Non-precious catalysts for alkaline hydrogen evolution reaction (HER) face a fundamental multi-scale challenge: lack of synergy between electronic structure tuning for balancing H adsorption and water dissociation, active site stabilization for boosting intrinsic turnover frequency (TOF), and mass transport. Even Pt loses 2–3 orders of magnitude activity in alkaline media due to inefficient water dissociation, a synergistic gap unresolved by the Sabatier principle alone. Existing strategies only address isolated aspects: phase engineering optimizes electronic structure but not active site stability; heteroatom doping introduces defects unlinked to mass transport; and nanostructuring enhances mass transfer but not atomic-level activity. None of them address multi-scale mechanistic synergy. Herein, we design a hierarchically porous P-doped NiCo alloy (hpP-NiCo) with an aim of achieving this synergy via integrating α-FCC/ε-HCP phases, P-induced defects, and 3D porosity. The formed α/ε interface tunes the d-band center to balance H adsorption and water dissociation; and the doped P stabilizes metal-vacancy sites to boost TOF. In addition, porosity matches mass transport with active site accessibility. In 1 M KOH, hpP-NiCo reaches 1000 mA cm⁻² at 185 mV overpotential and has a Tafel slope of 43.1 mV dec⁻¹, corresponding to electrochemical desorption as the rate-limiting step and verifying Volmer acceleration. Moreover, it also exhibits bifunctional oxygen evolution reaction (OER), achieving 100 mA cm⁻² at potential of 1.55 V. This work establishes a mechanistic synergy model for non-precious HER catalysts.

A surprising tribocatalytic capability has been discovered for Si single crystals to convert mechanical energy into chemical energy for organic dye degradation recently. In this study, their tribocatalytic capability has been explored for converting mechanical energy into chemical energy of water splitting. In glass reactors with Si single crystals coated on the bottoms and with H₂O and N₂ enclosed, Al₂O₃ nanoparticles, TiO₂ nanoparticles, and NiO particles were stimulated through magnetic stirring using home-made PTFE magnetic rotary disks separately. For Al₂O₃ nanoparticles, as much as 14,330 and 41,964 ppm H₂ were produced after 1 and 3 h of 400 rpm magnetic stirring, respectively, much higher than those obtained for TiO₂ and NiO, and for Al₂O₃ nanoparticles in glass-bottomed reactors as well. The tribocatalytic production of H₂ was further explored with respect to NaCl addition to H₂O and p/n doping in Si, with negative effects observed for them all. Photoluminescence spectroscopy revealed continuous generation of hydroxyl radicals in the course of magnetic stirring, which supports a tribocatalytic mechanism based on the excitation of electron–hole pairs in Si single crystals through mechanical energy absorbed through friction. These findings suggest a great potential for narrow-band semiconductors to utilize mechanical energy through friction to carry out important chemical reactions.