共价有机框架基光催化剂合成过氧化氢和高价值化学品的最新进展

Synthesis of H2O2 and high-value chemicals by covalent organic framework-based photocatalysts

过氧化氢(H_(2)O_(2))广泛用于废水处理、燃料电池及漂白剂等领域.尽管传统生产H_(2)O_(2)的蒽醌法拥有成熟的技术基础,但存在能耗高、爆炸风险、毒气排放以及环境污染等问题.太阳能驱动的光催化合成H_(2)O_(2)作为一种绿色、无污染、可持续的能源转换技术,展现出替代传统的蒽醌工艺的巨大潜力.共价有机框架(COFs)作为光催化合成H_(2)O_(2)的新兴催化剂,以可调节的能带结构、宽光吸收范围及高光催化效率在克服传统无机光催化剂低转化效率方面显示出优势.通过合理的结构设计调整氧还原反应(ORR)途径,COFs可提升光催化合成H_(2)O_(2)的产率,并可同时促进高附加值化学品的合成.本文综述了基于COFs的光催化剂在H_(2)O_(2)合成及选择性氧化高价值化学品领域的最新研究进展.首先,详细讨论了COFs基光催化剂在合成H_(2)O_(2)过程中的三种主要途径:(1)单步两电子氧还原反应;(2)两步单电子氧还原反应;(3)双通道反应机制.同时,强调了牺牲剂对光催化合成H_(2)O_(2)和高附加值化学品的影响.其次,总结了多种新颖的COF基光催化剂合成策略,包括静电自组装、原位合成、蒸汽辅助工艺、孔隙划分和界面聚合等,这些策略在光催化生产H_(2)O_(2)及高价值化学品方面发挥了关键作用.接下来,深入探讨了提升COFs在H_(2)O_(2)和高价值化学品生成效率方面的策略,主要包括单原子生长、异质结构建、活性位点调节和催化环境控制等四种修饰策略.这些策略涉及材料的贵金属改性、材料相互作用促进、官能团设计以及反应界面的亲疏水性质,旨在从整体上推动COFs在光催化的可持续性和增值化学合成方向的研究与创新.最后,提出了COFs基光催化剂面临的挑战与当前进展.其中,COFs的薄膜制备和多相体系构建对于解决催化剂的分离与回收问题至关重要.同时,强调了机理表征在提升COF基光催化剂整体性能中的重要性.综上,COFs基光催化剂在合成设计、反应途径的调控以及牺牲剂的引入等方面都会对合成H_(2)O_(2)和高值化学品产生重要影响.本文旨在为构建COF基光催化剂提升整体光催化性能提供一定的参考和借鉴.

Hydrogen peroxide(H_(2)O_(2))is a versatile and environmentally friendly oxidizer widely used in diverse fields.The solar-driven photocatalytic oxygen reduction reaction generates H_(2)O_(2)from air and water,avoiding undesirable byproducts.This green and pollution-free route is applicable to various domains.Although extensive research covers covalent organic framework(COF)-based photocatalysts for H_(2)O_(2),little attention has been paid to systems that generate high-value chemicals in the presence of scavengers.To address this gap,we systematically discuss the simultaneous photocatalytic generation of H_(2)O_(2)and valuable chemicals.We emphasize the pathways for H_(2)O_(2)generation using COF-based photocatalysts and highlight the role of sacrificial agents.Novel synthetic methodologies and modification strategies for enhancing the photocatalytic yield are presented.Our work aims to strengthen the identification and discussion of the challenges faced by photocatalysts in this field.This study aims to inspire further investigations and innovations in COF-based photocatalysis for sustainable and value-added chemical synthesis by presenting a holistic view.