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Published on: October 14, 2020
Coordination engineering breaks the inertness of Mn single-atom for ultrafast peracetic acid activation
Yudan Dong1, Yang Wang2, Zhihui Xie3
1State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu 610065, China; Chengdu Academy of Environmental Science, Chengdu 610072, China; Sino-German Centre for Water and Health Research, Sichuan University, Chengdu 610065, China.
Abstract:
The prevalence of persistent organic pollutants in water bodies demands advanced oxidation processes that are both highly efficient and environmentally sustainable. Single-atom manganese catalysts can enable the green activation of peracetic acid (PAA), a promising alternative oxidant, but the catalytic performance is often limited by the inherent chemical inertness of the Mn sites. In this study, we modulated the electronic structure of the coordination microenvironment of ecofriendly and low-toxicity manganese single-atom catalysts through O doping. This strategy enhanced the electron delocalization ability of tricoordinated MnN2O, established a built-in electric field to strengthen the Mn-O covalency, and significantly boosted its intrinsic mechanism for activating PAA to selectively generate singlet oxygen (1O2). The remarkable Fenton-like performance of MnN2O was reflected by an 8.8-9.9 fold improvement in the bisphenol A (BPA) degradation kinetic rate. Moreover, the practical application potential of this proposed Fenton-like process is enhanced by the average BPA removal rate of 97.96% ± 2.65% for tap water and 95.46% ± 4.96% for the secondary effluent of a sewage treatment plant over 120 h in a continuous-flow device. Density functional theory calculations elucidated that the tricoordinated structure and electron delocalization of MnN2O can effectively optimize the d-band electronic structure of adjacent Mn centers and promote the formation of 1O2 through a Mn-O covalence-dependent mechanism. This study breaks the symmetric coordination constraint to optimize the electron distribution, unlocking broad avenues for designing PAA-based Fenton-like process catalysts.
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