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

Abstract

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 H 2 O * 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.