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

Abstract 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 (Pt_SA‐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 Pt_SA‐CdS is more positive than Nernstian equation. These characteristics allow Pt_SA‐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 , would collect electrons to expedite HER. Consequently, Pt_SA‐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.