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Title: Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.
Authors:
 [1] ;  [2] ;  [3] ;  [2] ;  [4] ;  [1] ;  [4] ;  [5] ;  [6] ;  [3] ;  [3] ;  [2]
  1. Georgia Institute of Technology and Emory University, Atlanta, GA (United States); Xiamen Univ., Xiamen (China)
  2. Georgia Institute of Technology and Emory University, Atlanta, GA (United States)
  3. University of Wisconsin-Madison, Madison, WI (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Arizona State Univ., Tempe, AZ (United States)
  6. Xiamen Univ., Xiamen (China)
Publication Date:
Grant/Contract Number:
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231; AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1259678
Alternate Identifier(s):
OSTI ID: 1337045; OSTI ID: 1395953

Wang, Xue, Choi, Sang-Il, Roling, Luke T., Luo, Ming, Ma, Cheng, Zhang, Lei, Chi, Miaofang, Liu, Jingyue, Xie, Zhaoxiong, Herron, Jeffrey A., Mavrikakis, Manos, and Xia, Younan. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. United States: N. p., Web. doi:10.1038/ncomms8594.
Wang, Xue, Choi, Sang-Il, Roling, Luke T., Luo, Ming, Ma, Cheng, Zhang, Lei, Chi, Miaofang, Liu, Jingyue, Xie, Zhaoxiong, Herron, Jeffrey A., Mavrikakis, Manos, & Xia, Younan. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. United States. doi:10.1038/ncomms8594.
Wang, Xue, Choi, Sang-Il, Roling, Luke T., Luo, Ming, Ma, Cheng, Zhang, Lei, Chi, Miaofang, Liu, Jingyue, Xie, Zhaoxiong, Herron, Jeffrey A., Mavrikakis, Manos, and Xia, Younan. 2015. "Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction". United States. doi:10.1038/ncomms8594. https://www.osti.gov/servlets/purl/1259678.
@article{osti_1259678,
title = {Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction},
author = {Wang, Xue and Choi, Sang-Il and Roling, Luke T. and Luo, Ming and Ma, Cheng and Zhang, Lei and Chi, Miaofang and Liu, Jingyue and Xie, Zhaoxiong and Herron, Jeffrey A. and Mavrikakis, Manos and Xia, Younan},
abstractNote = {Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.},
doi = {10.1038/ncomms8594},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {7}
}

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