Ce掺杂对Ru/TiO2催化氯苯性能的影响

doi:10.11949/0438-1157.20200261

摘要/Abstract

摘要：

采用等体积浸渍法制备了单贵金属Ru/TiO₂和双金属Ru-Ce/TiO₂系列催化剂，测试了其对氯苯的催化活性，并通过N₂吸脱附、扫描电镜(SEM)、程序升温还原(H₂-TPR)进行表征，旨在考察稀土元素Ce掺杂对Ru/TiO₂催化氯苯性能的影响。结果表明，Ce的引入可使其在降低贵金属含量的基础上仍保持高的催化效率，且极大地提高了低温催化活性。0.4%Ru-1.0%Ce/TiO₂与0.4%Ru/TiO₂相比，其T₁₀和T₉₀分别降低了50℃和60℃。H₂-TPR表明引入Ce为催化剂提供了更多的表面氧空位，形成Ru-O-Ce增强了其氧化还原能力。掺杂Ce未改变Ru/TiO₂催化剂的结构形貌，仍保持介孔结构，但若负载量过多，会堵塞部分孔道，阻碍污染物吸附及反应，降低催化性能。

关键词: 氯苯, 催化氧化, Ru, Ce, Ru-Ce/TiO₂

Abstract:

A single metal Ru/TiO₂ catalyst and a Ru-Ce/TiO₂ catalyst were prepared by the equal-volume impregnation method to investigate their effect on the catalytic oxidation of chlorobenzene. The catalysts were characterized by N₂-desorption,SEM and H₂-TPR, which were used to investigate the effect of Ce doping on the catalytic oxidation of chlorobenzene. The results show that the introduction of Ce can maintain high catalytic efficiency while reducing the content of precious metals, and greatly improve the catalytic activity at low temperatures. Compared with the 0.4%Ru/TiO₂, T₁₀and T₉₀ of the 0.4%Ru-1.0%Ce/TiO₂ decreased by 50℃ and 60℃, respectively. H₂-TPR results showed that the introduction of Ce provided more surface oxygen vacancies on the catalyst, and the formation of Ru-O-Ce enhanced its REDOX capacity. The structure and morphology of the Ru/TiO₂ catalyst did not change with the Ce doping, and the mesoporous structure of the catalysts maintained. However, if the content of Ce was too large, some pores on the catalysts could be blocked, which would decrease the adsorption of pollutants and catalytic reaction, and its catalytic performance would be reduced.

Key words: chlorobenzene, catalytic oxidation, Ru, Ce, Ru-Ce/TiO₂

中图分类号:

X 511

梁文俊, 朱玉雪, 石秀娟, 孙慧频, 任思达. Ce掺杂对Ru/TiO₂催化氯苯性能的影响[J]. 化工学报, 2020, 71(8): 3585-3593.

Wenjun LIANG, Yuxue ZHU, Xiujuan SHI, Huipin SUN, Sida REN. Effect of Ce doping on catalytic chlorobenzene performance of Ru/TiO₂catalysts[J]. CIESC Journal, 2020, 71(8): 3585-3593.

图/表 10

图1 催化活性评价流程1—空压机；2—干燥管；3—质量流量计；4—氯苯发生瓶；5—水浴锅；6—缓冲混气瓶；7—电磁换向阀；8—石英反应管；9—立式管式加热炉；10—温控仪；11—尾气吸收瓶；12—在线气相色谱仪

Fig.1 Catalytic activity evaluation process

图2 Ru/TiO2催化剂催化氧化氯苯活性

Fig.2 Catalytic oxidation of chlorobenzene by Ru/TiO2 catalyst

图3 Ce/TiO2催化剂催化氧化氯苯活性

Fig.3 Catalytic oxidation of chlorobenzene by Ce/TiO2 catalyst

图4 Ru-Ce/TiO2催化剂催化氧化氯苯活性

Fig.4 Catalytic oxidation of chlorobenzene by Ru-Ce/TiO2 catalyst

表1 不同氯苯转化率下的有机副产物

Table 1 Organic by-products at different conversion of chlorobenzene

样品	转化率
样品	20%	40%	60%	80%	100%
0.4%Ru/TiO₂	DCB	DCB、TCB	DCB、PCB、BHC	DCB	—
0.4%Ru-1.0%Ce/TiO₂	DCB	DCB	DCB	苯	—

图5 出口气体中的有机副产物(氯苯转化率为60%)

Fig.5 Organic by-products in the outlet effluent (the conversion of chlorobenzene is 60%)

图6 不同催化剂的SEM图(×5000)

Fig.6 SEM images of different catalysts(×5000)

表2 催化剂比表面积及孔结构数据

Table 2 Specific surface area and pore structure of catalysts

催化剂	比表面积/(m²/g)	孔容/(cm³/g)	孔径/nm
TiO₂	71.72	0.39	12.6
1.0%Ce/TiO₂	70.02	0.37	15.8
0.4%Ru/TiO₂	70.73	0.37	11.4
0.4%Ru-0.5%Ce/TiO₂	69.30	0.38	14.8
0.4%Ru-1.0%Ce/TiO₂	68.92	0.37	14.2
0.4%Ru-4.0%Ce/TiO₂	67.42	0.36	14.4

图7 N2吸脱附等温线

Fig.7 N2 absorption and desorption isotherms

图8 不同催化剂H2-TPR图

Fig.8 H2-TPR profiles of different catalysts

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Ce掺杂对Ru/TiO₂催化氯苯性能的影响

Effect of Ce doping on catalytic chlorobenzene performance of Ru/TiO₂catalysts

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