Rhodium Single‐Atom Decorated CeO ₂ :Yb,Er/Rh‐ZnIn ₂ S ₄ With Enhanced Photo‐Thermo‐Electric Effects for Efficient H ₂ Evolution and Biomass Valorization

ABSTRACT Most widely‐studied semiconductor catalysts have low efficiency in utilizing near‐infrared (NIR) light in the solar spectrum, while also facing major issues such as slow charge‐carrier migration rate and lack of active sites that limit photocatalytic performance. Here, a new strategy to promote the solar‐light driven photocatalytic activity of ZnIn ₂ S ₄ was proposed by introducing Rh single atom (SAs) into CeO ₂ :Yb,Er/ZnIn ₂ S ₄ with photo‐thermo‐electric effects. The introduction of Rh SAs into ZnIn ₂ S ₄ effectively suppresses charge recombination, and improves reaction rate through photo‐thermal effect. CeO ₂ :Yb, Er converts NIR light into visible light via up‐conversion photo‐optical processes and generates high‐energy electrons via two‐photon photo‐electronic process, both of which can activate ZnIn ₂ S ₄ . Large contact area and strong interface electric field between CeO ₂ and ZnIn ₂ S ₄ enhance photo‐electric conversion efficiency. The CeO ₂ :Yb,Er/Rh‐ZnIn ₂ S ₄ exhibits a hydrogen production rate of up to 99.68 mmol·g ⁻¹ ·h ⁻¹ at 10°C and 148.06 mmol·g ⁻¹ ·h ⁻¹ with non‐temperature‐controlled conditions. Under mild conditions, the photocatalysts can convert glucose into high‐value‐added chemicals (e.g., arabinose) while simultaneously generating hydrogen. This work provides a new strategy to improve NIR light utilization efficiency and enhance charge‐carrier separation capability through photo‐thermo‐electric effects, promoting the production of green hydrogen and biomass conversion into high‐value‐added chemicals.