Oxygen-Bridged Stabilization of Single Atomic W on Rh Metallenes for Robust and Efficient pH-Universal Hydrogen Evolution

Highly efficient and durable electrocatalysts are of the utmost importance for the sustainable generation of clean hydrogen by water electrolysis. Here, we present a report of an atomically thin rhodium metallene incorporated with oxygen-bridged single atomic tungsten (Rh–O–W) as a high-performance electrocatalyst for pH-universal hydrogen evolution reaction. The Rh–O–W metallene delivers ascendant electrocatalytic HER performance, characterized by exceptionally low overpotentials, ultrahigh mass activities, excellent turnover frequencies, and robust stability with negligible deactivation, in pH-universal electrolytes, outperforming that of benchmark Pt/C, Rh/C and numerous other reported precious-metal HER catalysts. Interestingly, the promoting feature of −O–W single atomic sites is understood via operando X-ray absorption spectroscopy characterization and theoretical calculations. On account of electron transfer and equilibration processes take place between the binary components of Rh–O–W metallenes, fine-tuning of the density of states and electron localization at Rh active sites is attained, hence promoting HER via a near-optimal hydrogen adsorption.