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Effect of MnO₂ Phase Structure on the Oxidative Reactivity toward Bisphenol A Degradation

Huang, Jianzhi, Zhong, Shifa, Dai, Yifan, Liu, Chung-Chiun, Zhang, Huichun
Environmental science & technology 2018 v.52 no.19 pp. 11309-11318
bisphenol A, cost effectiveness, crystal structure, manganese, manganese dioxide, oxidants, oxidation, oxygen, surface area, wastewater treatment
Manganese dioxides (MnO₂) are among important environmental oxidants in contaminant removal; however, most existing work has only focused on naturally abundant MnO₂. We herein report the effects of different phase structures of synthetic MnO₂ on their oxidative activity with regard to contaminant degradation. Bisphenol A (BPA), a frequently detected contaminant in the environment, was used as a probe compound. A total of eight MnO₂ with five different phase structures (α-, β-, γ-, δ-, and λ-MnO₂) were successfully synthesized with different methods. The oxidative reactivity of MnO₂, as quantified by pseudo-first-order rate constants of BPA oxidation, followed the order of δ-MnO₂-1 > δ-MnO₂-2 > α-MnO₂-1 > α-MnO₂-2 ≈ γ-MnO₂ > λ-MnO₂ > β-MnO₂-2 > β-MnO₂-1. Extensive characterization was then conducted for MnO₂ crystal structure, morphology, surface area, reduction potential, conductivity, and surface Mn oxidation states and oxygen species. The results showed that the MnO₂ oxidative reactivity correlated highly positively with surface Mn(III) content and negatively with surface Mn average oxidation state but correlated poorly with all other properties. This indicates that surface Mn(III) played an important role in MnO₂ oxidative reactivity. For the same MnO₂ phase structure synthesized by different methods, higher surface area, reduction potential, conductivity, or surface adsorbed oxygen led to higher reactivity, suggesting that these properties play a secondary role in the reactivity. These findings provide general guidance for designing active MnO₂ for cost-effective water and wastewater treatment.