CeMn复合氧化物的制备及氯苯催化氧化性能

doi:10.11896/cldb.23050133

材料导报

2024, Vol. 38

Issue (16): 23050133-9 https://doi.org/10.11896/cldb.23050133

无机非金属及其复合材料

CeMn复合氧化物的制备及氯苯催化氧化性能

罗宁^1,†, 高凤雨^1,†, 陈都¹, 张辰骁¹, 段二红², 赵顺征¹, 易红宏¹, 唐晓龙^1,*

1 北京科技大学能源与环境工程学院,北京 100083
2 河北科技大学环境科学与工程学院,石家庄 050018

Preparation of CeMn Composite Oxide and Catalytic Oxidation of Chlorobenzene

LUO Ning^1,†, GAO Fengyu^1,†, CHEN Du¹, ZHANG Chenxiao¹, DUAN Erhong², ZHAO Shunzheng¹, YI Honghong¹, TANG Xiaolong^1,*

1 School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2 School of Environmental Science and Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China

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摘要氯苯作为一种含氯代苯环的物质,具有高生物毒性和化学稳定性,难以降解,亟需治理。在诸多治理技术中,催化氧化法因深度降解能力有较好的应用前景。本研究基于资源丰富的稀土金属氧化物CeO₂,探究了不同制备方法以及不同过渡金属元素掺杂对催化氧化氯苯活性的影响,分析了催化剂的理化性能和反应路径。结果显示,与直接焙烧、乙酸+水热,尿素水解+水热等方法相比,NaOH沉淀+水热法合成的CeO₂催化剂性能较好。通过掺杂不同元素(Mn、Fe、Co)发现,Ce-Mn催化剂的氯苯氧化活性的提升效果较为明显,于450 ℃、含H₂O(5%(体积分数,下同))条件下取得95%的催化转化率。分析表明,Mn掺杂后催化剂表面酸性位点以及氧化还原位点显著增加,其中Brønsted/Lewis(B/L)酸比值由0.259升高至0.419,促进了更多的电子循环(Ce⁴⁺/Ce³⁺)以及氧物种迁移(O_α↔O_β)产生。反应路径研究表明,氯苯分子首先吸附在催化剂表面的活性位点(酸位点或氧空位)上发生亲核取代反应,脱氯形成苯酚/苯醌等物质,在活性氧物种的作用下,逐渐开环氧化为乙酸盐等中间物种,最终转化为CO₂、H₂O和HCl等小分子的最终产物。

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	罗宁
	高凤雨
	陈都
	张辰骁
	段二红
	赵顺征
	易红宏
	唐晓龙

关键词: CeMn氧化物水热法元素掺杂氯苯降解催化氧化反应路径

Abstract: Chlorobenzene, as a chlorobenzene ring substance, has high biological toxicity and chemical stability, is difficult to degrade, and needs urgent treatment. Among many treatment technologies, catalytic oxidation has a good application prospect because of its deep degradation ability. In this study, based on the rare earth metal oxide CeO₂, which is rich in resources, the effects of different preparation methods and doping of different transition metal elements on the catalytic oxidation of chlorobenzene were investigated. The physicochemical properties and reaction paths of the catalyst were analyzed and the results showed that compared with the direct calcination, acetic acid+hydrothermal, urea hydrolysis+hydrothermal methods, the CeO₂ catalyst prepared by NaOH precipitation+hydrothermal method has better performance. The study of doping with different elements (Mn, Fe, Co) found that the chlorobenzene oxidation activity of Ce-Mn catalyst was significantly improved, and the catalytic conversion rate was 95% at 450 ℃ containing H₂O (5vol%, the same below). The analysis showed that Mn doping significantly increased the acidic sites and REDOX sites on the surface of the catalyst, and the Brønsted/Lewis (B/L) acid ratio was increased from 0.259 to 0.419, which promoted more electron cycling (Ce⁴⁺/Ce³⁺) and reactive oxidizing species mobility (O_α↔O_β). Chlorobenene molecules adsorbed on the active site (acid site or oxygen vacancy) on the catalyst surface underwent nucleophilic substitution reaction, dechlorinated to form phenol. Under the action of reactive oxygen species, chlorobenene gradually opened to intermediate species such as acetate, and finally converted to small molecular products such as CO₂, H₂O and HCl.

Key words: CeMn oxide hydrothermal method element doping chlorobenzene degradation catalytic oxidation reaction pathway

出版日期: 2024-08-25 发布日期: 2024-09-10

ZTFLH:

X511

基金资助: 国家重点研发计划(2023YFB3810800);国家自然科学基金(U20A20130);中央高校基本科研业务费专项资金(FRF-EYIT-23-07)

通讯作者: *唐晓龙,北京科技大学能源与环境工程学院教授、博士研究生导师,教育部新世纪优秀人才。现任北京科技大学科学技术研究院副院长,兼任中国工程教育认证协会环境类分委会委员、中国有色金属学会环境保护学术委员会委员等。2006年于北京理工大学(清华联合培养)获博士学位。长期以来主要从事烟气脱硫脱硝技术、工业废气资源化、环境功能材料研究与开发等工作。近年来发表论文300余篇,包括Applied Catalysis B: Environmental、Journal of Materials Chemistry A、Nano Research、Chemical Engineering Journal、Applied Surface Science等。txiaolong@126.com

作者简介: 罗宁,2021年3月于天津工业大学取得硕士学位,硕士在读期间曾多次获得校级奖学金和校三好学生等荣誉称号。现为北京科技大学能源与环境工程学院博士研究生,在唐晓龙教授的指导下进行研究。目前主要研究领域为大气污染控制以及多污染物协同催化。高凤雨,北京科技大学副教授、硕士研究生导师,北京市科协青年人才托举工程获得者、“千人进千企”产业特派员、小米青年学者。长期致力于气态污染物净化与资源化技术(环境催化、小分子氧化、CO₂RR等)以及关键催化材料的研究工作。以第一或通信作者在Applied Catalysis B: Environmental、Chemical Engineering Journal、Separation and Purification Technology、Journal of Environmental Sciences、Catalysis Science & Technology、《物理化学学报》等国内外重要学术刊物发表科研论文40余篇。
^†共同第一作者

引用本文:

罗宁, 高凤雨, 陈都, 张辰骁, 段二红, 赵顺征, 易红宏, 唐晓龙. CeMn复合氧化物的制备及氯苯催化氧化性能[J]. 材料导报, 2024, 38(16): 23050133-9.
LUO Ning, GAO Fengyu, CHEN Du, ZHANG Chenxiao, DUAN Erhong, ZHAO Shunzheng, YI Honghong, TANG Xiaolong. Preparation of CeMn Composite Oxide and Catalytic Oxidation of Chlorobenzene. Materials Reports, 2024, 38(16): 23050133-9.

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http://www.mater-rep.com/CN/10.11896/cldb.23050133 或 http://www.mater-rep.com/CN/Y2024/V38/I16/23050133

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