非水沉淀法制备纳米氧化钛及其光催化性能研究

doi:10.15541/jim20170532

摘要/Abstract

摘要：

采用非水沉淀工艺制备了锐钛矿型纳米氧化钛(TiO₂)。在冰醋酸的催化作用下, 钛酸丁酯在乙醇中发生非水解反应。冰醋酸的引入增加了钛酸丁酯中Ti-O键和C-O键的极性, 进而促进其在溶剂乙醇中发生非水解脱醚缩聚反应形成Ti-O-Ti键合。经过80℃回流24 h, Ti-O-Ti键重排形成锐钛矿型纳米TiO₂。其粒径为5~20 nm; 比表面积为169.4 m²/g。非水沉淀法制备的纳米氧化钛分散性良好, 光催化性能优异。紫外光照2 h, 纳米氧化钛对甲基橙的降解率达99.81%, 具有良好的污水处理应用前景。

关键词: TiO₂, 非水沉淀法, 光催化性能, 低温合成

Abstract:

A facile strategy for anatase titanium dioxide (TiO₂) nanoparticle preparation was proposed via a non-aqueous precipitation method. With the aid of glacial acetic acid, tetrabutyl titanate underwent non-hydrolytic reaction in solvent ethanol. Glacial acetic acid increased polarity of Ti-O and C-O bonds of tetrabutyl titanate, and promoted non-hydrolytic de-etherization poly condensation reaction to form Ti-O-Ti bond in the solvent. After refluxing at 80℃ for 24 h, the Ti-O-Ti bond was rearranged to form anatase TiO₂ nanoparticles with the particle size of 5 nm-20 nm and specific surface area of 169.4 m²/g, which exhibited good dispersion and excellent photocatalytic activity. The degradation rate against methyl orange under ultraviolet radiation for 2 h reached 99.81%, showing promising prospect in wastewater treatment process.

Key words: TiO₂, non-aqueous precipitation method, photocatalytic property, low temperature synthesis

中图分类号:

TQ174

江峰, 于云, 冯爱虎, 于洋, 米乐, 宋力昕. 非水沉淀法制备纳米氧化钛及其光催化性能研究[J]. 无机材料学报, 2018, 33(10): 1136-1140.

JIANG Feng, YU Yun, FENG Ai-Hu, YU Yang, MI Le, SONG Li-Xin. Anatase TiO₂ Nanoparticles: Facile Synthesis via Non-aqueous Precipitation and Photocatalytic Property[J]. Journal of Inorganic Materials, 2018, 33(10): 1136-1140.

图/表 8

Fig. 1 (a, b) TEM, (c) HRTEM images and (d) SAED pattern of the as-prepared TiO2 nanoparticles

Fig. 2 FT-IR spectra of samples at different reaction stages

Table 1 Peak position of samples at different reaction stages (cm-1)

Ti(OBu)₄	Ti(OBu)₄+ AcOH	Precipitate slurry	Precipitate	Attribution	Ref.
3334	-	3334	-	OH	[19]
2958	2958	2958	-	C-H	[20]
2933	2933	2933	-	aromatic C-C	[21]
2873	2873	2873	-	C-H	[20]
2700	-	-	-	C-H	[20]
1460	-	-	-	-CH₂	[22]
1379	1419	-	-	-CH₃	[22]
1124	-	-	-	Ti-O-C	[23]
1096	-	-	-	Ti-O-C	[23]
1039	-	-	-	Ti-O-C-	[23]
611	613	-	-	Ti-O	[24]
-	1724	1735	-	-C==O	[25]
-	1547	-	-	COO-group	[26]
-	1290	-	-	C-O	[27]
-	1070	1074	-	C-O	[28]
-	1028	1045	-	C-O	[29]
-	-	1458	-	CH₂	[30]
-	-	1378	-	Sym COO	[31]
-	-	1189	-	C-O	[32]
-	-	881	-	C-COO	[31]
-	-	438	455	Ti-O-Ti	[33]

Fig. 3 Mechanism of acetic acid coordinated with butyl titanate

Fig. 4 FT-IR spectrum of the non-hydrolytic polycondensation by-product

Fig. 5 Schematic diagram of the proposed mechanism for the formation of TiO2 nanoparticles

Fig. 6 Photodegradation effect of TiO2 nanoparticles(a) UV-Vis absorption spectra of MO solutions after photocatalytic performance test at different time intervals; (b) Photodegradation rate of MO after photocatalysis by TiO2 nanoparticles and commercial P25 powders

Fig. 7 Kinetics of MO photodegradation (linear transform ln(c/c0) vs t in photocatalytic experiments)

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