共价有机框架中氢键的构筑: 加速质子耦合电子转移以提升光催化合成过氧化氢性能

doi:10.1016/S1872-2067(26)64975-3

摘要/Abstract

摘要： 过氧化氢(H₂O₂)作为一种重要的绿色氧化剂, 在环境治理与清洁能源领域具有广泛应用. 目前, 其生产仍严重依赖高能耗的蒽醌法, 开发高效、可持续的光催化合成方法具有重要意义. 共价有机框架(COFs)因其可调控的孔道结构、高比表面积和优异的光电性能, 在光催化H₂O₂合成中展现出潜力. 然而, 其性能受限于质子耦合电子转移(PCET)过程的动力学迟缓, 尤其是水氧化反应(WOR)与氧还原反应(ORR)之间的质子供需失衡. 传统策略依赖外源质子给体, 不仅增加成本, 也加剧材料腐蚀. 因此, 构建内源性质子传递通道成为突破该瓶颈的关键.
针对上述挑战, 本文创新性地提出了一种基于射频等离子体后修饰的氢键工程策略, 通过在COF骨架中精准构建氢键强度梯度(OH···N与SH···N), 系统研究氢键强度对PCET路径的调控机制与增效原理. 该策略的核心在于利用等离子体技术在温和条件下对COF骨架中的亚胺键(C=N)进行选择性官能化, 分别引入羟基(-OH)和巯基(-SH), 形成具有不同氢键强度的功能化COF材料(OH-COF与SH-COF). 研究结果表明, 适度增强的SH···N氢键不仅可作为“动态质子储库”, 有效缓冲由缓慢WOR过程产生的质子, 还能构建起高效的“质子传递高速通道”, 实现质子的快速迁移与按需释放, 从而协同促进质子迁移与电子传输过程. 实验与理论计算(DFT)相结合的结果进一步表明, SH-COF中的SH···N氢键能够显著降低直接2e^- ORR路径的反应能垒达19.6%, 同时将4e^- WOR过程的能垒大幅降低49.7%, 并有效抑制高能中间体(如^•O₂^-)的生成, 从而引导反应优先沿高效的直接2e^- ORR路径进行, 极大提升了H₂O₂合成的选择性与效率. SH-COF在纯水条件下、无助剂参与时, 光催化H₂O₂产率高达1963.7 μmol g^-1 h^-1, 分别为OH-COF和原始COF的2.97倍与4.70倍, 展现出卓越的光催化性能. 通过H₂¹⁸O同位素标记实验进一步证实, 所产生的H₂O₂中的氧原子同时来源于水分子和氧气, 为氢键网络促进的PCET协同机制提供了直接证据. 此外, 研究还通过集成晶体轨道哈密顿布居(ICOHP)分析, 定量揭示了氢键强度与电荷转移效率之间的内在构效关系, 明确了氢键能量与PCET动力学之间的直接关联, 为理解氢键在光催化多电子反应中的热力学调控作用提供了坚实的理论依据.
综上, 本研究不仅提供了一种快速、绿色的等离子体修饰策略用于COF材料的后合成功能化, 更从机制层面深化了对氢键在光催化多电子反应中作用的理解, 为实现高效、稳定、可持续的光催化过氧化氢合成开辟了新路径.

关键词: 共价有机框架, 氢键, 过氧化氢, 光催化, 氧还原, 质子耦合电子转移

Abstract: The photocatalytic efficiency of covalent organic frameworks (COFs) toward sustainable H₂O₂ synthesis via oxygen reduction reaction (ORR) is intrinsically constrained by compromised proton-coupled electron transfer (PCET) dynamics, where retarded water oxidation reaction kinetics and exogenous proton donor dependence create a dual kinetic-thermodynamic constraint. This work presents a precision hydrogen‒bond engineering strategy through the radio-frequency plasma modification of COF linkages, establishing a hydrogen‒bond strength gradient (OH···N vs. SH···N) to probe the structure-function interplay that modulates PCET pathways. Systematic investigations reveal that hydrogen‒bond strengthening at imine linkages enables dual functionality: creating both dynamic proton reservoirs and more accessible proton conduction pathways. This synergistic regulation reduces the energy barrier for direct 2e^‒ ORR by 19.6% while suppressing high-energy intermediates in stepwise pathways, as confirmed by experiments and density functional theory calculations. The optimized SH-COF with appropriately stronger hydrogen bonds achieves exceptional photocatalytic H₂O₂ production: 2.97 and 4.70 times that of corresponding OH-COF and pristine COF, respectively. Integrated crystal orbital Hamilton population analysis quantitatively correlates hydrogen‒bond strength with charge transfer efficiency, establishing a relationship between hydrogen‒bond energy and PCET kinetics. Our findings not only demonstrate plasma modification as an effective strategy for post-synthetic hydrogen‒bond tuning but fundamentally advance the understanding of how hydrogen-bond thermodynamics govern PCET mechanisms.

Key words: Covalent organic framework, Hydrogen-bond, Hydrogen peroxide, Photocatalysis, Oxygen reduction reaction, Proton-coupled electron transfer

孙冉, 张雨琦, 侯琨格, 谭钰杰, 刘新刚, 侯剑源, 赵玮璇, Andrew E. H. Wheatley, 张仁熙. 共价有机框架中氢键的构筑: 加速质子耦合电子转移以提升光催化合成过氧化氢性能[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64975-3.

Ran Sun, Yuqi Zhang, Kunge Hou, Yujie Tan, Xingang Liu, Jianyuan Hou, Weixuan Zhao, Andrew E. H. Wheatley, Renxi Zhang. Designing hydrogen-bonds in covalent organic frameworks: accelerating proton-coupled electron transfer for enhanced photocatalytic H₂O₂ synthesis[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64975-3.

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