甲基空间位阻诱导的扭曲共轭多孔聚合物用于1O2驱动的高效光催化产过氧化氢

doi:10.1016/S1872-2067(26)65227-8

催化学报 ›› 2027, Vol. 92: 145-156.DOI: 10.1016/S1872-2067(26)65227-8

甲基空间位阻诱导的扭曲共轭多孔聚合物用于¹O₂驱动的高效光催化产过氧化氢

李国邦^a^,¹(), 王之林^a^,¹, 王梦凯^a, 刘彦春^a, 王聪^b^,^*(), 周香港^a, 王永慧^a^,^*(), 曹旭铮^a, 谭华桥^a^,^*()

^a 东北师范大学化学学院多酸与网格材料化学教育部重点实验室, 吉林长春 130024
^b 长春理工大学材料科学与工程学院, 吉林长春 130022

收稿日期:2026-02-04 接受日期:2026-04-17 出版日期:2027-01-02 发布日期:2026-10-30
通讯作者: *电子信箱: wangc813@cust.edu.cn (王聪),
wangyh319@nenu.edu.cn (王永慧),
tanhq870@nenu.edu.cn (谭华桥).
作者简介:第一联系人：
¹共同第一作者.
基金资助:
国家自然科学基金(22575038);国家自然科学基金(22401018);国家自然科学基金(22171041);国家自然科学基金(22379024);吉林省自然科学基金(YDZJ202601ZYTS101);吉林省科技厅自然科学基金(学科布局项目)(20230508094RC);吉林省教育厅(JJKH20261180KJ);吉林省教育厅(JJKH20240928KJ)

Methyl steric-hindrance-induced twisted acridine-based conjugated porous polymers for efficient¹O₂-driven photocatalytic H₂O₂ production

Guobang Li^a^,¹(), Zhilin Wang^a^,¹, Mengkai Wang^a, Yanchun Liu^a, Cong Wang^b^,^*(), Xianggang Zhou^a, Yonghui Wang^a^,^*(), Xuzheng Cao^a, Huaqiao Tan^a^,^*()

^a Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry,Northeast Normal University, Changchun 130024, Jilin, China
^b School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, Jilin, China

Received:2026-02-04 Accepted:2026-04-17 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: wangc813@cust.edu.cn (C. Wang),
wangyh319@nenu.edu.cn (Y. Wang),
tanhq870@nenu.edu.cn (H. Tan).
About author:First author contact:
¹ Contributed to this work equally.
Supported by:
National Natural Science Foundation of China(22575038);National Natural Science Foundation of China(22401018);National Natural Science Foundation of China(22171041);National Natural Science Foundation of China(22379024);Natural Science Foundation of Jilin Province of China(YDZJ202601ZYTS101);Natural Science Foundation of Jilin Province Science and Technology Department (discipline layout project)(20230508094RC);Education Department of Jilin Province of China(JJKH20261180KJ);Education Department of Jilin Province of China(JJKH20240928KJ)

摘要/Abstract

摘要：

过氧化氢(H₂O₂)是一种绿色环保型化学品, 广泛应用于化学合成、环境修复、医疗消毒及燃料电池等领域. 近年来, 太阳能驱动的H₂O₂光合成技术因其仅需水和氧气作为原料而备受关注, 这避免了传统蒽醌法的高能耗与环境污染问题. 然而, 由于其反应路径的复杂性, 该技术长期面临着热力学能垒较高、竞争反应显著等关键问题, 从而导致H₂O₂产率不足. 在此背景下, 单线态氧(¹O₂)介导的光催化H₂O₂合成路径展现出广阔的应用前景, 其强亲电性显著促进了氧物种在光催化剂表面的吸附及后续的质子耦合电子转移过程. 然而, 目前能够高效产生¹O₂以实现光催化H₂O₂合成的无金属光催化剂仍十分匮乏. 特别是, 在聚合物体系中, 系间穿越过程和激子解离行为难以精准控制, 这限制了H₂O₂合成效率和选择性的提升. 因此, 迫切需要开发一种可以定向调控激子行为, 实现高效高选择性光催化H₂O₂合成的聚合物光催化剂.

本文提出一种基于空间位阻调控的分子工程策略, 通过在共轭多孔聚合物(CPPs)的吖啶连接单元中引入甲基(从吖啶至吖啶黄G), 成功将平面结构的CPP-A转化为扭曲结构的CPP-G, 使七嗪与吖啶单元之间形成约65°的二面角. 这种构象变化极大改变了激子特性. 实验与理论计算表明, 平面结构的CPP-A有利于激子解离, 主要通过电荷转移路径生成超氧自由基(O₂^•-); 而扭曲结构的CPP-G则展现出增强的自旋轨道耦合和系间穿越效率, 促进了三重态激子的积累, 从而主导能量转移路径实现¹O₂的高效生成. 值得注意的是, 亲电性的¹O₂在催化剂表面具有更低的吸附能垒, 同时富氮的七嗪和吖啶单元提供了优异的质子富集能力, 进一步促进了吸附的氧物种在催化剂表面的质子耦合电子转移过程. 得益于此, CPP-G在纯水中无需任何牺牲剂即可实现8.97 mmol g^-1 h^-1的H₂O₂生成速率, 是O₂^•-主导的CPP-A (5.13 mmol g^-1 h^-1)的1.7倍, 显著优于大多数已报道的氮化碳基光催化剂. 此外, CPP-G在¹O₂介导的[3+2]环加成和脱羧氧化反应中同样展现出优异的光催化活性与选择性, 验证了其广泛的适用性.

综上, 本工作发展了普适的空间位阻调控策略, 不仅阐明了分子扭曲、激子行为、活性氧调控与光催化性能之间的内在构效关系, 还证实对无金属CPP光催化体系进行简单结构修饰, 即可实现活性氧生成路径从电荷转移向能量转移的定向切换.

关键词: 共轭多孔聚合物, 扭曲结构, 激子行为, 单线态氧, 光催化过氧化氢生产

Abstract:

The effective generation and utilization of singlet oxygen (¹O₂) offers a promising yet challenging route for photocatalytic hydrogen peroxide (H₂O₂) production. In this work, we describe a molecular engineering strategy regulated by steric hindrance to control excitonic behavior and oxygen activation pathways in conjugated porous polymers (CPPs). When methyl groups are introduced into the acridine linker (from acriflavine to acridine yellow G), a planar CPP-A converts into a twisted CPP-G which has an approximately 65° dihedral angle. This change in conformation drastically alters the photophysical properties. The planar structure of CPP-A facilitates exciton dissociation and results in the development of superoxide radical (O₂^•-) via charge transfer. Conversely, the twisted conformation of CPP-G assists in enhancing spin-orbit coupling and intersystem crossing efficiency. These lead to an accumulation of triplet excitons and dominant ¹O₂ generation through energy transfer. The electrophilic ¹O₂ possesses a lower adsorption energy barrier on the photocatalyst surface, favoring subsequent proton-coupled electron transfer reactions. Consequently, ¹O₂-dominated CPP-G exhibits a remarkable H₂O₂ production rate of 8.97 mmol g^-1 h^-1 in pure water without sacrificial agents, significantly outperforming the O₂^•--dominated CPP-A (5.13 mmol g^-1 h^-1). Furthermore, CPP-G demonstrates high efficiency and selectivity in ¹O₂-mediated organic transformations. This work demonstrates that steric hindrance engineering serves as a generalizable strategy, enabling a fundamental shift in the reactive oxygen species generation pathway, from charge transfer to energy transfer, via simple structural modifications in metal-free CPP photocatalytic systems.

Key words: Conjugated porous polymers, Twisted structure, Excitonic behavior, Singlet oxygen, Photocatalytic H₂O₂ production

李国邦, 王之林, 王梦凯, 刘彦春, 王聪, 周香港, 王永慧, 曹旭铮, 谭华桥. 甲基空间位阻诱导的扭曲共轭多孔聚合物用于¹O₂驱动的高效光催化产过氧化氢[J]. 催化学报, 2027, 92: 145-156.

Guobang Li, Zhilin Wang, Mengkai Wang, Yanchun Liu, Cong Wang, Xianggang Zhou, Yonghui Wang, Xuzheng Cao, Huaqiao Tan. Methyl steric-hindrance-induced twisted acridine-based conjugated porous polymers for efficient¹O₂-driven photocatalytic H₂O₂ production[J]. Chinese Journal of Catalysis, 2027, 92: 145-156.

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图/表 5

Scheme 1. The method for constructing CPPs from the relevant precursors.

Fig. 1. SEM and TEM images of CPP-A (a) and CPP-G (b). (c) FT-IR spectra for the CPPs and C6N7Cl3. (d) XRD spectra of the CPPs and C6N7Cl3. (e) C 1s spectra of XPS related to the CPPs. (f) N 1s spectra of XPS corresponding to the CPPs.

Fig. 2. (a) UV-vis DRS of the CPPs. (b) Tauc-plots related to the CPPs. (c) Energy band structures pertaining to the CPPs. (d) EIS plots and transient photocurrent (inset) of CPPs. (e) PL spectra recorded at 300 K for the CPPs. (f) TR-PL of the CPPs. Integrated PL intensity as a function of temperature for CPP-A (g) and CPP-G (h) (with inset showing the relevant temperature-dependent PL spectra). The value of Eb is obtained using the Arrhenius equation. (i) Delayed phosphorescence spectra of the CPPs measured at 77 K after 1 ms.

Fig. 3. (a) The photocatalytic activities of CPPs. (b) H2O2 production rates of CPP-G under different conditions. H2O2 production rates of CPP-G (c) and CPP-A (d) when different scavengers are present. (e) ESR spectra obtained from TEMP-1O2 radical trapping experiments facilitated by CPPs. (f) ESR spectra from DMPO-O2•- radical trapping experiments conducted using CPPs. (g) The AQY of CPP-G under different wavelengths. (h) The photocatalytic production of H2O2 catalyzed by recycled CPP-G for five times. (i) Comparison of CPPs with representative materials in terms of the H2O2 production rate.

Fig. 4. (a) Schematic structures of CPPs optimized by DFT. (b) Theoretical vertical excitation energy for singlet and triplet states, along with SOC constants for S1 and Tn. (c) Radar plot with the major characteristics of CPP-A and CPP-G. SOC refers to theoretical spin-orbit coupling constant measured in cm-1. Eb is experimentally measured exciton binding energy in meV. S1 → Tn pathway indicates calculated number of transition pathways shifting from singlet to triplet excited states. 1O2 is used to roughly evaluate the energy transfer process in CPPs. O2•- employed to assess the charge transfer processes occurring within CPPs. (d) Gibbs free energy diagrams for the reduction of O2 to H2O2 via 1O2 pathway on the CPP-G.

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甲基空间位阻诱导的扭曲共轭多孔聚合物用于¹O₂驱动的高效光催化产过氧化氢

Methyl steric-hindrance-induced twisted acridine-based conjugated porous polymers for efficient¹O₂-driven photocatalytic H₂O₂ production

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