Boosting CO2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters

Li, Site; Nagarajan, Anantha Venkataraman; Alfonso, Dominic R.; Sun, Mingkang; Kauffman, Douglas R.; Mpourmpakis, Giannis; Jin, Rongchao

doi:10.1002/anie.202016129

Boosting CO₂ Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters

Journal Article · Fri Feb 12 00:00:00 EST 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202016129· OSTI ID:1849193

Li, Site ^[1]; Nagarajan, Anantha Venkataraman ^[2]; Alfonso, Dominic R. ^[3]; Sun, Mingkang ^[4]; Kauffman, Douglas R. ^[3]; Mpourmpakis, Giannis ^[2]; ^[4]

Carnegie Mellon University, Pittsburgh, PA (United States); National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States); OSTI
University of Pittsburgh, PA (United States)
National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)
Carnegie Mellon University, Pittsburgh, PA (United States)

Thiolate-protected gold nanoclusters (NCs) are promising catalytic materials for the electrochemical CO₂ reduction reaction (CO₂RR). In this work an atomic level modification of a Au₂₃ NC is made by substituting two surface Au atoms with two Cd atoms, and it enhances the CO₂RR selectivity to 90–95 % at the applied potential between -0.5 to -0.9 V, which is doubled compared to that of the undoped Au₂₃. Additionally, the Cd-doped Au₁₉Cd₂ exhibits the highest CO₂RR activity (2200 mA mg^-1 at -1.0 V vs. RHE) among the reported NCs. This synergetic effect between Au and Cd is remarkable. Density-functional theory calculations reveal that the exposure of a sulfur active site upon partial ligand removal provides an energetically feasible CO₂RR pathway. The thermodynamic energy barrier for CO formation is 0.74 eV lower on Au₁₉Cd₂ than on Au₂₃. Here these results reveal that Cd doping can boost the CO₂RR performance of Au NCs by modifying the surface geometry and electronic structure, which further changes the intermediate binding energy. This work offers insights into the surface doping mechanism of the CO₂RR and bimetallic synergism.

View Accepted Manuscript (DOE)

Research Organization:: Carnegie Mellon University, Pittsburgh, PA (United States); Pennsylvania State University, University Park, PA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; FE0026825

OSTI ID:: 1849193

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 12 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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doping effects
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References (55)

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