Li Sizhe, Yin Jie, Zhang Hao, Zhang Kai A I
Department of Materials Science, Fudan University, 200433 Shanghai, P. R. China.
ACS Appl Mater Interfaces. 2023 Jan 18;15(2):2825-2831. doi: 10.1021/acsami.2c16581. Epub 2023 Jan 4.
Oxidative formation of high value compounds involving active oxygen species using heterogeneous polymeric photocatalysts has become a useful tool in catalysis. Controlling the interaction between the active sites on polymer photocatalysts and oxygen molecules is still challenging due to the rather large polymer backbone structure. Here, we design a triazine-containing donor acceptor-type conjugated microporous polymer (CMP) containing dual major active sites at F and N atoms for molecular oxygen activation. Introducing fluorine atoms on the CMP backbone led to a combined effect of enhanced adsorption and electron transfer of oxygen. Time-resolved photoluminescence, electronic paramagnetic resonance spectra, and DFT calculation revealed favorable absorption energy and electron transfer kinetics between the CMP and oxygen molecules, thus efficiently generating superoxide radicals (O) and singlet oxygen (O) as main active oxygen species. The photocatalytic activity, selectivity, and reusability of the CMP was demonstrated by the photocatalytic formation of a variety of benzothiazoles.
使用多相聚合物光催化剂通过活性氧物种进行高价值化合物的氧化形成已成为催化领域的一种有用工具。由于聚合物主链结构相当大，控制聚合物光催化剂上的活性位点与氧分子之间的相互作用仍然具有挑战性。在此，我们设计了一种含三嗪的供体-受体型共轭微孔聚合物（CMP），其在F和N原子处含有两个主要活性位点用于分子氧活化。在CMP主链上引入氟原子导致氧的吸附和电子转移增强的综合效应。时间分辨光致发光、电子顺磁共振光谱和密度泛函理论计算表明CMP与氧分子之间具有良好的吸收能量和电子转移动力学，从而有效地产生超氧自由基（O）和单线态氧（O）作为主要活性氧物种。通过多种苯并噻唑的光催化形成证明了CMP的光催化活性、选择性和可重复使用性。
