Minutely surficial functionalization of Ce-O-Pt linkages on Pt/C for enhanced electrocatalytic methanol oxidation

Slight cerium oxides bond well with Pt atoms to form Ce-O-Pt linkages and induce an obvious charge transfer interaction, resulting in facilitated adsorption of oxygen-containing species and oxidation of CO intermediates, promoting the methanol conversion. • A coating-annealing-etching route is elaborately applied to achieve minutely surficial functionalization of Ce-O-Pt linkages on Pt/C. • Benefiting from the synthetic route, a valid contact and a strong interaction between slight CeO x and Pt NPs are efficiently established. • Despite of the little amount, the formed Ce-O-Pt linkages induce an obvious electron redistribution and modulate d-band state of Pt appropriately. • The optimized Pt electronic structure consequently facilitates the adsorption of *OH and oxidation of *CO, promoting the methanol conversion. Methanol oxidation reaction (MOR) performance can be effectively regulated by tuning the electronic state of catalyst via surface functionalization strategy. Herein, a surface functionalized Pt/C catalyst with minute Ce-O-Pt linkages decorating on Pt surface (denoted as Ce-O-Pt/C) is synthesized via a coating-annealing-etching route, in which a valid contact and a strong interaction between CeO x and Pt NPs are established. Experimental and theoretical results suggest that in this unique Ce-O-Pt/C catalyst, the slight cerium oxides bond well with Pt atoms to form Ce-O-Pt linkages and induce an obvious charge transfer interaction, resulting in an electron redistribution and modulated d-band state of Pt. The optimized Pt electronic structure consequently facilitates the adsorption of oxygen-containing species and oxidation of CO intermediates, promoting the methanol conversion. Benefiting from that, the as-synthesized Ce-O-Pt/C catalyst exhibits much better catalytic MOR activity, stability and anti-CO poisoning ability as compared to the un-functionalized Pt/C.