Citation: Xiaole Weng, Yu Long, Wanglong Wang, Min Shao, Zhongbiao Wu. Structural effect and reaction mechanism of MnO₂ catalysts in the catalytic oxidation of chlorinated aromatics[J]. Chinese Journal of Catalysis, ;2019, 40(5): 638-646. doi: S1872-2067(19)63322-X shu

Structural effect and reaction mechanism of MnO₂ catalysts in the catalytic oxidation of chlorinated aromatics

Xiaole Weng ^a,b, ,
Yu Long ^a ,
Wanglong Wang ^a ,
Min Shao ^c,d ,
Zhongbiao Wu ^a,b

a Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, Zhejiang, China;
b Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310058, Zhejiang, China;
c State Joint Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China;
d Environmental and climate Research institute, Jinan University, Guangzhou 511443, Guangdong, China

Received Date: 29 December 2018
Revised Date: 31 January 2019

Fund Project: This work was supported by the Outstanding Youth Project of Zhejiang Natural Science Foundation (LR19E080004) and the National Natural Science Foundation of China (51478418).

Various MnO₂ structures have been extensively applied in catalysis. In this study, γ-MnO₂, α-MnO_2, and δ-MnO₂ with corresponding rod, tube, and hierarchical architecture morphologies were prepared and applied for the catalytic oxidation of chlorobenzene (CB). The redox ability, H₂O activation behavior, and acidity of MnO₂ were analyzed using a range of techniques, including TPR, H₂O-TPD, XPS, and pyridine-IR. The catalytic activities in CB oxidation were assessed; this revealed that γ-MnO₂ exhibited the highest activity and best stability, owing to its enriched surface oxygen vacancies that functioned to activate O₂ and H₂O, and capture labile chlorine, which reacted with dissociated H₂O to form HCl. All the MnO₂ phases generated toxic polychlorinated by-products, including CHCl₃, CCl₄, C₂HCl₃, and C₂Cl₄, indicating the occurrence of electrophilic chlorination during CB oxidation. In particular, the dichlorobenzene detected in the effluents of α-MnO₂ might generate unintended dioxins via a nucleophilic substitution reaction.
- MnO₂,
- Chlorobenzene,
- Catalytic oxidation,
- Polychlorinated byproducts,
- Environmental risk
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Structural effect and reaction mechanism of MnO2 catalysts in the catalytic oxidation of chlorinated aromatics

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通讯作者: 陈斌, bchen63@163.com

Structural effect and reaction mechanism of MnO₂ catalysts in the catalytic oxidation of chlorinated aromatics