Synergistic Electronic and Bifunctional Effects in Amorphous BiSx-Decorated Porous Pt Nanorods for CO-Tolerant Methanol Oxidation.

The acidic methanol oxidation reaction (MOR) suffers from severe CO poisoning with conventional Pt-based catalysts. Introducing oxophilic species into Pt catalysts can mitigate this poisoning by promoting the oxidation of adsorbed CO via OH* generated on such species. However, rational construction of Pt-oxophilic heterojunctions is often hindered by their significant lattice mismatch. Here, amorphous BiSx-decorated porous Pt nanorods (a-BiSx/Pt NRs) are prepared through acid etching of Pt2Bi2/Pt NRs, which are templated by Bi2S3 nanorods. The resulting a-BiSx/Pt NRs exhibit a mass activity of 2.05 A mgPt-1 for acidic MOR, which is 12.8 times higher than that of commercial Pt/C (0.16 A mgPt-1). In situ infrared spectroscopy and density functional theory calculations reveal that the a-BiSx-Pt heterointerface synergistically weakens CO adsorption on Pt via electronic modification and promotes OH* generation through the bifunctional mechanism of oxophilic Bi sites, thereby facilitating the oxidative removal of CO intermediates and enhancing MOR performance.