Substrate co-doping modulates electronic metal-support interactions and significantly enhances single-atom catalysis.
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 O2adsorption 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 O2molecule, 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 O2molecule 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.
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China. sflizzu@zzu.edu.cn.
J L
JL
Shi
Department of Physics, Henan Institute of Education, Zhengzhou, 450046, China.
J H
JH
Wu
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China. sflizzu@zzu.edu.cn.
X J
XJ
Zhao
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China. sflizzu@zzu.edu.cn.
X L
XL
Xue
Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996, USA and Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
Y F
YF
Gao
Department of Chemistry, University College London, London WC1H 0AJ, UK and International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China. sflizzu@zzu.edu.cn.
Z X
ZX
Guo
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China. sflizzu@zzu.edu.cn.
S F
SF
Li