Rhodium Single-Atom Decorated CeO2:Yb,Er/Rh-ZnIn2S4 With Enhanced Photo-Thermo-Electric Effects for Efficient H2 Evolution and Biomass Valorization.

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 ZnIn2S4 was proposed by introducing Rh single atom (SAs) into CeO2:Yb,Er/ZnIn2S4 with photo-thermo-electric effects. The introduction of Rh SAs into ZnIn2S4 effectively suppresses charge recombination, and improves reaction rate through photo-thermal effect. CeO2: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 ZnIn2S4. Large contact area and strong interface electric field between CeO2 and ZnIn2S4 enhance photo-electric conversion efficiency. The CeO2:Yb,Er/Rh-ZnIn2S4 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.