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Title: Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions

Abstract

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mgPt, ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions.more » Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.« less

Authors:
 [1];  [2];  [2];  [3]; ORCiD logo [3];  [4];  [4];  [4];  [3];  [3];  [3];  [3]; ORCiD logo [3];  [5]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [3]
  1. Hunan Univ., Changsha (China); State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Central Michigan Univ., Mount Pleasant, MI (United States)
  3. State Univ. of New York (SUNY), Binghamton, NY (United States)
  4. CCDC Army Research Lab., Adelphi, MD (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Hunan Univ., Changsha (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); China Scholarship Council
OSTI Identifier:
1598311
Grant/Contract Number:  
AC02-06CH11357; SC0006877
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 3; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; twisty nanowires; platinum-iron alloy electrocatalysts; realloying; oxygen reduction reaction; synchrotron X-ray diffraction; pair distribution function analysis; fuel cell

Citation Formats

Kong, Zhijie, Maswadeh, Yazan, Vargas, Jorge A., Shan, Shiyao, Wu, Zhi-Peng, Kareem, Haval, Leff, Asher C., Tran, Dat T., Yan, Shan, Nam, Sanghyun, Zhao, Xingfang, Lee, Jason M., Luo, Jin, Shastri, Sarvjit, Yu, Gang, Petkov, Valeri, and Zhong, Chuan-Jian. Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions. United States: N. p., 2019. Web. https://doi.org/10.1021/jacs.9b10239.
Kong, Zhijie, Maswadeh, Yazan, Vargas, Jorge A., Shan, Shiyao, Wu, Zhi-Peng, Kareem, Haval, Leff, Asher C., Tran, Dat T., Yan, Shan, Nam, Sanghyun, Zhao, Xingfang, Lee, Jason M., Luo, Jin, Shastri, Sarvjit, Yu, Gang, Petkov, Valeri, & Zhong, Chuan-Jian. Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions. United States. https://doi.org/10.1021/jacs.9b10239
Kong, Zhijie, Maswadeh, Yazan, Vargas, Jorge A., Shan, Shiyao, Wu, Zhi-Peng, Kareem, Haval, Leff, Asher C., Tran, Dat T., Yan, Shan, Nam, Sanghyun, Zhao, Xingfang, Lee, Jason M., Luo, Jin, Shastri, Sarvjit, Yu, Gang, Petkov, Valeri, and Zhong, Chuan-Jian. Mon . "Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions". United States. https://doi.org/10.1021/jacs.9b10239. https://www.osti.gov/servlets/purl/1598311.
@article{osti_1598311,
title = {Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions},
author = {Kong, Zhijie and Maswadeh, Yazan and Vargas, Jorge A. and Shan, Shiyao and Wu, Zhi-Peng and Kareem, Haval and Leff, Asher C. and Tran, Dat T. and Yan, Shan and Nam, Sanghyun and Zhao, Xingfang and Lee, Jason M. and Luo, Jin and Shastri, Sarvjit and Yu, Gang and Petkov, Valeri and Zhong, Chuan-Jian},
abstractNote = {The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mgPt, ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.},
doi = {10.1021/jacs.9b10239},
journal = {Journal of the American Chemical Society},
number = 3,
volume = 142,
place = {United States},
year = {2019},
month = {12}
}

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