In Situ Regulation of MnO₂ Structural Characteristics by Oxyanions to Boost Permanganate Autocatalysis for Phenol Removal

Abstract

Oxyanions, a class of constituents naturally occurring in water, have been widely demonstrated to enhance permanganate (Mn(VII)) decontamination efficiency. However, the detailed mechanism remains ambiguous, mainly because the role of oxyanions in regulating the structural parameters of colloidal MnO2 to control the autocatalytic activity of Mn(VII) has received little attention. Herein, the origin of oxyanion-induced enhancement is systematically studied using theoretical calculations, electrochemical tests, and structure–activity relation analysis. Using bicarbonate (HCO3 –) as an example, the results indicate that HCO3 – can accelerate the degradation of phenol by Mn(VII) by improving its autocatalytic process. Specifically, HCO3 – plays a significant role in regulating the structure of in situ produced MnO2 colloids, i.e., increasing the surface Mn(III)s content and restricting particle growth. These structural changes in MnO2 facilitate its strong binding to Mn(VII), thereby triggering interfacial electron transfer. The resultant surface-activated Mn(VII)* complexes demonstrate excellent degrading activity via directly seizing one electron from phenol. Further, other oxyanions with appropriate ionic potentials (i.e., borate, acetate, metasilicate, molybdate, and phosphate) exhibit favorable influences on the oxidative capability of Mn(VII) through an activation mechanism similar to that of HCO3 –. These findings considerably improve our fundamental understanding of the oxidation behavior of Mn(VII) in actual water environments and provide a theoretical foundation for designing autocatalytically boosted Mn(VII) oxidation systems.

Trace Br– Inhibits Halogenated Byproduct Formation in Saline Wastewater Electrochemical Treatment

“…The KIE has been a valuable tool in the study of reaction mechanisms for decades, as it provides insights into the formation or breaking of bonds involving isotopically substituted atoms. − To further support our findings and clarify the underlying reaction mechanisms, we conducted a KIE study using deuterated phenols (C 6 D 5 OD and C 6 D 5 OH), − which were subjected to electrochemical oxidation under different conditions. The KIE value is defined as the ratio of the reaction rate constants, i.e., k H / k D , where k H and k D represent the apparent rate constants for the removal of phenol and deuterated phenol, respectively.…”

“…For C 6 D 5 OD, where the BDE of the O–D bond is distinctly higher than that of the O–H bond, the HAA pathway with phenolic hydroxyl groups as reaction sites is expected to lead to a significantly large KIE value. , For C 6 D 5 OH, an insignificant isotope effect (where k H is approximately equivalent to k D ) is expected if the HAA pathway dominates. In addition, phenol oxidation through the SET pathway is likely to result in a KIE value close to 1.0 for both C 6 D 5 OD and C 6 D 5 OH, as the reactive site is located on the benzene ring Figure f shows that the KIE values of C 6 D 5 OH and C 6 D 5 OD in Cl 2 •– -dominated systems were 1.52 and 1.34, respectively.…”