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Selective Electrocatalytic Reduction of CO2 into CO at Small, Thiol-Capped Au/Cu Nanoparticles

Journal Article · · Journal of Physical Chemistry. C
 [1];  [1];  [2];  [2];  [2];  [2];  [1];  [2];  [1];  [1];  [1];  [3];  [4];  [5]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); AECOM, South Park, PA (United States)
  3. Louisiana State Univ., Baton Rouge, LA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations
The electrochemical CO2 reduction reaction (CO2RR) is a promising approach for converting fossil fuel emissions into environmentally sustainable chemicals and fuels. The ability to control the surface structure of CO2RR nanocatalysts provides an opportunity to tune product selectivity. Bimetallic gold–copper catalysts have been identified as emerging electrocatalyst candidates, but Cu incorporation typically lowers product selectivity compared with pure Au. Here we show sustained CO selectivity and activity up to 49% Cu content in small (<2 nm), thiol-capped Au/Cu nanoparticles (NPs). Bimetallic NPs containing 49% Cu selectivity converted CO2 into CO with 100 ± 6% CO Faradaic efficiency and average mass activity of ~500 mA/mg during a 12 h electrolysis experiment at –0.8 V vs RHE. Au/Cu NPs synthesized without thiol ligands selectively produced H2, whereas larger (>10 nm), thermally dethiolated Au/Cu NPs produced a wider product distribution including H2, CO, and C2H4. Density functional theory (DFT) modeling of CO2RR and H2 evolution at realistic, thiol-capped Au/Cu NP structures indicated that copper–thiol surface structures sustained CO selectivity by stabilizing key *CO intermediates while making *H binding less favorable. Calculations also predicted that removing a significant fraction of the thiol ligands would increase *CO binding strength such that desorption of CO product molecules could become the most thermodynamically challenging step. This result, coupled with increased *H stability on dethiolated nanoclusters, points to decreased CO2RR selectivity for small, ligand-free catalysts, which is in line with experimental observations from our group and others. Here, our results demonstrate that thiol-ligand surface structures can sustain the CO selectivity of bimetallic Au/Cu NPs and reduce precious metal requirements for CO2RR.
Research Organization:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Organization:
USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-76SF00515; FE0004000; SC0012704
OSTI ID:
1477176
Report Number(s):
NETL-PUB-22320
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 49 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Noble Metal Nanostructured Materials for Chemical and Biosensing Systems journal January 2020
Galvanic Replacement of Electrochemically Restructured Copper Electrodes with Gold and Its Electrocatalytic Activity for Nitrate Ion Reduction journal September 2018
Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO 2 to CO journal July 2019
Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY