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Unveiling the latent reactivity of imines on pyridine-functionalized covalent organic frameworks for H2O2 photosynthesis

吡啶功能化的亚胺类共价有机框架材料在光合成H2O2中的潜在活性

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Abstract

Unveiling the active site for the oxygen reduction reaction (ORR) holds the key to understanding and improving the photocatalytic activity of covalent organic frameworks (COFs) for H2O2 evolution. However, for imine-linked COFs, the role of the imine group is often overlooked in photosynthesis compared with other groups with electrophilicity or light-harvesting capabilities. Herein, a strategy is presented for eliciting the latent photoreactivity of imines by introducing an electron-acceptor structure (pyridine unit) near the imine bonds to enhance the kinetic and thermodynamic advantages of imines for the photocatalytic ORR to H2O2. Experiments and theoretical simulations indicate that the hindered visible light absorption and charge carrier separation caused by the weak electron delocalization can be substantially improved by introducing pyridinic N, leading to full solar spectrum absorption. Meanwhile, the pyridinic N can act with the N atom of the imine as an enhanced site for O2 adsorption and activation, and the strong electron transfers from COFs to O2 and ORR intermediates enable a two-step single-electron reduction route of O2 in pyridine-functionalized COFs for a more feasible H2O2 generation (706.2 µmol g−1 h−1) than original imine-linked COF (372.7 µmol g−1 h−1) under visible light irradiation. This work provides a new idea for designing and modifying imine-linked COFs in advanced photocatalytic applications.

摘要

探究氧还原反应(ORR)进行的位点是了解和提高亚胺类共价有机框架(COFs)材料光催化H2O2演化活性的关键. 然而, 与亚胺COFs中其他具有亲电或光捕获能力的基团相比, 亚胺键在光化学反应中的作用往往被忽视. 因此, 本文提出了一种通过在亚胺键周围引入电子受体结构(吡啶单元)来激发亚胺潜在光反应性的策略, 以增强亚胺在光催化ORR制备H2O2的动力学和热力学优势. 实验和理论模拟结果表明, 吡啶N的引入显著改善了TAPT-PA-COF中由弱电荷离域引起的光谱吸收和载流子分离的不足, 并在TAPT-PDA-COF上表现出全光谱吸收和快速电荷转移特性. 同时, 吡啶N与亚胺N原子共同作为活性位点可提高O2吸附和活化, 增强光生电子在TAPT-PDA-COF表面与反应物分子间的转移. 在可见光照射下, TAPT-PDA-COF的H2O2产率高达706.2 µmol g−1 h−1, 约为TAPT-PA-COF (372.7 µmol g−1 h−1)的1.9倍.该工作为亚胺类COFs在高级光催化应用中的设计和改性提供了新思路.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21776129, 21706121, and U22B6011), the Natural Science Foundation of Jiangsu Province (BK20170995 and BK20201120), and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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  1. These authors contribute equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 210009, China

    Shijian Zhou  (周诗健), Hao Hu  (胡浩), Huikang Hu  (胡会康), Qichao Jiang  (蒋其超), Haoran Xie  (谢浩然), Changlai Li  (李常来), Shuying Gao  (高树英) & Yan Kong  (孔岩)

  2. Key Laboratory of Advanced Functional Materials of Nanjing, Nanjing Xiaozhuang University, Nanjing, 211171, China

    Yingjie Hu  (胡应杰)

  3. Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou, 341119, China

    Huikang Hu  (胡会康)

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  1. Shijian Zhou  (周诗健)
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Contributions

Kong Y and Zhou S led the whole project. Zhou S and Hu H conceived the concept of material design. Hu H and Hu HK prepared and tested the samples and wrote the paper. Jiang Q participated in data curation. Hu Y contributed to the DFT simulation. Xie H, Li C and Gao S contributed to the sample preparation. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yan Kong  (孔岩) or Yingjie Hu  (胡应杰).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Shijian Zhou received his PhD degree from Ming-Yu Zhou’s group at Southeast University in 2015 and was also a visiting student in Professor Johannes Schwank’s group at the University of Michigan, Ann Arbor. He is now an associate professor at the State Key Laboratory of Materials-Oriented Chemical Engineering and the College of Chemical Engineering, Nanjing Tech University. His current research interests include the design of functionalized photocatalysts for advanced applications.

Hao Hu is a PhD student in the group of Professor Yan Kong at the College of Chemical Engineering, Nanjing Tech University, China. His recent work is related to the functionalization of covalent organic frameworks for advanced photocatalytic applications.

Yan Kong received his PhD degree from the Logistic Engineering University of PLA in 2000. He is now a professor at the State Key Laboratory of Materials-Oriented Chemical Engineering and the College of Chemical Engineering, Nanjing Tech University. His current research interests include the selective oxidation of aromatic hydrocarbon compounds and the degradation of organic pollutants.

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40843_2022_2337_MOESM1_ESM.pdf

Unveiling the latent reactivity of imines on pyridine-functionalized covalent organic frameworks for H2O2 photosynthesis

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Zhou, S., Hu, H., Hu, H. et al. Unveiling the latent reactivity of imines on pyridine-functionalized covalent organic frameworks for H2O2 photosynthesis. Sci. China Mater. 66, 1837–1846 (2023). https://doi.org/10.1007/s40843-022-2337-7

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