................................................49 5.3 Electrolyzer Used in Low-Temperature Electrochemical Process ......................................................................................51 5.4 Catalyst/Electrode Used in Low-Temperature Electrochemical Process ...........................................................51 5.5 Summary and Outlook ..............................................................55 References ..........................................................................................55 Chapter 6 High-Temperature Electrochemical Process of CO Conversion 2 with SOCs 1: Introduction and Fundamentals ...................................57 6.1 Introduction of Solid Oxide Cells (SOCs) .................................57 6.2 Fundamentals of High-Temperature CO Conversion 2 through Electrochemical Approaches .......................................58 6.2.1 Thermodynamics of High-Temperature CO /H O 2 2 Co-electrolysis ...............................................................58 6.2.2 Kinetics of High-Temperature CO /H O 2 2 Co-electrolysis ...............................................................62 6.2.3 C omparisons between Water Electrolysis, CO 2 Electrolysis, and H O/CO Co-electrolysis ...................64 2 2 6.2.4 Key Material Selection and Components of SOCs .......64 6.3 Summary ...................................................................................67 References ..........................................................................................67 Chapter 7 High-Temperature Electrochemical Process of CO Conversion 2 with SOCs 2: Research Status ............................................................71 7.1 Brief History .............................................................................71 7.2 Research Status of HTCE with SOC in the United States ........74 7.3 HTCE Research towards Sustainable Hydrocarbon Fuels in Europe ...................................................................................86 7.4 Research Status of HTCE with SOC in China .........................98 7.5 Summary .................................................................................103 References ........................................................................................103 Chapter 8 High-Temperature Electrochemical Process of CO Conversion 2 with SOCs 3: Key Materials .............................................................113 8.1 Materials and Microstructures of Electrodes ..........................113 8.2 Fuel Electrode Materials .........................................................114 8.3 Oxygen Electrode Materials ...................................................119 Contents vii 8.3.1 Reaction Mechanism of Oxygen Electrode Process .....................................................................119 8.3.2 Mixed Ionic and Electronic Materials ......................120 8.3.2.1 Perovskites (ABO ) ................................120 3±δ 8.3.2.2 Double Perovskites (AA′BO ) ...............122 2 6−δ 8.3.2.3 Ruddlesden-Popper (A BO ) ..................124 2 4+δ 8.3.3 Main Issues of the Oxygen Electrode ......................127 8.4 Electrolyte ............................................................................128 8.5 Interconnect Materials .........................................................129 8.6 Cell Sealing Materials ..........................................................130 8.7 Summary ..............................................................................131 References .......................................................................................132 Chapter 9 High-Temperature Electrochemical Process of CO  Conversion 2 with SOCs 4: Measurement, Characterization, and Simulation .....139 9.1 Electrochemical Measurement .............................................139 9.2 Microstructure Characterization ..........................................141 9.2.1 SEM, TEM, and STEM ............................................141 9.2.2 FIB-SEM and XCT ..................................................142 9.2.3 STM/STS and AFM .................................................144 9.3 Surface Analysis ..................................................................145 9.4 Simulation and Calculation Method ....................................148 9.5 Product Analysis ..................................................................149 9.6 Summary ..............................................................................150 References .......................................................................................150 Chapter 10 High-Temperature Electrochemical Process of CO  Conversion 2 with SOCs 5: Advanced Fabrication Methods (Infiltration and Freeze Casting) ...............................................................................155 10.1 Infiltration for Nano-Structured Ln1−xSrxMO3−δ (Ln=La, Sm; B=Mn, Co, Fe) SOC Electrode ..............................................................................155 10.1.1 Introduction of Infiltration Used in SOCs ..............155 10.1.2 Process of Infiltration .............................................156 10.1.3 Infiltration with Various Ln Sr MO SOC 1−x x 3−δ Electrodes ...............................................................157 10.1.3.1 LSM-YSZ Electrode ...............................157 10.1.3.2 LSC-YSZ Electrode ...............................160 10.1.3.3 LSF-YSZ Electrode ................................161 10.1.3.4 LSCF-YSZ Electrode .............................163 10.1.3.5 SSC-Infiltrated Electrodes .....................164 10.1.3.6 Comparison of Infiltrated Electrodes’ Performance ...........................................165 10.1.4 Conclusions and Future Prospects..........................167 viii Contents 10.2 An Electrolyte-Electrode Interface Structure with Directional Micro-Channel Fabricated by Freeze Casting ....167 10.2.1 Freeze Casting Technology Used in SOCs ............167 10.2.2 The Process and Critical Factors of Freeze Casting Technology ................................................168 10.2.2.1 The Process of Freeze Casting ...............168 10.2.2.2 Effect of Critical Factors on Morphologies .........................................169 10.2.3 Summary and Perspectives ....................................175 References ........................................................................................177 Chapter 11 High-Temperature Electrochemical Process of CO Conversion 2 with SOCs 6: Advanced Structure (Heterostructure) .......................187 11.1 Brief Introduction for Heterostructure .................................187 11.2 Heterostructure of ABO/A BO in SOCs ...........................189 3 2 4 11.3 Mechanism of ORR/OER in ABO/A BO Heterostructure ...192 3 2 4 11.3.1 Electronic Structure ...............................................192 11.3.2 Anisotropy ..............................................................194 11.3.3 Lattice Strain (or the Mismatch in Lattice Parameter) ..............................................................194 11.3.4 Cation Inter-diffusion .............................................195 11.4 Current Challenges for ABO/A BO Heterostructure ........196 3 2 4 11.4.1 Barriers to Accurately Detecting the Performance of a Heterointerface ..........................197 11.4.2 Invisibility of Heterointerface and its Unclear Mechanism .............................................................197 11.4.3 The Gap Between Theoretical Investigation and Practical Application ..............................................198 References ........................................................................................198 Chapter 12 High-Temperature Electrochemical Process of CO  Conversion 2 with SOCs 7: The Significant Phenomenon of Cation Segregation ......203 12.1 Introduction of Cation Segregation in Perovskite-Based SOC Electrodes ....................................................................203 12.2 Characterization of Surface Segregation .............................204 12.2.1 Low-Energy Ion Scattering ....................................205 12.2.2 Auger Electron Spectroscopy and Scanning Electron Microscope ..............................................207 12.2.3 X-Ray Photoelectron Spectroscopy ........................209 12.2.4 Scanning Transmission Electron Microscope and Energy-Dispersive X-Ray Spectroscopy .........210 12.2.5 Secondary Ion Mass Spectroscopy ........................211 12.2.6 Atomic Force Microscope and Scanning Tunneling Microscope ............................................211 Contents ix 12.2.7 X-Ray Diffraction ...................................................214 12.2.8 State-of-the-Art Characterization Methods for Surface Segregation ................................................215 12.2.8.1 In Situ XPS ............................................215 12.2.8.2 Environmental Transmission Electron Microscopy ..............................216 12.2.8.3 In Situ SIMS ..........................................217 12.2.8.4 Resonant Soft X-Ray Reflectivity and Resonant Anomalous X-Ray Reflectivity .............................................218 12.2.8.5 Raman Spectroscopy and In Situ Raman Spectroscopy .............................218 12.2.8.6 In Situ X-Ray Fluorescence ...................219 12.3 Factors Influencing Segregation Level in Perovskite- Based Oxides .......................................................................221 12.3.1 The Effect of Cation Non-Stoichiometry ...............221 12.3.2 The Effect of the Cation Species ............................223 12.3.3 The Effect of Crystallinity .....................................224 12.3.4 The Effect of Lattice Strain ....................................225 12.3.5 The Effect of Temperature and Thermal History ....225 12.3.6 The Effect of Atmosphere ......................................227 12.3.7 The Effect of Electrical Polarization ......................228 12.4 Influences of Cation Segregation on Electrochemical Activity of SOC Electrodes .................................................229 12.4.1 Influence of Sr Segregation ....................................230 12.4.1.1 Mechanism 1: Blocking Effects .............231 12.4.1.2 Mechanism 2: Inducing Detrimental Side Reactions ........................................234 12.4.1.3 Mechanism 3: Generating Active Phases .....................................................235 12.4.2 A-Site Segregation on Sr-Free Electrode Materials ..............................................................236 12.4.3 Influence of B-Site Segregation..............................238 12.5 S urface Engineering Promotes ORR/OER Activity for Perovskite Electrodes ...........................................................239 12.5.1 Surface Decoration with Alkaline Earth Metal Oxides .....................................................................240 12.5.2 Surface Decoration of Transition Metal Cations ........240 12.5.3 Surface Decoration by Secondary Perovskite- Based Phase ............................................................242 12.5.4 Surface Decoration by Less Activated Phase .........245 12.6 Conclusion and Outlook .......................................................246 References .......................................................................................247