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Biomass photorefinery provides a promising strategy for value-added chemical production from natural feedstocks. Herein, we designed and fabricated three-dimensionally ordered macroporous (3DOM) ternary composite for the photoreforming of hemicellulose and...

The synergistic promotion by photocatalysis and thermocatalysis is a promising approach for sustainable hydrogen (H2) production. Herein, we rationally design a perovskite-based catalyst with three-dimensionally ordered macroporous structure (3DOM CaTiO3-Au) for photothermal catalytic H2 production from different substrates. The hierarchical 3DOM structure facilitates light harvesting and mass diffusion of the substrates, while the gold nanoparticles (Au NPs) promote charge separation. The photogenerated and hot electrons are oriented accumulated on the surface of Au NPs. The non-metallic gold species [Au(I)] show more activity for H2 evolution. As a result, 3DOM CaTiO3-Au exhibits excellent activity for H2 production from glycerol and other substrates with hydroxyl groups. The present work demonstrates a feasible approach to improve sustainable H2 production by rationally designing and fabricating efficient photothermal catalysts.

Photocatalytic hydrogen production is a promising route to the provision of sustainable and green energy. However, the excess addition of traditional electron donors as the sacrificial agents to consume photogenerated holes greatly reduces the feasibility of this approach for commercialization. Herein, considering the abundant hydroxyl groups in cellulose, the major component of biomass, we adopted glucose (a component unit of cellulose), cellobiose (a structure unit of cellulose) and dissolving pulp (a pretreated cellulose) as electron donors for photocatalytic hydrogen production over a TiO2-Au-CdS material. The well-designed ternary TiO2-Au-CdS possesses a hierarchical three-dimensional ordered macroporous (3DOM) structure, which not only benefits light harvesting but can also facilitate mass diffusion to boost the reaction kinetics. As expected, the fabricated photocatalyst exhibits considerable hydrogen production from glucose (645.1 μmol·h−1·g−1), while the hydrogen production rates gradually decrease with the increased complexity in structure from cellobiose (273.9 μmol·h−1·g−1) to dissolving pulp (79.7 μmol·h−1·g−1). Other gaseous components such as CO and CH4 are also produced, indicating the partial conversion of biomass during the photoreforming process. This work demonstrates the feasibility of sustainable hydrogen production from biomass by photoreforming with a rational photocatalyst design.