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Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0059363· OSTI ID:1825919
 [1];  [2];  [1];  [1];  [1];  [3];  [1];  [3];  [1];  [4]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
+ Show Author Affiliations
Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au25 nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO2 to CO. The Au25 nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤-0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au25 nanoclusters concomitantly. The thermally and electrochemically treated Au25 nanoclusters show enhanced activity and selectivity for the electrochemical CO2-to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515
OSTI ID:
1825919
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 155; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY