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Synergy between Silver-Copper Surface Alloy Composition and Carbon Dioxide Adsorption and Activation

Ye, Yifan and Qian, Jin and Yang, Hao and Su, Hongyang and Lee, Kyung-Jae and Etxebarria, Ane and Cheng, Tao and Xiao, Hai and Yano, Junko and Goddard, William A., III and Crumlin, Ethan J. (2020) Synergy between Silver-Copper Surface Alloy Composition and Carbon Dioxide Adsorption and Activation. ACS Applied Materials & Interfaces, 12 (22). pp. 25374-25382. ISSN 1944-8244. doi:10.1021/acsami.0c02057.

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Bimetallic electrocatalysts provide a promising strategy for improving performance, especially in the enhancement of selectivity of CO₂ reduction reactions. However, the first step of CO₂ activation on bimetallic materials remains obscure. Considering bimetallic silver–copper (AgCu) as an example, we coupled ambient pressure X-ray photoelectron spectroscopy (APXPS) and quantum mechanics (QM) to examine CO₂ adsorption and activation on AgCu exposed to CO₂ with and without H₂O at 298 K. The interplay between adsorbed species and the surface alloy composition of Cu and Ag is studied in atomic details. The APXPS experiment and density functional theory (DFT) calculations indicate that the clean sample has a Ag-rich surface layer. Upon adsorption of CO₂ and surface O, we found that it is thermodynamically more favorable to induce subsurface Cu atoms substitution for some surface Ag atoms, modifying the stability and activation of CO₂-related chemisorbed species. We further characterized this substitution effect by correlating the new adsorption species with the observed binding energy (BE) shift and intensity change in APXPS.

Item Type:Article
Related URLs:
URLURL TypeDescription
Qian, Jin0000-0002-0162-0477
Yang, Hao0000-0002-8241-6231
Cheng, Tao0000-0003-4830-177X
Xiao, Hai0000-0001-9399-1584
Yano, Junko0000-0001-6308-9071
Goddard, William A., III0000-0003-0097-5716
Crumlin, Ethan J.0000-0003-3132-190X
Additional Information:© 2020 American Chemical Society. Received: February 3, 2020; Accepted: May 8, 2020; Published: May 8, 2020. This work was supported through the Office of Science, Office of Basic Energy Science (BES), of the US Department of Energy (DOE) under Award DE-SC0004993 to the Joint Center for Artificial Photosynthesis, DOE Energy Innovation Hubs. The Advanced Light Source was supported by the Director, Office of Science, Office of BES, of the US DOE under contract DE-AC02-05CH11231. H.Y. and H.S. gratefully acknowledge the China Scholarship Council (CSC, nos. 201608320161 and 201706340112) for financial support. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by the National Science Foundation grant number ACI-1548562. Y.Y., J.Q., and E.J.C. were partially supported by an Early Career Award in the Condensed Phase and Interfacial Molecular Science Program, in the Chemical Sciences Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the U.S. Department of Energy under contract no. DE-AC02-05CH11231. T.C. and H.Y. thank the financial support by the National Natural Science Foundation of China (21975148), the Natural Science Foundation of Jiangsu Higher Education Institutions (SBK20190810), Jiangsu Province High-Level Talents (JNHB-106), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). T.C. and H.Y. were supported by grants from startup supports of Soochow University and the Program for Jiangsu Specially-Appointed Professors to T.C. H.Y. thanks the China Postdoctoral Science Foundation (2019M660128) for financial support. This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology. Author Contributions: Y.Y., J.Q., and H.Y. contributed equally to this work. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
China Scholarship Council201608320161
China Scholarship Council201706340112
National Natural Science Foundation of China21975148
Natural Science Foundation of Jiangsu Higher Education InstitutionsSBK20190810
Jiangsu Province High-Level TalentsJNHB-106
Jiangsu Higher Education InstitutionsUNSPECIFIED
Soochow UniversityUNSPECIFIED
China Postdoctoral Science Foundation2019M660128
Suzhou Nano Science and TechnologyUNSPECIFIED
Subject Keywords:CO2 adsorption; CO2 activation; Surface reconstruction; Density Functional Theory (DFT); Ambient Pressure XPS (APXPS)
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Issue or Number:22
Record Number:CaltechAUTHORS:20200511-094745730
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Official Citation:Synergy between a Silver–Copper Surface Alloy Composition and Carbon Dioxide Adsorption and Activation. Yifan Ye, Jin Qian, Hao Yang, Hongyang Su, Kyung-Jae Lee, Ane Etxebarria, Tao Cheng, Hai Xiao, Junko Yano, William A. Goddard, and Ethan J. Crumlin. ACS Applied Materials & Interfaces 2020 12 (22), 25374-25382; DOI: 10.1021/acsami.0c02057
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103095
Deposited By: Tony Diaz
Deposited On:11 May 2020 17:35
Last Modified:16 Nov 2021 18:18

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