整体式钴基复合金属催化剂微波催化燃烧甲苯特性

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摘要以蜂窝状堇青石为载体,通过将钴与过渡金属铜锰铈复合,浸渍法制备系列整体式钴基复合金属催化剂,探究其在微波辐照下对典型VOCs—甲苯的催化活性.结果表明,甲苯进气浓度1000mg/m³,进气流速4L/min时,催化剂对甲苯的催化活性为CoCuCeO_x>CoCuO_x>CoCuMnCeO_x>CoCuMnO_x, CoCuCeO_x对甲苯的T₅₀=220℃、T₉₀=295℃.表征可知,钴铜氧化物的复合使得催化剂表面颗粒态的CoO_x、CuO_x和CuCo₂O₄尖晶石相互搭建形成有空隙的球状结构,而锰的加入不利于该球状结构生成.Cu²⁺取代了一部分Co₃O₄尖晶石结构中的Co²⁺形成CuCo₂O₄尖晶石,CuCo₂O₄尖晶石中的Co-O和Cu-O键容易断裂,从而促进气态氧的吸附与活化,产生表面活性氧物种参与甲苯的氧化反应.Ce的加入会存在Ce³⁺/Ce⁴⁺价态的转化,促使CoCuCeO_x催化剂表面产生丰富的氧空位,进而作为活性中心促进甲苯的氧化降解.钴、铜、铈之间的复合改变了活性组分结构,提高了催化剂的吸波性能与催化活性,可应用于微波催化燃烧VOCs技术中.

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关键词 ：钴基复合金属, 钴铜尖晶石, 整体式催化剂, 微波催化燃烧, 甲苯

Abstract：A series of monolithic cobalt-based composite metal catalysts were prepared through impregnation method by combining cobalt (Co) with transitional metals copper (Cu), Manganese (Mn) and Cerium (Ce) as active components and using honeycomb cordierite as carrier. The catalytic activity of the catalysts was investigated using toluene as a kind of typical VOCs under microwave irradiation. The results showed that the catalytic activity of Co-based catalysts for toluene removal was in the order of CoCuCeO_x> CoCuO_x> CoCuMnCeO_x> CoCuMnO_x when the inlet toluene concentration was 1000mg/m³with flow rate of 4L/min. The T₅₀and T₉₀of toluene achieved by CoCuCeO_x catalyst was 220℃ and 295℃, respectively. According to the characterizations analysis, CoO_x, CuO_x, and CuCo₂O₄spinel particles on the surface of the catalyst were formed into spherical structures with voids by the recombination of cobalt and copper oxides. However, the addition of manganese was not conducive to the formation of this spherical structure. The CuCo₂O₄ spinel was formed by the replacement of partial Co²⁺ in the structure of Co₃O₄ with Cu²⁺. The easily breakage of Co-O and Cu-O bonds in CuCo₂O₄ spinel promoted the adsorption and activation of gaseous oxygen, which was beneficial to the generation of surface reactive oxygen species that participated in the oxidation of toluene. The addition of Ce led to the conversion of Ce³⁺/Ce⁴⁺, which promoted the formation of abundant oxygen vacancies on the surface of CoCuCeO_x catalyst and then acted as the active centers to promote the oxidative degradation of toluene. The coupling of cobalt, copper, and cerium changed the structure of the active components, which effectively improved the absorption performance and catalytic activity of the catalyst. It provided extensive application prospects in the technology of microwave catalytic combustion of VOCs.

Key words： cobalt-based composite metal cobalt copper spinel monolithic catalyst microwave catalytic combustion toluene

收稿日期: 2023-07-02

PACS:

X511

基金资助:陕西省自然科学基础研究计划项目(2021JM-364)

作者简介: 赵思蕊(1998-),女,陕西西安人,西安建筑科技大学硕士研究生,主要从事大气污染控制化学方面研究.921585505@qq.com.

引用本文:

赵思蕊, 卜龙利, 代菁雯, 黄思宁, 罗梦垚, 刘楠, 王嘉乐. 整体式钴基复合金属催化剂微波催化燃烧甲苯特性[J]. 中国环境科学, 2024, 44(3): 1253-1264. ZHAO Si-rui, BO Long-li, DAI Jing-wen, HUANG Si-ning, LUO Meng-yao, LIU Nan, WANG Jia-le. Microwave catalytic combustion of toluene by monolithic cobalt-based composite metal catalysts. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(3): 1253-1264.

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