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Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts

Journal Article · · Nature Chemical Engineering
 [1];  [2];  [3];  [1];  [4];  [5];  [6];  [1];  [1];  [1];  [1];  [3];  [3];  [3];  [1];  [7];  [5];  [8];  [2];  [1]
  1. University of Cincinnati, OH (United States)
  2. Rice University, Houston, TX (United States)
  3. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  4. Stony Brook University, NY (United States)
  5. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  6. Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source (NSLS)
  7. Stony Brook University, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
  8. Arizona State University, Tempe, AZ (United States)
+ Show Author Affiliations

Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C2 product specificity during electrocatalytic CO2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm-2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO2 electroreduction to a single C2 product.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; SC0012704; EE0010836
OSTI ID:
2301665
Journal Information:
Nature Chemical Engineering, Journal Name: Nature Chemical Engineering Journal Issue: 2 Vol. 1; ISSN 2948-1198
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon capture and storage
chemical engineering
electrocatalysis