离子液体对可磁分离TiO2光催化材料结构和性能的影响

doi:10.15541/jim20140687

摘要/Abstract

摘要：

采用溶胶-凝胶法分别在离子液体1-丁基-3-甲基咪唑四氟硼酸盐[BMim]BF₄、1-丁基-吡啶四氟硼酸盐[BPy]BF₄和1-丁基-3-甲基咪唑醋酸盐[BMim]Ac的辅助下制备可磁分离TiO₂/CoFe₂O₄(TCF)光催化材料, 采用X射线衍射分析(XRD)、N₂吸附-脱附分析(BET)和透射电子显微镜(TEM)研究了离子液体结构对可磁分离TiO₂的结构和性能的影响。结果显示: 200 ℃焙烧后样品[BMim]BF₄-TCF和[BPy]BF₄-TCF有锐钛矿相TiO₂生成, 而样品[BMim]Ac-TCF和TCF只有经400 ℃焙烧才出现锐钛矿相的衍射峰。当焙烧温度为800 ℃时, 样品[BMim]BF₄-TCF主要以锐钛矿相TiO₂存在(相对含量为92.6%), 说明离子液体中含有[BF₄^-]基团能降低锐钛矿相的晶化温度和能提高锐钛矿相高温稳定性。400 ℃焙烧后[BMim]BF₄-TCF和[BPy]BF₄-TCF的比表面积分别为125.7和120.3 m²/g, 高于[BMim]Ac-TCF(77.8 m²/g)和不加离子液体所制备样品TCF(63.7 m²/g)。说明阴离子BF₄^-有利于形成较大比表面积的TiO₂。在模拟太阳光照射120 min后, 经400 ℃焙烧后的样品[BMim]BF₄-TCF、[BPy]BF₄-TCF、[BMim]Ac- TCF对亚甲基蓝的降解速率分别为96%、87%、64%。

关键词: 离子液体, 可磁分离, 二氧化钛, 溶胶-凝胶法

Abstract:

Magnetically separable TiO₂/CoFe₂O₄ (TCF) photocatalytic materials were prepared by Sol-Gel method with the assistance of ionic liquids [BMim]BF₄, [BPy]BF₄ and [BMim]Ac, respectively. The influence of ionic liquids on structure and properties of the magnetically separable TiO₂ was characterized by X-ray diffraction (XRD), N₂ adsorption-desorption measurement (BET), transmission electron microscope (TEM). The results showed that anatase TiO₂ was formed in [BMim]BF₄-TCF and [BPy]BF₄-TCF after calcination at 200 ℃, while anatase TiO₂ was not formed in [BMim]Ac-TCF and TCF until the calcination temperature was increased to 400 ℃. When the calcination temperature was increased to 800 ℃, TiO₂ in [BMim]BF₄-TCF predominantly existed in the form of anatase structure (92.6%). These results indicated that BF₄^- anions in ionic liquids might reduce the crystallization temperature of anatase and improve the thermal stability of anatase at high temperatures. Samples prepared with the assistance of [BMim]BF₄ or [BPy]BF₄ exhibited larger specific surface areas (125.7 and 120.3 m²/g) than that of prepared by using [BMim]Ac (77.8 m²/g) or without addition of ionic liquid (63.7 m²/g). Photocatalytic activity of the samples was tested by photodegradation of methylene blue (MB) under simulated sunlight. MB photodegradation rates after 2 h irradiation over [BMim]BF₄-TCF, [BPy]BF₄-TCF, [BMim]Ac-TCF calcined at 400 ℃ were 96%, 87% and 64%, respectively.

Key words: ionic liquid, magnetically separable, titanium dioxide, Sol-Gel method

中图分类号:

O649

李燕春, 张秀玲, 詹志彬, 底兰波. 离子液体对可磁分离TiO₂光催化材料结构和性能的影响[J]. 无机材料学报, 2015, 30(7): 706-712.

LI Yan-Chun, ZHANG Xiu-Ling, ZHAN Zhi-Bin, DI Lan-Bo. Influence of Ionic Liquids on Structure and Properties of Magnetically Separable TiO₂ Photocatalytic Materials[J]. Journal of Inorganic Materials, 2015, 30(7): 706-712.

图/表 7

图1 不同温度焙烧[BMim]BF4-TCF (a)、[BPy]BF4-TCF(b)、[BMim]Ac-TCF(c)和TCF(d)的XRD谱图

Fig. 1 XRD patterns of [BMim]BF4-TCF (a), [BPy]BF4-TCF (b), [BMim]Ac-TCF (c) and TCF (d) calcined at different temperatures

图2 400 ℃焙烧样品[BMim]BF4-TCF(a)、[BPy]BF4-TCF(b)和[BMim]Ac-TCF(c)的TEM照片

Fig. 2 TEM images of [BMim]BF4-TCF (a), [BPy]BF4-TCF (b) and [BMim]Ac-TCF (c) calcined at 400 ℃

图3 400 ℃焙烧不同样品的N2吸附-脱附等温线(a)和孔径分布曲线(b)

Fig. 3 Nitrogen adsorption-desorption isotherms (a) and pore size distribution curves (b) of different samples calcined at 400 ℃

表1 400 ℃焙烧不同样品的结构参数

Table 1 Structural parameters of different samples calcined at 400 ℃

Sample	Pore volume /(cm³·g^-1)	Pore diameter/nm	Surface area /(m²·g^-1)	Particle size/nm
[BMim]BF₄-TCF	0.24	7.6	125.7	7.2
[BPy]BF₄-TCF	0.23	6.6	120.3	8.5
[BMim]Ac-TCF	0.05	1.8	77.8	8.7
TCF	0.08	1.9	63.7	9.3

图4 400 ℃焙烧不同样品的光催化降解曲线(a), ln(c0/c)与τ 关系曲线(b)及相应降解速率常数(c)

Fig. 4 Photocatalytic MB degradation (a), ln(c0/c) as a function of τ (b), degradation rate constants (c) of different samples calcined at 400 ℃

图5 CoFe2O4和[BMim]BF4-TCF磁性能曲线

Fig. 5 Magnetic curves of CoFe2O4 and [BMim]BF4-TCF

图6 [BMim]BF4-TCF重复使用光降解曲线

Fig. 6 Recycling experiments for [BMim]BF4-TCF

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离子液体对可磁分离TiO₂光催化材料结构和性能的影响

Influence of Ionic Liquids on Structure and Properties of Magnetically Separable TiO₂ Photocatalytic Materials

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