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Title: Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO 2 reduction

Abstract

Here, electrocatalytic CO 2 reduction to higher-value hydrocarbons beyond C 1 products is desirable for applications in energy storage, transportation and the chemical industry. Cu catalysts have shown the potential to catalyse C–C coupling for C 2+ products, but still suffer from low selectivity in water. Here, we use density functional theory to determine the energetics of the initial C–C coupling steps on different Cu facets in CO 2 reduction, and suggest that the Cu(100) and stepped (211) facets favour C 2+ product formation over Cu(111). To demonstrate this, we report the tuning of facet exposure on Cu foil through the metal ion battery cycling method. Compared with the polished Cu foil, our 100-cycled Cu nanocube catalyst with exposed (100) facets presents a sixfold improvement in C 2+ to C 1 product ratio, with a highest C 2+ Faradaic efficiency of over 60% and H 2 below 20%, and a corresponding C 2+ current of more than 40 mA cm –2.

Authors:
ORCiD logo [1];  [2];  [1];  [2];  [1];  [3];  [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Harvard Univ., Cambridge, MA (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1457051
Alternate Identifier(s):
OSTI ID: 1490974
Grant/Contract Number:  
AC02-76SF00515; SC0004993; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal Issue: 2; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jiang, Kun, Sandberg, Robert B., Akey, Austin J., Liu, Xinyan, Bell, David C., Norskov, Jens K., Chan, Karen, and Wang, Haotian. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. United States: N. p., 2018. Web. doi:10.1038/s41929-017-0009-x.
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Jiang, Kun, Sandberg, Robert B., Akey, Austin J., Liu, Xinyan, Bell, David C., Norskov, Jens K., Chan, Karen, & Wang, Haotian. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. United States. doi:10.1038/s41929-017-0009-x.
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Jiang, Kun, Sandberg, Robert B., Akey, Austin J., Liu, Xinyan, Bell, David C., Norskov, Jens K., Chan, Karen, and Wang, Haotian. Mon . "Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction". United States. doi:10.1038/s41929-017-0009-x. https://www.osti.gov/servlets/purl/1457051.
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@article{osti_1457051,
title = {Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction},
author = {Jiang, Kun and Sandberg, Robert B. and Akey, Austin J. and Liu, Xinyan and Bell, David C. and Norskov, Jens K. and Chan, Karen and Wang, Haotian},
abstractNote = {Here, electrocatalytic CO2 reduction to higher-value hydrocarbons beyond C1 products is desirable for applications in energy storage, transportation and the chemical industry. Cu catalysts have shown the potential to catalyse C–C coupling for C2+ products, but still suffer from low selectivity in water. Here, we use density functional theory to determine the energetics of the initial C–C coupling steps on different Cu facets in CO2 reduction, and suggest that the Cu(100) and stepped (211) facets favour C2+ product formation over Cu(111). To demonstrate this, we report the tuning of facet exposure on Cu foil through the metal ion battery cycling method. Compared with the polished Cu foil, our 100-cycled Cu nanocube catalyst with exposed (100) facets presents a sixfold improvement in C2+ to C1 product ratio, with a highest C2+ Faradaic efficiency of over 60% and H2 below 20%, and a corresponding C2+ current of more than 40 mA cm–2.},
doi = {10.1038/s41929-017-0009-x},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 2,
volume = 1,
place = {United States},
year = {2018},
month = {1}
}
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Journal Article:
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DOI:  10.1038/s41929-017-0009-x
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Figures / Tables:

Figure 1 Figure 1: DFT simulations of C-C coupling on Cu facets. (a) Contour plot of the electric field in the vicinity of an ion and its image charge on a Cu(100) surface. (b) Binding free energies in vacuum for 2*CO and *OCCO as a function of electric field strength along themore » z-direction perpendicular to the slab (c) Free energy diagram at 0 V (RHE) for the energetics of the dimerization of *CO to form *OCCO and the subsequent surface hydrogenation (solid lines) and proton-electron transfer (dashed lines) to form *OCCHO in the presence of a solvent and cation-induced field (d) *OCCO configurations on the (100), (111) and (211) facets, where solvent molecules have been removed to show the adsorbate configurations« less
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    Carbon dioxide electroreduction to C2 products over copper-cuprous oxide derived from electrosynthesized copper complex
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