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Title: Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts

Abstract

The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal–support interactions can be exploited to optimize metal active-site properties are lacking. Here in this paper, we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCO x) on reducible oxide supports (TiO 2 and Nb 2O 5) that induce oxygen-vacancy formation in the support and cause HCO x-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO 2-reduction selectivity.

Authors:
 [1];  [2];  [1];  [3];  [4];  [2];  [5];  [6]
  1. University of California, Riverside, CA (United States). Department of Chemical and Environmental Engineering
  2. University of California, Irvine, CA (United States). Department of Chemical Engineering and Materials Science; Univ. of Michigan, Ann Arbor, MI (United States). Department of Materials Science and Engineering
  3. Columbia Univ., New York, NY (United States). Department of Chemical Engineering,
  4. Columbia Univ., New York, NY (United States). Department of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Department
  5. University of California, Irvine, CA (United States). Department of Chemical Engineering and Materials Science and Department of Physics and Astronomy
  6. University of California, Riverside, CA (United States). Department of Chemical and Environmental Engineering, Program in Materials Science, and UCR Center for Catalysis
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); National Science Foundation (NSF)
OSTI Identifier:
1358016
Report Number(s):
BNL-113828-2017-JA
Journal ID: ISSN 1755-4330; R&D Project: CO035; KC0302010
Grant/Contract Number:  
SC0012704; SC0012335; CHE-1301019; CBET-1159240; DMR-0723032
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalytic mechanisms; Heterogeneous catalysis

Citation Formats

Matsubu, John C., Zhang, Shuyi, DeRita, Leo, Marinkovic, Nebojsa S., Chen, Jingguang G., Graham, George W., Pan, Xiaoqing, and Christopher, Phillip. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. United States: N. p., 2016. Web. doi:10.1038/NCHEM.2607.
Matsubu, John C., Zhang, Shuyi, DeRita, Leo, Marinkovic, Nebojsa S., Chen, Jingguang G., Graham, George W., Pan, Xiaoqing, & Christopher, Phillip. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. United States. doi:10.1038/NCHEM.2607.
Matsubu, John C., Zhang, Shuyi, DeRita, Leo, Marinkovic, Nebojsa S., Chen, Jingguang G., Graham, George W., Pan, Xiaoqing, and Christopher, Phillip. Mon . "Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts". United States. doi:10.1038/NCHEM.2607. https://www.osti.gov/servlets/purl/1358016.
@article{osti_1358016,
title = {Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts},
author = {Matsubu, John C. and Zhang, Shuyi and DeRita, Leo and Marinkovic, Nebojsa S. and Chen, Jingguang G. and Graham, George W. and Pan, Xiaoqing and Christopher, Phillip},
abstractNote = {The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal–support interactions can be exploited to optimize metal active-site properties are lacking. Here in this paper, we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCOx) on reducible oxide supports (TiO2 and Nb2O5) that induce oxygen-vacancy formation in the support and cause HCOx-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO2-reduction selectivity.},
doi = {10.1038/NCHEM.2607},
journal = {Nature Chemistry},
number = 2,
volume = 9,
place = {United States},
year = {Mon Sep 19 00:00:00 EDT 2016},
month = {Mon Sep 19 00:00:00 EDT 2016}
}

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