可见光响应Fe3+-聚酰亚胺网络的合成及光诱导自由基聚合

doi:10.1016/S1872-2067(20)63610-5

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 141-151.DOI: 10.1016/S1872-2067(20)63610-5

可见光响应Fe³⁺-聚酰亚胺网络的合成及光诱导自由基聚合

丁钢^a^,^b, 王秦^a, 刘飞^a, 淡宜^a^,^#(), 江龙^a^,^*()

^a高分子材料工程国家重点实验室(四川大学), 四川大学高分子研究所, 四川成都610065
^b西南科技大学材料科学与工程学院, 四川绵阳621000

收稿日期:2020-02-29 接受日期:2020-04-12 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 淡宜,江龙
基金资助:
国家自然科学基金课题(51573109);高分子材料工程国家重点实验室(四川大学)自主课题(sklpme 2016-3-02, 2019-2-08);中央高校基本科研业务费专项资金

A novel iron-chelating polyimide network as a visible-light-driven catalyst for photoinduced radical polymerization

Gang Ding^a^,^b, Qin Wang^a, Fei Liu^a, Yi Dan^a^,^#(), Long Jiang^a^,^*()

^aState Key Laboratory of Polymer Materials Engineering of China (Sichuan University), Polymer Research Institute of Sichuan University, Chengdu 610065, Sichuan, China
^bSchool of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621000, Sichuan, China

Received:2020-02-29 Accepted:2020-04-12 Online:2021-01-18 Published:2021-01-18
Contact: Yi Dan,Long Jiang
About author:^#Tel: +86-28-85405410; Fax: +86-28-85402465; E-mail: danyi@scu.edu.cn
^*Tel: +86-28-85405410; Fax: +86-28-85402465; E-mail: jianglong@scu.edu.cn;
Supported by:
National Natural Science Foundations of China(51573109);State Key Laboratory of Polymer Materials Engineering(sklpme 2016-3-02, 2019-2-08);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

将清洁、安全的太阳能(尤其是可见光)转化为化学能以合成高分子材料, 一直是光催化领域的研究热点和难点. 其关键问题是发展新型光催化材料, 提升其在高分子合成环境下的光催化活性及稳定性. 由于共轭微孔聚合物网络的独特优点, 例如光电性能易调控、比表面积高以及结构相对稳定等, 在光催化领域应用日益广泛. 与其它共轭微孔聚合物网络相比, 聚酰亚胺网络具有更高的光稳定性和耐化学腐蚀能力; 同时, 可用于合成聚酰亚胺网络的单体丰富, 合成方法可靠, 易于从分子层面调控其光电活性, 提升其光催化活性. 由于以上优点, 基于聚酰亚胺网络的光催化体系在光诱导合成高分子材料领域展现出良好的应用前景. 然而在实际应用中, 聚酰亚胺网络却面临光催化活性不足的困扰. 为解决此问题, 本研究组曾设计, 合成了以4,4',4''-三氨基三苯胺为核的聚酰亚胺网络, 利用4,4',4''-三氨基三苯胺的给电子能力, 促进聚酰亚胺网络中光生电子/空穴对的分离, 有效提升了聚酰亚胺网络在可见光作用下对水相中有机污染物的光降解效率.
在已有工作的基础上, 本文设计、合成出一种新型聚酰亚胺网络, 并通过配位作用, 在聚酰亚胺网络网络中引入Fe³⁺离子掺杂, 提升其光催化性能, 在有机环境中实现可见光诱导自由基聚合. 首先, 以三聚氰胺为电子给体单元, 以1,4,5,8-萘四甲酸二酐为电子受体单元, 通过酰亚胺缩聚反应构建出含电子给体-受体交替结构的聚酰亚胺网络(MPI); 然后, 通过浸渍法将Fe³⁺离子引入到MPI网络内, 制备出Fe³⁺-聚酰亚胺网络(Fe@MPI). 通过傅里叶变换红外光谱, 粉末X射线衍射(XRD)和X射线光电子能谱对Fe@MPI的结构进行表征. 结果显示, Fe³⁺主要通过配位键的形式与MPI网络结合. 同时, 结合XRD谱图与扫描电子显微镜和透射电子显微镜结果可见, Fe³⁺并非以氧化物或其它铁盐的形式简单地沉积在聚酰亚胺网络上, 而是以Fe³⁺-MPI配位作用均匀分布在MPI网络内. 此外, XRD及氮气吸附实验结果表明, 引入Fe³⁺会破坏MPI网络的有序程度, 导致复合材料的结晶度下降, 但并不影响其多孔结构. 通过紫外漫反射光谱和光电流谱对Fe@MPI的光吸收能力和光生电子/空穴对分离能力进行表征, 结果显示, MPI网络与Fe³⁺配位后, 其光谱响应范围可拓宽至1250 nm, 而其光电流响应强度也较纯MPI提升了3.5倍, 表明引入Fe³⁺配位可有效促进光生电子/空穴对的分离. 基于其优异的光电性能, 我们以Fe@MPI为光催化剂, 在30 °C下实现了甲基丙烯酸甲酯的可见光诱导自由基聚合, 制备出分子量可达31.3 × 10 ⁴ g mol^-1的聚甲基丙烯酸甲酯. 同时, 与MPI和FeCl₃相比, Fe@MPI在相同条件下具有更高的催化效率, 与其光电性能相吻合. 最后, 催化剂回收、循环实验表明, Fe@MPI易于回收, 且具有良好的结构和性能稳定性: 四次循环实验后, 其结构和光催化活性均可基本保持不变.

关键词: 可见光, 光聚合, 聚酰亚胺基光催化剂, 铁离子配位

Abstract:

With the aim of developing a low-cost and efficient visible-light-driven photocatalyst for radical polymerization, iron-chelating polyimide networks (Fe@MPI) was fabricated by firstly synthesizing photoactive melamine-containing polyimide (MPI) networks and then incorporating Fe(III) cations into the polymer networks. Fe@MPI exhibits a wide absorption spectrum ranging from 220 to 1250 nm and 3.5 times higher photocurrent intensity as compared with the pristine MPI. Based on its excellent photo-electric properties, Fe@MPI was employed as a recyclable heterogeneous catalyst, providing sufficient activity for the visible-light driven radical polymerization to synthesize poly(methyl methacrylate) with molecular weight up to 31.3 × 10 ⁴ g/mol. Taking advantage of the heterogeneous nature of the catalyst, Fe@MPI could be facilely regenerated from the polymerization solution by filtration without an obvious loss of its activity. This research provides a novel recyclable catalyst for visible-light driven radical polymerization.

Key words: Visible-light, Photopolymerization, Polyimide photocatalyst, Iron chelating

丁钢, 王秦, 刘飞, 淡宜, 江龙. 可见光响应Fe³⁺-聚酰亚胺网络的合成及光诱导自由基聚合[J]. 催化学报, 2021, 42(1): 141-151.

Gang Ding, Qin Wang, Fei Liu, Yi Dan, Long Jiang. A novel iron-chelating polyimide network as a visible-light-driven catalyst for photoinduced radical polymerization[J]. Chinese Journal of Catalysis, 2021, 42(1): 141-151.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63610-5

https://www.cjcatal.com/CN/Y2021/V42/I1/141

图/表 12

Fig. 1. (a) Schematic diagram of the synthesis of MPI and Fe@MPI; (b) full FT-IR spectra of NTCDA, melamine, MPI and Fe@MPI; (c) the zoom-in FT-IR spectra of MPI and Fe@MPI.

Fig. 2. XRD patterns of MPI and Fe@MPI.

Fig. 3. XPS survey spectra (a) and high-resolution XPS spectra of Fe 2p (b), C 1s (c), O 1s (d) and N 1s (e) of MPI and Fe@MPI.

Fig. 4. SEM (a) and TEM (b) and HRTEM (c-d) images and the insert is FFT of the chosen area of Fe@MPI; (e) N2 adsorption-desorption isotherm of Fe@MPI at 77 K; (f) the corresponding pore size distribution.

Fig. 5. SEM-EDS mapping images of Fe@MPI for C, N, Fe and O elements.

Fig. 6. (a) UV-vis absorption spectra and photograph (inset) of MPI and Fe@MPI; (b) photocurrent transient response of MPI and Fe@MPI.

Table 1 Results from photopolymerizations of MMA using different catalysts.

No.	Catalyst	[M]₀/[C]₀	Conv. (%)	Mn(10⁴g mol^-1)	MWD
1	—	100/0	0.2	—	—
2	FeCl₃	100/1	5.6	—	—
3	MPI	100/1	14.9	12.1	2.0
4	Fe@MPI	100/1	21.7	31.3	2.2

Fig. 7. The tauc plot (a) and the Mott-Schottky plot (b) of Fe@MPI, (c) The band structure of Fe@MPI.

Fig. 8. (a) The monomer conversion vs. time plots for the polymerization of MMA in the presence of different catalyst; (b) the radical quenching experiments of Fe@MPI-induced photo-polymerization; (c) EPR spectra of the .dioxane solution of Fe@MPI/triethylamine before and after light irradiation; (d) schematic diagram of the radical generation mechanism during the photo-irradiation of Fe@MPI in the presence of triethylamine (Et3N).

Fig. 9. Four successive photopolymerization kinetic plots of MMA using Fe@MPI as photocatalyst.

Fig. 10. FT-IR (a) and XRD (b) patterns of original and cycled-used Fe@MPI; (c) Fe 2p core-level XPS spectra of cycle-used Fe@MPI; (d) SEM-EDX mapping images of cycle-used Fe@MPI for C, N, Fe and O elements.

Table 2 Elemental percentage of C, N, O and Fe present in Fe@MPI before and after 4 successive recycle runs.

Sample	C (%)	N (%)	O (%)	Fe (%)
original Fe@MPI	53.82	17.62	20.42	6.48
cycle-used Fe@MPI	54.89	17.03	20.67	6.23

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可见光响应Fe³⁺-聚酰亚胺网络的合成及光诱导自由基聚合

A novel iron-chelating polyimide network as a visible-light-driven catalyst for photoinduced radical polymerization

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