Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis [electronic resource].

Published:: Washington, D.C. : United States. Dept. of Energy. Office of Science, 2016.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description:: pages 19,256-19,262 : digital, PDF file
Additional Creators:: Oak Ridge National Laboratory
United States. Department of Energy. Office of Science
United States. Department of Energy. Office of Scientific and Technical Information
Access Online:: www.osti.gov

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Summary:

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.

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Published through SciTech Connect.
10/07/2016.
"KC0202040"
"ERKCM06"
Nanoscale 8 46 ISSN 2040-3364; NANOHL AM
Jinlei Shi; Jinghe Wu; Xingju Zhao; Xinlian Xue; Yanfei Gao; Zheng Xiao Guo; Shunfang Li.

Funding Information:

AC05-00OR22725

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