Universal Strategy for Ultrathin Pt–M (M = Fe, Co, Ni) Nanowires for Efficient Catalytic Hydrogen Generation

Methanol (CH3OH) reformation with water (H2O) to in situ release hydrogen (H2) is regarded as a hopeful H2 production approach for polymer electrolyte membrane fuel cells, while developing highly efficient CH3OH reformation catalysts still remains a great challenge. Herein, a series of Pt-based ultrafine nanowires (UNWs) with high surface atom ratio are used as highly active and stable catalysts for CH3OH reformation to H2. By tuning Pt3M (M = Fe, Co, Ni), support and the composition of the PtxFe UNWs, the optimized Pt4Fe UNWs/Al2O3 exhibits excellent catalytic behaviors with the high H2 turnover frequency reaching to 2035.8 h–1, more than 4 times higher than that of Pt UNWs/Al2O3. The reaction mechanism investigated by diffuse reflectance infrared Fourier transform spectroscopy turns out that the production of H2 undergoes the CH3OH decomposition to *CO and gas-shift reaction of *CO with H2O. Combing with the XPS result and the density functional theory calculations, the high CH3OH reformation activity of Pt4Fe UNWs/Al2O3 is attributable to synergism between Pt and Fe, which facilitates H2 desorption and intermediate HCOO* and *COO formations via the reaction between *CO and OH–.