State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, PR China.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, PR China.
J Colloid Interface Sci. 2023 Jul 15;642:648-657. doi: 10.1016/j.jcis.2023.03.196. Epub 2023 Apr 3.
Conjugated microporous polymers (CMPs) have been considered a type of promising visible-light-driven, organic photocatalysts. However, apart from designing high-performance CMPs from a molecular perspective, little attention is paid to improving the photocatalytic properties of these polymers through macrostructural regulation. Herein, we prepared a kind of hollow spherical CMPs involving carbazole monomers and studied their performance on the selective photocatalytic oxidation of benzyl alcohol under visible light irradiation. The results demonstrate that the introduction of a hollow spherical structure improves the physicochemical properties of the as-designed CMPs, including the specific surface areas, optoelectronic characteristics, as well as photocatalytic performance, etc. In particular, the hollow CMPs can more effectively oxidize benzyl alcohol compared to pristine ones under blue light illumination, and produce >1 mmol of benzaldehyde in 4.5 h with a yield of up to 9 mmol·g·h, which is almost 5 times higher than that of the pristine ones. Furthermore, such hollow architecture has a similar enhanced effect on the oxidation of some other aromatic alcohols. This work shows that the deliberate construction of specific macrostructures can better arouse the photocatalytic activity of the as-designed CMPs, which will contribute to the further use of these organic polymer semiconductors in photocatalysis areas.
共轭微孔聚合物(CMPs)被认为是一类很有前途的可见光驱动的有机光催化剂。然而,除了从分子角度设计高性能的 CMPs 外,通过宏观结构调控来提高这些聚合物的光催化性能还没有得到太多关注。本文制备了一种包含咔唑单体的空心球形 CMPs,并研究了它们在可见光照射下选择性催化氧化苄醇的性能。结果表明,引入空心球形结构提高了所设计的 CMPs 的物理化学性质,包括比表面积、光电特性以及光催化性能等。特别是,与原始 CMPs 相比,空心 CMPs 在蓝光照射下更有效地氧化苄醇,在 4.5 小时内产生了超过 1mmol 的苯甲醛,产率高达 9mmol·g·h,几乎是原始 CMPs 的 5 倍。此外,这种空心结构对一些其他芳香醇的氧化也有类似的增强效果。这项工作表明,刻意构建特定的宏观结构可以更好地激发所设计的 CMPs 的光催化活性,这将有助于进一步将这些有机聚合物半导体应用于光催化领域。