新型亲水性共轭聚合物的制备及光催化制氢性能

doi:10.7503/cjcu20190647

摘要/Abstract

摘要：

制备了聚({4,8-双[(2,5,8,11,14,17,20-七氧二十二烷-22-基)氧基]苯并[1,2-b∶4,5-b']二噻吩}-交替-[2,5-二(噻唑-2-基)吡嗪])(P7O-2N-2N)和聚({4,8-双[(2,5,8,11,14,17,20-七氧二十二烷-22-基)氧基]苯并[1,2-b∶4,5-b']二噻吩}-交替-[3,6-双(5-溴-2-噻吩基)-1,2,4,5-四嗪])(P7O-4N)2个亲水性共轭聚合物, 通过调节主链含氮杂环上氮原子的位置, 系统研究了主链结构对材料吸收光谱、能级、氢结合自由能及光催化性能的影响. 研究发现, 与P7O-2N-2N相比, P7O-4N表现出更强的链间聚集、更低的氢结合自由能及更好的光催化制氢性能.

关键词: 共轭聚合物, 光催化制氢, 含氮杂环, 亲水侧链

Abstract:

The application of organic conjugated polymers in photocatalytic hydrogen production has received increasing attention. However, most conjugated polymer photocatalysts showed unsatisfied photocatalytic hydrogen evolution, and the structure-performance relationship of conjugated polymers-based photocatalysts needs further exploration. In this study, we designed two conjugated polymers[poly({4, 8-bis[(2, 5, 8, 11, 14, 17, 20-heptaoxadocosan-22-yl)oxy]benzo[1, 2-b∶4, 5-b']dithiophene}-alt-[2, 5-di(thiazol-2-yl)pyrazine])(P7O-2N-2N) and poly({4, 8-bis[(2, 5, 8, 11, 14, 17, 20-heptaoxadocosan-22-yl)oxy]benzo[1, 2-b∶4, 5-b']dithiophene}-alt-[3, 6-di(thiophen-2-yl)-1, 2, 4, 5-tetrazine])(P7O-4N)] with hydrophilic side chains and nitrogen-contained heterocycles in backbones. The chemicals tructures and their influence on the absorption spectrum, energy level, free energy of hydrogen adsorption and photocatalytic performance of the material were systematically studied. The results showed that the conjugated polymer P7O-4N having a 3, 6-bis(thien-2-yl)-1, 2, 4, 5-tetrazine structure showed stronger inter-chain aggregation, lower hydrogen bonding free energy, and better photocatalytic hydrogen production performance than polymer P7O-2N-2N with 2, 5-bis(thiazole-2-yl)-pyrazide structure.

Key words: Conjugated polymer, Photocatalytic hydrogen evolution, Nitrogen-containing heterocycle, Hydrophilic side chain

中图分类号:

O631.1 ⁺1

TrendMD:

罗威, 梁佑才, 胡志诚, 唐浩然, 刘孝诚, 邢晔彤, 黄飞. 新型亲水性共轭聚合物的制备及光催化制氢性能. 高等学校化学学报, 2020, 41(3): 456.

LUO Wei, LIANG Youcai, HU Zhicheng, TANG Haoran, LIU Xiaocheng, XING Yetong, HUANG Fei. Preparation of Novel Hydrophilic Conjugated Polymers and Their Applicationin Photocatalytic Hydrogen Evolution ^†. Chem. J. Chinese Universities, 2020, 41(3): 456.

图/表 9

Fig.1 Chemical structures of P7O-2N-2N(A) and P7O-4N(B)

Scheme 1 Synthetic routes of 2,5-bis(5-bromothiazol-2-yl)pyrazine(2N-2N, 3), 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine)(4N, 6), P7O-2N-2N and P7O-4N

Table 1 Molecular weights, optical properties, and energy levels of P7O-2N-2N and P7O-4N

Polymer	M_n	λ_edge/nm		HOMO/eV	LUMO/eV	E_opt/eV
Polymer	M_n	Solution	Film	HOMO/eV	LUMO/eV	E_opt/eV
P7O-2N-2N	15600	604	629	-5.14	-3.67	1.89
P7O-4N	12700	624	655	-5.09	-3.48	1.97

Fig.2 Chemical structures of 2N-2N and 4N(A) and ΔGH values of nitrogen site in 2N-2N and 4N(B)

Fig.3 UV-Vis absorption spectra of P7O-2N-2N(a) and P7O-4N(b) in chloroform(A) and thin film(B)

Fig.4 CV curves(A) and energy level alignment diagram(B) of P7O-2N-2N(a) and P7O-4N(b)

Fig.5 TEM images of P7O-2N-2N(A) and P7O-4N(B) dispersed in water Insets: enlarged TEM images of the corresponding polymer.

Fig.6 Photocatalytic hydrogen evolution rates of P7O-4N(a, b) and P7O-2N-2N(c, d) with Pt(a, c) and without Pt(b, d)

Fig.7 Photocurrent response of P7O-4N(a) and P7O-2N-2N(b) at applied voltages of 0 V(A) and -0.2 V(B)

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