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:

Shi, Jinlei ^[1]; Wu, Jinghe ^[2]; Zhao, Xingju ^[1]; Xue, Xinlian ^[1]; Gao, Yanfei ^[3]; Guo, Zheng Xiao ^[4]; Li, Shunfang ^[1]

---

+ Show Author Affiliations

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:

2016-10-07

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