基于噻唑并噻唑的共价有机框架微球用于蓝光光催化胺的选择性需氧氧化

doi:10.1016/S1872-2067(22)64127-5

摘要/Abstract

摘要：

含有光活性单元的共价有机框架材料由于具有高结晶度、均匀的孔隙、大的比表面积以及较好的光电性能等优势, 已在可见光光催化领域引起了研究者们的广泛关注, 为氧气分子的活化提供了一种非金属的选择. 目前, 已有很多关于将光活性单元引入共价有机框架构建高效可见光光催化体系的报道. 作为一种典型的光活性单元, 具有缺电子性质的噻唑并噻唑基团有着稳定的共轭平面结构以及很好的氧化稳定性. 此外, 基于噻唑并噻唑的有机聚合物材料往往表现出较好的可见光吸收能力. 因此, 噻唑并噻唑单元在构建高效可见光光催化剂方面具有较好的应用潜力. 但是由于其涉及的反应过程可逆性低, 所以噻唑并噻唑很少被引入到共价有机框架中构建光催化体系. 为了克服该困难, 可以将噻唑并噻唑基团嵌入到具有良好可逆性端基基团的结构单元中再将其用于共价有机框架的构建.

根据该策略, 本文将噻唑并噻唑基团嵌入到二氨甲基联苯(BD)中, 得到了噻唑并噻唑基二苯胺(DTz). 在有机碱四氢吡咯的催化下, 利用溶剂热方法, 将三甲酰基间苯三酚(Tp)分别与BD和DTz组装, 成功制得两种β-酮烯胺连接的共价有机框架(TpBD-COF和TpDTz-COF), 并将其应用于可见光光催化胺的选择性氧化反应. 使用粉末晶体衍射、氮气吸脱附测试和扫描与透射电镜对两种共价有机框架进行表征. 结果表明, 两种共价有机框架均具有高结晶度、丰富的孔隙和大的比表面积, 且两者均呈现为微米球形貌, 这些性质为光化学反应的进行提供了较好的条件. 对两种共价有机框架材料进行光电性能测试, TpDTz-COF表现出了更高的电荷分离效率和载流子迁移率, 即TpDTz-COF作为光化学反应平台时, 光生电荷的产生与传输更快, 这将大大提升光化学反应速率.

TpDTz-COF在蓝光光催化胺的选择性氧化反应中表现出远高于TpBD-COF的光催化效率. 在1.7 h内, TpDTz-COF可以转化92%的苄胺, 而TpBD-COF仅能转化52%. 同时, TpDTz-COF具有很好的循环稳定性, 在四次循环测试后转化率降低不超过20%. 而且一系列含有不同取代基的苄胺以及杂环胺均能在蓝光下被TpDTz-COF催化转化为相应的亚胺产物. 通过捕获实验和电子自旋顺磁共振测试对反应过程中的活性氧物种以及反应机理进行了系统探究, 并提出了可能的反应机理. 综上, 本文展现了基于噻唑并噻唑的共价有机框架在设计高效光催化体系中的优势.

关键词: 共价有机框架, 噻唑并噻唑, 可见光, 光催化, 选择性氧化

Abstract:

Covalent organic frameworks (COFs) with photoactive units have attracted significant interest in visible light photocatalysis and can present a metal-free scenario for activating O₂. As a typical photoactive unit, thiazolo[5,4-d]thiazole (TzTz) has rarely been added to COFs. However, circumventing the low reversibility of TzTz, it could be embedded into the building blocks beforehand, along with other bonds like β-ketoenamine in forming COFs. TzTz was embedded into 1,1′-biphenyl-4,4′-diamine (BD) using this approach to produce 4,4′-(TzTz-2,5-diyl)dianiline (DTz). Under organobase-modulated solvothermal conditions, combining 1,3,5-triformylphloroglucinol (Tp) with BD and DTz resulted in the production of β-ketoenamine-linked TpBD-COF and TpDTz-COF. Both TpDTz-COF and TpBD-COF are microspheres. TpDTz-COF possessed more adequate separation and charge migration than TpBD-COF. This resulted in superior performance for the blue light photocatalytic selective oxidation of benzylamine with O₂. Furthermore, with O₂ as the main oxidant, a wealth of benzylamines could be converted into imines over TpDTz-COF. Mechanistic investigations substantiate that oxidation of benzylamines obeys an electron transfer pathway, in which superoxide anion (O₂^•-) is the crucial reactive oxygen species. This study highlights the superiority of TzTz-embedded COFs in developing effective photocatalytic systems for organic transformations.

Key words: Covalent organic framework, Thiazolo[5,4-d]thiazole, Visible light, Photocatalysis, Selective oxidation

张富林, 李霞, 董晓芸, 郝慧敏, 郎贤军. 基于噻唑并噻唑的共价有机框架微球用于蓝光光催化胺的选择性需氧氧化[J]. 催化学报, 2022, 43(9): 2395-2404.

Fulin Zhang, Xia Li, Xiaoyun Dong, Huimin Hao, Xianjun Lang. Thiazolo[5,4-d]thiazole-based covalent organic framework microspheres for blue light photocatalytic selective oxidation of amines with O₂[J]. Chinese Journal of Catalysis, 2022, 43(9): 2395-2404.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64127-5

https://www.cjcatal.com/CN/Y2022/V43/I9/2395

图/表 10

Fig. 1. Schematic illustration of TpDTz-COF and TpBD-COF.

Fig. 2. SEM images of TpDTz-COF (a) and TpBD-COF (b). TEM images of TpDTz-COF (c) and TpBD-COF (d).

Fig. 3. PXRD pattern of TpDTz-COF (a) and TpBD-COF (b). Nitrogen sorption isotherm of TpDTz-COF (c) and TpBD-COF (d).

Fig. 4. FTIR spectra of Tp, DTz, and TpDTz-COF (a) and Tp, BD, and TpBD-COF (b). (c) UV-vis DRS spectra of TpDTz-COF and TpBD-COF. (d) Optical bandgaps (Eg) calculated from the Kubelka-Munk formula.

Fig. 5. Mott-Schottky plots of TpDTz-COF (a) and TpBD-COF (b) at frequencies of 500, 1000, and 1500 Hz. (c) Photocurrent densities vs. time of TpDTz-COF (red) and TpBD-COF (blue). (d) EIS of TpDTz-COF (red) and TpBD-COF (blue).

Fig. 6. (a) Blue light photocatalytic oxidation of benzylamine over TpDTz-COF and TpBD-COF, reaction time: 1.7 h. (b) The influence of various light sources on the oxidation of benzylamine over TpDTz-COF. (c) Recycling stability of TpDTz-COF for the photocatalytic oxidation of benzylamine. (d) Control experiments for the selective oxidation of benzylamine over TpDTz-COF. Standard reaction conditions: COF (5 mg), CH3CN (1 mL), benzylamine (0.3 mmol), blue LEDs (460 ± 10 nm), O2 (0.1 MPa), and 1.3 h.

Table 1 Photocatalytic selective oxidation of primary amines into imines using O2 over TpDTz-COF a.

Entry	Conv.^b (%)	Sel.^b (%)
1	92	99
2	95	99
3	89	99
4	90	99
5	93	99
6	95	100
7	77	99
8	86	99
9	84	99
10	86	99
11	99	100
12	86	99

Table 2 Photocatalytic selective oxidation of secondary amines into imines with O2 over TpDTz-COF a.

Entry	Conv.^b (%)	Sel. ^b (%)
1	82	84
2	85	80
3	52	96
4	77	88
5	93	80

Fig. 7. (a) Quenching experiments to confirm the ROS for the photocatalytic selective oxidation of benzylamine with O2 over TpDTz-COF. The EPR spectra of electrons (b), O2•- (c), and 1O2 (d) generated by TpDTz-COF under blue light.

Fig. 8. A plausible mechanism for the blue light photocatalytic selective oxidation of benzylamine using O2 over TpDTz-COF.

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