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Abstract Plasmonic metal–semiconductor nanocomposites are promising candidates for considerably enhancing the solar‐to‐hydrogen conversion efficiency of semiconductor‐based photocatalysts across the entire solar spectrum. However, the underlying enhancement mechanism remains unclear, and the overall efficiency is still low. Herein, a hollow C@MoS 2 ‐Au@CdS nanocomposite photocatalyst is developed to achieve improved photocatalytic hydrogen evolution reaction (HER) across a broad spectral range. Transient absorption spectroscopy experiments and electromagnetic field simulations demonstrate that compared to the treated sample, the untreated sample exhibits a high density of sulfur vacancies. Consequently, under near‐field enhancement, photogenerated electrons from CdS and hot electrons generated by intra‐band or inter‐band transitions of Au nanoparticles are efficiently transferred to the CdS surface, thus significantly improving the HER activity of CdS. Additionally, in situ, Raman spectroscopy provided spectral evidence of S─H intermediate species on the CdS surface during the HER process, which is verified through isotope experiments. Density functional theory simulations identify sulfur atoms in CdS as the catalytic active sites for HER. These findings enhance the understanding of charge transfer mechanisms and HER pathways, offering valuable insights for the design of plasmonic photocatalysts with enhanced efficiency.
Xu et al. (Mon,) studied this question.