Interfacial water engineering boosts neutral water reduction.

Hydrogen evolution reaction (HER) in neutral media is of great practical importance for sustainable hydrogen production, but generally suffers from low activities, the cause of which has been a puzzle yet to be solved. Herein, by investigating the synergy between Ru single atoms (RuNC) and RuSe x cluster compounds (RuSe x ) for HER using ab initio molecular dynamics, operando X-ray absorption spectroscopy, and operando surface-enhanced infrared absorption spectroscopy, we establish that the interfacial water governs neutral HER. The rigid interfacial water layer in neutral media would inhibit the transport of H 2 O*/OH* at the electrode/electrolyte interface of RuNC, but the RuSe x can promote H 2 O*/OH* transport to increase the number of available H 2 O* on RuNC by disordering the interfacial water network. With the synergy of RuSe x and RuNC, the resulting neutral HER performance in terms of mass-specific activity is 6.7 times higher than that of 20 wt.% Pt/C at overpotential of 100 mV.