Imrich T, Neumann-Spallart M, Krýsa J
Department of Inorganic Technology, University of Chemistry and Technology Prague, Technická 5, 16628, Prague 6, Czech Republic.
Photochem Photobiol Sci. 2023 Feb;22(2):419-426. doi: 10.1007/s43630-022-00324-x. Epub 2022 Nov 1.
The photoelectrochemical degradation of selected aromatic substances, acid orange 7 (AO7), salicylic acid (SA), benzoic acid (BA), and 4-chlorophenol (4-CP) was studied on hematite (α-FeO) and compared with titanium dioxide (TiO), both deposited as thin films on conducting substrates (FTO/glass). Batch type reactors were used under backside and front side illumination. Electrical bias was applied on the semiconducting electrodes, such that only valence band processes leading to oxidative pathways were followed. The initial Faradaic efficiency, f, of degradation processes was determined from the UV-Vis absorbance decrease of the starting materials. f for 1 mM AO7 degradation in 0.01 M sulphuric acid was found to be 7.5%. When the pH of the solution was neutral (pH 7.2) or alkaline (pH 13), f decreased to 1.7%. For 1 mM SA, f was 6.2% on hematite photoanodes and 6.1% on titanium dioxide. For 1 mM benzoic acid and 4-chlorophenol, f was an order of magnitude lower, but only on hematite. This is ascribed to the lack of OH· radical formation on hematite, which seems to be essential for the photooxidation of these compounds.
研究了在赤铁矿(α-Fe₂O₃)上对选定的芳香族物质(酸性橙7(AO7)、水杨酸(SA)、苯甲酸(BA)和4-氯苯酚(4-CP))进行的光电化学降解,并与二氧化钛(TiO₂)进行了比较,二者均以薄膜形式沉积在导电基底(FTO/玻璃)上。在背面和正面光照条件下使用间歇式反应器。对半导体电极施加电偏压,以便仅追踪导致氧化途径的价带过程。降解过程的初始法拉第效率f由起始原料的紫外-可见吸光度降低来确定。发现在0.01 M硫酸中1 mM AO7降解的f为7.5%。当溶液的pH为中性(pH 7.2)或碱性(pH 13)时,f降至1.7%。对于1 mM SA,在赤铁矿光阳极上f为6.2%,在二氧化钛上为6.1%。对于1 mM苯甲酸和4-氯苯酚,f低一个数量级,但仅在赤铁矿上如此。这归因于赤铁矿上缺乏羟基自由基的形成,而羟基自由基的形成似乎对于这些化合物的光氧化至关重要。