Deciphering Interfacial Water Configuration via Nucleophilic Doping: Highly Connected H‐Bond Networks for Efficient Neutral Hydrogen Evolution

ABSTRACT Neutral hydrogen evolution reaction (HER) faces sluggish kinetics due to strong cation hydration disrupting interfacial hydrogen‐bond (H‐bond) networks, impeding mass transport. Herein, we propose a nucleophilic doping strategy to reconstruct the interfacial water structure and boost neutral HER performance. By engineering a nucleophilic oxygen‐doped molybdenum selenide/molybdenum phosphide hybrid on carbon cloth (O x ‐MoSe 2‐x /MoP/CC), we successfully manipulate the local electronic environment to attenuate cation hydration effects. Ab initio molecular dynamics (AIMD) simulations coupled with in situ Raman spectroscopy provide compelling evidence that the incorporated nucleophilic O species trigger a reconfiguration of interfacial water, fostering the formation of highly connected H‐bond networks. These optimized networks serve as efficient highways for intermediate transport, significantly lowering the mass transfer resistance. Furthermore, density functional theory (DFT) calculations reveal a synergistic mechanism where the MoP phase acts as a potent water dissociation promoter, facilitating the Volmer step. Consequently, the O x ‐MoSe 2‐x /MoP/CC electrode delivers a remarkable overpotential of only 34 mV at 10 mA cm −2 in 1 M phosphate buffer solution, surpassing commercial Pt/C, and exhibits superior long‐term stability. This work not only presents a high‐performance electrocatalyst but also highlights the pivotal role of nucleophilic modulation in engineering interfacial H‐bond networks for efficient neutral electrocatalysis.