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Title: Understanding cation effects in electrochemical CO2 reduction

Journal Article · · Energy & Environmental Science
DOI: https://doi.org/10.1039/c9ee01341e · OSTI ID:1576947
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [6]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Technical Univ. of Denmark (Denmark)
  3. Univ. of California, Santa Barbara, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Technical Univ. of Denmark (Denmark)
  6. Technical Univ. of Denmark, Kongens Lyngby (Denmark)

Solid–liquid interface engineering has recently emerged as a promising technique to optimize the activity and product selectivity of the electrochemical reduction of CO2. In particular, the cation identity and the interfacial electric field have been shown to have a particularly significant impact on the activity of desired products. Using a combination of theoretical and experimental investigations, we show the cation size and its resultant impact on the interfacial electric field to be the critical factor behind the ion specificity of electrochemical CO2 reduction. We present a multi-scale modeling approach that combines size-modified Poisson–Boltzmann theory with ab initio simulations of field effects on critical reaction intermediates. The model shows an unprecedented quantitative agreement with experimental trends in cation effects on CO production on Ag, C2 production on Cu, CO vibrational signatures on Pt and Cu as well as Au(111) single crystal experimental double layer capacitances. The insights obtained represent quantitative evidence for the impact of cations on the interfacial electric field. Lastly, we present design principles to increase the activity and selectivity of any field-sensitive electrochemical process based on the surface charging properties: the potential of zero charge, the ion size, and the double layer capacitance.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515; 9455; AC02-05CH11231; SC0004993
OSTI ID:
1576947
Alternate ID(s):
OSTI ID: 1542475
Journal Information:
Energy & Environmental Science, Vol. 12, Issue 10; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 361 works
Citation information provided by
Web of Science

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Cited By (10)

Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal March 2020
Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal January 2020
Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO 2 Reduction journal November 2019
Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold journal January 2020
Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials journal January 2020
How cations affect the electric double layer and the rates and selectivity of electrocatalytic processes journal October 2019
Parameter-free coordination numbers for solutions and interfaces journal January 2020
Cover Picture: Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper (Angew. Chem. Int. Ed. 11/2020) journal January 2020
Titelbild: Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper (Angew. Chem. 11/2020) journal March 2020
Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO 2 Reduction journal December 2019

Figures / Tables (9)