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Title: High-indexed Pt 3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching

Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi 4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel component in the <100> direction through carbon monoxide etching of carbon-supported PtNi 4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt 3Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support throughmore » thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [4] ;  [3] ;  [1] ;  [5] ;  [6] ;  [7] ;  [8] ;  [5] ;  [9] ; ORCiD logo [1]
  1. State Univ. of New York at Binghamton, Binghamton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Miami Univ., Oxford, OH (United States)
  4. Arizona State Univ., Tempe, AZ (United States)
  5. Chinese Academy of Sciences, Shanxi (China); Synfuels China Co. Ltd., Beijing (China)
  6. Univ. of South Dakota, Vermillion, SD (United States)
  7. China Univ. of Petroleum, Shandong (China)
  8. Hitachi High Technologies America, Inc., Clarksburg, MD (United States)
  9. Miami Univ., Oxford, OH (United States); American Univ., Washington, D.C. (United States)
Publication Date:
Report Number(s):
BNL-113996-2017-JA
Journal ID: ISSN 1530-6984; R&D Project: 16060; 16060; KC0403020
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 4; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; nanoframe; tetrahexahedron; high-index; preferential etching; Pt3Ni; Center for Functional Nanomaterials
OSTI Identifier:
1368669

Wang, Chenyu, Zhang, Lihua, Yang, Hongzhou, Pan, Jinfong, Liu, Jingyue, Dotse, Charles, Luan, Yiliang, Gao, Rui, Lin, Cuikun, Zhang, Jun, Kilcrease, James P., Wen, Xiaodong, Zou, Shouzhong, and Fang, Jiye. High-indexed Pt3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching. United States: N. p., Web. doi:10.1021/acs.nanolett.6b04731.
Wang, Chenyu, Zhang, Lihua, Yang, Hongzhou, Pan, Jinfong, Liu, Jingyue, Dotse, Charles, Luan, Yiliang, Gao, Rui, Lin, Cuikun, Zhang, Jun, Kilcrease, James P., Wen, Xiaodong, Zou, Shouzhong, & Fang, Jiye. High-indexed Pt3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching. United States. doi:10.1021/acs.nanolett.6b04731.
Wang, Chenyu, Zhang, Lihua, Yang, Hongzhou, Pan, Jinfong, Liu, Jingyue, Dotse, Charles, Luan, Yiliang, Gao, Rui, Lin, Cuikun, Zhang, Jun, Kilcrease, James P., Wen, Xiaodong, Zou, Shouzhong, and Fang, Jiye. 2017. "High-indexed Pt3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching". United States. doi:10.1021/acs.nanolett.6b04731. https://www.osti.gov/servlets/purl/1368669.
@article{osti_1368669,
title = {High-indexed Pt3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching},
author = {Wang, Chenyu and Zhang, Lihua and Yang, Hongzhou and Pan, Jinfong and Liu, Jingyue and Dotse, Charles and Luan, Yiliang and Gao, Rui and Lin, Cuikun and Zhang, Jun and Kilcrease, James P. and Wen, Xiaodong and Zou, Shouzhong and Fang, Jiye},
abstractNote = {Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel component in the <100> direction through carbon monoxide etching of carbon-supported PtNi4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt3Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support through thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.},
doi = {10.1021/acs.nanolett.6b04731},
journal = {Nano Letters},
number = 4,
volume = 17,
place = {United States},
year = {2017},
month = {3}
}