Both the adsorption/dissociation of water molecules and hydrogen intermediate (H*) are the major limitations to hydrogen evolution reaction (HER). Herein, the modulation of electronic structure and geometric configuration are combined to design one-dimensional electrocatalyst with outstanding HER activity in a wide pH range. The catalyst was composed of molybdenum trioxide doped molybdenum nickel alloy supported by copper nanowires (MoO₃-MoNi₄@Cu NWs). As revealed by the experimental characterizations and theoretical calculations, Cu NWs act as the electron donator to MoNi₄, resulting in up shift of the d-band center in MoNi₄, thus expediting H₂O adsorption and dissociation. Moreover, the introduction of amorphous MoO₃ sets up a unique geometric configuration on MoNi₄ for the accelerated H* transfer via hydrogen-bond and hydrogen spillover. This work provides a synergetic route for constructing HER freeway and promotes further investigations on more versatile electrocatalysis involving H₂O or H*.

The adjustable intermediate binding capacity in electrocatalytic carbon dioxide (CO₂) reduction is critical for varying the reaction pathways to desired products. Herein, we first report the synthesis of boron-doped amorphous zinc oxide with (B-a-ZnO-Sb) or without antimony nanoparticles embedding (B-a-ZnO) via one-step wet chemical method, which is easy to scale up by enlarging the vessel and increasing feeding. Sb successfully realizes the product switching from CO on B-a-ZnO to formate on B-a-ZnO-Sb. Both experimental and theoretical results reveal that Sb weakens the charge interaction on Zn atoms. Based on the moderate adsorption of *COOH and strong adsorption of *OCHO and *HCOOH for B-a-ZnO, the foreign Sb weakens the adsorption of these intermediates and brings about a favor formate production instead of CO. This work points out a new direction for the synthesis of amorphous ZnO-based catalysts and provides advanced insights into the aimed selectivity switch for CO₂ reduction by electronic effect.