Direct Electron-Transfer-Based Peroxymonosulfate Activation by Iron-Doped Manganese Oxide (δ-MnO2) and the Development of Galvanic Oxidation Processes (GOPs)

Cite this: Environ. Sci. Technol. 2019, 53, 21, 12610–12620
Publication Date (Web):October 10, 2019
Copyright © 2019 American Chemical Society
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Manganese oxides have been recently investigated as excellent catalysts for peroxymonosulfate (PMS) activation, and the reported mechanisms are mostly forming reactive oxygen species (ROSs). This study investigated the use of iron-doped manganese oxide, synthesized via air oxidation under strong alkaline conditions. The oxidation of three substrates was affected by their adsorption at the catalyst surface, solution pH, and co-solutes. Common ROS scavengers inhibited the oxidation of bisphenol A (BPA), suggesting the possible involvement of ROSs; however, the PMS decomposition tests with and without BPA and the comparison with a 1O2-generation system ruled out the formation of ROSs and pointed to direct electron transfer between the adsorbed BPA and complexed PMS as the mechanism. To prove this mechanism, the catalyst was coated to graphite sheets and a galvanic oxidation process (GOP) was developed to separate BPA and PMS into two half cells. Upon PMS addition into one cell, BPA was quickly oxidized in the other cell, confirming the occurrence of electron transfer. The GOP system successfully degraded BPA in both surface water and hypersaline shale gas-produced water. Overall, this study developed a new catalyst for PMS activation and unveiled the advantages and potential applications of electron shuttling catalysts.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.9b03648.

  • Details of reagents used in this study (Text S1), effect of iron doping on the properties of MnO2 (Table S1), HPLC analytical parameters for BPA, 2,4,6-TCP, CBZ, and FFA (Table S2), water quality parameters of synthetic Marcellus shale gas-produced water (Table S3), possible BPA degradation products detected in Fe0.15Mn0.85O2/PMS and Co3O4/PMS systems on a LC-MS (Table S4), BPA degradation and PMS decomposition rate constants in the GOP and batch-mixed systems (Table S5), rate constants of BPA degradation by PMS activated by iron-doped manganese oxides with different Fe/Mn ratios and calcination temperatures (Figure S1), BPA degradation in the presence of Fe0.15Mn0.85O2 or PMS or both and comparison with two benchmark catalysts Co3O4 and Mn2O3 (Figure S2), stability and reusability test of the catalyst (Figure S3), effect of ionic strength on BPA degradation (Figure S4), the aggregation of the catalyst due to the addition of 1 M of methanol or TBA into the system at the beginning of the reaction (Figure S5), effect of 1 M methanol or TBA on PMS decomposition during the oxidation of 5 μM BPA (Figure S6), LC-MS-MS full scan chromatograms for the intermediate detection of BPA degradation in Fe0.15Mn0.85O2/PMS and Co3O4/PMS systems (Figure S7), BPA degradation in solvents H2O and D2O at pH 5 and 10.5 (Figure S8), BPA degradation and PMS decomposition in the GOP system using graphite sheets coated with Co3O4 as electrodes (Figure S9), BPA degradation in DI water, surface water, and shale gas-produced water in the batch system (Figure S10), and the plot of the amount of BPA degraded versus the amount of PMS consumed in those three waters in the GOP system (Figure S11) (PDF)

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