Fluorine‐Induced d‐p‐d Orbital Hybridization Promotes Hydrogen Spillover for Efficient Hydrogen Evolution

ABSTRACT

The conventional metal‐metal oxide configuration as a catalyst support is often considered to excite hydrogen spillover. However, it is difficult to precisely regulate hydrogen spillover. Herein, a metal‐metal oxide‐doped carbon configuration, Ru@ZrO ₂ /FC, featuring a ZrO ₂ ‐anchored Ru cluster over F‐doped carbon, is proposed to more easily trigger hydrogen spillover. The F‐doped carbon support strengthens the d‐p‐d hybridization effect of Ru‐O‐Zr and facilitates interfacial electron transfer due to F‐induced electronic asymmetry, thereby accelerating hydrogen spillover with lower energy barriers of water dissociation, H* migration, and adsorption. Consequently, the catalyst exhibits excellent hydrogen evolution reaction activity: an ultralow overpotential of 17 mV@10 mA cm ⁻² in alkaline media, and 23.6 fold mass activity compared to that of benchmark Pt/C. Besides, the high performance is also demonstrated in the Ru@ZrO ₂ /FC‐based anion exchange membrane water electrolyzer (AEMWE) test: only a low cell operating voltage of 1.73 V is required to achieve a current density of 1.0 A cm ⁻² . Both in situ spectroscopy and theoretical calculations reveal that H* intermediates transfer from the Zr sites on the ZrO ₂ /FC to Ru clusters through an enhanced hydrogen spillover process. This work highlights interfacial d‐p‐d hybridization as essential for hydrogen spillover, offering insights for rational electrocatalyst design.