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

doi:10.6023/cjoc202203056

摘要/Abstract

共轭微孔聚合物(CMPs)由于良好的稳定性和性能可调性已在光催化水分解制氢领域显示出诱人的应用前景. 为了开发新型的CMPs类光催化剂多官能团构筑砌块, 探索有效的材料性能调节手段, 通过Sonogashira-Hagihara偶联反应合成了4种基于三(4-乙炔苯基)胺(TEA)单元和具有不同连接位置的苯并噻二唑(BT)单元的CMPs: FS1、FS2、FS3和FS4, 其中, BT单元的连接位置分别为: 5,6、4,5、4,6、4,7. 研究发现: 可见光驱动下, 四种聚合物均具有稳定的光催化析氢性能, 其中4,7-位连接的聚合物FS4性能最好, 析氢效率高达115.74×10^–3 μmol•mg^–1•h^–1, 为FS1的近3倍. 说明TEA为一种性能优异的CMPs类光催化剂多官能团构筑砌块, BT单元的连接位置调控是一种有效的TEA类CMPs的性能调节手段.

关键词: 三(4-乙炔苯基)胺, 苯并噻二唑, 连接位置, 共轭微孔聚合物, 光催化

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

引用此文

杜俊平, 封珊珊, 张婕, 张永辉, 王诗文, 韩莉峰, 陈俊利. 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[J]. 有机化学, 2022, 42(9): 2967-2974.

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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图/表 12

图式1. 聚合物的合成路线

Scheme 1. Synthesis route of the polymers

图1. 单体M0及聚合物的红外光谱图

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

图2. 聚合物的热失重曲线

Figure 2. Thermogravimetric analysis of the polymers

图3. 聚合物的粉末X衍射图

Figure 3. PXRD profile for the polymers

图4. 聚合物的扫描电镜照片

Figure 4. SEM images of the polymers

图5. 聚合物的氮气吸附-脱附等温曲线

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

表1. 聚合物的比表面积和多孔性质

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

图6. (a)聚合物的紫外-可见吸收光谱和(b)聚合物的光致发光光谱

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

表2. 聚合物的光物理和光催化性能

Table 2. Photophysical and photocatalytic properties of the polymers

图7. 聚合物的循环伏安曲线

Figure 7. Cyclic voltammetry curves of the polymers

图8. (a)聚合物的光催化水分解产氢量与时间的关系图(λ>420 nm)和(b) FS4的循环稳定性

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

图9. (a)聚合物的光电流随时间变化曲线图和(b)电化学交流阻抗图(EIS)

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

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