多孔钼钛氧化物的自支撑制备及其结构转变

doi:10.15541/jim20160069

摘要/Abstract

摘要：

通过MoO₃与TiO₂相互支撑的方法制备了一系列多孔钼钛氧化物, 并在此基础上研究了该材料结构在随焙烧温度变化过程中的转变机制, 通过XRD、BET、FESEM、TG/DTG等表征分析, 当焙烧温度低于600℃时, MoO₃呈固体状态, 通过MoO₃与TiO₂相互支撑可以制备出比表面积高达182 m²/g的介孔钼钛氧化物, 可负载更多分散良好的MoO₃, 其加氢脱硫性能显著优于常规浸渍法制备的催化材料; 当焙烧温度高于600℃时, MoO₃呈熔融状态, “自支撑效应”消失, 钼钛氧化物孔结构发生坍塌。

关键词: 钼钛氧化物, 自支撑, 比表面积, 结构转变, 加氢脱硫

Abstract:

A series of porous molybdenum-titanium oxide (Mo-TiO₂) were prepared by mutual support of MoO₃ and TiO₂, and the resulting structural transformation with calcination temperature was also studied in the present study. The as-prepared samples were characterized mainly by XRD, BET, FESEM, and TG/DSC. When the calcination temperature was lower than 600℃, MoO₃ can maintain solid state. Mesoporous Mo-TiO₂ with surface area of 182 m²/g was obtained via mutual support of MoO₃ and TiO₂. The oxide loaded by more well-dispersed MoO₃ possessed significantly better hydrodesulfurization performance than that prepared by impregnation did. As MoO₃ was fused at above 600℃, “self supported effect” was disappeared and the porous structure of Mo-TiO₂ collapsed finally.

Key words: molybdenum-titanium oxide, self support, surface area, structural transformation, hydrodesulfurization

中图分类号:

TQ34

李力成, 何甜甜, 赵学娟, 钱祺, 王磊, 李小保. 多孔钼钛氧化物的自支撑制备及其结构转变[J]. 无机材料学报, 2016, 31(11): 1198-1204.

LI Li-Cheng, HE Tian-Tian, ZHAO Xue-Juan, QIAN Qi, WANG Lei, LI Xiao-Bao. Self Supported Synthesis of Porous Molybdenum-titanium Oxide and the Resulting Structural Transformation[J]. Journal of Inorganic Materials, 2016, 31(11): 1198-1204.

图/表 10

表1 不同钼钛氧化物的结构数据

Table 1 Structural data of various porous molybdenum-titanium oxides

Samples	Crystalline phase	Crystalline particle size / nm^αα	Surface area / (m²·g^-1)	Pore volume / (cm³·g^-1)	Average pore size / nm	MoO₃ content / %
Titanate derivate	Amorphous	/	234	0.17	3.2	/
TiO₂	Anatase	8.6 ^A	103	0.20	5.9	/
Mo-TiO₂(400)	Anatase	4.7 ^A	182	0.14	3.7	16.1
Mo-TiO₂(500)	Anatase	6.2 ^A	173	0.21	4.9	14.0
Mo-TiO₂(600)	Anatase/rutile	14.1 ^A, 19.3 ^R	39	0.16	14.1	9.2
Mo-TiO₂(700)	Rutile	19.0 ^R	7.0	0.03	/	2.9
Mo-TiO₂(800)	Rutile	21.5 ^R	3.2	<0.01	/	2.5

图1 不同焙烧温度制备多孔钼钛氧化物的N2吸附/脱附等温曲线(a)和孔径分布图(b)

Fig. 1 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of porous Mo-TiO2 with different calcination temperatures

图2 不同焙烧温度制备多孔钼钛氧化物的FESEM照片

Fig. 2 FESEM images of porous Mo-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

图3 不同焙烧温度制备Mo-TiO2和TiO2比表面积的比较

Fig. 3 Comparison on the surface area of Mo-TiO2 and TiO2 calcined at different temperatures

图4 不同多孔钼钛氧化物和对比样品的加氢脱硫性能图

Fig. 4 Hydrodesulfurization performance of various porous Mo-TiO2

图5 不同焙烧温度制备多孔钼钛氧化物的XRD图谱

Fig. 5 XRD patterns of porous Mo-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

图6 不同焙烧温度制备Mo(I)-TiO2前驱体的XRD图谱

Fig. 6 XRD patterns of precursor Mo(I)-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

图7 多孔钼钛氧化物的峰高比值对比图

Fig. 7 Peak height ratio of porous Mo-TiO2 composites

图8 钼酸铵与钛酸盐衍生物混合物的TG和DSC曲线图

Fig. 8 TG and DSC curves of hybrid of ammonium molybdate and titanate derivative

图9 各种多孔钼钛氧化物的制备过程示意图

Fig. 9 Scheme for preparation process of various porous Mo-TiO2 composites

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