Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling

Lum, Yanwei; Ager, Joel W.

doi:10.1002/anie.201710590

Title: Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO₂ Reduction Investigated with ¹⁸O Labeling

Journal Article · Tue Nov 07 00:00:00 EST 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201710590· OSTI ID:1530326

^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Abstract Oxide‐derived (OD) Cu catalysts have high selectivity towards the formation of multi‐carbon products (C ₂ /C ₃ ) for aqueous electrochemical CO ₂ reduction (CO ₂ R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing ¹⁸ O‐enriched OD Cu catalysts and testing them for CO ₂ R. These catalysts maintain a high selectivity towards C ₂ /C ₃ products (ca. 60 %) for up to 5 h in 0.1 m KHCO ₃ at −1.0 V vs. RHE. However, secondary‐ion mass spectrometry measurements show that only a small fraction (<1 %) of the original ¹⁸ O content remains, showing that residual oxides are not present in significant amounts during CO ₂ R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation Singapore

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1530326

Alternate ID(s):: OSTI ID: 1412581

Journal Information:: Angewandte Chemie (International Edition), Vol. 57, Issue 2; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 261 works

Citation information provided by
Web of Science

References (30)

CO₂ Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu₂O Films Li, Christina W.; Kanan, Matthew W. Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234 https://doi.org/10.1021/ja3010978	journal	April 2012
Oxidation of Polycrystalline Copper Thin Films at Ambient Conditions Platzman, Ilia; Brener, Reuven; Haick, Hossam The Journal of Physical Chemistry C, Vol. 112, Issue 4 https://doi.org/10.1021/jp076981k	journal	January 2008
Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO ₂ over Cu Nanowire Arrays Ma, Ming; Djanashvili, Kristina; Smith, Wilson A. Angewandte Chemie, Vol. 128, Issue 23 https://doi.org/10.1002/ange.201601282	journal	April 2016
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
Influence on the oxidation kinetics of metals by control of the structure of oxide scales Matsnnaga, S.; Homma, T. Oxidation of Metals, Vol. 10, Issue 6 https://doi.org/10.1007/BF00612048	journal	December 1976
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R. Journal of the American Chemical Society, Vol. 136, Issue 40 https://doi.org/10.1021/ja505791r	journal	August 2014
Electrocatalytic Production of C3-C4 Compounds by Conversion of CO ₂ on a Chloride-Induced Bi-Phasic Cu ₂ O-Cu Catalyst Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201505730	journal	October 2015
Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO ₂ over Cu Nanowire Arrays Ma, Ming; Djanashvili, Kristina; Smith, Wilson A. Angewandte Chemie International Edition, Vol. 55, Issue 23 https://doi.org/10.1002/anie.201601282	journal	April 2016
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO ₂ Reduction Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter The Journal of Physical Chemistry C, Vol. 121, Issue 26 https://doi.org/10.1021/acs.jpcc.7b03673	journal	June 2017
Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides Gattinoni, Chiara; Michaelides, Angelos arXiv https://doi.org/10.48550/arxiv.1508.01005	text	January 2015
Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides Gattinoni, Chiara; Michaelides, Angelos Surface Science Reports, Vol. 70, Issue 3 https://doi.org/10.1016/j.surfrep.2015.07.001	journal	November 2015
Comparison Study on the Stability of Copper Nanowires and Their Oxidation Kinetics in Gas and Liquid Xu, Liang; Yang, Yuan; Hu, Zeng-Wen ACS Nano, Vol. 10, Issue 3 https://doi.org/10.1021/acsnano.6b00704	journal	February 2016
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders Angewandte Chemie International Edition, Vol. 54, Issue 17 https://doi.org/10.1002/anie.201412214	journal	February 2015
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b06227	journal	July 2015
Sustainable hydrocarbon fuels by recycling CO 2 and H 2 O with renewable or nuclear energy Graves, Christopher; Ebbesen, Sune D.; Mogensen, Mogens Renewable and Sustainable Energy Reviews, Vol. 15, Issue 1 https://doi.org/10.1016/j.rser.2010.07.014	journal	January 2011
A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan ACS Central Science, Vol. 2, Issue 3 https://doi.org/10.1021/acscentsci.6b00022	journal	March 2016
Cu metal embedded in oxidized matrix catalyst to promote CO ₂ activation and CO dimerization for electrochemical reduction of CO ₂ Xiao, Hai; Goddard, William A.; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1702405114	journal	June 2017
Electrochemical CO ₂ Reduction: Recent Advances and Current Trends Jones, John-Paul; Prakash, G. K. Surya; Olah, George A. Israel Journal of Chemistry, Vol. 54, Issue 10 https://doi.org/10.1002/ijch.201400081	journal	September 2014
Electrochemical CO ₂ reduction on Cu ₂ O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons Kas, Recep; Kortlever, Ruud; Milbrat, Alexander Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/C4CP01520G	journal	January 2014
Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols Gao, Dunfeng; Zegkinoglou, Ioannis; Divins, Nuria J. ACS Nano, Vol. 11, Issue 5 https://doi.org/10.1021/acsnano.7b01257	journal	April 2017
Early and transient stages of Cu oxidation: Atomistic insights from theoretical simulations and in situ experiments Zhu, Qing; Zou, Lianfeng; Zhou, Guangwen Surface Science, Vol. 652 https://doi.org/10.1016/j.susc.2016.03.003	journal	October 2016
New model for low-temperature oxidation of copper single crystal Fujita, Kensuke; Ando, Daisuke; Uchikoshi, Masahito Applied Surface Science, Vol. 276 https://doi.org/10.1016/j.apsusc.2013.03.096	journal	July 2013
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts Ren, Dan; Deng, Yilin; Handoko, Albertus Denny ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs502128q	journal	March 2015
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders Angewandte Chemie, Vol. 127, Issue 17 https://doi.org/10.1002/ange.201412214	journal	February 2015
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12123	journal	June 2016
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
Electrocatalytic Production of C3-C4 Compounds by Conversion of CO ₂ on a Chloride-Induced Bi-Phasic Cu ₂ O-Cu Catalyst Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung Angewandte Chemie, Vol. 127, Issue 49 https://doi.org/10.1002/ange.201505730	journal	October 2015
Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction Eilert, André; Cavalca, Filippo; Roberts, F. Sloan The Journal of Physical Chemistry Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acs.jpclett.6b02273	journal	December 2016
Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂ Favaro, Marco; Xiao, Hai; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1701405114	journal	June 2017

Cited By (33)

Formation of carbon–nitrogen bonds in carbon monoxide electrolysis Jouny, Matthew; Lv, Jing-Jing; Cheng, Tao Nature Chemistry, Vol. 11, Issue 9 https://doi.org/10.1038/s41557-019-0312-z	journal	August 2019
Facile Deposition of Cu−SnO _x Hybrid Nanostructures on Lightly Boron‐Doped Diamond Electrodes for CO ₂ Reduction Roy, Nitish; Suzuki, Norihiro; Nakabayashi, Yukihiro ChemElectroChem, Vol. 5, Issue 18 https://doi.org/10.1002/celc.201800460	journal	September 2018
Reactivity Determinants in Electrodeposited Cu Foams for Electrochemical CO ₂ Reduction Klingan, Katharina; Kottakkat, Tintula; Jovanov, Zarko P. ChemSusChem, Vol. 11, Issue 19 https://doi.org/10.1002/cssc.201801582	journal	August 2018
Structure‐Sensitivity and Electrolyte Effects in CO ₂ Electroreduction: From Model Studies to Applications Sebastián‐Pascual, Paula; Mezzavilla, Stefano; Stephens, Ifan E. L. ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900552	journal	June 2019
Metal-based heterogeneous electrocatalysts for reduction of carbon dioxide and nitrogen: mechanisms, recent advances and perspective Zhou, Jun-Hao; Zhang, Ya-Wen Reaction Chemistry & Engineering, Vol. 3, Issue 5 https://doi.org/10.1039/c8re00111a	journal	January 2018
On the Oxidation State of Cu ₂ O upon Electrochemical CO ₂ Reduction: An XPS Study Permyakova, Anastasia A.; Herranz, Juan; El Kazzi, Mario ChemPhysChem, Vol. 20, Issue 22 https://doi.org/10.1002/cphc.201900468	journal	July 2019
Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2 Liang, Zhi-Qin; Zhuang, Tao-Tao; Seifitokaldani, Ali Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06311-0	journal	September 2018
A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO ₂ to Value‐Added Chemicals and Fuel Daiyan, Rahman; Saputera, Wibawa Hendra; Masood, Hassan Advanced Energy Materials, Vol. 10, Issue 11 https://doi.org/10.1002/aenm.201902106	journal	November 2019
CO ₂ reduction using paper-derived carbon electrodes modified with copper nanoparticles Gomez, Federico J. V.; Chumanov, George; Silva, Maria Fernanda RSC Advances, Vol. 9, Issue 58 https://doi.org/10.1039/c9ra07430a	journal	January 2019
A new tri-nuclear Cu-carbonate cluster utilizing CO ₂ as a C1-building block – reactive intermediates, a probable mechanism, and EPR and magnetic studies Das, Biswanath; Bhadbhade, Mohan; Thapper, Anders Dalton Transactions, Vol. 48, Issue 11 https://doi.org/10.1039/c8dt04858d	journal	January 2019
Self‐Supported Nanoporous Au ₃ Cu Electrode with Enriched Gold on Surface for Efficient Electrochemical Reduction of CO ₂ Ma, Xiaoming; Shen, Yongli; Yao, Shuang Chemistry – A European Journal https://doi.org/10.1002/chem.201904619	journal	January 2020
Enhanced CO ₂ electroreduction via interaction of dangling S bonds and Co sites in cobalt phthalocyanine/ZnIn ₂ S ₄ hybrids Chen, Chunjun; Sun, Xiaofu; Yang, Dexin Chemical Science, Vol. 10, Issue 6 https://doi.org/10.1039/c8sc03986k	journal	January 2019
Partially Oxidized Palladium Nanodots for Enhanced Electrocatalytic Carbon Dioxide Reduction Lu, Hui; Zhang, Le; Zhong, Ju Hua Chemistry - An Asian Journal, Vol. 13, Issue 19 https://doi.org/10.1002/asia.201800946	journal	August 2018
Nitride‐Derived Copper Modified with Indium as a Selective and Highly Stable Catalyst for the Electroreduction of Carbon Dioxide Veenstra, Florentine L. P.; Martín, Antonio J.; Pérez‐Ramírez, Javier ChemSusChem, Vol. 12, Issue 15 https://doi.org/10.1002/cssc.201901309	journal	June 2019
Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction Huang, Jianfeng; Hörmann, Nicolas; Oveisi, Emad Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05544-3	journal	August 2018
Heterogeneous catalysts for catalytic CO2 conversion into value-added chemicals Whang, Ho Seok; Lim, Jinkyu; Choi, Min Suk BMC Chemical Engineering, Vol. 1, Issue 1 https://doi.org/10.1186/s42480-019-0007-7	journal	March 2019
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A. Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0139-9	journal	October 2018
Nitride-Derived Copper Modified with Indium as a Selective and Highly Stable Catalyst for the Electroreduction of Carbon Dioxide Veenstra, Florentine L. P.; Martín, Antonio J.; Pérez-Ramírez, Javier ETH Zurich https://doi.org/10.3929/ethz-b-000366265	text	January 2019
Quantitatively Unraveling the Redox Shuttle of Spontaneous Oxidation/Electroreduction of CuO _x on Silver Nanowires Using in Situ X-ray Absorption Spectroscopy Chang, Chia-Jui; Hung, Sung-Fu; Hsu, Chia-Shuo ACS Central Science, Vol. 5, Issue 12 https://doi.org/10.1021/acscentsci.9b01142	journal	December 2019
Origin of the selective electroreduction of carbon dioxide to formate by chalcogen modified copper Rodrigo, García-Muelas,; Federico, Dattila,; Tatsuya, Shinagawa, ETH Zurich https://doi.org/10.3929/ethz-b-000384043	text	January 2018
Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction Martić, Nemanja; Reller, Christian; Macauley, Chandra Advanced Energy Materials, Vol. 9, Issue 29 https://doi.org/10.1002/aenm.201901228	journal	June 2019
Electrochemical Reduction of CO ₂ over Heterogeneous Catalysts in Aqueous Solution: Recent Progress and Perspectives Long, Chang; Li, Xiang; Guo, Jun Small Methods https://doi.org/10.1002/smtd.201800369	journal	December 2018
Strategies for Designing Nanoparticles for Electro‐ and Photocatalytic CO ₂ Reduction Choi, Ji Yong; Choi, Woong; Park, Joon Woo Chemistry – An Asian Journal, Vol. 15, Issue 2 https://doi.org/10.1002/asia.201901533	journal	December 2019
Electrochemical CO ₂ Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design Kibria, Md Golam; Edwards, Jonathan P.; Gabardo, Christine M. Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201807166	journal	December 2018
Emerging Carbon‐Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value‐Added Chemicals Wu, Jingjie; Sharifi, Tiva; Gao, Ying Advanced Materials, Vol. 31, Issue 13 https://doi.org/10.1002/adma.201804257	journal	December 2018
Zn nanosheets coated with a ZnS subnanometer layer for effective and durable CO ₂ reduction Li, Chenglong; Shen, Gurong; Zhang, Rui Journal of Materials Chemistry A, Vol. 7, Issue 4 https://doi.org/10.1039/c8ta10799h	journal	January 2019
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C. Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0450-y	journal	September 2019
Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products Gao, Dunfeng; Arán-Ais, Rosa M.; Jeon, Hyo Sang Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0235-5	journal	March 2019
Heteroatom-doped carbon materials and their composites as electrocatalysts for CO ₂ reduction Cui, Huijuan; Guo, Yibo; Guo, Limin Journal of Materials Chemistry A, Vol. 6, Issue 39 https://doi.org/10.1039/c8ta07430e	journal	January 2018
Simultaneous Achieving of High Faradaic Efficiency and CO Partial Current Density for CO ₂ Reduction via Robust, Noble‐Metal‐Free Zn Nanosheets with Favorable Adsorption Energy Liu, Kaihua; Wang, Jiazhi; Shi, Miaomiao Advanced Energy Materials, Vol. 9, Issue 21 https://doi.org/10.1002/aenm.201900276	journal	April 2019
Core–shell nanoporous AuCu ₃ @Au monolithic electrode for efficient electrochemical CO ₂ reduction Ma, Xiaoming; Shen, Yongli; Yao, Shuang Journal of Materials Chemistry A, Vol. 8, Issue 6 https://doi.org/10.1039/c9ta09471g	journal	January 2020
Self-assembling of formic acid on the partially oxidized p (2 × 1) Cu(110) surface reconstruction at low coverages Chen, Zhu; Martirez, John Mark P.; Zahl, Percy The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5046697	journal	January 2019
Cu ₂ O Nanoparticles with Both {100} and {111} Facets for Enhancing the Selectivity and Activity of CO ₂ Electroreduction to Ethylene Gao, Yugang; Wu, Qian; Liang, Xizhuang Advanced Science, Vol. 7, Issue 6 https://doi.org/10.1002/advs.201902820	journal	March 2020

Figures / Tables (4)

Similar Records

Stability of Residual Oxides in Oxide‐Derived Copper Catalysts for Electrochemical CO ₂ Reduction Investigated with ¹⁸ O Labeling

Journal Article · Fri Dec 08 00:00:00 EST 2017 · Angewandte Chemie · OSTI ID:1530326

Lum, Yanwei; Ager, Joel W.

Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO₂ Reduction

Journal Article · Thu Jul 06 00:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1530326

Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter; +2 more

Synthesis of alcohols from carbon oxides and hydrogen. VII. Preparation, activation, and catalytic behavior of a ZnMnCrK-oxide catalyst

Journal Article · Sun May 01 00:00:00 EDT 1988 · J. Catal.; (United States) · OSTI ID:1530326

Forzatti, P; Cristiani, C; Ferlazzo, N; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
copper oxides
electrocatalysis
isotope labeling
oxide stability

Title: Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling

Citation Formats