A First-Principle Study of Synergized O2 Activation and CO Oxidation by Ag Nanoparticles on TiO2(101) Support

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Guizhou Provincial Key Laboratory of Computational Nano-material Science, Institute of Applied Physics and Guizhou Synergetic Innovation Center of Scientific Big Data for Advance Manufacturing Technology, Guizhou Education University, Guiyang 550018, China
School of Chemistry and Materials Science, Hefei National Laboratory for Physical Sciences at the Microscale and CAS Key Laboratory of Mechanical Behavior and Design of Materials (LMBD, University of Science and Technology of China (USTC), Hefei 230026, China
*E-mail: [email protected]. Phone: +86 551 63600029.
Cite this: ACS Appl. Mater. Interfaces 2016, 8, 16, 10315–10323
Publication Date (Web):April 6, 2016
Copyright © 2016 American Chemical Society
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We performed density functional theory (DFT) calculations to investigate the synergized O2 activation and CO oxidation by Ag8 cluster on TiO2(101) support. The excellent catalytic activity of the interfacial Ag atoms in O2 dissociation is ascribed to the positive polarized charges, upshift of Ag d-band center, and assistance of surface Ti5c atoms. CO oxidation then takes place via a two-step mechanism coupled with O2 dissociation: (i) CO + O2 → CO2 + O and (ii) CO + O → CO2. The synergistic effect of CO and O2 activations reduces the oxidation energy barrier (Ea) of reaction (i), especially for the up-layered Ag atoms not in contact with support. It is found that the coadsorbed CO and O2 on the up-layered Ag atoms form a metal-stable four-center O–O–CO structure motif substantially promoting CO oxidation. On the oxygen defective Ag8/TiO2(101) surface, because of the decreased positive charges and the down-shift of d-band centers in Ag, the metal cluster exhibits low O2 adsorption and activation abilities. Although the dissociation of O2 is facilitated by the TiO2(101) defect sites, the dissociated O atoms would cover the defects so strongly that further CO oxidation would be prohibited unless much extra energy is introduced to recreate oxygen defects.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b01369.

  • Convergence test for Monkhorst-Pack grid, geometry optimizations for various binding structures and binding sites of Ag8 cluster on the stoichiometric TiO2(101) surface, the work functions of the pure silver and the bare stoichiometric TiO2(101) surface, the model structure of Ag7, the adsorption states of CO on the stoichiometric Ag8/TiO2(101) surface, the adsorption states of O2 on the Vo2c and Vo3c defective Ag8/TiO2(101) surface. (PDF)

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