Direct S-H Evidence Revealing the Photo-electrocatalytic Hydrogen Evolution Reaction Mechanism on CdS Using Surface-Enhanced Raman Spectroscopy.

Photoelectrocatalytic water splitting using metal sulfides is a promising method for green hydrogen production. However, in situ probing of the hydrogen evolution reaction (HER) on sulfides with excellent performance remains a challenge. Here, we construct Au@CdS core-shell nanoparticles to study the HER on CdS, a typical HER catalyst, by surface-enhanced Raman spectroscopy (SERS) using a "borrowing" strategy. We directly capture the spectroscopic evidence of S-H intermediate under HER condition, further verified by isotopic experiments. Moreover, the population of S-H intermediates is improved by injecting charge carriers through light illumination and the S-H bond is weakened by introducing Pt to form a Au@Pt@CdS structure to change the interfacial electronic structure, both of them resulting in significant HER performance improvement. These findings can deepen the understanding of the HER mechanism and offer strategies for designing of cost-effective HER catalyst with high performance.