单原子取代调控三(4-乙炔基苯基)胺类共轭多孔聚合物的光催化水分解析氢性能

doi:10.6023/cjoc202603040

有机化学 ›› 2026, Vol. 46 ›› Issue (10): 4077-4086.DOI: 10.6023/cjoc202603040 上一篇下一篇

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单原子取代调控三(4-乙炔基苯基)胺类共轭多孔聚合物的光催化水分解析氢性能

杜俊平^*(), 井森彪, 张鲜放, 韩莉锋, 张捷, 王诗文, 陈俊利, 绪连彩^*()

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河南省环己醇催化分离工程研究中心郑州 450002

收稿日期:2026-03-30 修回日期:2026-05-18 发布日期:2026-07-06
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科研基金(2013BSJJ017)

Efficient Modulation of Photocatalytic Water Splitting Hydrogen Evolution Performance for Tris(4-ethynylphenyl)amine-Based Conjugated Porous Polymers via Single-Atom Substitution

Junping Du^*(), Senbiao Jing, Xianfang Zhang, Lifeng Han, Jie Zhang, Shiwen Wang, Junli Chen, Liancai Xu^*()

Henan Cyclohexanol Catalytic Separation Engineering Research Center, Department of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002

Received:2026-03-30 Revised:2026-05-18 Published:2026-07-06
Contact:
^* Corresponding authors. E-mail: dujunping@zzuli.edu.cn;
miss_xulc@126.com;
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 Foundation of Zhengzhou University of Light Industry(2013BSJJ017)

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摘要/Abstract

光催化水分解制氢是实现太阳能高效转化利用、缓解目前环境与能源危机的理想途径之一. 新型、高性能且具备应用潜力的光催化剂, 是推动该技术走向实用化的关键. 分别以2,7-二溴-9-芴酮及其9-位被单原子硫取代的结构类似物3,7-二溴-5,5-二氧-二苯并噻吩作为共聚双官能团单体, 运用Sonogashira-Hagihara偶联反应, 制备得到两种三(4-乙炔基苯基)胺(TEA)类共轭多孔聚合物TEA-FON和TEA-DTS. 研究结果表明, 两种聚合物均表现出优异的溶剂稳定性、化学稳定性和热稳定性, 同时具备较高的比表面积; 无助催化剂存在下, 均展现出良好的光催化水分解制氢活性. 相同反应及测试条件下, TEA-FON的光催化析氢效率是TEA-DTS的1.5倍. 深入研究证实, 析氢效率差异源于共聚单体的单原子取代效应, 该取代效应有效调控了聚合物的光吸收性能、光生载流子分离能力及电荷迁移速率. 该研究证实通过共聚单体单原子取代效应能够实现TEA类共轭多孔聚合物的高效调控.

关键词: 单原子取代, 三(4-乙炔基苯基)胺, 共轭多孔聚合物, 光催化, 析氢

Photocatalytic water splitting hydrogen evolution has been widely recognized as one of the most promising strategies for the exploitation and utilization of solar energy, thereby alleviating the pressing environmental and energy crises. To realize this technology, one of the key factors is the development of novel, high-performance, and practically applicable photocatalysts. Herein, two tris(4-ethynylphenyl)amine (TEA)-based conjugated porous polymers (CPPs) TEA-FON and TEA-DTS have been synthesized via the Sonogashira-Hagihara coupling reaction with 2,7-dibromo-9-fluorenone and its structural analog 3,7-dibromo-5,5-dioxidodibenzothiophene which has been substituted at 9-position with single-atom sulfur as the difunctional comonomers, respectively. It has been demonstrated that both polymers possess excellent solvent, chemical, and thermal stabilities, along with a large specific surface area. More importantly, they exhibit remarkable photocatalytic hydrogen evolution activity even without the assistance of any cocatalysts. Notably, under identical reaction conditions, the hydrogen evolution rate (HER) of TEA-FON is 1.5 times higher than that of TEA-DTS. Further systematic investigations have revealed that the discrepancy in HER originates from the single-atom substitution, which efficiently modulates the light-harvesting efficiency, photogenerated carrier separation efficiency, and charge transfer rate of the polymers. It has suggested that photocatalytic performance of TEA-based CPPs can been modulated efficiently with the regulation of single-atom substitution of comonomers.

Key words: single-atom substitution, tris(4-ethynylphenyl)amine, conjugated porous polymer, photocatalysis, hydrogen evolution

引用此文

杜俊平, 井森彪, 张鲜放, 韩莉锋, 张捷, 王诗文, 陈俊利, 绪连彩. 单原子取代调控三(4-乙炔基苯基)胺类共轭多孔聚合物的光催化水分解析氢性能[J]. 有机化学, 2026, 46(10): 4077-4086.

Junping Du, Senbiao Jing, Xianfang Zhang, Lifeng Han, Jie Zhang, Shiwen Wang, Junli Chen, Liancai Xu. Efficient Modulation of Photocatalytic Water Splitting Hydrogen Evolution Performance for Tris(4-ethynylphenyl)amine-Based Conjugated Porous Polymers via Single-Atom Substitution[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4077-4086.

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图/表 16

图式1. 聚合物TEA-FON和TEA-DTS的合成路线

Scheme 1. Synthesis route of TEA-FON and TEA-DTS

Polymer	Color	Yield/%	T₅^a/℃	Elemental analysis (theoretical/experimental)
Polymer	Color	Yield/%	T₅^a/℃	C	H	N
TEA-FON	Red powder	91	363	89.89/82.47	3.63/4.88	2.83/2.22
TEA-DTS	Yellow powder	82	372	81.26/71.66	3.39/4.31	2.63/1.97

表1. 聚合物的合成与元素分析结果

Table 1. Synthetic and elemental analysis results of the polymers

图1. TEA及聚合物的红外光谱图

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

图2. (a, b)聚合物的XPS谱图; (c, d)聚合物C1s的高分辨率XPS谱图

Figure 2. (a, b) XPS survey spectrum of the polymers; (c, d) high resolution XPS of C1s for the polymers

图3. 聚合物的热失重曲线

Figure 3. Thermogravimetric analysis of the polymers

图4. 聚合物的粉末X射线衍射图

Figure 4. PXRD profile for the polymers

图5. 聚合物的SEM图(上)和TEM图(下)

Figure 5. SEM images (top) and TEM images (bottom) for the polymers

图6. 聚合物的紫外吸收光谱和Tauc曲线

Figure 6. UV-vis light absorption spectra and Tauc plots of the polymers

图7. 聚合物的光致发光光谱

Figure 7. Photoluminescence spectra of the polymers

图8. (a)双官能团单体模型化合物最优构象下反应位点电荷分布和(b)聚合物模型化合物优势构象下的二面角和关键角计算结果

Figure 8. (a) Charge distribution of reaction sites under optimal conformations of bifunctional monomer model compounds and (b) calculation results of dihedral angle and key angles under optimal conformations of polymer model compounds

图9. 聚合物的循环伏安曲线

Figure 9. Cyclic voltammetry curves of the polymers

Polymer	$E_{\mathrm{OX}}^{\text {onset }}$/V	$E_{\text {red }}^{\text {onset }}$/V	E_HOMO/eV	E_LUMO/eV	$E_{\mathrm{g}}^{\text {elec }}$ ^a/eV	$E_{\mathrm{g}}^{\mathrm{opt}}{\scriptsize }$ ^b/eV
TEA-FON	0.67	-0.47	-5.07	-3.93	1.14	2.27
TEA-DTS	0.59	-0.43	-4.99	-3.97	1.02	2.09

表2. 聚合物的光物理性能和电化学性能

Table 2. Electrochemical and photophysical properties of the polymers

图10. (a)聚合物的氮气吸附(实心符号)和脱附(空心符号)曲线, 以及(b)聚合物的孔径分布图

Figure 10. (a) N2 adsorption (filled symbols) and desorption (empty symbols) curves, and (b) pore size distribution of the polymers

Polymer	S_BET/(m²•g^-1)	V_micro/(cm³•g^-1)	V_total/(cm³•g^-1)	V_micro/V_total	HER
TEA-FON	452.24	0.12	0.29	0.42	129.73
TEA-DTS	513.35	0.15	0.31	0.46	84.3

表3. 聚合物的孔性能

Table 3. Porosity properties of the polymers

图11. (a)聚合物紫外光催化析氢效率和循环稳定性; (b)聚合物紫外光催化析氢效率和循环稳定性柱状图

Figure 11. (a) HERs and cycling stability of the polymers under UV/Vis light; (b) Bar chart for HERs and cycling stability of the polymers under UV/Vis light

图12. (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

Figure 12. (a) Time-dependent photocurrent curves and (b) electrochemical AC impedance curves of the polymers

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单原子取代调控三(4-乙炔基苯基)胺类共轭多孔聚合物的光催化水分解析氢性能

Efficient Modulation of Photocatalytic Water Splitting Hydrogen Evolution Performance for Tris(4-ethynylphenyl)amine-Based Conjugated Porous Polymers via Single-Atom Substitution

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