Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions.

This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O(2), C(2)H(4), SO(2), thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO(2) at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O(2) and perform the 2CO + O(2)→ 2CO(2) reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS(x) catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.