Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Kecheng Wei; Honghong Lin; Xueru Zhao; Zhonglong Zhao; Nebojsa Marinkovic; Michael Morales; Zhennan Huang; Laura Perlmutter; Huanqin Guan; Cooro Harris; Miaofang Chi; Gang Lu; Kotaro Sasaki; Shouheng Sun

doi:10.1021/jacs.3c07027

Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Kecheng Wei, Honghong Lin, Xueru Zhao, Zhonglong Zhao, Nebojsa Marinkovic, Michael Morales, Zhennan Huang, Laura Perlmutter, Huanqin Guan, Cooro Harris, Miaofang Chi, Gang Lu, Kotaro Sasaki, Shouheng Sun

electron Microscopy and Microanalysis

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

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 Au_1.0/Pt_0.2 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/mg_Pt (32.5 A/mg_Pt+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. 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.

Original language	English
Pages (from-to)	19076-19085
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	145
Issue number	34
DOIs	https://doi.org/10.1021/jacs.3c07027
State	Published - Aug 30 2023

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.

Funding

The work was supported in part by the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, and by Toyota. This work used the 7-BM QAS beamline of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium under U.S. DOE, Office of Basic Energy Sciences Grant No. DE-SC0012335. Z.Z. was supported by the National Natural Science Foundation of China under grant no. 22102077, and the work at California State University Northridge was supported by the US NSF-PREM program (DMR-1828019). Microscopy was supported by DOE-BES early career award ERKCZ55 and conducted at ORNL’s Center for Nanophase Materials Sciences (CNMS), which is a US-DOE, Office of Science User Facility.

Funders	Funder number
Synchrotron Catalysis Consortium
US NSF-PREM	DMR-1828019
US-DOE
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences	DE-SC0012335
Brookhaven National Laboratory	DE-SC0012704
Hydrogen and Fuel Cell Technologies Office
National Natural Science Foundation of China	22102077

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Wei, K., Lin, H., Zhao, X., Zhao, Z., Marinkovic, N., Morales, M., Huang, Z., Perlmutter, L., Guan, H., Harris, C., Chi, M., Lu, G., Sasaki, K., & Sun, S. (2023). Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions. Journal of the American Chemical Society, 145(34), 19076-19085. https://doi.org/10.1021/jacs.3c07027

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title = "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. 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.",

author = "Kecheng Wei and Honghong Lin and Xueru Zhao and Zhonglong Zhao and Nebojsa Marinkovic and Michael Morales and Zhennan Huang and Laura Perlmutter and Huanqin Guan and Cooro Harris and Miaofang Chi and Gang Lu and Kotaro Sasaki and Shouheng Sun",

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Wei, K, Lin, H, Zhao, X, Zhao, Z, Marinkovic, N, Morales, M, Huang, Z, Perlmutter, L, Guan, H, Harris, C, Chi, M, Lu, G, Sasaki, K & Sun, S 2023, 'Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions', Journal of the American Chemical Society, vol. 145, no. 34, pp. 19076-19085. https://doi.org/10.1021/jacs.3c07027

TY - JOUR

T1 - Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions

AU - Wei, Kecheng

AU - Lin, Honghong

AU - Zhao, Xueru

AU - Zhao, Zhonglong

AU - Marinkovic, Nebojsa

AU - Morales, Michael

AU - Huang, Zhennan

AU - Perlmutter, Laura

AU - Guan, Huanqin

AU - Harris, Cooro

AU - Chi, Miaofang

AU - Lu, Gang

AU - Sasaki, Kotaro

AU - Sun, Shouheng

PY - 2023/8/30

Y1 - 2023/8/30

N2 - 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. 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.

AB - 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. 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.

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DO - 10.1021/jacs.3c07027

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AN - SCOPUS:85169184723

SN - 0002-7863

VL - 145

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EP - 19085

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Abstract

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