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Title: Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Abstract

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39more » ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [4];  [5];  [1];  [6];  [3];  [2];  [4];  [1]
  1. Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045, United States; Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, United States
  2. Department of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
  3. Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
  4. Department of Physics, Yeshiva University, New York, New York 10016, United States
  5. Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045, United States; Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, United States; College of Chemistry, Peking University, Beijing 10080, China
  6. College of Chemistry, Peking University, Beijing 10080, China
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409632
Report Number(s):
BNL-114684-2017-JA¿¿¿
Journal ID: ISSN 2155-5435
DOE Contract Number:  
SC0012704
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shan, Junjun, Zhang, Shiran, Choksi, Tej, Nguyen, Luan, Bonifacio, Cecile S., Li, Yuanyuan, Zhu, Wei, Tang, Yu, Zhang, Yawen, Yang, Judith C., Greeley, Jeffrey, Frenkel, Anatoly I., and Tao, Franklin. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b02054.
Shan, Junjun, Zhang, Shiran, Choksi, Tej, Nguyen, Luan, Bonifacio, Cecile S., Li, Yuanyuan, Zhu, Wei, Tang, Yu, Zhang, Yawen, Yang, Judith C., Greeley, Jeffrey, Frenkel, Anatoly I., & Tao, Franklin. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase. United States. doi:10.1021/acscatal.6b02054.
Shan, Junjun, Zhang, Shiran, Choksi, Tej, Nguyen, Luan, Bonifacio, Cecile S., Li, Yuanyuan, Zhu, Wei, Tang, Yu, Zhang, Yawen, Yang, Judith C., Greeley, Jeffrey, Frenkel, Anatoly I., and Tao, Franklin. Mon . "Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase". United States. doi:10.1021/acscatal.6b02054.
@article{osti_1409632,
title = {Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase},
author = {Shan, Junjun and Zhang, Shiran and Choksi, Tej and Nguyen, Luan and Bonifacio, Cecile S. and Li, Yuanyuan and Zhu, Wei and Tang, Yu and Zhang, Yawen and Yang, Judith C. and Greeley, Jeffrey and Frenkel, Anatoly I. and Tao, Franklin},
abstractNote = {Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.},
doi = {10.1021/acscatal.6b02054},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 1,
volume = 7,
place = {United States},
year = {2016},
month = {12}
}