MnO2催化剂用于催化氧化含氯芳香烃的形貌效应与反应机制研究

doi:10.1016/S1872-2067(19)63322-X

催化学报 ›› 2019, Vol. 40 ›› Issue (5): 638-646.DOI: 10.1016/S1872-2067(19)63322-X

MnO₂催化剂用于催化氧化含氯芳香烃的形貌效应与反应机制研究

翁小乐^a,b, 龙宇^a, 王望龙^a, 邵敏^c,d, 吴忠标^a,b

a 浙江大学环境与资源科学学院, 教育部环境修复与生态健康重点实验室, 浙江杭州 310058;
b 浙江省工业锅炉炉窑烟气污染控制工程技术研究中心, 浙江杭州 310058;
c 北京大学环境科学与工程学院, 国家环境模拟与污染控制联合重点实验室, 北京 100871;
d 暨南大学环境与气候研究所, 广东广州 511443

收稿日期:2018-12-29 修回日期:2019-01-31 出版日期:2019-05-18 发布日期:2019-03-30
通讯作者: 吴忠标
基金资助:
浙江省杰出青年基金（LR19E080004）；国家自然科学基金（51478418）.

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:2018-12-29 Revised:2019-01-31 Online:2019-05-18 Published:2019-03-30
Contact: S1872-2067(19)63322-X
Supported by:
This work was supported by the Outstanding Youth Project of Zhejiang Natural Science Foundation (LR19E080004) and the National Natural Science Foundation of China (51478418).

摘要/Abstract

摘要：

含氯挥发性有机物（Chlorinated VOCs）被广泛应用于工业、农业、医药、有机合成等领域，在使用过程中会通过挥发、泄漏、废气排放等途径进入大气环境中，造成臭氧层破坏与光化学烟雾，且很难被生物降解，对人体具有很强的“三致”效应.在众多治理方法中，催化燃烧因高效低能耗的特点而被认为是具有应用前景的含氯VOCs处理方式，然而催化剂中毒以及毒副产物生成极大限制了该技术的工业应用.锰基催化剂由于价格低廉、来源广泛以及价态多变等特点被广泛应用于环境催化领域，包括甲醛、甲苯、CO催化氧化以及选择性催化还原脱硝等.MnO₂的晶体形貌与其催化性能息息相关，二者的构效关系已有广泛研究，但在含氯VOCs催化氧化中，MnO₂的形貌特征与催化活性、反应稳定性、副产物等的关系尚不明晰.因此，本文通过水热法制备了纳米棒状γ-MnO₂，纳米管状α-MnO₂以及具有层状结构的δ-MnO₂，系统研究了这三种形貌结构在氯苯催化氧化中的反应特征，利用XRD，XPS，TPR，TPD，吡啶-IR等手段对催化剂的形貌、表面元素价态、氧化还原性能以及表面酸性等进行了表征，获得了MnO₂在含氯VOCs催化氧化应用中的构效关系.
XRD以及SEM分析结果表明，三种形貌的MnO₂样品均由水热法成功制得.H₂-TPR和O₂-TPD测试分析显示，MnO₂催化剂的氧化还原性能按如下顺序递减δ-MnO₂≥ γ-MnO₂ > α-MnO₂，与这些催化剂活性测试中的氯苯转化率结果一致，但与其CO₂选择性的结果不一致.氧化还原能力最佳的δ-MnO₂上CO₂选择性表现最差，即使提高温度仍无法提升.XPS结果表明，三种催化剂的Mn元素平均价态高低顺序为δ-MnO₂（3.80） > α-MnO₂（3.75）≥ γ-MnO₂（3.74）.δ-MnO₂催化剂表面因具有最丰富的Mn⁴⁺，反应过程中易生成强的Mn-Cl键，从而抑制了Cl与解离水反应生成HCl，导致催化剂富集氯失活，CO₂选择性差.对反应尾气及催化剂表面产物分析后发现，三种MnO₂催化剂均生成了具有更高毒性的多氯副产物，其中主要有CHCl₃，CCl₄，C₂HCl₃，C₂Cl₄等，尤其在α-MnO₂催化剂表面发现了二氯苯存在，其可能通过进一步的亲核取代生成氯苯酚，并最终聚合成二噁英类物质.

关键词: MnO₂, 氯苯, 催化氧化, 多氯副产物, 环境风险

Abstract:

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.

Key words: MnO₂, Chlorobenzene, Catalytic oxidation, Polychlorinated byproducts, Environmental risk

翁小乐, 龙宇, 王望龙, 邵敏, 吴忠标. MnO₂催化剂用于催化氧化含氯芳香烃的形貌效应与反应机制研究[J]. 催化学报, 2019, 40(5): 638-646.

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.

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MnO₂催化剂用于催化氧化含氯芳香烃的形貌效应与反应机制研究

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

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