Abstract
Electrochemical water splitting provides a sustainable method for hydrogen production. However, the primary challenge for electrochemical hydrogen generation is the high cost and limited availability of platinum-based noble-metal catalysts. Transition-metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction (HER) in alkaline electrolytes. Nonetheless, the identification of active sites and the underlying catalytic mechanism remain elusive. In this study, phosphorus-doped nickel sulfide has been successfully synthesized, demonstrating enhanced activity for alkaline HER. Investigating surface chemistry through X-ray photoelectron spectroscopy (XPS), depth profiling revealed that surface restructuring occurs during the HER process. The presence of phosphorus significantly influences this transformation, promoting the formation of a novel active Ni-O layer. This Ni-O layer is responsible for enhanced catalytic activity by upshifting the d-band center and increasing the density of states near the Fermi level, along with expanding the electrochemical surface area. This study reveals that the surface restructuring of transition-metal sulfides is highly tied to the electronic structure of the parent catalysts. Gaining a comprehensive understanding of this surface restructuring is essential for predicting and exploring more efficient non-precious transition-metal sulfide electrocatalysts.