Photocatalysis is an emerging approach for sustainable chemical production from renewable biomass under mild conditions. Active radicals are always generated as key intermediates, in which their high reactivity renders them versatile for various upgrading processes. However, controlling their reaction is a challenge, especially in highly functionalized biomass frameworks. In this Review, we summarize recent advanced photocatalytic systems for selective biomass valorization, with an emphasis on their distinct radical-mediated reaction patterns. The strategies for generating a specific radical intermediate and controlling its subsequent conversion towards desired chemicals are also highlighted, aiming to provide guidance for future studies. We believe that taking full advantage of the unique reactivity of radical intermediates would provide great opportunities to develop more efficient photocatalytic systems for biomass valorization.

光催化是一种在温和条件下利用可再生生物质进行可持续化学生产的新兴方法。活性自由基总是作为关键中间体产生，其中它们的高反应性使它们在各种升级过程中具有通用性。然而，控制它们的反应是一个挑战，特别是在高度功能化的生物质框架中。在这篇综述中，我们总结了最近用于选择性生物质增值的先进光催化系统，重点是它们独特的自由基介导的反应模式。还强调了生成特定自由基中间体并控制其随后向所需化学品转化的策略，旨在为未来的研究提供指导。