Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

doi:10.1021/acscatal.7b03477

Title: Mechanism of CO₂ Reduction at Copper Surfaces: Pathways to C₂ Products

Journal Article · Thu Jan 11 00:00:00 EST 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b03477· OSTI ID:1464161

Garza, Alejandro J. ^[1];

^[2];

^[3]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

On the basis of constraints from reported experimental observations and density functional theory simulations, in this paper we propose a mechanism for the reduction of CO₂ to C₂ products on copper electrodes. To model the effects of an applied potential bias on the reactions, calculations are carried out with a variable, fractional number of electrons on the unit cell, which is optimized so that the Fermi level matches the actual chemical potential of electrons (i.e., the applied bias); an implicit electrolyte model allows for compensation of the surface charge so that neutrality is maintained in the overall simulation cell. Our mechanism explains the presence of the seven C₂ species that have been detected in the reaction, as well as other notable experimental observations. Furthermore, our results shed light on the difference in activities toward C₂ products between the (100) and (111) facets of copper. Finally, we compare our methodologies and findings with those in other recent mechanistic studies of the copper-catalyzed CO₂ reduction reaction.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

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

OSTI ID:: 1464161

Journal Information:: ACS Catalysis, Vol. 8, Issue 2; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 420 works

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A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction Lv, Jing-Jing; Jouny, Matthew; Luc, Wesley Advanced Materials, Vol. 30, Issue 49 https://doi.org/10.1002/adma.201803111	journal	October 2018
Surface Reconstruction of Polycrystalline Cu Electrodes in Aqueous KHCO3 Electrolyte at Potentials in the Early Stages of CO2 Reduction Kim, Youn-Geun; Baricuatro, Jack H.; Soriaga, Manuel P. Electrocatalysis, Vol. 9, Issue 4 https://doi.org/10.1007/s12678-018-0469-z	journal	April 2018
Toward Computational Design of Catalysts for CO ₂ Selective Reduction via Reaction Phase Diagram Analysis Han, Mengru; Fu, Xiaoyan; Cao, Ang Advanced Theory and Simulations, Vol. 2, Issue 3 https://doi.org/10.1002/adts.201800200	journal	January 2019
Electrochemical CO ₂ reduction on Cu and Au electrodes studied using in situ sum frequency generation spectroscopy Huang-fu, Zhi-Chao; Song, Qian-Tong; He, Yu-Han Physical Chemistry Chemical Physics, Vol. 21, Issue 45 https://doi.org/10.1039/c9cp04346b	journal	January 2019
Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide Chen, Ruixue; Su, Hai‐Yan; Liu, Deyu Angewandte Chemie International Edition, Vol. 59, Issue 1 https://doi.org/10.1002/anie.201910662	journal	December 2019
Review of two‐dimensional materials for electrochemical CO ₂ reduction from a theoretical perspective Zhu, Xiaorong; Li, Yafei Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6 https://doi.org/10.1002/wcms.1416	journal	April 2019
Carbon monoxide electroreduction as an emerging platform for carbon utilization Jouny, Matthew; Hutchings, Gregory S.; Jiao, Feng Nature Catalysis, Vol. 2, Issue 12 https://doi.org/10.1038/s41929-019-0388-2	journal	December 2019
Metal-free graphdiyne doped with sp-hybridized boron and nitrogen atoms at acetylenic sites for high-efficiency electroreduction of CO ₂ to CH ₄ and C ₂ H ₄ Zhao, Jia; Chen, Zhe; Zhao, Jingxiang Journal of Materials Chemistry A, Vol. 7, Issue 8 https://doi.org/10.1039/c8ta11825f	journal	January 2019
Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels Ren, Dan; Gao, Jing; Pan, Linfeng Angewandte Chemie International Edition, Vol. 58, Issue 42 https://doi.org/10.1002/anie.201909610	journal	September 2019
Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO ₂ Reduction Wang, Jiong; Huang, Xiang; Xi, Shibo Angewandte Chemie, Vol. 131, Issue 38 https://doi.org/10.1002/ange.201906475	journal	August 2019
High-rate electroreduction of carbon monoxide to multi-carbon products Jouny, Matthew; Luc, Wesley; Jiao, Feng Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0133-2	journal	August 2018
Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics Cheng, Tao; Fortunelli, Alessandro; Goddard, William A. Proceedings of the National Academy of Sciences, Vol. 116, Issue 16 https://doi.org/10.1073/pnas.1821709116	journal	March 2019
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
Mechanism and kinetics for both thermal and electrochemical reduction of N ₂ catalysed by Ru(0001) based on quantum mechanics Chen, Liang-Yu; Kuo, Tung-Chun; Hong, Zih-Siang Physical Chemistry Chemical Physics, Vol. 21, Issue 32 https://doi.org/10.1039/c9cp03187a	journal	January 2019
Silicon-doped graphene edges: an efficient metal-free catalyst for the reduction of CO ₂ into methanol and ethanol Mao, Xin; Kour, Gurpreet; Zhang, Lei Catalysis Science & Technology, Vol. 9, Issue 23 https://doi.org/10.1039/c9cy01709g	journal	January 2019
Reduction of carbon dioxide on photoexcited nanoparticles of VIII group metals Dai, Xinyan; Sun, Yugang Nanoscale, Vol. 11, Issue 36 https://doi.org/10.1039/c9nr05971g	journal	January 2019
Regulating C–C coupling in thermocatalytic and electrocatalytic CO x conversion based on surface science Jiang, Yawen; Long, Ran; Xiong, Yujie Chemical Science, Vol. 10, Issue 31 https://doi.org/10.1039/c9sc02014d	journal	January 2019
Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO ₂ Reduction to Formate Han, Na; Ding, Pan; He, Le Advanced Energy Materials, Vol. 10, Issue 11 https://doi.org/10.1002/aenm.201902338	journal	November 2019
Mononuclear Fe in N-doped carbon: computational elucidation of active sites for electrochemical oxygen reduction and oxygen evolution reactions Shang, Rui; Steinmann, Stephan N.; Xu, Bo-Qing Catalysis Science & Technology, Vol. 10, Issue 4 https://doi.org/10.1039/c9cy01935a	journal	January 2020
Copper adparticle enabled selective electrosynthesis of n-propanol Li, Jun; Che, Fanglin; Pang, Yuanjie Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-07032-0	journal	November 2018
Potential-Dependent CO₂ Electroreduction Pathways on Cu(111) Based on an Improved Electrode/Aqueous Interface Model: Determination of the Origin of the Overpotentials Ou, Lihui; Zhao, Kexin ACS Omega, Vol. 4, Issue 17 https://doi.org/10.1021/acsomega.9b01917	journal	October 2019
Galvanic Replacement of Electrochemically Restructured Copper Electrodes with Gold and Its Electrocatalytic Activity for Nitrate Ion Reduction Balkis, Ali; Crawford, Jessica; O’Mullane, Anthony Nanomaterials, Vol. 8, Issue 10 https://doi.org/10.3390/nano8100756	journal	September 2018