Coupled Photocatalytic Hydrogen Production With Selective Biomass Valorization via Active Sites Construction and Electron Transport Channels Engineering

ABSTRACT Regulation of interfacial electronics and the construction of active sites are essential for the efficient utilization of photogenerated electrons and holes. Here, we employ a simple hydrothermal method to in situ anchor cadmium sulfide (CdS) onto 1T phase‐tungsten disulfide nanosheets/carbon nanotubes (1T‐WS 2 /CNTs), forming a ternary heterojunction (CdS/1T‐WS 2 /CNTs). This innovative structure is utilized for photocatalytic hydrogen production coupled with the oxidation of biomass‐derived alcohols and lignin. The optimized CdS/1T‐WS 2 /CNTs photocatalyst exhibits exceptional performance, achieving a hydrogen production rate of 26.17 mmol/g/h and a benzaldehyde generation rate of 8.29 mmol/g/h from benzyl alcohol (BA). The selectivity for benzaldehyde (BD) and furfural (FD) reaches 90.06% and 100%, respectively. Furthermore, the photocatalyst demonstrates strong photocatalytic activity for the co‐production of aromatic monomers and hydrogen from lignin model compounds and larch lignin. Comprehensive characterizations reveal that the 1T‐WS 2 /CNTs not only endows the material with photothermal properties and abundant active sites but also enables the formation of Schottky junctions, promoting the directional transfer of photogenerated charges. The synergistic effect of electronic coupling at the interface and CNTs modulating local electron density achieves a significant downward shift in the S p band center, reducing the adsorption barriers for water molecules and proton intermediates (H*), thereby enhancing photocatalytic hydrogen production activity. This study provides a promising photocatalyst design strategy for improving the resource utilization of biomass.