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高效激活六价铁:胶态二氧化锰表面促进机制的综合阐述。

Efficient activation of ferrate(VI) by colloid manganese dioxide: Comprehensive elucidation of the surface-promoted mechanism.

机构信息

State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu 610065, China; Sino-German Centre for Water and Health Research, Sichuan University, Chengdu 610065, China.

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.

出版信息

Water Res. 2022 May 15;215:118243. doi: 10.1016/j.watres.2022.118243. Epub 2022 Mar 1.

Abstract

Current research focuses on introducing additional energy or reducing agents to directly accelerate the formation of Fe(IV) and Fe(V) from ferrate (Fe(VI)), thereby ameliorating the oxidation activity of Fe(VI). Interestingly, this study discovers that colloid manganese dioxide (cMnO) can remarkably promote Fe(VI) to remove various contaminants via a novel surface-promoted pathway. Many lines of evidence suggest that high-valent Fe species are the primary active oxidants in the cMnO-Fe(VI) system, however, the underlying activation mechanism for the direct reduction of Fe(VI) by cMnO to generate Fe(IV)/Fe(V) is eliminated. Further analysis found that Fe(VI) can combine with the vacancies in cMnO to form precursor complex (cMnO-Fe(VI)), which possesses a higher oxidation potential than Fe(VI). This makes cMnO-Fe(VI) is more vigorous to oxidize pollutants with electron-rich moieties through the electron transfer step than alone Fe(VI), resulting in producing Fe(V) and Fe(IV). The products of Fe(VI) decay (i.e., Fe(II), Fe(III), and HO) are revealed to play vital roles in further boosting the formation of Fe(IV) and Fe(V). Most importantly, the catalytic stability of cMnO in complicated waters is superior to popular reductants, suggesting its outstanding application potential. Taken together, this work provides a full-scale insight into the surface-promoted mechanism in Fe(VI) oxidation process, thus providing an efficient and green strategy for Fe(VI) activation.

摘要

目前的研究重点是引入额外的能量或还原剂,直接促进高铁酸盐(Fe(VI))中 Fe(IV)和 Fe(V)的形成,从而改善 Fe(VI)的氧化活性。有趣的是,本研究发现胶体二氧化锰 (cMnO) 可以通过一种新颖的表面促进途径显著促进 Fe(VI)去除各种污染物。许多证据表明,高价 Fe 物种是 cMnO-Fe(VI)体系中主要的活性氧化剂,但 cMnO 直接还原 Fe(VI)生成 Fe(IV)/Fe(V)的潜在活化机制被消除。进一步分析发现,Fe(VI)可以与 cMnO 中的空位结合形成前体配合物(cMnO-Fe(VI)),其氧化电位高于 Fe(VI)。这使得 cMnO-Fe(VI) 通过电子转移步骤比单独的 Fe(VI)更能氧化具有富电子部分的污染物,从而产生 Fe(V)和 Fe(IV)。Fe(VI)衰减产物(即 Fe(II)、Fe(III)和 HO)被揭示在进一步促进 Fe(IV)和 Fe(V)形成方面发挥重要作用。最重要的是,cMnO 在复杂水体中的催化稳定性优于常用还原剂,这表明其具有突出的应用潜力。总之,这项工作全面深入地了解了 Fe(VI)氧化过程中的表面促进机制,为 Fe(VI)的活化提供了一种高效、绿色的策略。

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