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Title: Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

Abstract

Here, an effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@Pt nL (n = 1–6) core–shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects,more » which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt 2–3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt 1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [1];  [4];  [2];  [2];  [5];  [3];  [6]
  1. Georgia Institute of Technology and Emory Univ., Atlanta, GA (United States); Xiamen Univ., Fujian (China)
  2. Univ. of Texas at Dallas, Richardson, TX (United States)
  3. Univ. of Wisconsin-Madison, Madison, WI (United States)
  4. Georgia Inst. of Technology, Atlanta, GA (United States)
  5. Xiamen Univ., Fujian (China)
  6. Georgia Institute of Technology and Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
EMSL; CNM at ANL; and NERSC
OSTI Identifier:
1396241
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 14; Journal Issue: 6; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bimetallic catalyst; core−shell nanostructure; fuel cell; oxygen reduction reaction; Platinum-based catalyst

Citation Formats

Xie, Shuifen, Choi, Sang -Il, Lu, Ning, Roling, Luke T., Herron, Jeffrey A., Zhang, Lei, Park, Jinho, Wang, Jinguo, Kim, Moon J., Xie, Zhaoxiong, Mavrikakis, Manos, and Xia, Younan. Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction. United States: N. p., 2014. Web. doi:10.1021/nl501205j.
Xie, Shuifen, Choi, Sang -Il, Lu, Ning, Roling, Luke T., Herron, Jeffrey A., Zhang, Lei, Park, Jinho, Wang, Jinguo, Kim, Moon J., Xie, Zhaoxiong, Mavrikakis, Manos, & Xia, Younan. Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction. United States. doi:10.1021/nl501205j.
Xie, Shuifen, Choi, Sang -Il, Lu, Ning, Roling, Luke T., Herron, Jeffrey A., Zhang, Lei, Park, Jinho, Wang, Jinguo, Kim, Moon J., Xie, Zhaoxiong, Mavrikakis, Manos, and Xia, Younan. Mon . "Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction". United States. doi:10.1021/nl501205j. https://www.osti.gov/servlets/purl/1396241.
@article{osti_1396241,
title = {Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction},
author = {Xie, Shuifen and Choi, Sang -Il and Lu, Ning and Roling, Luke T. and Herron, Jeffrey A. and Zhang, Lei and Park, Jinho and Wang, Jinguo and Kim, Moon J. and Xie, Zhaoxiong and Mavrikakis, Manos and Xia, Younan},
abstractNote = {Here, an effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PtnL (n = 1–6) core–shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2–3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.},
doi = {10.1021/nl501205j},
journal = {Nano Letters},
number = 6,
volume = 14,
place = {United States},
year = {2014},
month = {5}
}

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