化学学报 ›› 2012, Vol. 70 ›› Issue (22): 2347-2352.DOI: 10.6023/A12080562 上一篇    下一篇

研究论文

不同晶型二氧化锰纳米棒催化氧化氯苯性能的研究

李经纬, 宋灿, 刘善堂   

  1. 武汉工程大学化工制药学院 绿色化工过程教育部重点实验室 武汉 430074
  • 投稿日期:2012-08-18 发布日期:2012-10-18
  • 通讯作者: 刘善堂 E-mail:liushantang@mail.wit.edu.cn
  • 基金资助:
    项目受国家自然科学基金(Nos. 20873097, 21071113)、湖北省自然科学基金(No. 2011CDA049)、武汉市学科带头人(No. 200951830551)和湖北省教育厅科学技术研究重大项目(No. Z20091502)资助.

Catalytic Oxidation of Chlorobenzene over MnO2 Nanorods with Different Phase Structures

Li Jingwei, Song Can, Liu Shantang   

  1. Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074
  • Received:2012-08-18 Published:2012-10-18
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 20873097, 21071113), Natural Science Foundation of Hubei Province (No. 2011CDA049), Wuhan Municipal Scientific Leader Program (No. 200951830551) and Key Project of Hubei Provincial Department of Education (No. Z20091502)

采用水热法分别合成了α-, β-, γ-MnO2纳米棒, 使用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、氢气程序升温还原(H2-TPR)和X射线光电子能谱(XPS)等技术对三种晶型MnO2纳米棒的结构和形貌进行了表征, 并以氯苯(CB)为探针考察了其催化活性和稳定性. 结果表明, 三种晶型MnO2纳米棒在低温范围内均有较高的催化活性, 且活性顺序为α-MnO2γ-MnO2β-MnO2. 此外, 还发现三种晶型MnO2纳米棒比无定形MnO2有更强的抗氯中毒能力. 在三种晶型MnO2纳米棒中, α-MnO2纳米棒催化氧化氯苯的活性最佳, 主要是由于该种MnO2纳米棒含有丰富的晶格氧并且具有较强的可还原能力.

关键词: α-, β-, γ-MnO2, 纳米棒, 晶型, 氯苯, 催化燃烧

Mn-containing catalysts are widely used owing to their excellent redox properties, while in most cases they would deactivate to some extent in the oxidation process of the chloride volatile organic compounds (CVOCs) due to chlorine poisoning. In this work α-, β-, γ-MnO2 nanorods were synthesized via a hydrothermal route, and their catalytic performance for chlorobenzene (CB, as a model of CVOCs) and resistance to chlorine poisoning were studied. The results showed that the MnO2 nanorods with different phase structures exhibited high activities for low temperature catalytic oxidation of CB, and the catalytic activities of the MnO2 nanorods depended on the crystal phase of MnO2, following in the order of α-MnO2γ-MnO2β-MnO2. Moreover, the MnO2 nanorods showed high resistance to chlorine poisoning compared to the amorphous MnO2. The experiment results indicated that the conversion of CB over α-, β-, γ-MnO2 nanorods at 250 ℃ remained stable at about 98%, 82% and 90% respectively for 35 h. Contrasted to MnO2 nanorods, the conversion of CB over amorphous MnO2 dropped from 80% to 32% in the same condition. Additionally, the as-synthesized MnO2 nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). XRD results showed that the crystallinity of α-, β-, γ-MnO2 nanorods were different, and decreased in the order: βαγ, implying that the crystallinity of α-, β-, γ-MnO2 nanorods had no significant effect on its catalytic performance. SEM and TEM showed that three kinds of nanorods were well dispersed, and exhibited one-dimensional nanorods. H2-TPR and XPS results demonstrated that the high catalytic activity of α-MnO2 nanorods resulted from their rich lattice oxygen and good reducibility. Therefore, the enrichment of the lattice oxygen with excellent reducibility was considered as main reason of high activity of α-MnO2 nanorods for low temperature catalytic destruction of CB.

Key words: α-, β-, γ-MnO2, nanorods, phase structure, chlorobenzene, catalytic combustion