Tuning Pt-skinned PtAg nanotubes in nanoscales to efficiently modify electronic structure for boosting performance of methanol electrooxidation

[Display omitted] •Pt-skinned PtAg bimetallic nanotubes with the Pt skin as thin as 1.5 nm are prepared.•The electronic structure of Pt in PtAgNTs is prominently optimized by Pt skin.•The dissociation of methanol molecules is highly enhanced by PtAgNTs.•PtAgNTs could reduce the adsorption energy of CO molecules.•PtAgNTs/C show much higher catalytic activity and stability than commercial Pt/C. The modification of electronic structure can significantly affect electrocatalytic activity. An architecture art of Pt-skinned PtAg bimetallic nanotubes is successfully synthesized, delivering much higher catalytic activity and better stability toward methanol electrooxidation than PtAg bimetallic nanoparticles and commercial Pt/C catalysts. Theoretical studies reveal that the Pt skin on PtAg bimetallic nanotubes prominently optimize the electronic structure of Pt to greatly enhance the dissociative adsorption of methanol while increasing CO poisoning resistance for fast electrode kinetics, high catalytic current density and stability. This work offers a low Pt loading but highly active anode catalyst for direct methanol fuel cells, demonstrating that rationally tuning the electronic structure by well-controlling surface morphology in nanoscales could open new opportunities to greatly improve the electrocatalytic properties.