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Title: Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2

Abstract

Catalysts consisting of atomically dispersed Pt (Ptiso) species on CeO2 supports have received recent interest due to their potential for efficient metal utilization in catalytic convertors. However, discrepancies exist between the behavior (reducibility, interaction strength with adsorbates) of high surface area Ptiso/CeO2 systems and of well-defined surface science and computational model systems, suggesting differences in Pt local coordination in the two classes of materials. Here, we reconcile these differences by demonstrating that high surface area Ptiso/CeO2 synthesized at low Pt loadings (<0.1% weight) exhibit resistance to reduction and sintering up to 500 °C in 0.05 bar H2 and minimal interactions with CO—properties previously seen only for model system studies. Alternatively, Pt loadings >0.1 weight % produce a distribution of sub-nanometer Pt structures, which are difficult to distinguish using common characterization techniques, and exhibit strong interactions with CO and weak resistance to sintering, even in 0.05 bar H2 at 50 °C—properties previously seen for high surface area materials. This work demonstrates that low metal loadings can be used to selectively populate the most thermodynamically stable adsorption sites on high surface area supports with atomically dispersed metals. Further, the site uniformity afforded by this synthetic approach is critical for the development ofmore » relationships between atomic scale local coordination and functional properties. Comparisons to recent studies of Ptiso/TiO2 suggest a general compromise between the stability of atomically dispersed metal catalysts and their ability to interact with and activate molecular species.« less

Authors:
 [1];  [1]; ORCiD logo;  [1];  [2]; ORCiD logo [3]; ORCiD logo [1];  [1];  [4];  [5];  [4];  [3]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering
  2. Fok Ying Tung Research Institute, Hong Kong University of Science and Technology, Guangzhou 511458, PR China
  3. Univ. of California, Irvine, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605339
Grant/Contract Number:  
AC02-76SF00515; CBET-1554112; DMR-1720256
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 1; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; Platinum; Adsorption; Catalysts; Cluster chemistry

Citation Formats

Resasco, Joaquin, DeRita, Leo, Dai, Sheng, Chada, Joseph P., Xu, Mingjie, Yan, Xingxu, Finzel, Jordan, Hanukovich, Sergei, Hoffman, Adam S., Graham, George W., Bare, Simon R., Pan, Xiaoqing, and Christopher, Phillip. Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2. United States: N. p., 2019. Web. https://doi.org/10.1021/jacs.9b09156.
Resasco, Joaquin, DeRita, Leo, Dai, Sheng, Chada, Joseph P., Xu, Mingjie, Yan, Xingxu, Finzel, Jordan, Hanukovich, Sergei, Hoffman, Adam S., Graham, George W., Bare, Simon R., Pan, Xiaoqing, & Christopher, Phillip. Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2. United States. https://doi.org/10.1021/jacs.9b09156
Resasco, Joaquin, DeRita, Leo, Dai, Sheng, Chada, Joseph P., Xu, Mingjie, Yan, Xingxu, Finzel, Jordan, Hanukovich, Sergei, Hoffman, Adam S., Graham, George W., Bare, Simon R., Pan, Xiaoqing, and Christopher, Phillip. Mon . "Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2". United States. https://doi.org/10.1021/jacs.9b09156. https://www.osti.gov/servlets/purl/1605339.
@article{osti_1605339,
title = {Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO2},
author = {Resasco, Joaquin and DeRita, Leo and Dai, Sheng and Chada, Joseph P. and Xu, Mingjie and Yan, Xingxu and Finzel, Jordan and Hanukovich, Sergei and Hoffman, Adam S. and Graham, George W. and Bare, Simon R. and Pan, Xiaoqing and Christopher, Phillip},
abstractNote = {Catalysts consisting of atomically dispersed Pt (Ptiso) species on CeO2 supports have received recent interest due to their potential for efficient metal utilization in catalytic convertors. However, discrepancies exist between the behavior (reducibility, interaction strength with adsorbates) of high surface area Ptiso/CeO2 systems and of well-defined surface science and computational model systems, suggesting differences in Pt local coordination in the two classes of materials. Here, we reconcile these differences by demonstrating that high surface area Ptiso/CeO2 synthesized at low Pt loadings (<0.1% weight) exhibit resistance to reduction and sintering up to 500 °C in 0.05 bar H2 and minimal interactions with CO—properties previously seen only for model system studies. Alternatively, Pt loadings >0.1 weight % produce a distribution of sub-nanometer Pt structures, which are difficult to distinguish using common characterization techniques, and exhibit strong interactions with CO and weak resistance to sintering, even in 0.05 bar H2 at 50 °C—properties previously seen for high surface area materials. This work demonstrates that low metal loadings can be used to selectively populate the most thermodynamically stable adsorption sites on high surface area supports with atomically dispersed metals. Further, the site uniformity afforded by this synthetic approach is critical for the development of relationships between atomic scale local coordination and functional properties. Comparisons to recent studies of Ptiso/TiO2 suggest a general compromise between the stability of atomically dispersed metal catalysts and their ability to interact with and activate molecular species.},
doi = {10.1021/jacs.9b09156},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 142,
place = {United States},
year = {2019},
month = {12}
}

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