An electronic perturbation in TiC supported platinum monolayer catalyst for enhancing water-gas shift performance: DFT study.

The water-gas shift (WGS) reaction behaviors over the TiC(0 0 1) supported Pt monolayer catalyst (Pt/TiC(0 0 1)) are investigated by using the spin-unrestricted density functional theory calculations. Importantly, we find that the Pt/TiC(0 0 1) system exhibits a much lower density of Pt-5d states nearby the Fermi level compared with that for Pt(1 1 1), and the monolayer Pt atoms undergo an electronic perturbation when in contact with TiC(0 0 1) support that would strongly improve the WGS activity of supported Pt atoms. Our calculations clearly indicate that the dominant reaction path follows a carboxyl mechanism involving a key COOH intermediate, rather than the common redox mechanism. Furthermore, through the detailed comparisons, the results demonstrate that the strong interactions between the monolayer Pt atoms and TiC(0 0 1) support make Pt/TiC(0 0 1) a highly active catalyst for the low-temperature WGS reaction. Following the route presented by Bruix et al (2012 J. Am. Chem. Soc. 134 8968-74), the positive effect derived from strong metal-support interaction in the metal/carbide system is revealed.