空穴限域效应促进共价有机框架光催化分解水制过氧化氢和氢气

doi:10.1016/S1872-2067(26)65148-0

摘要/Abstract

摘要：

光催化全解水同步产氢(H₂)与过氧化氢(H₂O₂)是实现太阳能向高附加值化学品转化的理想途径. 然而, 迟缓的水氧化动力学及严重的载流子复合极大制约了传统共价有机框架(COFs)光催化剂的能量转换效率. 为破解该瓶颈, 本文提出了一种“空穴空间限域”设计策略. 通过分子工程, 将光生空穴定向富集于特定的水氧化活性中心以提高局部氧化电位, 同时促使光生电子在骨架内高度离域. 该策略在大幅延长电荷分离寿命的同时, 最大限度地激发了位点的本征反应活性, 从而在无牺牲剂的纯水体系中实现了高效的全解水反应.
本研究以三嗪环为电子离域受体, 结合不同供电基团, 成功构筑了三种具有差异化激发态电荷分布的酰腙键链接COFs. 光电与原位光谱表征证实, 具有完美供受体结构的TFT-COF展现出最佳的电荷分离动力学. 开尔文探针力显微镜检测到93 mV的表面光电压, 显著高于其他两例同类型酰腙键COFs; 原位X-射线光电子能谱直接印证了空穴被精准限域于酰腙位点, 而电子向三嗪环发生离域; 瞬态吸收光谱显示其载流子寿命延长至318.7 ps. 密度泛函理论计算表明, 酰腙限域位点作为热力学最优的水吸附中心; Pt助催化剂的引入有效重构了后续基元反应的热力学势能面, 大幅降低了决速步的活化能. 在这种协同机制下, 光生空穴得以通过单电子路径驱动水分子氧化生成•OH, 并最终偶联为H₂O₂. 最终, 在可见光驱动下, TFT-COF的H₂与H₂O₂产率分别高达311.2和278.6 μmol·g^-1·h^-1.
综上, 本文通过分子结构设计实现了光生空穴在空间上的选择性限域与水吸附位点的精准匹配, 协同促进了电荷分离与水氧化动力学, 在纯水中实现了高效的全解水同步产H₂与H₂O₂, 为COF基光催化剂的设计提供了“空穴限域”新策略.

关键词: 共价有机框架, 光催化, 空穴积累, 全解水, 氢气和过氧化氢

Abstract:

Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalysis, however, their efficiency in converting water into value-added chemicals is often severely constrained by sluggish water-oxidation kinetics. Herein, we demonstrate a strategy of confining photogenerated holes at specific water oxidation active sites in COFs to enhance simultaneous H₂ and H₂O₂ co-generation from water. We designed three hydrazone-linked COFs capable of driving overall water splitting without the use of sacrificial agents. Mechanistic studies reveal that the capability to confine photogenerated holes at hydrazone linkages directly correlates with superior water-splitting activity. Specifically, the accumulation of holes at these thermodynamically preferred water-adsorption sites, coupled with electron delocalization, results in a unique spatial charge separation. This configuration not only significantly suppresses recombination to extend excited-state lifetimes but also creates hole-rich local environments that accelerate water oxidation kinetics. Consequently, the optimal COF achieves H₂ and H₂O₂ production rates of 311.2 and 278.6 μmol·g^-1·h^-1, respectively. This work establishes the spatial accumulation of photogenerated holes as a pivotal, engineerable design principle for advancing COF-based photocatalytic water splitting.

Key words: Covalent organic frameworks, Photocatalysis, Hole accumulation, Overall water splitting, H₂ and H₂O₂ production

李增, 于明飞, 李留义, 于岩. 空穴限域效应促进共价有机框架光催化分解水制过氧化氢和氢气[J]. 催化学报, 2026, 91: 263-273.

Zeng Li, Mingfei Yu, Liuyi Li, Yan Yu. Hole-confining covalent organic frameworks for photosynthesis of H₂O₂ and H₂ from pure water[J]. Chinese Journal of Catalysis, 2026, 91: 263-273.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65148-0

https://www.cjcatal.com/CN/Y2026/V91/I12/263

图/表 6

Fig. 1. (a) Schematic illustration of TFT-COF, TFB-COF, and TFS-COF. PXRD patterns of the three COFs with the experimental profiles in orange, Pawley-refined in purple (AA stacking), predicted in red, differences in sky blue, and the Bragg positions in brown for TFT-COF (Rwp=6.76%) (b), TFB-COF (Rwp=3.99%) (c), and TFS-COF (Rwp=4.26%) (d).

Fig. 2. UV-vis DRS (a), band alignments (b), transient photocurrent spectra (c), EIS plots (d), profiles of fluorescence lifetime (e), and EPR spectra (f) under dark and light conditions.

Fig. 3. KPFM images of TFT-COF (a), TFB-COF (b), and TFS-COF (c) under dark and illumination. In-situ XPS spectra of N 1s for TFT-COF (d), TFB-COF (e), and TFS-COF (f). TAS spectra

Fig. 4. (a) Electron-hole distributions of excited TFT-COF, TFB-COF, and TFS-COF. Orange and blue represent the increase and decrease in electron density, respectively. (b) Corresponding heatmap of electrons and holes. (c) Water adsorption enthalpy. (d) Corresponding electronic charge transfer between water molecules and the framework in the excited state. (e) Schematic illustration of electron and hole distributions. (f) Radar chart comparing key properties of the three COFs.

Fig. 5. (a) Photocatalytic water splitting activity of TFT-COF, TFB-COF, and TFS-COF. (b) H218O isotope experiment of TFT-COF. (c) Wavelength-dependent AQY of water splitting for TFT-COF. (d) Recycling test of water splitting for the TFT-COF.

Fig. 6. In-situ DRIFTS spectra (a) and EPR DMPO-•OH signal (b) in aqueous solution of Pt-loaded TFT-COF. (c) DFT calculated Gibbs free energy profiles for water splitting. (d) Schematic representation of photocatalytic water decomposition of the Pt-loaded TFT-COF.

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