不同物相TiO2对H2O2/O3氧化效能的影响

doi:10.11949/j.issn.0438-1157.20141858

摘要/Abstract

摘要：

研究了不同物相TiO₂对H₂O₂/O₃氧化效能的影响,目标有机物为羟基自由基探针化合物乙酸。结果表明,在初始pH为7.0和10.0时,加入TiO₂反而降低了H₂O₂/O₃的氧化效率,其中锐钛矿TiO₂比金红石TiO₂的减弱作用更为明显。当初始pH为3.0时,金红石TiO₂能显著提高H₂O₂/O₃的氧化效率,但锐钛矿TiO₂影响不明显。机理分析表明,H₂O₂浓度及其衰减速率与乙酸的去除效率有很大的相关性。在pH为7.0和10.0时,两种物相TiO₂均能加快H₂O₂的分解,其中锐钛矿TiO₂作用更为显著。此条件下HO₂^-能有效引发臭氧分解产生羟基自由基,故H₂O₂过快分解反而降低了乙酸的去除效果。在pH为3.0时,H₂O₂去质子化反应困难,故O₃/H₂O₂氧化效率极低,H₂O₂浓度也几乎不变。加入TiO₂能明显提高H₂O₂的分解速率,相比金红石TiO₂,锐钛矿TiO₂使H₂O₂在5 min内基本分解完毕,但其对H₂O₂/O₃氧化效率几乎没有影响。饱和臭氧水分解速度的批处理实验也有相似的结果。由此可见,合适引发剂浓度可能是保证臭氧类高级氧化技术较高效率的关键,否则只会导致氧化剂的无效过快分解。利用氯化硝基四氮唑蓝法对比分析了酸性条件下H₂O₂/O₃、锐钛矿TiO₂/H₂O₂/O₃和金红石TiO₂/H₂O₂/O₃体系产生超氧自由基(·O₂^-)的量,其大小顺序为:H₂O₂/O₃< 金红石TiO₂/H₂O₂/O₃< 锐钛矿TiO₂/H₂O₂/O₃,这与前面结果吻合很好。

关键词: 臭氧, 双氧水, 氧化, 催化剂, 二氧化钛, 物相, 自由基

Abstract:

The oxidation efficiency of H₂O₂/O₃ catalyzed by titanium dioxide (TiO₂) for acetic acid (HAc) degradation, a probe compound for hydroxyl radical in ozonation, was investigated, with a focus on the effect of TiO₂ crystal phase. The results indicated that the addition of TiO₂ showed negative effect on the oxidation efficiency when the initial pH was at 7.0 and 10.0, and among all crystal phases of TiO₂ anatase had the biggest negative effect. However, when the initial pH was at 3.0, rutile could significantly improve the oxidation efficiency of the H₂O₂/O₃ system, and anatase had negligible effect. The mechanism study showed that there existed a good correlation between degradation rate of HAc and concentration of H₂O₂ (or its decomposition rate). Both anatase and rutile could accelerate decomposition of H₂O₂ at initial pH of 7.0 and 10.0, and faster was for the former than the latter. Too high decomposition rate of H₂O₂ could reduce removal rate of HAc at the two pH, because the conjugate base HO₂^- of H₂O₂ generated could react with ozone to effectively produce hydroxyl radicals (·OH). At initial pH 3.0, the oxidation efficiency of H₂O₂/O₃ system was very low due to the difficulty of H₂O₂ deprotonation, so the concentration of H₂O₂ had almost no change. Addition of TiO₂ could markedly accelerate the decomposition rate of H₂O₂, including deprotonation step, and anatase made H₂O₂ decomposition finish in 5 min and too fast, leading to have no effect on the oxidation efficiency. However, rutile had no such high decomposition rate for H₂O₂ and could generate HO₂^--similar species which could react with ozone to produce hydroxyl radicals (·OH) to degrade acetic acid. The batch test carried out also gave a similar result. Therefore, it can be concluded that suitable initiator and its concentration may play an important role in ozone-based advanced oxidation process, and that too high concentration of initiator might lead to rapid consumption of oxidants. The amounts of superoxide ion radical (·O₂^-) in H₂O₂/O₃, anatase TiO₂/H₂O₂/O₃ and rutile TiO₂/H₂O₂/O₃ systems were determined by capturing method of Nitro Blue Tetrazolium Chloride (NBT), the order was as follows: H₂O₂/O₃< rutile TiO₂/H₂O₂/O₃< anatase TiO₂/H₂O₂/O₃, which was in accord with the results of the results of HAc degradation.

Key words: ozone, hydrogen peroxide, oxidation, catalyst, titanium dioxide, crystal phase, radical

中图分类号:

X703

倪金雷, 彭若帆, 童少平, 马淳安. 不同物相TiO₂对H₂O₂/O₃氧化效能的影响[J]. 化工学报, 2015, 66(10): 3950-3956.

NI Jinlei, PENG Ruofan, TONG Shaoping, MA Chun'an. Effect of TiO₂ crystal phase on oxidation efficiency of H₂O₂/O₃[J]. CIESC Journal, 2015, 66(10): 3950-3956.

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不同物相TiO₂对H₂O₂/O₃氧化效能的影响

Effect of TiO₂ crystal phase on oxidation efficiency of H₂O₂/O₃

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