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Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions
Abstract
Efficient C–C bond cleavage and oxidation of alcohols to CO2 is the key to developing highly efficient alcohol fuel cells for renewable energy applications. In this work, we report the synthesis of core/shell Au/Pt nanowires (NWs) with stepped Pt clusters deposited along the ultrathin (2.3 nm) stepped Au NWs as an active catalyst to effectively oxidize alcohols to CO2. The catalytic oxidation reaction is dependent on the Au/Pt ratios, and the Au1.0/Pt0.2 NWs have the largest percentage (~75%) of stepped Au/Pt sites and show the highest activity for ethanol electro-oxidation, reaching an unprecedented 196.9 A/mgPt (32.5 A/mgPt+Au). This NW catalyst is also active in catalyzing the oxidation of other primary alcohols, such as methanol, n-propanol, and ethylene glycol. In situ X-ray absorption spectroscopy and infrared spectroscopy are used to characterize the catalyst structure and to identify key reaction intermediates, providing concrete evidence that the synergy between the low-coordinated Pt sites and the stepped Au NWs is essential to catalyze the alcohol oxidation reaction, which is further supported by DFT calculations that the C–C bond cleavage is indeed enhanced on the undercoordinated Pt–Au surface. Here, our study provides important evidence that a core/shell structure with stepped core/shell sites is essential tomore »
- Authors:
-
[1];
[3];
[4];
[1];
[5];
[6];
[2];
[1]
- Brown Univ., Providence, RI (United States)
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Inner Mongolia Univ., Hohhot (China)
- Columbia Univ., New York, NY (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- California State University, Northridge (CSUN), CA (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)
- OSTI Identifier:
- 2005159
- Report Number(s):
- BNL-224823-2023-JAAM; GRP-COSC-4
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- SC0012704; SC0012335; DMR-1828019
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 145; Journal Issue: 34; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; ethanol; electro-oxidation; catalysts; gold; oxidation; platinum; bimetallic nanowires; low-coordination surface; carbon-carbon bond cleavage; alcohol oxidation reaction; in situ spectroscopy; DFT calculations
Citation Formats
Wei, Kecheng, Lin, Honghong, Zhao, Xueru, Zhao, Zhonglong, Marinkovic, Nebojsa, Morales, Michael, Huang, Zhennan, Perlmutter, Laura, Guan, Huanqin, Harris, Cooro, Chi, Miaofang, Lu, Gang, Sasaki, Kotaro, and Sun, Shouheng. Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions. United States: N. p., 2023.
Web. doi:10.1021/jacs.3c07027.
Wei, Kecheng, Lin, Honghong, Zhao, Xueru, Zhao, Zhonglong, Marinkovic, Nebojsa, Morales, Michael, Huang, Zhennan, Perlmutter, Laura, Guan, Huanqin, Harris, Cooro, Chi, Miaofang, Lu, Gang, Sasaki, Kotaro, & Sun, Shouheng. Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions. United States. https://doi.org/10.1021/jacs.3c07027
Wei, Kecheng, Lin, Honghong, Zhao, Xueru, Zhao, Zhonglong, Marinkovic, Nebojsa, Morales, Michael, Huang, Zhennan, Perlmutter, Laura, Guan, Huanqin, Harris, Cooro, Chi, Miaofang, Lu, Gang, Sasaki, Kotaro, and Sun, Shouheng. Tue .
"Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions". United States. https://doi.org/10.1021/jacs.3c07027.
@article{osti_2005159,
title = {Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions},
author = {Wei, Kecheng and Lin, Honghong and Zhao, Xueru and Zhao, Zhonglong and Marinkovic, Nebojsa and Morales, Michael and Huang, Zhennan and Perlmutter, Laura and Guan, Huanqin and Harris, Cooro and Chi, Miaofang and Lu, Gang and Sasaki, Kotaro and Sun, Shouheng},
abstractNote = {Efficient C–C bond cleavage and oxidation of alcohols to CO2 is the key to developing highly efficient alcohol fuel cells for renewable energy applications. In this work, we report the synthesis of core/shell Au/Pt nanowires (NWs) with stepped Pt clusters deposited along the ultrathin (2.3 nm) stepped Au NWs as an active catalyst to effectively oxidize alcohols to CO2. The catalytic oxidation reaction is dependent on the Au/Pt ratios, and the Au1.0/Pt0.2 NWs have the largest percentage (~75%) of stepped Au/Pt sites and show the highest activity for ethanol electro-oxidation, reaching an unprecedented 196.9 A/mgPt (32.5 A/mgPt+Au). This NW catalyst is also active in catalyzing the oxidation of other primary alcohols, such as methanol, n-propanol, and ethylene glycol. In situ X-ray absorption spectroscopy and infrared spectroscopy are used to characterize the catalyst structure and to identify key reaction intermediates, providing concrete evidence that the synergy between the low-coordinated Pt sites and the stepped Au NWs is essential to catalyze the alcohol oxidation reaction, which is further supported by DFT calculations that the C–C bond cleavage is indeed enhanced on the undercoordinated Pt–Au surface. Here, our study provides important evidence that a core/shell structure with stepped core/shell sites is essential to enhance electrochemical oxidation of alcohols and will also be central to understanding electro-oxidation reactions and to the future development of highly efficient direct alcohol fuel cells for renewable energy applications.},
doi = {10.1021/jacs.3c07027},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 145,
place = {United States},
year = {Tue Aug 22 00:00:00 EDT 2023},
month = {Tue Aug 22 00:00:00 EDT 2023}
}
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