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Oxidation State and Surface Reconstruction of Cu under CO2 Reduction Conditions from In Situ X-ray Characterization

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.0c10017· OSTI ID:1764558
 [1];  [2];  [1];  [3];  [2];  [3];  [1];  [4];  [1];  [5];  [5];  [2];  [6];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations
The electrochemical CO2 reduction reaction (CO2RR) using Cu-based catalysts holds great potential for producing valuable multi-carbon products from renewable energy. However, the chemical and structural state of Cu catalyst surfaces during the CO2RR remains a matter of debate. In this paper, we show the structural evolution of the near-surface region of polycrystalline Cu electrodes under in situ conditions through a combination of grazing incidence X-ray absorption spectroscopy (GIXAS) and X-ray diffraction (GIXRD). The in situ GIXAS reveals that the surface oxide layer is fully reduced to metallic Cu before the onset potential for CO2RR, and the catalyst maintains the metallic state across the potentials relevant to the CO2RR. We also find a preferential surface reconstruction of the polycrystalline Cu surface toward (100) facets in the presence of CO2. Quantitative analysis of the reconstruction profiles reveals that the degree of reconstruction increases with increasingly negative applied potentials, and it persists when the applied potential returns to more positive values. These findings show that the surface of Cu electrocatalysts is dynamic during the CO2RR, and emphasize the importance of in situ characterization to understand the surface structure and its role in electrocatalysis.
Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; SC0004993; SC0021266
OSTI ID:
1764558
Alternate ID(s):
OSTI ID: 1778826
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 2 Vol. 143; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrolytes
Oxides
Probes
Surface chemistry
Thin films