Tris(4-ethynylphenyl)amine-Based Conjugated Microporous Polymers and Its Photocatalytic Water Splitting Hydrogen Evolution

doi:10.6023/cjoc202203056

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (9): 2967-2974.DOI: 10.6023/cjoc202203056 Previous Articles Next Articles

NOTES

三(4-乙炔苯基)胺类共轭微孔聚合物及其光催化水分解性能研究

杜俊平^*(), 封珊珊, 张婕, 张永辉, 王诗文, 韩莉峰, 陈俊利^*()

郑州轻工业大学材料与化学工程学院河南省环己醇催化分离工程研究中心郑州 450002

收稿日期:2022-03-29 修回日期:2022-05-10 发布日期:2022-06-16
通讯作者: 杜俊平, 陈俊利
基金资助:
国家自然科学基金(21805248); 国家自然科学基金(U2004196); 河南省自然科学基金(162300410318); 中国科学院上海有机化学研究所开放(K2016-8); 郑州轻工业学院博士基金(2013BSJJ017)

Tris(4-ethynylphenyl)amine-Based Conjugated Microporous Polymers and Its Photocatalytic Water Splitting Hydrogen Evolution

Junping Du(), Shanshan Feng, Jie Zhang, Yonghui Zhang, Shiwen Wang, Lifeng Han, Junli Chen()

Henan Cyclohexanol Catalytic Separation Engineering Research Center, Zhengzhou University of Light Industry, Zhengzhou, 450002

Received:2022-03-29 Revised:2022-05-10 Published:2022-06-16
Contact: Junping Du, Junli Chen
Supported by:
National Natural Science Foundation of China(21805248); National Natural Science Foundation of China(U2004196); Natural Science Foundation of Henan Province(162300410318); Open Project of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences(K2016-8); Doctor Research Project of Zhengzhou University of Light Industry(2013BSJJ017)

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Abstract

Conjugated microporous polymers (CMPs) have shown attractive application prospects in the field of photocatalytic water splitting hydrogen evolution because of their excellent stability and adjustable properties. To develop novel multi-functional building blocks for CMPs photocatalysts and explore effective methods to tune their properties, based on tris- (4-ethynylphenyl) amine (TEA) unit and benzothiadiazole (BT) unit with different linking positions, four CMPs FS1, FS2, FS3 and FS4 have been synthesized with Sonogashira-Hagihara coupling reaction. The linking positions of BT units in them are 5,6, 4,5, 4,6 and 4,7, respectively. It suggests that the four polymers all have stable photocatalytic hydrogen evolution performance under visible light driving. FS4 with 4,7-linked polymer has the best performance, and its hydrogen evolution efficiency is as high as 115.74×10^–3 μmol•mg^–1•h^–1, nearly three times than that of FS1. It shows that TEA is an excellent multi-functional building block of CMPs photocatalyst, and the linking position regulation of BT unit is an effective means to tune the performance of TEA based CMPs.

Key words: tris(4-ethynylphenyl)amine, benzothiadiazole, linking position, conjugated microporous polymers, photocatalysis

Cite this article

Junping Du, Shanshan Feng, Jie Zhang, Yonghui Zhang, Shiwen Wang, Lifeng Han, Junli Chen. Tris(4-ethynylphenyl)amine-Based Conjugated Microporous Polymers and Its Photocatalytic Water Splitting Hydrogen Evolution[J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2967-2974.

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Fig. & Tab. 12

Scheme 1. Synthesis route of the polymers

Figure 1. FT-IR spectra of M0 and the polymers

Figure 2. Thermogravimetric analysis of the polymers

Figure 3. PXRD profile for the polymers

Figure 4. SEM images of the polymers

Figure 5. N2 adsorption (filled symbols) and desorption (empty symbols) curves of the polymers

Polymer	S_BET/(m²•g^-1)	V_micro/(cm³•g^-1)	V_total/(cm³•g^-1)	V_micro/V_total
FS1	5.20	0.0002	0.001	2.00
FS2	11.86	0.002	0.015	0.13
FS3	89.95	0.022	0.071	0.31
FS4	367.57	0.110	0.247	0.44

Table 1. BET surface areas and porosity properties of the polymers

Figure 6. (a) UV-Vis light absorption of the polymers and (b) photoluminescence spectra of the polymers

Polymer	E_Ox^onset/eV	E_Red^onset/eV	E_LUMO/eV	E_HOMO/eV	E_g^elec^a/eV	E_g^opt^b/eV	HER^c
FS1	0.76	–0.62	–3.78	–5.16	1.38	1.83	34.93
FS2	0.70	–0.59	–3.81	–5.1	1.29	1.79	45.58
FS3	0.72	–0.64	–3.76	–5.12	1.36	2.06	90.43
FS4	0.69	–0.57	–3.83	–5.09	1.26	1.74	115.74

Table 2. Photophysical and photocatalytic properties of the polymers

Figure 7. Cyclic voltammetry curves of the polymers

Figure 8. (a) Time course of hydrogen evolution of the polymers (λ>420 nm), and (b) cyclic stability of polymer FS4

Figure 9. (a) Time-dbependent photocurrent of the polymer and (b) electrochemical AC impedance (EIS)

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三(4-乙炔苯基)胺类共轭微孔聚合物及其光催化水分解性能研究

Tris(4-ethynylphenyl)amine-Based Conjugated Microporous Polymers and Its Photocatalytic Water Splitting Hydrogen Evolution

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