Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However, design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. Here we theoretically profile that the interfacial charge accumulation induces by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation, thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally, a series of Pt alloys-CoP catalysts with tailorable ∆Φ show a strong ∆Φ-dependent HER activity, in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivers the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts.

The multi-functional Ni₃C cocatalyst has been demonstrated to markedly boost the robust photocatalytic H₂ evolution g-C₃N₄ nanosheets.

Carbon neutrality initiative has stimulated the development of the sustainable methodologies for hydrogen generation and safe storage. Aqueous-phase reforming methanol and H₂O (APRM) has attracted the particular interests for their high gravimetric density and easy availability. Thus, to efficiently release hydrogen and significantly suppress CO generation at low temperatures without any additives is the sustainable pursuit of APRM. Herein, we demonstrate that the dual-active sites of Pt single-atoms and frustrated Lewis pairs (FLPs) on porous nanorods of CeO₂ enable the efficient additive-free H₂ generation with a low CO (0.027%) through APRM at 120 °C. Mechanism investigations illustrate that the Pt single-atoms and Lewis acidic sites cooperatively promote the activation of methanol. With the help of a spontaneous water dissociation on FLPs, Pt single-atoms exhibit a significantly improved reforming of *CO to promote H₂ production and suppress CO generation. This finding provides a promising path towards the flexible hydrogen utilizations.