Activation of Manganese Oxidants with Bisulfite for Enhanced Oxidation of Organic Contaminants: The Involvement of Mn(III)
Activation of Manganese Oxidants with Bisulfite for Enhanced Oxidation of Organic Contaminants: The Involvement of Mn(III)
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DOI：
10.1021/acs.est.5b03111
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发表时间：
2015-10-20
影响因子：
11.4
通讯作者：
Tratnyek, Paul G.
中科院分区：
文献类型：
--
作者：
Sun, Bo;Guan, Xiaohong;Tratnyek, Paul G.
MnO 4-被HSO 3-激活，导致以非常高的速率氧化有机污染物的过程。高锰酸盐/亚硫酸氢盐（PM/BS）工艺在pH（ini）5.0下氧化苯酚、环丙沙星和甲基蓝的速率（k（obs）约为60-150 s（-1））比单独高锰酸盐所测得的速率快5-6个数量级，并且比用于水处理的常规高级氧化工艺快5 - 7个数量级。苯酚的氧化在pH 4.0时最快，但在pH 7.0时仍然有效，并且在自来水中进行时仅稍微慢一些。一个较小的，但仍然相当大的（类似3个数量级）增加甲基蓝的氧化速率观察与二氧化锰活化HSO 3-（MO/BS）。上述结果、各种条件下锰物质的时间分辨光谱、pH变化的化学计量分析以及焦磷酸盐对UV吸收光谱的影响表明，PM/BS工艺中负责有机污染物极快速氧化的反应性中间体涉及锰（III）物质，其通过络合作用具有最小的稳定性。PM/BS工艺可能会导致一类新的高级氧化技术，其基于通过活性锰（III）物种而不是羟基和硫酸根的污染物氧化。
MnO4- was activated by HSO3-, resulting in a process that oxidizes organic contaminants at extraordinarily high rates. The permanganate/bisulfite (PM/BS) process oxidized phenol, ciprofloxacin, and methyl blue at pH(ini) 5.0 with rates (k(obs) approximate to 60-150 s(-1)) that were 5-6 orders of magnitude faster than those measured for permanganate alone, and similar to 5 to 7 orders of magnitude faster than conventional advanced oxidation processes for water treatment. Oxidation of phenol was fastest at pH 4.0, but still effective at pH 7.0, and only slightly slower when performed in tap water. A smaller, but still considerable (similar to 3 orders of magnitude) increase in oxidation rates of methyl blue was observed with MnO2 activated by HSO3- (MO/BS). The above results, time-resolved spectroscopy of manganese species under various conditions, stoichiometric analysis of pH changes, and the effect of pyrophosphate on UV absorbance spectra suggest that the reactive intermediate(s) responsible for the extremely rapid oxidation of organic contaminants in the PM/BS process involve manganese(III) species with minimal stabilization by complexation. The PM/BS process may lead to a new category of advanced oxidation technologies based on contaminant oxidation by reactive manganese(III) species, rather than hydroxyl and sulfate radicals.