Explicit Roles of Au and TiO2 in a Bifunctional Au/TiO2 Catalyst for the Water-Gas Shift Reaction: A DFT Study

Authors

  • Dr. Akhtar Hussain,

    Corresponding author
    1. Theoretical Plasma Physics Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P.O. Nilore, Islamabad, 44000 (Pakistan)
    2. Nano Science & Catalysis Division, National Centre for Physics (NCP), Quaid-i-Azam University, Islamabad, 44000 (Pakistan)
    • Theoretical Plasma Physics Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P.O. Nilore, Islamabad, 44000 (Pakistan)
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  • Dr. Jose Gracia,

    1. Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands)
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  • Dr. Ben E. Nieuwenhuys,

    1. Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands)
    2. Leiden Institute of Chemistry, Leiden University, PO box 9502, 2300 RA Leiden (The Netherlands)
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  • Prof. Dr. J. W. (Hans) Niemantsverdriet

    1. Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands)
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Abstract

The water–gas shift reaction has been investigated by using DFT applied to Au(1 0 0), stepped Au(3 1 0), and TiO2 anatase (0 0 1) surfaces. The results show that neither Au nor TiO2 can catalyze the reaction by themselves. Of CO, CO2, H2O, and H2, only CO adsorbs with moderate adsorption energy at low-coordinated sites, whereas other molecules interact only weakly with Au. The activation of H2O is impossible on Au surfaces. However, H2O adsorbs dissociatively on the anatase (0 0 1) surface and the diffusion of OH and H is feasible. The energetic data indicate that the rest of the process is possible on the Au surface. Two mechanisms were investigated and compared for the water–gas shift reaction, with H2O dissociation on the TiO2 surface and diffusion of OH and H on Au surfaces in common. The latter is, in principle, the rate-limiting step. The first mechanism occurs through the disproportionation of two OH groups on Au into H2O and an O atom. The latter reacts with CO. In the alternative mechanism, CO combines with OH to give a COOH intermediate, which subsequently reacts with another OH group to form CO2 and H2O. Finally, H atoms recombine on the Au surface to complete the catalytic cycle.

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