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Title: Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis

Abstract

Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO 2(110) can be tuned into a highly effective catalyst, e.g. for O 2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhanced EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O 2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O 2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The presentmore » findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [4];  [1]
  1. Zhengzhou University (China). International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering
  2. Henan Institute of Education, Zhengzhou (China). Department of Physics
  3. Univ. of Tennessee, Knoxville, TN (United States). Department of Materials Science and Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  4. University College London (United Kingdom). Department of Chemistry; Zhengzhou University (China). International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1357996
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 8; Journal Issue: 46; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shi, Jinlei, Wu, Jinghe, Zhao, Xingju, Xue, Xinlian, Gao, Yanfei, Guo, Zheng Xiao, and Li, Shunfang. Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis. United States: N. p., 2016. Web. doi:10.1039/C6NR04292A.
Shi, Jinlei, Wu, Jinghe, Zhao, Xingju, Xue, Xinlian, Gao, Yanfei, Guo, Zheng Xiao, & Li, Shunfang. Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis. United States. https://doi.org/10.1039/C6NR04292A
Shi, Jinlei, Wu, Jinghe, Zhao, Xingju, Xue, Xinlian, Gao, Yanfei, Guo, Zheng Xiao, and Li, Shunfang. Fri . "Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis". United States. https://doi.org/10.1039/C6NR04292A. https://www.osti.gov/servlets/purl/1357996.
@article{osti_1357996,
title = {Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis},
author = {Shi, Jinlei and Wu, Jinghe and Zhao, Xingju and Xue, Xinlian and Gao, Yanfei and Guo, Zheng Xiao and Li, Shunfang},
abstractNote = {Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO2(110) can be tuned into a highly effective catalyst, e.g. for O2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhanced EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The present findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts.},
doi = {10.1039/C6NR04292A},
url = {https://www.osti.gov/biblio/1357996}, journal = {Nanoscale},
issn = {2040-3364},
number = 46,
volume = 8,
place = {United States},
year = {2016},
month = {10}
}

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