Phosphorus-induced d-p orbital hybridization in PtFeCoCuMo alloys: Regulating active hydrogen supply to enhance alkaline hydrogen evolution reaction

Rationally designing electrocatalyst/electrolyte interfaces with excellent active hydrogen supply capability is crucial for the hydrogen evolution reaction (HER), a core step in alkaline anion exchange membrane water electrolysis (AEMWE). Herein, phosphorus (P)-surface-coordinated PtFeCoCuMo quinary alloys are synthesized via a two-step wet-chemical method. P-induced d-p orbital hybridization enables the synergistic regulation of two key factors: it optimizes the hydrogen adsorption free energy (ΔG H∗ ) and water dissociation barrier (thermodynamic modulation), while tailoring the potential of zero charge (PZC) to accelerate proton transport (kinetic modulation). The optimized P 16 -PtFeCoCuMo catalyst exhibits outstanding alkaline HER activity, with a turnover frequency (TOF) 5-fold and 3-fold higher than those of commercial Pt/C and pristine PtFeCoCuMo alloy, respectively. This work overcomes thermodynamic and kinetic limitations simultaneously through heteroatom doping, providing a promising strategy for the design of high-performance alkaline HER catalysts.