Band Structure Tuning via Pt Single Atom Induced Rapid Hydroxyl Radical Generation toward Efficient Photocatalytic Reforming of Lignocellulose into H2

Photocatalytic lignocellulose reforming for H2 production presents a compelling solution to solve environmental and energy issues. However, achieving scalable conversion under benign conditions faces consistent challenges including insufficient active sites for H2 evolution reaction (HER) and inefficient lignocellulose oxidation directly by photogenerated holes. Herein, it is found that Pt single atom‐loaded CdS nanosheet (PtSA‐CdS) would be an active photocatalyst for lignocellulose‐to‐H2 conversion. Theoretical and experimental analyses confirm that the valence band of CdS shifts downward after depositing isolated Pt atoms, and the slope of valence band potential on pH for PtSA‐CdS is more positive than Nernstian equation. These characteristics allow PtSA‐CdS to generate large amounts of •OH radicals even at pH 14, while the capacity is lacking with CdS alone. The employment of •OH/OH− redox shuttle succeeds in relaying photoexcited holes from the surface of photocatalyst, and the •OH radicals can diffuse away to decompose lignocellulose efficiently. Simultaneously, surface Pt atoms, featured with a thermoneutral ΔGH∗$\Delta G_{\mathrm{H}}^{\mathrm{*}}$, would collect electrons to expedite HER. Consequently, PtSA‐CdS performs a H2 evolution rate of 10.14 µmol h−1 in 1 m KOH aqueous solution, showcasing a remarkable 37.1‐fold enhancement compared to CdS. This work provides a feasible approach to transform waste biomass into valuable sources. Pt single atom is anchored on CdS nanosheet for lignocellulose photoreforming. The strong metal–substrate interaction can induce a downward shift valence band for PtSA‐CdS, thus enabling the generation of •OH/OH− redox shuttle under benign condition. Additionally, the Pt single atom with thermoneutral ΔGH∗$\Delta G_{\mathrm{H}}^{\mathrm{*}}$ can serve as active sites for HER. These features contribute to a remarkable activity for lignocellulose‐to‐H2 conversion.