基于电子顺磁共振的锌卟啉敏化TiO2光催化性机理的研究

为了研究锌卟啉/TiO₂复合光催化剂的光催化效率及电子转移问题, 本文采用溶胶凝胶法制备了锌卟啉/TiO₂的混合光催化材料, 并利用紫外可见光谱、电子顺磁共振谱对锌卟啉/TiO₂复合光催化剂进行了表征与分析. 采用溶胶凝胶法制备了锌卟啉-TiO₂的混合光催化材料, 通过比较纯P25型TiO₂和掺入质量比分别为0.2%, 0.5%, 0.9%锌卟啉敏化剂的锌卟啉/TiO₂混合光催化材料的紫外可见光谱图可知, 加入适量锌卟啉敏化剂可提高TiO₂对甲基橙溶液的降解效率, 过多的掺入锌卟啉敏化剂会导致TiO₂表面被敏化剂覆盖, 从而影响了其对光子的吸收, 降低TiO₂的光催化效率, 降低TiO₂的光降解率, 甚至低于纯TiO₂的光降解率. 应用电子顺磁共振技术对锌卟啉敏化TiO₂光催化剂的光催化机理进行了合理的解释, 当使用紫外可见光源对粉末样品进行辐照时, 锌卟啉受光辐照产生的激发态电子促进具有强氧化性的Ti³⁺和超氧根自由基的生成, 从而有效的促进了光生空穴-电子对的分离, 提高了TiO₂的光催化性能.

Study on the photocatalytic mechanism of tio2 sensitized by zinc porphyrin

We have investigated the photocatalysis efficiency and electron transfer of the znic prophyrin/TiO₂ composite photocatalyst, a sensitised hybrid porphyrin material, and prepared it successfully by sol-gel method. The UV-visible spectroscopy and electron paramagnetic resonance spectra are used to analyze and characterize the znic prophyrin/TiO₂ composite photocatalyst. The proportions 0%, 0.2%, 0.5% and 0.9% (mass ratio) of zinc porphyrin, and the photocatalytic mechanism of TiO₂ sensitized by zinc porphyrin are reasonably explained by ultraviolet visible spectroscopy and electron paramagnetic resonance spectroscopy (EPR). Different samples' UV-visible spectra show that the degradation efficiency of methyl orange solution by TiO₂ may be improved via adding appropriate amount of zinc porphyrin sensitizer. Prohibitive incorporation of the sensitizer would cause excess of particles in the mixed catalyst, leading to the TiO₂ surface covered by the sensitizer, thus affecting the absorption of photons, and the light degradation rate of TiO₂ may be lowered, even lower than the pure TiO₂. EPR spectra show the excited state of electrons in zinc prophyrin generated by irradiation of light can promote the generation of Ti³⁺ with strong oxidizing and superoxide radicals when using UV-visible light to irradiate the powder samples, thus effectively enhancing the separation of photogenerated electron-hole pairs, and improving the photocatalytic performance of TiO₂.