D-A共轭聚合强化光电性能及光催化CO2转化

doi:10.16085/j.issn.1000-6613.2023-1463

化工进展 ›› 2024, Vol. 43 ›› Issue (1): 292-301.DOI: 10.16085/j.issn.1000-6613.2023-1463

• 专栏：化工过程强化 • 上一篇

D-A共轭聚合强化光电性能及光催化CO₂转化

于笑笑¹(), 巢艳红¹, 刘海燕¹, 朱文帅²^,³(), 刘植昌²

^1.中国石油大学（北京）理学院，北京 102249
^2.中国石油大学（北京）化学工程与环境学院，北京 102249
^3.江苏大学化学化工学院, 江苏镇江 212013

收稿日期:2023-08-21 修回日期:2023-11-01 出版日期:2024-01-20 发布日期:2024-02-05
通讯作者: 朱文帅
作者简介:于笑笑（1991—），女，博士，副教授，研究方向为CO2催化转化。E-mail：xiaoxiaoyu@cup.edu.cn。
基金资助:
国家自然科学基金(22178154);中国石油大学（北京）科学基金(2462023QNXZ009);重质油全国重点实验室自主研究项目(2023-12);海南省水环境污染治理与资源化重点实验室(SHJKFKT202306)

Enhanced photoelectric properties and photocatalytic CO₂ conversion by D-A conjugated polymerization

YU Xiaoxiao¹(), CHAO Yanhong¹, LIU Haiyan¹, ZHU Wenshuai²^,³(), LIU Zhichang²

^1.College of Science, China University of Petroleum (Beijing), Beijing 102249, China
^2.College of Chemical Engineering and Environment, China University of Petroleum (Beijing), Beijing 102249, China
^3.School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2023-08-21 Revised:2023-11-01 Online:2024-01-20 Published:2024-02-05
Contact: ZHU Wenshuai

摘要/Abstract

摘要：

2,6-二溴蒽醌（2,6-dibromoanthraquinone，AQ）分别与三(4-乙炔苯基)胺（tris(4-ethynylphenyl)amine，TEA）和1,3,5-三乙炔基苯（1,3,5-triethynylbenzene，TEB），通过Sonogashira偶联反应制备得到两种蒽醌功能化的给体-受体（D-A）共轭聚合物催化剂（AQ-TEA和AQ-TEB）。采用FTIR、XPS、XRD和TEM 对其化学结构和形貌进行了表征。通过固体紫外/可见漫反射光谱、稳态荧光光谱、时间分辨荧光光谱和电化学表征探究了两种催化材料的光学和电学性能。结果表明，三(4-乙炔苯基)胺与2,6-二溴蒽醌构筑的AQ-TEA表现出更强的可见光吸收和电荷转移性能。研究了两种光催化剂在H₂O环境下光还原CO₂的催化性能。特别是AQ-TEA表现出更好的光催化性能，其CO的生成速率为392μmol/(g·h)，是AQ-TEB的1.8倍。基于实验和理论计算的结果，推测共轭聚合物中强的分子内电荷转移（intramolecular charge transfer，ICT）可促进其光吸收、光电转换和光催化效率的提升。本研究为设计和制备高效的光催化活性共轭聚合物催化剂提供了新的思路。

关键词: 聚合物, 催化剂, 光化学, 二氧化碳

Abstract:

Herein, two anthraquinone-functionalized donor-acceptor (D-A) conjugated polymeric catalysts (AQ-TEA and AQ-TEB), were prepared via Sonogashira cross-coupling of 2,6-dibromoanthraquinone (AQ) with tris(4-ethynylphenyl)amine (TEA) and 1,3,5-triethynylbenzene (TEB), respectively. The chemical structures and morphologies of the catalysts were characterized by FTIR, XPS, XRD and TEM. The optical and electronic properties of two catalysts were investigated by solid UV/Vis diffuse reflectance spectroscopy, steady-state fluorescence spectroscopy, time-resolved fluorescence spectroscopy, and electrochemical characterization. The results indicated that AQ-TEA derived from 2,6-dibromoanthraquinone and tris(4-ethynylphenyl)amine exhibited stronger visible-light absorption and charge-transfer performance. The catalytic performance of two photocatalysts for the photoreduction of CO₂ in the presence of H₂O was studied. AQ-TEA showed better performance, with a CO production rate of 392μmol/(g·h), which was 1.8 times that of AQ-TEB. Based on the results of experiments and theoretical calculations, we deduced that the strong intramolecular charge transfer (ICT) in the conjugated polymers could promote their light absorption, photoelectric conversion and photocatalytic performance. This work provides a new insight into design and fabrication of active conjugated polymeric catalysts with high photocatalytic efficiency for solar-energy conversion.

Key words: polymers, catalyst, photochemistry, carbon dioxide

中图分类号:

O643.3

于笑笑, 巢艳红, 刘海燕, 朱文帅, 刘植昌. D-A共轭聚合强化光电性能及光催化CO₂转化[J]. 化工进展, 2024, 43(1): 292-301.

YU Xiaoxiao, CHAO Yanhong, LIU Haiyan, ZHU Wenshuai, LIU Zhichang. Enhanced photoelectric properties and photocatalytic CO₂ conversion by D-A conjugated polymerization[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 292-301.

图/表 11

图1 两种D-A共轭聚合物的结构设计与合成过程示意图

图2 两种D-A共轭聚合物的化学结构表征

图3 两种D-A共轭聚合物的晶型和形貌结构表征

图4 两种D-A共轭聚合物的光吸收及带隙结构表征

图5 两种D-A共轭聚合物在0.2mol/L Na2SO4（pH=6.8）中的Motto-Schottky曲线图及带隙结构

图6 两种D-A共轭聚合物的PL及TRFDS光谱

图7 两种D-A共轭聚合物的瞬时光电流响应和EIS光谱[在暗处/光照条件下，0.2mol/L的Na2SO4电解质溶液（pH=6.8）中，0.01V偏压（vs. Ag/AgCl）]

图8 AQ-TEA和AQ-TEB的模型化合物M-1和M-2及其HOMO与LUMO轨道图

图9 各种反应条件下CO2还原反应的光催化效率及AQ-TEA的循环测试

表1 光催化CO2还原制CO催化剂

催化剂	波长/nm	添加剂	产CO效率/ μmol·g^-1·h^-1	参考文献
40NU@FNBZ	>420	H₂O	18.78	[40]
TAPBB-COF	>200, 60℃	H₂O	24.6	[41]
CB-COP-mpd	>420	H₂O	191.46	[42]
P₃HT/TiO₂/RePc226	>500	H₂O，16.7% TEOA（体积分数）	138.9	[43]
CoPor-DBBP	>400	H₂O∶MeCN∶TEA= 4∶1∶2	286.7	[44]
AQ-TEA	>300	H₂O，16.7% TEOA（体积分数）	392	本工作

图10 AQ-TEA光催化CO2还原可能的机理

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D-A共轭聚合强化光电性能及光催化CO₂转化

Enhanced photoelectric properties and photocatalytic CO₂ conversion by D-A conjugated polymerization

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