Efficient Hydrogen Evolution Promoted by Short Pathway-Hydrogen Spillover Over P-Doped Pt3Co

Developing highly active electrocatalysts for operating at industrial current density with a low overpotential still remains a major challenge. Herein, we developed a strategy of short pathway-hydrogen spillover to facilitate the high current density operation, in which the hydrogen-enriched phases transfer to hydrogen-deficient phases in P-doped Pt3Co anchored on N-doped carbon (P-Pt3Co/NC). This strategy alleviated the compromise between the long reaction pathway and the undesirable interfacial barrier of hydrogen spillover for metal–support electrocatalysts. Consequently, P-Pt3Co/NC demonstrates a low overpotential of 219 mV at 1.5 A cm–2 in acidic media. Comprehensive experiment and theoretical calculation results revealed that the doped and negatively charged P site possesses a large capacity for storing protons and subsequently transferring to the nearby hydrogen-deficient Pt site with favorable H2 desorption. This significantly increases the hydrogen coverage on the Pt to break the limitation of hydrogen transfer kinetics with a low energy carrier.