Photocatalytic Biomass Platform Molecule Conversion Coupled With Synergistic Hydrogen Production: Reaction Pathways, Catalyst Design, and Prospects

ABSTRACT

The high‐value conversion of biomass platform molecules is a key pathway for substituting fossil resources with renewables and promoting sustainable green chemical manufacturing. However, conventional thermocatalytic processes suffer from harsh reaction conditions, high energy consumption, and poor selectivity, whereas photocatalysis enables targeted transformation under mild conditions. Against the backdrop of China's dual‐carbon strategy (carbon peaking and carbon neutrality), the synergistic strategy of photocatalytic biomass platform molecule conversion coupled with hydrogen production has emerged as an important route for green chemical manufacturing and clean energy co‐generation. Unlike previous reviews that categorize catalysts by material type, this work adopts a reaction‐oriented framework, classifying synergistic reactions into four categories: oxidative dehydrogenation, reductive amination, cross‐coupling, and biomass decomposition/reforming, with corresponding catalyst design principles discussed for each type. The microscopic mechanisms of photogenerated charge separation and half‐reaction matching are first elucidated for each reaction type, revealing the decisive roles of charge separation and interfacial charge transfer in catalytic performance. Subsequently, catalyst design strategies—including single‐atom catalysis, heterojunction construction, defect engineering, and interfacial modulation—are systematically summarized, with emphasis on how metal active centers and defect engineering steer reaction pathways through modulation of intermediate adsorption configurations, reaction energy barriers, and reactive oxygen species evolution pathways. The activity–selectivity trade‐off and deactivation mechanisms are then analyzed, and core challenges are identified, including insufficient product controllability, poor catalyst durability, weak compatibility with real biomass feedstocks, high economic costs, and ecological risks. Finally, prospects are outlined in the areas of precise catalysis, in situ mechanistic studies, process integration, and industrialization. This review aims to provide theoretical guidance and research insights for the rational construction of efficient, green, economical, and stable biorefining systems for co‐production of hydrogen and valuable chemicals from biomass platform molecules.