催化学报 ›› 2016, Vol. 37 ›› Issue (8): 1193-1205.DOI: 10.1016/S1872-2067(16)62457-9

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有序多孔过渡金属氧化物及其负载贵金属催化剂对挥发性有机物氧化的催化性能

刘雨溪, 邓积光, 谢少华, 王治伟, 戴洪兴   

  1. 北京工业大学环境与能源工程学院化学化工系, 绿色催化与分离北京市重点实验室, 区域大气污染控制北京市重点实验室, 新型功能材料教育部重点实验室, 催化化学与纳米科学研究室, 北京 100124
  • 收稿日期:2016-03-31 修回日期:2016-05-03 出版日期:2016-07-29 发布日期:2016-08-01
  • 通讯作者: Hongxing Dai
  • 基金资助:

    国家高技术研究发展计划(863计划,2015AA034603);国家自然科学基金(21377008,201077007,20973017);北京市高校创新团队推进计划;科研基地建设-科技创新平台-国家材料研究基地建设.

Catalytic removal of volatile organic compounds using ordered porous transition metal oxide and supported noble metal catalysts

Yuxi Liu, Jiguang Deng, Shaohua Xie, Zhiwei Wang, Hongxing Dai   

  1. Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, Key Laboratory of Advanced Functional Materials, Education Ministry of China, and Laboratory of Catalysis Chemistry and Nanoscience, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China
  • Received:2016-03-31 Revised:2016-05-03 Online:2016-07-29 Published:2016-08-01
  • Contact: Hongxing Dai
  • Supported by:

    This work was supported by the National High Technology Research and Development Program (863 Program, 2015AA034603), the National Natural Science Foundation of China (21377008, 201077007, 20973017), Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions, and Scientific Research Base Construction-Science and Technology Creation Platform National Materials Research Base Construction.

摘要:

大部分的挥发性有机物(VOCs)污染环境,危害人身健康.目前,我国虽然已开展了治理VOCs污染的工作,但还缺乏有效的、拥有自主知识产权的VOCs治理技术,因此研发新型高效VOCs处理技术迫在眉睫.催化氧化法是公认的最有效消除VOCs的途径之一,而高性能催化剂的研发是实现该过程的关键.近年来,人们围绕消除VOCs的高效且价廉的催化剂的研发开展了卓有成效的工作,许多过渡金属氧化物、混合或复合金属氧化物及其负载贵金属催化剂均被认为是有效的催化氧化材料.与体相材料相比,多孔材料具有发达的孔道结构和高的比表面积,一方面有利于反应物的扩散、吸附和脱附,因而具有更高的催化活性和选择性;另一方面有利于活性组分(如贵金属等)在多孔材料表面的高分散,抑制活性组分的烧结,因而具有更好的催化稳定性.本文简述了近年来多孔金属氧化物在环境污染物消除领域的研究进展,阐述了以有序介孔或大孔过渡金属氧化物、钙钛矿型氧化物和负载贵金属催化剂的制备及其对典型VOCs(如苯系物、醇类、醛类及酮类等)氧化的催化性能,重点介绍了四类催化材料,包括有序介孔过渡金属氧化物或复合氧化物(Co3O4,MnO2,Fe2O3,Cr2O3和LaFeO3等)催化剂,有序介孔金属氧化物负载贵金属(Au/Co3O4,Au/MnO2和Pd/Co3O4等)催化剂,三维有序大孔过渡金属氧化物或复合氧化物(Fe2O3,LaMnO3,La0.6Sr0.4MnO3和La2CuO4等)催化剂,以及三维有序大孔金属氧化物负载贵金属(Au/Co3O4,Au/LaCoO3,Au/La0.6Sr0.4MnO3和AuPd/Co3O4等)催化剂的制备及其物化性质与对苯、甲苯、二甲苯、乙醇、丙酮、甲醛、甲烷或氯甲烷等VOCs氧化的催化性能之间的相关性.借助二氧化硅或聚甲基丙烯酸甲酯微球等硬模板,采用纳米浇铸法可制备出二维或三维的有序单一或多级孔道结构的金属氧化物.研究表明,多孔金属氧化物的催化性能远优于其体相甚至纳米催化剂的.有序多孔材料的优异催化性能与其拥有大的比表面积、高的吸附氧物种浓度、优良的低温还原性、独特的孔道结构、活性组分的高分散以及贵金属与氧化物载体之间的强相互作用等有关.探明影响催化剂活性的因素有利于从原子水平上认识催化过程,为新型高效催化剂的设计与制备奠定基础.本文还指出了此类研究中存在的一些问题,例如利用硬模板法制备多孔材料的缺点是目标催化剂的收率低,硬模板浪费严重,大规模制备多孔催化剂势必增加制备成本,这些问题有待于妥善解决.与此同时,还展望了VOCs消除技术的未来发展趋势,采用多种技术联用的方法有望最大程度地提高VOCs的消除效率.

关键词: 挥发性有机物, 催化燃烧, 多孔过渡金属氧化物, 钙钛矿型氧化物, 负载贵金属催化剂

Abstract:

Most of volatile organic compounds (VOCs) are harmful to the atmosphere and human health. Catalytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high performance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and supported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excellent catalytic performance was due to their high surface areas, high concentration of adsorbed oxygen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and proposed future work for the removal of VOCs.

Key words: Volatile organic compound, Catalytic combustion, Porous transition metal oxide, Perovskite-type oxide, Supported noble metal catalyst