光催化技术制备过氧化氢研究综述

A Review on the Preparation of Hydrogen Peroxide by Photocatalytic Technology

摘要: 过氧化氢(H₂O₂)是重要的绿色氧化剂与能量载体，传统蒽醌法生产存在诸多缺陷，光催化合成技术因绿色可持续成为理想替代方案，而共价有机框架(COFs)凭借独特结构优势，成为该领域极具潜力的光催化剂。本文综述COFs基光催化剂用于光催化合成H₂O₂的研究进展，阐述其反应原理为氧还原与水氧化两个互补半反应，直接两电子氧还原是最高效路径，同时介绍生成速率、AQY、SCC效率等核心评估指标。为提升COFs催化性能，研究开发了官能团修饰、构建D-A结构、异质结及杂原子掺杂等优化策略，通过调控电子结构、促进电荷分离、拓宽光响应范围等，大幅提高H₂O₂产率与选择性。目前该领域虽取得显著进展，却仍面临实际工况长期稳定性不足、规模化制备复杂、产物选择性待提升、催化机理未完全明晰等关键挑战。本文深入剖析COFs结构设计与性能调控的内在关联，梳理现存问题并展望发展方向，旨在为开发高效、稳定、可规模化的COFs基光催化体系提供理论支撑与技术参考，助力绿色化学工业发展。

Abstract: Hydrogen peroxide is an important green oxidant and promising energy carrier. The traditional anthraquinone process for its production suffers from numerous drawbacks, while photocatalytic synthesis technology has emerged as an ideal alternative due to its green and sustainable features. Covalent organic frameworks (COFs), endowed with unique structural advantages, have become highly potential photocatalysts in this field. This paper reviews the research progress of COFs-based photocatalysts for the photocatalytic synthesis of H₂O₂, and elaborates that the reaction mechanism consists of two complementary half-reactions, namely oxygen reduction and water oxidation, with direct two-electron oxygen reduction being the most efficient pathway. Meanwhile, it introduces the core evaluation indicators including production rate, apparent quantum yield (AQY) and solar-to-chemical conversion (SCC) efficiency. To improve the catalytic performance of COFs, a series of optimization strategies has been developed, such as functional group modification, construction of donor-acceptor (D-A) structures, fabrication of heterojunctions and heteroatom doping. These strategies can significantly enhance the H₂O₂ yield and selectivity by regulating the electronic structure, promoting charge separation and broadening the light response range. Despite the remarkable progress achieved in this field, several critical challenges remain, including insufficient long-term stability under practical operating conditions, complicated large-scale preparation, unsatisfactory product selectivity and incomplete clarification of the catalytic mechanism. This paper deeply analyzes the intrinsic correlation between the structural design and performance regulation of COFs, summarizes the existing problems and prospects the future development directions. It aims to provide theoretical support and technical reference for the development of efficient, stable and scalable COFs-based photocatalytic systems, thus boosting the advancement of the green chemical industry.