Electron-distribution control via Pt/NC and MoC/NC dual junction: Boosted hydrogen electro-oxidation and theoretical study

The scarcity, high cost and susceptibility to CO of Platinum severely restrict its application in alkaline hydrogen oxidation reaction (HOR). Hybridizing Pt with other transition metals provides an effective strategy to modulate its catalytic HOR performance, but at the cost of mass activity due to the coverage of modifiers on Pt surface. Herein, we constructed dual junctions’ Pt/nitrogen-doped carbon (Pt/NC) and δ-MoC/NC to modify electronic structure of Pt via interfacial electron transfer to acquire Pt-MoC@NC catalyst with electron-deficient Pt nanoparticles, simultaneously endowing it with high mass activity and durability of alkaline HOR. Moreover, the unique structure of Pt-MoC@NC endows Pt with a high CO-tolerance at 1,000 ppm CO/H₂, a quality that commercial Pt-C catalyst lacks. The theoretical calculations not only confirm the diffusion of electrons from Pt/NC to MoC/NC could occur, but also demonstrate the negative shift of Pt d-band center for the optimized binding energies of *H, *OH and CO.