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

Methanol (CH 3 OH) reformation with water (H 2 O) to in situ release hydrogen (H 2 ) is regarded as a hopeful H 2 production approach for polymer electrolyte membrane fuel cells, while developing highly efficient CH 3 OH 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 CH 3 OH reformation to H 2 . By tuning Pt 3 M (M = Fe, Co, Ni), support and the composition of the Pt x Fe UNWs, the optimized Pt 4 Fe UNWs/Al 2 O 3 exhibits excellent catalytic behaviors with the high H 2 turnover frequency reaching to 2035.8 h –1, more than 4 times higher than that of Pt UNWs/Al 2 O 3 . The reaction mechanism investigated by diffuse reflectance infrared Fourier transform spectroscopy turns out that the production of H 2 undergoes the CH 3 OH decomposition to *CO and gas-shift reaction of *CO with H 2 O. Combing with the XPS result and the density functional theory calculations, the high CH 3 OH reformation activity of Pt 4 Fe UNWs/Al 2 O 3 is attributable to synergism between Pt and Fe, which facilitates H 2 desorption and intermediate HCOO* and *COO formations via the reaction between *CO and OH – .