Theory-guided design of electron-deficient ruthenium cluster for ampere-level current density electrochemical hydrogen evolution

Ru-based materials have regarded as ideal alternatives to Pt-based catalysts for hydrogen evolution reaction (HER), however, strong adsorption of H intermediate for Ru-based catalysts results in an unsatisfactory HER activity. Herein, we perform a high-throughput computational screening of different Ru clusters that supported on a carbon substrate embedded with various non-precious metals by comparing their structure stability and adsorption energy of H intermediate. Guided by the computational predictions, a unique 3D catalyst of Ru cluster with a size of < 2 nm anchored on spherical carbon shell confining Ni particles (Ru/Ni@C) is developed. Owing to the strong metal-substrate interaction and optimized electronic structure, Ru/Ni@C exhibits an outstanding HER performance with an ultra-low overpotential of 309 mV at 1.0 A cm−2, outperformed commercial Pt/C and Ru/C catalysts. Experimental observations and theoretical calculations demonstrate the efficient electron transfer from anchored Ru cluster to core Ni particles via carbon layer, which leads to the formation of electron-deficient Ru site, beneficial to adjust the ability of H adsorption and eventually promotes the whole HER process.