共价有机框架双电场叠加实现高效光催化产氢

doi:10.1016/S1872-2067(24)60075-6

催化学报 ›› 2024, Vol. 63: 164-175.DOI: 10.1016/S1872-2067(24)60075-6

共价有机框架双电场叠加实现高效光催化产氢

厉超^a, 王朔^a, 刘媛^b, 黄细河^c^,^*(), 庄严^a, 吴舒鸿^a, 汪颖^a^,^*(), 温娜^a, 吴凯丰^b, 丁正新^a, 龙金林^a^,^*()

^a福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州 350116
^b中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 辽宁大连 110623
^c福州大学化学学院, 福建福州 350116

收稿日期:2024-04-19 接受日期:2024-06-13 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子邮箱: xhhuang@fzu.edu.cn (黄细河),ywang@fzu.edu.cn (汪颖),jllong@fzu.edu.cn (龙金林).
基金资助:
国家自然科学基金(22302038);国家自然科学基金(22072022);福建省自然科学基金(2021L3003)

Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

Chao Li^a, Shuo Wang^a, Yuan Liu^b, Xihe Huang^c^,^*(), Yan Zhuang^a, Shuhong Wu^a, Ying Wang^a^,^*(), Na Wen^a, Kaifeng Wu^b, Zhengxin Ding^a, Jinlin Long^a^,^*()

^aState Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China
^bState Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 110623, Liaoning, China
^cCollege of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2024-04-19 Accepted:2024-06-13 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: xhhuang@fzu.edu.cn (X. Huang), ywang@fzu.edu.cn (Y. Wang), jllong@fzu.edu.cn (J. Long).
Supported by:
National Natural Science Foundation of China(22302038);National Natural Science Foundation of China(22072022);Natural Science Foundation of Fujian Province, China(2021L3003)

摘要/Abstract

摘要：

光催化水分解制氢是解决环境污染和能源危机的理想途径. 共价有机骨架(COFs)作为一类由共价键连接的周期性网状拓扑材料, 其电子结构和化学性质可在分子水平上进行定制和调控, 是研究半导体光催化剂构-效关系的理想模型. 为了提高COFs的电荷分离效率, 在COFs骨架上设计供体-受体(D-A)单元, 构筑分子内电场(IMEF)促进电荷定向迁移是一种行之有效的策略. 然而, 在亚胺键连接的COFs中, 亚胺键取向诱导产生的键内电场(IBEF)对光生激子的分离效率的影响往往被忽视. 因此, 进一步研究IMEF与IBEF之间的相互作用对COFs内光生电子转移动力学的影响具有重要意义, 可为深入揭示光催化产氢机制提供关键信息.

本文报道了一种基于COFs的双电场叠加策略, 用于提高光催化产氢反应效率. 首先, 通过将有机单元的末端官能团进行互换, 利用水热法成功制备了两种亚胺键取向相反的强D-A型COFs光催化剂, TNCA和TCNA. 其中, 官能团的微小变化保证了由D-A结构组成的IMEF方向和强度的一致性, 可以使得在仅改变IBEF的情况下全面研究COFs的电子结构. X射线粉末衍射、傅里叶变换红外光谱、固体核磁以及X射线光电子能谱等结果证实了两种COFs的成功合成. 随后, 扫描电镜、透射电镜和氮气等温吸脱附曲线结果表明两种COFs均为介孔材料. 紫外-可见漫反射光谱结果表明, 所制备的催化剂具有良好的可见光吸收能力, 结合莫特肖特基曲线结果, 表明催化剂在热力学上均满足光催化产氢的要求. 采用光致发光光谱、时间分辨荧光光谱、电子顺磁共振、光电流以及电化学阻抗研究了两种催化剂的载流子分离和转移行为, 并且利用飞秒瞬态吸收光谱进一步明确了COFs中光生电荷转移动力学过程. 结果表明, 相较于TCNA, TNCA在光照下能够产生更多的光生电子且具有更长的寿命. 光催化产氢活性评价结果显示, 在可见光(λ ≥ 420 nm)照射下, 具有同向叠加电场的TNCA, 光催化析氢速率高达57.3 mmol·g^‒1·h^‒1, 是具有相反电场取向TCNA (0.11 mmol·g^‒1·h^‒1)的520倍. 并且TNCA具有更负的导带能级, 有利于光生电子参与还原过程, 最终获得较好的光催化析氢性能. 此外, 理论计算结果表明, 当IMEF和IBEF取向一致时, 亚胺键不仅可以为载流子迁移提供强大的驱动力, 而且还能够有效地抑制载流子复合, 进一步提高光生电子的利用率.

综上所述, 本文提出了双电场叠加增强光生载流子高效分离的有效策略, 为设计具有特定电场性质的COFs光催化材料提供了理论及实际参考.

关键词: 共价有机框架, 分子内电场, 键内电场, 光催化, 制氢

Abstract:

Covalent organic frameworks (COFs) are promising materials for converting solar energy into green hydrogen. However, limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction (HER). In this study, the intrinsically tunable internal bond electric field (IBEF) at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field (IMEF) induced by the donor-acceptor (D-A) structure for an efficient HER. The aligned orientation of IBEF and IMEF resulted in a remarkable H₂ evolution rate of 57.3 mmol·g^-1·h^-1 on TNCA, which was approximately 520 times higher than that of TCNA (0.11 mmol·g^-1·h^-1) with the opposing electric field orientation. The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer, kinetically facilitating the migration of photogenerated electrons from D to A. Furthermore, theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only provides a strong driving force for carrier transfer but also effectively hinders the return of free electrons to the valence band, improving the utilization of photoelectrons. This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.

Key words: Covalent organic framework, Internal molecular electric field, Internal bond electric field, Photocatalysis, Hydrogen evolution

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: 164-175.

Chao Li, Shuo Wang, Yuan Liu, Xihe Huang, Yan Zhuang, Shuhong Wu, Ying Wang, Na Wen, Kaifeng Wu, Zhengxin Ding, Jinlin Long. Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2024, 63: 164-175.

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图/表 9

Fig. 1. (a) Schematic representation of the synthesis of TNCA and TCNA. Front view of TNCA (b) and TCNA (c) with opposite direction of electron transfer in imine linkage (Orange: nitrogen, Green: triazine carbon, Yellow: triphenylamine carbon, White: hydrogen).

Scheme 1. The synthetic procedure of TNCA.

Scheme 2. The synthetic procedure of TCNA.

Scheme 3. The synthetic procedure of TNNA.

Fig. 2. PXRD patterns of TNCA (a) and TCNA (b) with the Pawley refined in black cross, Experimental profiles in red and black, differences in blue, Braggs diffractions in green, and simulated AA stacking in purple. (c) FT-IR spectra of TNCA, TCNA, and relevant monomers. (d) 13C NMR pattern of TNCA and TCNA. (e) TEM image of TNCA, Inset: enlarged HR-TEM image from the yellow square selected area.

Fig. 3. (a) Solid state UV-vis DRS spectra of TNCA and TCNA. (b) Time-dependent hydrogen evolution production of TNCA and TCNA for 10 h under visible light irradiation. (c) Long-term HER activity for TNCA in 50 h recorded every 10 h for five times. (d) Steady-state photoluminescence spectra of TNCA and TCNA. (e) Time-resolved photoluminescence spectra of TNCA and TCNA. (f) EPR spectra of TEMPO for free electron detection in TNCA and TCNA under visible light irradiation using 300 W Xe lamp (λ > 420 nm).

Fig. 4. Time-resolved transient absorption spectra of TNCA (a,b) and TCNA (c,d) under 400 nm excitation in solid state. Comparison of the kinetic tendency of TNCA (e) and TCNA (f) at the appointed wavelength.

Fig. 5. Calculated surface electrostatic potential of TNCA (a) and TCNA (b). Local dipole moment of TNCA (c) and TCNA (d). Mulliken charge of TNCA (e) and TCNA (f).

Fig. 6. Calculated density of states and electronic band structures for TNCA (a,c) and TCNA (b,d). (e) Proposed reaction mechanism for photocatalytic hydrogen evolution over TNCA and TCNA.

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共价有机框架双电场叠加实现高效光催化产氢

Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

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