通过偶极极化调制乙烯键连接的共价有机框架以实现高效光催化析氢

doi:10.1016/S1872-2067(24)60113-0

催化学报 ›› 2024, Vol. 65: 103-112.DOI: 10.1016/S1872-2067(24)60113-0

通过偶极极化调制乙烯键连接的共价有机框架以实现高效光催化析氢

王明^a^,¹, 李亚玲^a^,¹, 严登鑫^b, 胡慧^a, 宋玉洁^a, 苏晓芳^a, 孙佳敏^a^,^*(), 肖松涛^c^,^*(), 高艳安^a^,^*()

^a海南大学热带岛屿资源先进材料教育部重点实验室, 海南海口570228, 中国
^b根特大学化学技术实验室, 根特, 比利时
^c中国原子能科学研究院, 北京102413, 中国

收稿日期:2024-06-26 接受日期:2024-07-30 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: jiamin.suny@gmail.com (孙佳敏), xiao200112@163.com (肖松涛), ygao@hainanu.edu.cn (高艳安).
作者简介:¹共同第一作者.
基金资助:
海南省重点研发计划(ZDYF2024GXJS005);海南省重大科技计划(ZDKJ202016);国家自然科学基金(21965011);国家自然科学基金(22105053)

Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

Ming Wang^a^,¹, Yaling Li^a^,¹, Dengxin Yan^b, Hui Hu^a, Yujie Song^a, Xiaofang Su^a, Jiamin Sun^a^,^*(), Songtao Xiao^c^,^*(), Yanan Gao^a^,^*()

^aKey Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, Hainan University, Haikou 570228, Hainan, China
^bLaboratory for Chemical Technology, Ghent University, Technologiepark 125, 9052 Gent, Belgium
^cChina Institute of Atomic Energy, Beijing 102413, China

Received:2024-06-26 Accepted:2024-07-30 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: jiamin.suny@gmail.com (J. Sun), xiao200112@163.com (S. Xiao), ygao@hainanu.edu.cn (Y. Gao).
About author:¹ Contributed equally to this work.
Supported by:
Key Research and Development Project of Hainan Province(ZDYF2024GXJS005);Major Science and Technology Plan of Hainan Province(ZDKJ202016);National Natural Science Foundation of China(21965011);National Natural Science Foundation of China(22105053)

摘要/Abstract

摘要：

利用太阳辐照直接从水中制备氢气被认为是一种环保的、可持续的氢气生产方式. 共价有机框架(COFs)因在光催化析氢反应中表现出良好的性能, 而成为研究热点. 在众多COFs类型中, 亚胺键连接的COFs因其独特的结构特性而得到了广泛关注. 然而, 亚胺键的存在往往伴随着稳定性不足和共轭性较弱的问题, 限制了其光催化性能. 相比之下, 乙烯键连接的COFs由于具有稳固的连接键, 显示出更高的稳定性. 此外, 局域偶极极化效应能够通过内置电场作用, 有效提升电子-空穴对的分离效率, 是优化光催化性能的重要途径之一. 然而, 目前关于乙烯键连接的COFs在局域偶极极化光催化方面的研究较少.

本文主要考察了光催化析氢反应中乙烯键连接的COFs的设计、合成及其性能研究. 首先, 以具有光活性的2,4,6-三甲基-1,3,5-三嗪(TMT)为构筑基元, 分别与4,4′-(苯并呋咱-4,7-二基)二苯甲醛(BO)、4,4′-(苯并噻二唑-4,7-二基)二苯甲醛(BS)和4,4'-(苯并硒二唑-4,7-二基)二苯甲醛(BSe)进行羟醛缩合反应, 成功合成了三种乙烯键连接的COFs, 即TMT-BO-COF, TMT-BS-COF和TMT-BSe-COF. 粉末X射线衍射、高分辨透射电镜和N₂吸脱附结果表明, 三种COFs均具有高结晶性和比表面积. 傅里叶红外光谱、固体核磁和X射线光电子能谱进一步证实了三种COFs材料的成功合成. 在性能测试中发现, 这些COFs在可见光区域具有强吸收能力, 且其光学带隙与导带位置适宜, 预示着可能具有较好的光催化析氢活性. 进一步研究表明, 局域偶极矩对光催化析氢效率有重要影响. 通过局域偶极矩计算和光催化析氢实验研究发现, TMT-BO-COF因其结构中高电负性氧原子的存在, 展现出最大的局域偶极矩(3.8992 D), 有效促进了电子-空穴对分离, 实现了高效的光催化析氢. 其产氢速率高达23.7 mmol g^-1 h^-1, 远高于TMT-BS-COF (9.45 mmol g^-1 h^-1)和TMT-BSe-COF (0.96 mmol g^-1 h^-1). 为了深入探究其机制, 进行了电子顺磁共振、光电流响应和电化学阻抗等测试. 结果表明, TMT-BO-COF不仅具有更高的电子-空穴分离效率, 还展现出更灵敏的光响应能力和更快速的电子转移能力. 此外, 变温荧光测试和开尔文探针力显微测试揭示了TMT-BO-COF具有最低的激子结合能(21.6 meV)和最大的表面电势(60.2 mV), 进一步证实了其优越的光催化性能. 最后, 理论计算结果表明, TMT-BO-COF具有最大扩散程度的最低未占据分子轨道和最大的电子析出系数(8.19), 从理论层面阐明了局域偶极矩增强对光催化析氢效率的积极影响. 同时, 基于对TMT-BO-COF光催化活性位点的密度泛函理论计算, 提出了一种新颖的光催化析氢机理, 该机制涉及发生在基于乙烯键COFs中三嗪环的氮原子上质子耦合电子转移过程.

综上, 本文设计合成了三种高结晶度和比表面积的乙烯键连接COFs, 通过原子电负性的精细调控, 阐明了COFs中局域偶极矩的差异如何影响光催化析氢的效率. 本研究对于开发新型光催化COFs以及优化其电子-空穴分离效率具有参考意义.

关键词: 共价有机框架, 乙烯键连接, 电负性, 偶极极化, 光催化析氢

Abstract:

Photocatalytic hydrogen (H₂) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H₂ evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H₂ production rate of 23.7 mmol g^-1 h^-1, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H₂ evolution and beyond.

Key words: Covalent organic framework, Vinylene linkage, Electronegativity, Dipole polarization, Photocatalytic hydrogen evolution

王明, 李亚玲, 严登鑫, 胡慧, 宋玉洁, 苏晓芳, 孙佳敏, 肖松涛, 高艳安. 通过偶极极化调制乙烯键连接的共价有机框架以实现高效光催化析氢[J]. 催化学报, 2024, 65: 103-112.

Ming Wang, Yaling Li, Dengxin Yan, Hui Hu, Yujie Song, Xiaofang Su, Jiamin Sun, Songtao Xiao, Yanan Gao. Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2024, 65: 103-112.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60113-0

https://www.cjcatal.com/CN/Y2024/V65/I10/103

图/表 5

Fig. 1. Synthetic routes (a) and dipole polarization ability (b) of the three COFs in this study.

Fig. 2. The experimental and simulated PXRD patterns of TMT-BO-COF (a), TMT-BS-COF (b), and TMT-BSe-COF (c). (d) The solid-state 13C NMR spectra of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF. Nitrogen adsorption isotherms (e) and pore size distributions (f) of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF. HRTEM images of TMT-BO-COF (g), TMT-BS-COF (h), and TMT-BSe-COF (i).

Fig. 3. (a) Energy band position. Photocatalytic H2 evolution rate of TMT-BO-COF in the presence of various scavengers (b), different catalyst dosages (c), and different Pt loadings (d). (e) Catalytic activity of TMT-BO-COF under different reaction conditions. H2 evolution performance (f) and photocatalytic H2 evolution rates (g) of TMT-BO-COF, TMT-BS-COF and TMT-BSe-COF. (h) Long-term H2 production of TMT-BO-COF. (i) The photocatalytic hydrogen evolution properties of vinylene-linked COFs.

Fig. 4. EPR spectra (a), photocurrent responses (b), EIS (c), and temperature-dependent PL spectra (d-f), excited at 400 nm and Arrhenius plots determining exciton binding energies of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF (inset). Electron (green regions)-hole (blue regions) distributions (iso-surface = 0.002 a.u.) of TMT-BO-COF (g), TMT-BS-COF (h), and TMT-BSe-COF (i) in the excited state. Surface potential of the TMT-BO-COF (j), TMT-BS-COF (k) and TMT-BSe-COF (l) examined by KPFM (green line shows the surface potential detection area).

Fig. 5. (a) Illustration of the calculated five possible active sites of TMT-BO-COF, and the adsorption Gibbs free energy diagram of hydrogen evolution reaction on five possible sites. (b) Mechanism of photocatalytic hydrogen evolution at TMT-BO-COF.

参考文献

[1]	M. Cai, Y. X. Wei, Y. K. Li, X. Li, S. B. Wang, G. S. Shao, P. Zhang, EcoEnergy, 2023, 1, 248-295.
[2]	Q. Niu, L. H. Mi, W. Chen, Q. J. Li, S. H. Zhong, Y. Yu, L. Y. Li, Chin. J. Catal., 2023, 50, 45-82.
[3]	X. M. Fu, H. B. Huan, G. G. Tang, J. M. Zhang, J. Y. Sheng, H. Tang, Chin. J. Struct. Chem., 2024, 43, 100214.
[4]	X. H. Yu, H. W. Su, J. P. Zou, Q. Q. Liu, L. L. Wang, H. Tang, Chin. J. Catal., 2022, 43, 421-432.
[5]	Y. Xu, M. Fan, W. Yang, Y. Xiao, L. Zeng, X. Wu, Q. Xu, C. Su, Q. He, Adv. Mater., 2021, 33, 2101455.
[6]	D. Wang, X. Q. Gong, Nat. Commun., 2021, 12, 158.
[7]	Y. Akinaga, T. Kawawaki, H. Kameko, Y. Yamazaki, K. Yamazaki, Y. Nakayasu, K. Kato, Y. Tanaka, A. T. Hanindriyo, M. Takagi, T. Shimazaki, M. Tachikawa, A. Yamakata, Y. Negishi, Adv. Funct. Mater., 2023, 33, 2303321.
[8]	M. X Yang, Y. J Li, Z. L. Jin, Adv. Sustainable Syst., 2023, 7, 2200344.
[9]	S. Ding, J. J. Duan, S. Chen, EcoEnergy, 2024, 2, 45-82.
[10]	H. Zhang, C. F. Shao, Z. L. Wang, J. F. Zhang, K. Dai, J. Mater. Sci. Technol., 2024, 195, 146-154.
[11]	F. Jin, B. L. Yang, X. P. Wang, T. Li, N. Tsubaki, Z. L. Jin, Chin. J. Struct. Chem., 2023, 42, 100198.
[12]	L. X. Zhu, F. L. Hu, B. Sun, S. N. Gu, T. T. Gao, G. W. Zhou, Adv. Sustainable Syst., 2023, 7, 2200394.
[13]	C. Ni, H. Zheng, W. Liu, L. Wu, R. Li, K. Zhou, W. Zhang, Adv. Funct. Mater., 2023, 33, 2301075.
[14]	C. Zhang, C. Xie, Y. Gao, X. Tao, C. Ding, F. Fan, H. Jiang, Angew. Chem. Int. Ed., 2022, 61, e202204108.
[15]	S. J. Li, X. B. Chen, Y. P. Yuan, Acta Phys.-Chim. Sin., 2023, 39, 2303032.
[16]	R. Q. Gao, J. X. Bai, R. C. Shen, L. Hao, C. Huang, L. Wang, G. J. Liang, P. Zhang, X. Li, J. Mater. Sci. Technol., 2023, 137, 223-231.
[17]	R. Liu, K. T. Tan, Y. Gong, Y. Chen, Z. Li, S. Xie, T. He, Z. Lu, H. Yang, D. Jiang, Chem. Soc. Rev., 2021, 50, 120-242.
[18]	W. X. Yang, J. F. Zhang, Q. L Xu, Y. Yang, L. J. Zhang, Acta Phys.-Chim. Sin., 2024, 40, 2312014.
[19]	S. Kandambeth, K. Dey, R. Banerjee, J. Am. Chem. Soc., 2019, 141, 1807-1822.
[20]	H. Lyu, C. S. Diercks, C. Zhu, O. M. Yaghi, J. Am. Chem. Soc., 2019, 141, 6848-6852.
[21]	S. Yang, D. Streater, C. Fiankor, J. Zhang, J. Huang, J. Am. Chem. Soc., 2021, 143, 1061-1068.
[22]	F. Meng, S. Bi, Z. Sun, D. Wu, F. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202210447.
[23]	S. Bi, Z. Zhang, F. Meng, D. Wu, J. Chen, F. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202111627.
[24]	S. Li, R. Ma, S. Xu, T. Zheng, G. Fu, Y. Wu, Z. Liao, Y. Kuang, Y. Hou, D. Wang, P. S. Petkov, K. Simeonova, X. Feng, L. Z. Wu, X. B. Li, T. Zhang, J. Am. Chem. Soc., 2022, 144, 13953-13960.
[25]	H. Ji, D. Qiao, G. Yan, B. Dong, Y. Feng, X. Qu, Y. Jiang, X. Zhang, ACS Appl. Mater. Interfaces, 2023, 15, 37845-37854.
[26]	Z. Xie, X. Yang, P. Zhang, X. Ke, X. Yuan, L. Zhai, W. Wang, N. Qin, C. X. Cui, L. Qu, X. Chen, Chin. J. Catal., 2023, 47, 171-180.
[27]	Z. Zhao, X. Chen, B. Li, S. Zhao, L. Niu, Z. Zhang, Y. Chen, Adv. Sci., 2022, 9, 2203832.
[28]	H. Yang, R. Zhao, J. Wang, X. Yin, Z. Lu, L. Hou, ACS Mater. Lett., 2023, 5, 2877-2886.
[29]	J. Xu, C. Yang, S. Bi, W. Wang, Y. He, D. Wu, Q. Liang, X. Wang, F. Zhang, Angew. Chem. Int. Ed., 2020, 59, 23845-23853.
[30]	H. Lin, J. Wang, J. Zhao, Y. Zhuang, B. Liu, Y. Zhu, H. Jia, K. Wu, J. Shen, X. Fu, X. Zhang, J. Long, Angew. Chem. Int. Ed., 2022, 61, e202117645.
[31]	H. A. Patel, V. J. Bhanvadia, H. M. Mande, S. S. Zade, A. L. Patel, Org. Biomol. Chem., 2019, 17, 9467-9478.
[32]	M. Roucan, M. Kielmann, S. J. Connon, S. S. R. Bernhard, M. O. Senge, Chem. Commun., 2018, 54, 26-29.
[33]	Y. Li, J. Chen, P. Cai, Z. Wen, J. Mater. Chem. A, 2018, 6, 4948-4954.
[34]	A. Acharjya, P. Pachfule, J. Roeser, F. Schmitt, A. Thomas, Angew. Chem. Int. Ed., 2019, 58, 14865-154870.
[35]	S. X. L. Luo, R. Y. Liu, S. Lee, T. M. Swager, J. Am. Chem. Soc., 2021, 143, 10441-10453.
[36]	N. Zheng, Y. Feng, Y. Zhang, R. Li, C. Bian, L. Bao, S. Du, H. Dong, Y. Shen, W. Feng, ACS Appl. Mater. Interfaces, 2019, 11, 24360-24366.
[37]	H. Peng, S. Huang, V. Montes-García, D. Pakulski, H. Guo, F. Richard, X. Zhuang, P. Samorì, A. Ciesielski, Angew. Chem. Int. Ed., 2023, 62, e202216136.
[38]	J. Yu, S. Chang, X. Xu, X. He, C. Zhang, J. Mater. Chem. C, 2020, 8, 8887-8895.
[39]	M. Lu, J. Liu, Q. Li, M. Zhang, M. Liu, J. Wang, D. Yuan, Y. Lan, Angew. Chem. Int. Ed., 2019, 58, 12392-12397.
[40]	M. Zhang, P. Huang, J. Liao, M. Yang, S. Zhang, Y. Liu, M. Lu, S. Li, Y. Cai, Y. Lan, Angew. Chem. Int. Ed., 2023, 62, e202311999.
[41]	K. Huang, J. Bai, R. Shen, X. Li, C. Qin, P. Zhang, X. Li, Adv. Funct. Mater., 2023, 33, 2307300.
[42]	C. Q. Han, X. Sun, X. Liang, L. Wang, H. Hu, X. Y. Liu, J. Mater. Chem. C, 2023, 11, 12000-12006.
[43]	Y. L. Yang, N. Luo, S. Y. Lin, H. Yao, Y. Q. Cai, ACS Catal., 2022, 12, 10718-10726.
[44]	P. J. Li, F. Y. Ge, Y. Yang, T. Y. Wang, X. Y. Zhang, K. Zhang, J. Y. Shen, Angew. Chem. Int. Ed., 2024, 63, e202319885.
[45]	C. Li, J. Liu, H. Li, K. Wu, J. Wang, Q. Yang, Nat. Commun., 2022, 13, 2357.
[46]	S. Wang, T. Wu, S. Wu, J. Guo, T. He, Y. Wu, W. Yuan, Z. Zhang, Y. Hua, Y. Zhao, Angew. Chem. Int. Ed., 2023, 62, e202311082.
[47]	H. L. Zhang, Z. Lin, P. Kidkhunthod, J. Guo, Angew. Chem. Int. Ed., 2023, 62, e202217527.
[48]	T. Lu, F. Chen, J. Comput. Chem., 2012, 33, 580-592.
[49]	L. Hao, R. Shen, C. Qin, N. Li, H. Hu, G. Liang, X. Li, Sci. China Mater., 2024, 67, 504-513.
[50]	T. Sun, S. Li, L. Zhang, Y. X. Xu, Angew. Chem. Int. Ed., 2023, 62, e202301865.
[51]	H. Y. Wu, X. He, X. Du, D. H. Wang, W. X. Li, H. Chen, W. Fang, L. Zhao, Small, 2023, 19, 2304367.

通过偶极极化调制乙烯键连接的共价有机框架以实现高效光催化析氢

Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 15

编辑推荐

Metrics

[1]	林铮, 谢婉婷, 朱梦静, 汪长春, 郭佳. 二氧化硅支撑的平行堆叠排列手性共价有机框架促进光催化析氢[J]. 催化学报, 2024, 64(9): 87-97.
[2]	赵艳艳, 杨春燕, 张淑敏, 孙国太, 朱必成, 王临曦, 张建军. 飞秒瞬态吸收光谱研究ZnSe QDs/COF S型异质结光催化产H₂O₂中载流子传输机理[J]. 催化学报, 2024, 63(8): 258-269.
[3]	厉超, 王朔, 刘媛, 黄细河, 庄严, 吴舒鸿, 汪颖, 温娜, 吴凯丰, 丁正新, 龙金林. 共价有机框架双电场叠加实现高效光催化产氢[J]. 催化学报, 2024, 63(8): 164-175.
[4]	刘高雄, 陈润东, 夏兵全, 吴珍, 刘善堂, 冉景润. 共价有机框架基光催化剂合成过氧化氢和高价值化学品的最新进展[J]. 催化学报, 2024, 61(6): 97-110.
[5]	黄浩铭, 林清清, 牛青, 宁江淇, 李留义, 毕进红, 于岩. 基于共价有机框架非金属位点的光催化CO₂还原[J]. 催化学报, 2024, 60(5): 201-208.
[6]	白浚贤, 沈荣晨, 梁桂杰, 秦朝朝, 许第发, 胡浩斌, 李鑫. 噻吩基二维共价有机框架中的拓扑结构诱导局部电荷极化促进光催化制氢[J]. 催化学报, 2024, 59(4): 225-236.
[7]	潘劲康, 张艾彩珺, 张莉华, 董鹏玉. 由质子化D-A型聚合物和MoS₂构建S型异质结实现高效光催化析氢[J]. 催化学报, 2024, 58(3): 180-193.
[8]	杨婷婷, 汪静, 王中辽, 张金锋, 代凯. 双聚合物Cd₃(C₃N₃S₃)₂/Zn₃(C₃N₃S₃)₂ S型异质结增强光催化产氢性能[J]. 催化学报, 2024, 58(3): 157-167.
[9]	张勇, 邱俊逸, 朱必成, 孙国太, 程蓓, 王临曦. 空心球状共价有机框架负载金纳米粒子用于光催化生产过氧化氢[J]. 催化学报, 2024, 57(2): 143-153.
[10]	张璐, 张候瑞, 朱东阳, 付紫涵, 董双石, 吕聪. 构筑多组分供体-受体共价有机框架以实现高效光催化氧化: 电子迁移率和超氧自由基生成量的调控[J]. 催化学报, 2024, 66(11): 181-194.
[11]	李春雪, 卢豪, 丁桂祥, 马天翼, 刘诗咏, 张力, 廖光福. 界面配位键加速S型异质结电荷分离用于高效光催化析氢[J]. 催化学报, 2024, 65(10): 174-184.
[12]	刘鑫, 王茂弟, 任亦起, 刘嘉立, 戴慧聪, 杨启华. 构建模块化催化体系用于氢转移反应: 氢键的促进作用[J]. 催化学报, 2023, 52(9): 207-216.
[13]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[14]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.
[15]	牛青, 米林华, 陈玮, 李秋军, 钟升红, 于岩, 李留义. 基于共价有机框架的单位点光(电)催化材料的研究进展[J]. 催化学报, 2023, 50(7): 45-82.