Photocatalysis has emerged as a green protocol for biorefineries thanks to sustainable energy input. The unique radical mechanism of photocatalysis allows the decomposition of raw biomass and the precise functionalization of platform molecules, but radicals with open-shell electronic structures are highly active, resulting in diverse products. Control of the radical mechanism relies on photocatalysts guiding interfacial charge transfer for chemical bond breaking. The reaction behaviour of radicals and the surface states of semiconductor photocatalysts are therefore crucial for controlling the efficiency and selectivity of biorefineries. Here we discuss the factors that influence the interfacial charge transfer and radical reactions in photocatalytic biorefineries, including the surface structure and electronic states of semiconductors and the catalytic properties of cocatalysts. Recognition of these factors will feed back the expected structure of semiconductors and cocatalysts, assisting with the design of photocatalysts for the efficient and selective refining of native biomass.

由于可持续的能源输入，光催化已成为生物炼制厂的绿色协议。光催化独特的自由基机制允许原始生物质的分解和平台分子的精确功能化，但具有开壳电子结构的自由基高度活跃，从而产生多样化的产物。自由基机制的控制依赖于光催化剂引导界面电荷转移以实现化学键断裂。因此，自由基的反应行为和半导体光催化剂的表面状态对于控制生物炼制的效率和选择性至关重要。在这里，我们讨论影响光催化生物炼制中界面电荷转移和自由基反应的因素，包括半导体的表面结构和电子态以及助催化剂的催化性能。对这些因素的认识将反馈半导体和助催化剂的预期结构，有助于光催化剂的设计，以有效和选择性地精炼天然生物质。