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Published June 3, 2020 | Supplemental Material
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Synergy between Silver-Copper Surface Alloy Composition and Carbon Dioxide Adsorption and Activation


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.

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.

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