Department of Process Engineering and Chemical Technology, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland.
Department of Physics of Electronic Phenomena, Gdansk University of Technology, Poland.
Sci Total Environ. 2020 Jul 1;724:138167. doi: 10.1016/j.scitotenv.2020.138167. Epub 2020 Mar 28.
In the present study, susceptibility to photocatalytic degradation of etodolac, 1,8-diethyl-1,3,4,9 - tetrahydro pyran - [3,4-b] indole-1-acetic acid, which is a non-steroidal anti-inflammatory drug frequently detected in an aqueous environment, was for the first time investigated. The obtained p-type TiO-based photocatalyst coupled with zinc ferrite nanoparticles in a core-shell structure improves the separation and recovery of nanosized TiO photocatalyst. The characterization of ZnFeO/SiO/TiO, including XRD, XPS, TEM, BET, DR/UV-Vis, impedance spectroscopy and photocatalytic analysis, showed that magnetic photocatalyst containing anatase phase revealed markedly improved etodolac decomposition and mineralization measured as TOC removal compared to photolysis reaction. The effect of irradiation and pH range on photocatalytic decomposition of etodolac was studied. The most efficient degradation of etodolac was observed under simulated solar light for a core-shell ZnFeO/SiO/TiO magnetic photocatalyst at pH above 4 (pKa = 4.7) and below 7. The irradiation of etodolac solution in a broader light range revealed a synergetic effect on its photodegradation performance. After only 20 min of degradation, about 100% of etodolac was degraded. Based on the photocatalytic analysis in the presence of scavengers and HPLC analysis, the transformation intermediates and possible photodegradation pathways of etodolac were studied. It was found that ∙O attack on C2-C3 bond inside pyrrole ring results mostly in the hydroxylation of the molecule, which next undergoes -CHCOOH detachment to give 1,9-diethyl-3,4-dihydro-pyrano[3,4-b]indol-4a-ol. The obtained compound should further undergo subsequent hydropyran and pyrrole ring breaking to give a family of benzene derivatives.
在本研究中,首次研究了在水环境中频繁检测到的非甾体抗炎药依托度酸的光催化降解的易感性。所获得的 p 型 TiO 基光催化剂与锌铁氧体纳米粒子结合在核壳结构中,提高了纳米 TiO 光催化剂的分离和回收。ZnFeO/SiO/TiO 的表征,包括 XRD、XPS、TEM、BET、DR/UV-Vis、阻抗谱和光催化分析,表明含有锐钛矿相的磁性光催化剂在测量 TOC 去除时,与光解反应相比,显著提高了依托度酸的分解和矿化。研究了光照和 pH 范围对依托度酸光催化分解的影响。在 pH 值高于 4(pKa = 4.7)和低于 7 的条件下,模拟太阳光下,核壳 ZnFeO/SiO/TiO 磁性光催化剂对依托度酸的降解效果最佳。在更宽的光照范围内照射依托度酸溶液显示出对其光降解性能的协同效应。仅 20 分钟的降解后,约 100%的依托度酸被降解。基于存在清除剂的光催化分析和 HPLC 分析,研究了依托度酸的转化中间产物和可能的光降解途径。结果发现,在吡咯环内 C2-C3 键上的 ∙O 攻击主要导致分子的羟化,然后发生 -CHCOOH 脱离,生成 1,9-二乙基-3,4-二氢-吡喃[3,4-b]吲哚-4a-醇。所得化合物应进一步经历随后的氢吡喃和吡咯环断裂,以生成一系列苯衍生物。