Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO
Abstract
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.
- Authors:
-
[1];
[2];
[1];
[1];
[3];
[1];
[3];
[1];
[4]
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH)
- OSTI Identifier:
- 1825919
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; S10OD024998
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 155; Journal Issue: 5; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chen, Shouping, Li, Mufan, Yu, Sunmoon, Louisia, Sheena, Chuang, Wesley, Gao, Mengyu, Chen, Chubai, Jin, Jianbo, Salmeron, Miquel B., and Yang, Peidong. Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO. United States: N. p., 2021.
Web. doi:10.1063/5.0059363.
Chen, Shouping, Li, Mufan, Yu, Sunmoon, Louisia, Sheena, Chuang, Wesley, Gao, Mengyu, Chen, Chubai, Jin, Jianbo, Salmeron, Miquel B., & Yang, Peidong. Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO. United States. https://doi.org/10.1063/5.0059363
Chen, Shouping, Li, Mufan, Yu, Sunmoon, Louisia, Sheena, Chuang, Wesley, Gao, Mengyu, Chen, Chubai, Jin, Jianbo, Salmeron, Miquel B., and Yang, Peidong. Mon .
"Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO". United States. https://doi.org/10.1063/5.0059363. https://www.osti.gov/servlets/purl/1825919.
@article{osti_1825919,
title = {Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO},
author = {Chen, Shouping and Li, Mufan and Yu, Sunmoon and Louisia, Sheena and Chuang, Wesley and Gao, Mengyu and Chen, Chubai and Jin, Jianbo and Salmeron, Miquel B. and Yang, Peidong},
abstractNote = {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.},
doi = {10.1063/5.0059363},
journal = {Journal of Chemical Physics},
number = 5,
volume = 155,
place = {United States},
year = {Mon Aug 02 00:00:00 EDT 2021},
month = {Mon Aug 02 00:00:00 EDT 2021}
}
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