Following our strategy to analyze the metal–support interaction, we present periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO2(110) surface (at low coverage, θ = 1/3) to investigate the interaction of an individual metal atom, M, with TiO2 and its consequence on the coadsorption of H and CO over M/TiO2. M under investigation varies in a systematic way from K to Zn. It is found that the presence of the support decreases or increases the strength of M–H or M–CO interaction according to the nature of M. The site of the adsorption for H and the formation of HCO/M also depend on M. From the left- to the right-hand side of the period, C and O both interact while O progressively detaches from M. On the contrary, for M = Fe–Cu, CO dissociation is more likely to happen. For CO and H coadsorption, two extreme cases emerge: For Ni, the hydrogen adsorbed should easily move on the support and CO dissociation is more likely. For Ti or Sc, H is easily coadsorbed with CO on the metal and CO hydrogenation could be the initial step.
DFT TiO2 rutile SMSI Metal–oxide interface Reduction Charge transfer
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We are grateful to CMCU-PHC (09G 1212) and the Institut Français de Cooperation in Tunisia (IFC) for their financial support. The authors thank GENCI and CCRE for computing facilities.
Shustorovich E (1990) The bond-order conservation approach to chemisorption and heterogeneous catalysis: applications and implications. In: Eley DD, Pines H, Weisz PB (eds) Advances in catalysis, vol 37. Academic Press, p 101. http://dx.doi.org/10.1016/S0360-0564(08)60364-8