尖晶石型AFe2O4催化剂的制备及其催化燃烧甲苯的研究

doi:10.15541/jim20160705

摘要/Abstract

摘要：

通过溶胶-凝胶-自蔓延燃烧法制备尖晶石型AFe₂O₄(A=Cu, Co, Ni, Mg, Zn)催化剂, 以甲苯为VOCs模拟气, 考察AFe₂O₄催化剂对VOCs的催化燃烧活性, 并采用XRD、N₂吸附-脱附、SEM、TEM、H₂-TPR、XPS对催化剂进行表征分析。结果表明: AFe₂O₄表现出较好的催化燃烧活性, 其中CuFe₂O₄的催化燃烧活性最佳, 起燃温度(T50)和完全燃烧温度(T90)分别为188℃、239℃。AFe₂O₄具有明显的片状尖晶石晶体, 并形成以介孔为主的多级孔结构, 该特点为催化剂提供了大量表面活性位。A位元素种类对其催化燃烧活性影响较大, 当A位元素为Cu时, Cu的H₂还原峰面积远大于其他元素, H₂还原温度仅为289℃, 表面亲电子氧和氧空位浓度占氧元素总量(O_ele/O_1S)的36%。CuFe₂O₄为片状反尖晶石晶型, 晶格体积仅为0.294 nm³, 并伴有CuO和α-Fe₂O₃物种。以介孔为主的多级孔结构、特有的片状反尖晶石晶型以及该晶型与CuO和α-Fe₂O₃的协同作用是CuFe₂O₄催化燃烧活性提高的主要原因。

null

关键词: 尖晶石, VOCs, 催化燃烧, 铁酸盐

Abstract:

Nanocrystalline AFe₂O₄(A=Cu, Co, Ni, Mg, Zn) ferrite spinel catalysts were prepared by Sol-Gel auto-combustion method. In order to investigate the influence of A sites in AFe₂O₄ spinel catalysts, the catalytic combustion of toluene was investigated, and the catalysts were characterized by XRD, N₂ adsorption-desorption, SEM, TEM, H₂-TPR, and XPS. It was found that AFe₂O₄ catalysts have excellent catalytic activity. Among the catalysts, the CuFe₂O₄ catalyst obtains the highest catalytic activity, and its light-off temperature (T₅₀) and the complete combustion temperature (T₉₀) of toluene were 188℃ and 239℃, respectively. And AFe₂O₄ catalysts have obviously lamellar spinel crystal structure and the multilevel pore structures with prevalence to mesoporous, which will improve the catalytic activity of the catalysts. It is concluded that the elements of A site on AFe₂O₄ have great influence on catalytic combustion activity. The H₂ reduction temperature is only 289℃, when A site was occupied by Cu. CuFe₂O₄ has crystal lattice volume of 0.294 nm³ with CuO and α-Fe₂O₃ formed in the crystal. The concentration of electrophilic oxygen and oxygen vacancy in all oxygens (O_ele/O_1S) is 36%. Lamellar trans spinel crystal lattice, the synergies of trans spinel CuFe₂O₄ with CuO and α-Fe₂O₃, and the multilevel pore structures with prevalence to mesoporous are the main reasons for the catalytic activity improvement of CuFe₂O₄.

Key words: spinel, VOCs, catalytic combustion, ferrite

中图分类号:

O643

王永强, 薛锐, 臧萌, 刘敏敏, 陈曦, 赵朝成. 尖晶石型AFe₂O₄催化剂的制备及其催化燃烧甲苯的研究[J]. 无机材料学报, 2017, 32(10): 1068-1074.

WANG Yong-Qiang, XUE Rui, ZANG Meng, LIU Min-Min, CHEN Xi, ZHAO Chao-Cheng. Spinel AFe₂O₄ Catalysts: Preparation and Catalytic Combustion of Toluene[J]. Journal of Inorganic Materials, 2017, 32(10): 1068-1074.

图/表 8

图1 催化燃烧固定床反应装置流程图

Fig. 1 Flow chart of fixed bed catalytic combustion

图2 AFe2O4催化燃烧甲苯曲线

Fig. 2 Catalytic combustion curves of toluene over AFe2O4

图3 AFe2O4的XRD图谱

Fig. 3 XRD patterns of AFe2O4

表1 AFe2O4的晶体结构及孔结构参数

Table 1 Crystalline and porous structure parameters of AFe2O4

Sample	S_BET/(m²·g^-1)	Pore size/nm	Pore volume/(cm³·g^-1)	Space group	Crystallite size/nm	Cell volume/nm³
MgFe₂O₄	21.5	19.8	0.11	Fd-3m	41.6	0.59057
ZnFe₂O₄	19.4	22.4	0.12	Fd-3m	31.5	0.60265
CuFe₂O₄	10.5	23.0	0.06	I4₁/amd	44.5	0.29402
CoFe₂O₄	15.1	19.7	0.07	Fd-3m	46.3	0.59099
NiFe₂O₄	5.4	21.9	0.03	Fd-3m	44.0	0.57966

图4 AFe2O4的孔分布曲线

Fig. 4 Pore size distribution curves of AFe2O4

图5 CuFe2O4的SEM(a)和TEM(b)照片

Fig. 5 SEM (a) and TEM (b) images of CuFe2O4

图6 CuFe2O4的XPS全谱图(a)和O1s的XPS谱图(b)

Fig. 6 Full XPS spectrum (a) and O1s spectrum (b) of CuFe2O4

图7 AFe2O4的H2-TPR图谱

Fig. 7 H2-TPR spectra of AFe2O4

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尖晶石型AFe₂O₄催化剂的制备及其催化燃烧甲苯的研究

Spinel AFe₂O₄ Catalysts: Preparation and Catalytic Combustion of Toluene

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