All-Round Enhancement of Wide pH Hydrogen Evolution Enabled by Tungsten-Based Amorphous Alloy-Mediated Adjacent Platinum Atoms.

Abstract

Electrochemical water splitting based on single-atom catalysts (SACs) offers a sustainable route for hydrogen production. However, conventional SACs suffer from weak synergistic effects in harsh electrolytes. Here, we report a tungsten-based amorphous alloy (FeNiWPB) supported adjacent Platinum single-atom catalyst (Pt_ASSA@FeNiWPB). Spectroscopic and computational analyses disclose that the amorphous W-based alloy matrix provides abundant defect sites to anchor and mediate adjacent Pt atoms, thereby boosting multiple H conversions via metal-metal synergy. Additionally, the catalyst's corrosion resistance is significantly enhanced through the formation of robust M─W bonds (M═Pt, Fe, Ni), which effectively suppress metal leaching across broad pH ranges. Furthermore, the formation of Pt-W/Fe/Ni polarized pairs at the alloy surface via Pt-support interactions induces electron redistribution and accelerates H^*/OH^* adsorption kinetics, thereby enhancing multiple H₂O^* dissociation pathways. Consequently, Pt_ASSA@FeNiWPB exhibits ultralow overpotentials of 17 mV (acidic) and 18 mV (alkaline) at -10 mA cm^-2, with mass activities 5.8 times (acidic) and 63.6 times (alkaline) higher than commercial Pt/C. Notably, it maintains performance for 600 h in both acidic and alkaline environments, far exceeding W-free counterparts (<50 h) and previous reports, positioning it at the forefront of HER performance. This work establishes a universal strategy for engineering durable electrocatalysts.Electrochemical water splitting based on single-atom catalysts (SACs) offers a sustainable route for hydrogen production. However, conventional SACs suffer from weak synergistic effects in harsh electrolytes. Here, we report a tungsten-based amorphous alloy (FeNiWPB) supported adjacent Platinum single-atom catalyst (Pt_ASSA@FeNiWPB). Spectroscopic and computational analyses disclose that the amorphous W-based alloy matrix provides abundant defect sites to anchor and mediate adjacent Pt atoms, thereby boosting multiple H conversions via metal-metal synergy. Additionally, the catalyst's corrosion resistance is significantly enhanced through the formation of robust M─W bonds (M═Pt, Fe, Ni), which effectively suppress metal leaching across broad pH ranges. Furthermore, the formation of Pt-W/Fe/Ni polarized pairs at the alloy surface via Pt-support interactions induces electron redistribution and accelerates H*/OH* adsorption kinetics, thereby enhancing multiple H2O* dissociation pathways. Consequently, Pt_ASSA@FeNiWPB exhibits ultralow overpotentials of 17 mV (acidic) and 18 mV (alkaline) at -10 mA cm^-2, with mass activities 5.8 times (acidic) and 63.6 times (alkaline) higher than commercial Pt/C. Notably, it maintains performance for 600 h in both acidic and alkaline environments, far exceeding W-free counterparts (<50 h) and previous reports, positioning it at the forefront of HER performance. This work establishes a universal strategy for engineering durable electrocatalysts.