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New hybrid materials based on halogenated metalloporphyrins for enhanced visible light photocatalysis

机译：基于卤化金属卟啉的新型杂化材料可增强可见光光催化作用

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Photophysical and photochemical studies on 5,10,15,20-tetrakis(2,6-difluoro-5-N-methylsulfamylophenyl)porphyrin (F(2)PMet) and its cobalt(III) and zinc(II) complexes, including spectroscopic characteristics, photostability and photocatalytic activity, were carried out. The hybrid materials resulting from adsorption of these tetrapyrroles at the surface of titanium dioxide were prepared and examined in terms of their morphological, optical and functional properties applying absorption spectroscopy, scanning electron microscopy (SEM), photoelectrochemistry and photocatalytic tests. Our studies revealed that MF(2)PMet@TiO2 photocatalysts can be considered as the hybrid organic/inorganic photoactive materials enabling photodegradation of a synthetic opioid such as tramadol hydrochloride (TRML) and a model pollutant, 4-chlorophenol, in aqueous solution under visible light irradiation (lambda > 400 nm). To elucidate mechanisms of photochemical processes, the photocatalytic activity of investigated metalloporphyrins was compared in homo- and heterogeneous systems. The results indicate that impregnation of TiO2 (P25) with functionalized porphyrins can improve its photoactivity. ZnF(2)PMet@TiO2 exhibited a superior photocatalytic performance towards TRML degradation. The role of singlet oxygen and hydroxyl radicals in photodegradation processes has been elucidated both for MF(2)PMet and MF(2)PMet@TiO2 systems.
机译：对5,10,15,20-四（2,6-二氟-5-N-甲基磺酰胺基苯基）卟啉（F（2）PMet）及其钴（III）和锌（II）配合物的光物理和光化学研究，包括光谱进行了特性，光稳定性和光催化活性。制备了由这些四吡咯在二氧化钛表面上吸附产生的杂化材料，并通过吸收光谱，扫描电子显微镜（SEM），光电化学和光催化测试对其形态，光学和功能性质进行了研究。我们的研究表明，MF（2）PMet @ TiO2光催化剂可以被认为是有机/无机杂化光敏材料，能够在可见光下水溶液中降解合成阿片类药物，例如盐酸曲马多（TRML）和模型污染物4-氯苯酚。光照射（λ> 400 nm）。为了阐明光化学过程的机理，在均相和异相系统中比较了所研究的金属卟啉的光催化活性。结果表明，用功能化的卟啉浸渍TiO2（P25）可以改善其光活性。 ZnF（2）PMet @ TiO2对TRML降解表现出优异的光催化性能。 MF（2）PMet和MF（2）PMet @ TiO2系统均已阐明了单线态氧和羟基自由基在光降解过程中的作用。

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