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铈掺杂 MCM-48(Ce-MCM-48)作为一种催化剂,用于抑制含溴水臭氧化过程中溴酸盐的形成:效果和机制。

Cerium incorporated MCM-48 (Ce-MCM-48) as a catalyst to inhibit bromate formation during ozonation of bromide-containing water: Efficacy and mechanism.

机构信息

Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing 100085, China.

Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing 100085, China.

出版信息

Water Res. 2015 Dec 1;86:2-8. doi: 10.1016/j.watres.2015.05.052. Epub 2015 Jun 4.

Abstract

The composite mesoporous sieve Ce-MCM-48 (cerium incorporated MCM-48) with different Si/Ce molar ratios were synthesized hydrothermally and characterized with X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area, and pHpzc. Results indicate that Ce-MCM-48, especially with a Si/Ce molar ratio of 66 (i.e., Ce66-MCM-48), could significantly inhibit bromate (BrO3(-)) formation during ozonation of Br(-)-containing water, achieving 91% of inhibition efficiency at pH 7.6 and 25 °C. An acidic or alkaline pH decreased the inhibition efficiency of Ce66-MCM-48 to some extent, but reaction temperature ranging from 15 to 30 °C had no significant impact. By comparing the bromine mass balance, aqueous O3 decomposition, and newly formed H2O2 between O3 and O3/Ce66-MCM-48 processes, the inhibition mechanism was proposed: Ce66-MCM-48 promoted aqueous O3 decomposition to generate hydroxyl radicals (OH) that could merge into H2O2, so the oxidative transformation of Br(-) and HOBr/OBr(-) by O3 and OH was primarily suppressed. The catalytic ability of Ce66-MCM-48 was continuously regenerated through the circulating reactions between Ce(III) and Ce(IV) occurring on the catalyst surface. Besides its inhibition on BrO3(-) formation, Ce66-MCM-48 could also enhance the degradation of refractory organic micropollutants. Because of these distinct merits, Ce66-MCM-48 has potential applications to water treatment by ozone.

摘要

合成了不同 Si/Ce 摩尔比的复合介孔分子筛 Ce-MCM-48(铈掺杂 MCM-48),并采用 X 射线衍射、X 射线光电子能谱、BET 比表面积和 pHpzc 对其进行了表征。结果表明,Ce-MCM-48,特别是 Si/Ce 摩尔比为 66(即 Ce66-MCM-48),在臭氧氧化含 Br-的水中时能显著抑制溴酸盐(BrO3(-))的形成,在 pH 7.6 和 25°C 时抑制效率达到 91%。酸性或碱性 pH 在一定程度上降低了 Ce66-MCM-48 的抑制效率,但反应温度在 15 至 30°C 范围内没有显著影响。通过比较臭氧和臭氧/Ce66-MCM-48 过程中的溴质量平衡、水相臭氧分解和新生成的 H2O2,提出了抑制机理:Ce66-MCM-48 促进水相臭氧分解生成羟基自由基(OH),这些 OH 可以合并成 H2O2,因此臭氧和 OH 对 Br(-)和 HOBr/OBr(-)的氧化转化主要受到抑制。Ce66-MCM-48 表面发生的 Ce(III)和 Ce(IV)循环反应,使催化剂的催化能力得以持续再生。除了抑制 BrO3(-)形成外,Ce66-MCM-48 还能增强难降解有机微污染物的降解。由于这些显著的优点,Ce66-MCM-48 有望在臭氧水处理中得到应用。

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