嵌段共聚物模板法制备La掺杂TiO2超滤膜

doi:10.15541/jim20140264

摘要/Abstract

摘要：

以钛酸四丁酯为Ti源, 氯化镧为La源, 采用嵌段共聚物模板法制备了La掺杂TiO₂超滤膜。通过动态热机械分析(DMA)、X射线衍射(XRD)、低温氮气吸附脱附和X射线光电子能谱(XPS)等表征方法, 考察了La掺杂对TiO₂凝胶的机械性能及其材料晶型、孔结构的影响。分析结果表明, La的引入显著提高了TiO₂凝胶的机械性能,避免了膜层在干燥阶段的开裂现象; 并有效抑制了晶粒增长和晶相转变, 使得锐钛矿相在800℃下仍能保持稳定。同时La的引入也提高了TiO₂材料的比表面积和孔隙率, 通过实验确定La掺杂量为0.74 g, 此时TiO₂溶胶的粒径分布最均一, 所得溶胶粒径为10 nm。采用该溶胶制备出的La-TiO₂超滤膜的孔径为2.3 nm, 而未掺杂时膜的孔径为2.7 nm。

关键词: 镧掺杂, 溶胶- 凝胶, TiO2, 超滤膜

Abstract:

La-doped TiO₂ ultrafiltration membrane was prepared via a block copolymer assisted polymeric Sol-Gel process. The effects of La doping on the mechanical property of TiO₂ gel, the crystal phase transformation and mesostructure of TiO₂materials were investigated by dynamic mechanical analysis (DMA), N₂ adsorption-desorption, X-ray diffraction (XRD), and X-ray photoelectron spectroscope (XPS) analysis. Results showed that the mechanical strength of the formed gel was significantly improved by the introduction of lanthanum, by which the risk of the membrane cracking could be reduced largely. X-ray diffraction analysis showed that La doping inhibited the TiO₂crystal phase transformation and the anatase phase could still keep stable at 800℃. Furthermore, the BET surface area and porosity of the materials were also increased. The optimal La doping amount was 0.74 g, and the formed TiO₂sol particle size was 10 nm. Futher more, the filtration experiments showed that the La-doped TiO₂ultrafiltration membrane possessed a pore size of 2.3 nm, while the pore size of the La-undoped TiO₂membrane was 2.7 nm.

Key words: La-doped, Sol-Gel, titania, ultrafiltration membrane

中图分类号:

TQ174

陈涛涛, 李丹, 景文珩, 范益群, 邢卫红. 嵌段共聚物模板法制备La掺杂TiO₂超滤膜[J]. 无机材料学报, 2015, 30(2): 171-176.

CHEN Tao-Tao, LI Dan, JING Wen-Heng, FAN Yi-Qun, XING Wei-Hong. Preparation of La-doped TiO₂Ultrafiltration Membrane by Templating of Block Copolymer[J]. Journal of Inorganic Materials, 2015, 30(2): 171-176.

图/表 9

图1 La掺杂对TiO2溶胶粒径的影响

Fig. 1 Effect of La doping on the particle size of TiO2 sol

图2 不同温度煅烧不同La掺杂量的TiO2材料的XRD图谱

Fig. 2 XRD patterns of TiO2 powders doped with different amounts of La and calcined at different temperatures

图3 不同La掺杂量对不同温度煅烧的TiO2粉末的晶粒尺寸的影响

Fig. 3 Effects of La-doping on the crystal size of TiO2 powder calcined at different temperatures

图4 经400℃煅烧的不同镧掺杂量的TiO2粉末的氮气吸附脱附等温线(a)和BJH孔径分布(b)

Fig. 4 N2 adsorption-desorption isotherms (a) and BJH pore size distributions (b) obtained from TiO2 powder doped with different amounts of La and calcined at 400℃

表1 经400℃煅烧的不同镧掺杂量的TiO2粉末的孔结构参数

Table 1 Pore properties of TiO2 powder doped with different amounts of La and calcined at 400℃

Samples	BET area/(m²·g^-1)	BJH pore diameter/nm	Total pore volume/(cm³·g^-1)	Porosity/%
La-undoped-400℃	102.3	3.70	0.1005	27.8
La-0.37g-400℃	144.3	3.28	0.1310	33.5
La-0.74g-400℃	169.6	3.70	0.1619	38.3
La-1.1 g-400℃	96.5	3.28	0.0949	26.7

图5 La掺杂前后TiO2凝胶的储存模量(a)和损耗模量(b)随温度的变化关系

Fig.5 Storage modulus (a) and loss modulus profiles (b) of La-undoped and -doped TiO2 gels

图6 La-0.74 g TiO2材料的高清XPS图谱

Fig. 6 XPS spectra of La-0.74 g TiO2 powders (a) and high-resolution XPS spectra of Ti2p (b), La3d (c), C1s (d) and O1s (e)

图7 支撑体和La-TiO2片式膜的纯水通量随操作压力变化关系(a)和PEG截留曲线(b)

Fig. 7 Pure water flux (a) and PEG retention curves (b) of La-TiO2 membrane

图8 TiO2片式膜表面及断面电镜照片

Fig. 8 FESEM micrographs of the surface (a) and cross- section (b) of La-doped TiO2 membrane

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嵌段共聚物模板法制备La掺杂TiO₂超滤膜

Preparation of La-doped TiO₂Ultrafiltration Membrane by Templating of Block Copolymer

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