Ru Nanoparticle Assemblies Modified with Single Mo Atoms for Hydrogen Evolution Reactions in Seawater Electrocatalysis

Ru-based catalysts manifest unparalleled hydrogen evolution reaction (HER) performance, but the hydrolysis of Ru species and the accumulation of corresponding reaction intermediates greatly limit HER activity and stability. Herein, Ru nanoparticle assemblies modified with single Mo atoms and supported on N-incorporated graphene (referred to as MoRu-NG) are compounded via hydrothermal and chemical vapor deposition (CVD) methods. The incorporation of single Mo atoms into Ru lattices modifies the local atomic milieu around Ru centers, significantly improving HER catalytic behavior and stability. More specifically, MoRu-NG achieves overpotentials of 53 mV and 28 mV at 10 mA cm⁻², with exceptional stability in acidic and alkaline seawater solutions, respectively. In MoRu-NG, Ru atoms have a special electronic structure and thus possess optimal hydrogen adsorption energy, which indicates that excellent HER activity mainly hinges upon Ru centers. To be specific, the d-electron orbitals of Ru atoms are close to half full, giving Ru atoms moderate bond energy for the assimilation and release of hydrogen, which is beneficial for the conversion of reaction intermediates. Moreover, the incorporation of single Mo atoms facilitates the formation of O and O’-bidentate ligands, significantly enhancing the structural stability of MoRu-NG in universal-pH seawater electrolysis. This work advances a feasible construction method of hexagonal octahedral configuration (Ru-O-Mo-N-C) and provides a route to synthesize an efficient and stable catalyst for electrocatalytic HER in universal-pH seawater.