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

Abstract

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.

Authors:
 [1];  [2];  [3];  [4];  [3];  [2]; ORCiD logo [4]
+ Show Author Affiliations
  1. Carnegie Mellon University, Pittsburgh, PA (United States); National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)
  2. University of Pittsburgh, PA (United States)
  3. National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)
  4. Carnegie Mellon University, Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States); Carnegie Mellon Univ., Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1849193
Grant/Contract Number:  
FE0026825; AC02-05CH11231; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 60; Journal Issue: 12; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanocluster; atomic precision; CO2 reduction; mechanism study; doping effects

Citation Formats

Li, Site, Nagarajan, Anantha Venkataraman, Alfonso, Dominic R., Sun, Mingkang, Kauffman, Douglas R., Mpourmpakis, Giannis, and Jin, Rongchao. Boosting CO2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters. United States: N. p., 2021. Web. doi:10.1002/anie.202016129.
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Li, Site, Nagarajan, Anantha Venkataraman, Alfonso, Dominic R., Sun, Mingkang, Kauffman, Douglas R., Mpourmpakis, Giannis, & Jin, Rongchao. Boosting CO2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters. United States. https://doi.org/10.1002/anie.202016129
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Li, Site, Nagarajan, Anantha Venkataraman, Alfonso, Dominic R., Sun, Mingkang, Kauffman, Douglas R., Mpourmpakis, Giannis, and Jin, Rongchao. Fri . "Boosting CO2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters". United States. https://doi.org/10.1002/anie.202016129. https://www.osti.gov/servlets/purl/1849193.
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@article{osti_1849193,
title = {Boosting CO2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters},
author = {Li, Site and Nagarajan, Anantha Venkataraman and Alfonso, Dominic R. and Sun, Mingkang and Kauffman, Douglas R. and Mpourmpakis, Giannis and Jin, Rongchao},
abstractNote = {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.},
doi = {10.1002/anie.202016129},
journal = {Angewandte Chemie (International Edition)},
number = 12,
volume = 60,
place = {United States},
year = {Fri Feb 12 00:00:00 EST 2021},
month = {Fri Feb 12 00:00:00 EST 2021}
}
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https://doi.org/10.1002/anie.202016129
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