铕掺杂的TiO2空心微球的制备及光催化性能

doi:10.15541/jim20140599

摘要/Abstract

摘要：

通过溶胶-凝胶法制备未掺杂和铕掺杂的TiO₂空心微球, 采用XRD、SEM、TEM、HRTEM、BET和XPS等技术对样品进行表征, 以亚甲基蓝的光催化降解为目标反应, 评价其光催化活性。结果表明, 钛酸四丁酯(TBOT)的加入量对微球的形貌影响较大, 当滴加1.5 mL的TBOT时, 可得结构清晰、分散性良好的TiO₂空心微球。XRD分析表明, 400℃煅烧的纳米TiO₂空心微球为锐钛矿, 掺铕可抑制TiO₂的晶相转变。光催化实验表明, 铕掺杂能显著提高TiO₂空心微球的活性。当铕掺量为0.7%时, 所得样品粒径和孔径最小, 比表面积最大, 光催化活性最高。

关键词: 二氧化钛, 空心, 铕掺杂, 溶胶-凝胶法, 煅烧温度, 钛酸四丁酯

Abstract:

Pure TiO₂ and Eu-doped TiO₂ hollow microspheres were prepared by Sol-Gel method and characterized by techniques such as XRD, SEM, TEM, HRTEM, BET and XPS. Photocatalytic degradation of methylene blue (MB) in aqueous solution was used as a probe reaction to evaluate their photocatalytic activity. The experimental results show that the dosage of TBOT has a great effect on the morphology of TiO₂ hollow microspheres. When the dosage of TBOT is 1.5 mL, the obtained hollow microspheres disperse well and show clear structure. XRD pattern indicates that TiO₂ hollow microspheres calcined at 400℃ present anatase structure and Eu-doped ones can restrain the anatase phase from converting to rutile phase. The experimental results suggest that Eu-doped can obviously improve the photocatalytic activity of TiO₂ hollow microsphere and when the doping of Eu is 0.7%, the photocatalytic degradation reaches the best because of its highest surface area and smallest crystallize size and pore diameter.

Key words: titanium dioxide, hollow, Eu-doped, Sol-Gel, calcination temperature, tetra-n-butyl titanate

中图分类号:

TF123

刘阳龙, 郑玉婴, 尚鹏博. 铕掺杂的TiO₂空心微球的制备及光催化性能[J]. 无机材料学报, 2015, 30(7): 699-705.

LIU Yang-Long, ZHENG Yu-Ying, SHANG Peng-Bo. Preparation, Characterization and Photocatalytic Property of Eu-doped TiO₂ Hollow Microspheres[J]. Journal of Inorganic Materials, 2015, 30(7): 699-705.

图/表 8

图1 制备TiO2空心微球的原理图

Fig. 1 Schematic diagram for the preparation of TiO2 hollow microspheres

图2 不同TBOT滴加量所得样品的SEM(a~d)和滴加1.5 mL的TBOT所得样品的TEM(e)和HRTEM(f)

Fig. 2 SEM images of hollow microspheres prepared from solution with different quantities of TBOT (a-d) and TEM (e) and HRTEM (f) images of hollow microspheres by adding 1.5 mL TBOT (a) TBOT, 0.5 mL; (b) TBOT, 1 mL; (c) TBOT, 1.5 mL; (d) TBOT, 2 mL

图3 不同温度煅烧所得TiO2空心微球的XRD图谱

Fig. 3 XRD patterns of TiO2 hollow microspheres after being calcined at different temperatures

图4 不同掺铕量的TiO2空心微球的XRD图谱

Fig. 4 XRD patterns of TiO2 hollow microspheres with different Eu doping concentrations

图5 不同掺铕量的TiO2空心微球样品的N2吸附-脱附等温线以及对应的孔径分布

Fig. 5 N2 adsorption-desorption isotherms and corresponding pore size distribution of TiO2 hollow microsphere samples with different Eu doping concentrations

表1 不同掺铕量的TiO2空心微球的物理参数

Table 1 Physical parameters of TiO2 hollow microsphere samples with different Eu doping concentrations

Sample	Crystallize size/nm	Surface area/(m²·g^-1)	Pore diameter/nm
TE(0)	12.9	221	5.5
TE(0.1%)	10.7	256	4.9
TE(0.3%)	9.5	275	4.2
TE(0.7%)	8.3	298	3.5
TE(1.2%)	10.0	268	4.5
TE(1.5%)	11.2	250	5.1

图6 400℃煅烧样品TE(0.7%)的XPS谱图

Fig. 6 XPS spectra of sample TE (0.7%) after being calcined at 400℃ (a) Full XPS spectra; (b) Ti2p; (c) O1s; (d) Eu4d

图7 不同掺铕量的样品对亚甲基蓝的光催化降解曲线

Fig. 7 Photocatalytic degradation curve of MB by samples with different Eu doping concentrations

参考文献 34

[1]	ALLINSON G, STAGNITTI F, COLVILLE S, et al.Growth of floating aquatic macrophytes in alkaline industrial wastewaters.Journal of Environmental Engineering, 2000, 126(12): 1103-1107.
[2]	GOSWAMI D Y.A review of engineering developments of aqueous phase solar photocatalytic detoxification and disinfection processes.Journal of Solar Energy Engineering, 1997, 119(3): 101-107.
[3]	ZHAO W, MA W H, CHEN C C.Efficient degradation of toxic organic pollutants with Ni2O3/TiO2-xBx under visible irradation.Journal of the American Chemical Society, 2004, 126(15): 4782-4783.
[4]	ZHANG QING-HONG, GAO LIAN, GUO JING-KUN.Photocatalytic activity of nanosized TiO2.Journal of Inorganic Materials, 2000, 15(3): 556-560.
[5]	JI BONG JOO, QIAO ZHANG, IIKEUN LEE, et al.Mesoporous anatase titania hollow nanostructures though silica-protected calcination.Advanced Functional Materials, 2012, 22(1): 166-174.
[6]	SUN B, VORONTSOV AV, SMIRNIOTIS PG.Role of platinum deposited on TiO2 in phenol photocatalytic oxidation.Langmuir, 2003, 19(8): 3151-3156.
[7]	CHOI W K, EAS TERMIN, MICHAEL R. HOFFMANN. The role of metal ion dopants in quantum-sized TiO2: correlation between photoreactivity and charge carrier recombination dynamic.The Journal of Physical Chemistry, 1994, 98(51): 13669-13679.
[8]	KARTHIK K, VICTOR JAYA N.High pressure electrical resistivity studies on Ni-doped TiO2 nanoparticles.Journal of Alloys and Compounds, 2011, 509(16): 5173-5176.
[9]	BAE E, CHOI W.Highly enhanced photoreductive degradation of perchlorinated compounds on dye-sen-sitized metal/TiO2 under visible light.Environ. Sci. Technol., 2003, 37(1): 147-152.
[10]	LIANG YU-CHUAN, WANG CHIH-CHIEH, KEI CHI-CHUNG, et al.Photocatalysis of Ag-loaded TiO2 nanotube arrays formed by atomic layer deposition.The Journal of Physical Chemistry C, 2011, 115(19): 9498-9502.
[11]	ZHONG LIANG-SHU, HU JIN-SONG, CUI ZHI-MIN, et al.In-situ loading of noble metal nanoparticles on hydroxyl- ground-rich titania precursor and their catalytic applications.Chemistry of Materials, 2007, 19(18): 4557-4562.
[12]	ZHOU WEI, ZHENG YU-HUI, WU GUANG-HUI.Novel luminescent RE/TiO2(RE=Eu, Gd)catalysts prepared by in-situation Sol-Gel approach construction of multi-functional precursors and their photo or photocatalytic oxidation properties.Applied Surface Science, 2006, 253(3): 1387-1392.
[13]	RANJIT K T, WILLNER I, BOSSMANN S H, et al.Lanthanide oxide doped titanium dioxide photocatalysts: effective photocatalysts for the enhanced degradation of salicylic acid and t-cinnamic acid.Journal of Catalysis, 2001, 204(2): 305-310.
[14]	LI F B, LI X Z, AO C H, et al.Enhaned photocatalytic degradation of VOCs using Ln3+-TiO2 catalysts for indoor air purification.Chemosphere, 2005, 59(6): 787-800.
[15]	LIANG CHUN-HUA, HOU MEI-FANG, ZHOU SHUN-GUI, et al. The effect of erbium on the adsorption and photodegradation of orange I in aqueous Er3+-TiO2 suspension. Journal of Hazardous Materials, 2006, 138(3): 471-478.
[16]	SYOUFIAN A, SATRIYAA O H, NAKASHIMA K.Photocatalytic activity of titania hollow spheres: photodecomposition of methylene blue as a target molecule.Catalysis Communications, 2007, 8(5): 755-759.
[17]	YU JIA-GUO, ZHANG LI-JUAN, BEI CHENG, et al.Hydrothermal preparation and photocatalytic activity of hierarchically sponge-like macro-/mesoporous titania.The Journal of Physical Chemistry. C, 2007, 111(28): 10582-10589.
[18]	SUN XIAO-MING, LI YA-DONG. Ga2O3 and GaN semiconductor hollow spheres. Angewandte Chemie, 2004, 43(29): 3827-3831.
[19]	YU JIA-GUO, LIU SHENG-WEI, YU HUO-GEN.Microstructures and photoactivity of mesoporous anatase hollow microspheres fabricated by fluoride-mediated self-transformation.Journal of Catalysis, 2007, 249(1): 59-66.
[20]	YU JIA-GUO, WANG GUO-HONG, CHENG BEI, et al.Effects of hydrothermaltemperature and time on the photocatalytic activity and microstructures of bimodal mesoporous TiO2 powders.Applied Catalysis B, 2007, 69(3): 171-180.
[21]	SYOUFIAN A, NAKASHIMA K.Degradation of methylene blue in aqueous dispersion of hollow titania photocatalyst: optimization of reaction by peroxydisulfate electron scavenger.Journal of Colloid and Interface Science, 2007, 313(1): 213-218.
[22]	LI GUI-CUN, ZHANG ZHI-KUN.Preparation and characterization of hollow titania microspheres.Journal of Functional Materials Contents, 2004, 35(1): 2786-2791.
[23]	AO YAN-HUI, XU JING-JING, FU DE-GANG, et al. A simple method to prepare N-doped titania hollow spheres with high photocatalytic activity under visible light. Journal of Hazardous Materials, 2009, 167(1/2/3): 413-417.
[24]	ZHANG QING-HONG, GAO LIAN, ZHENG SHAN.Preparation of mesoporous TiO2. photocatalyst by selective dissolving of titania-silica binary oxides.Chemistry Letters, 2001, 11: 1124-1125.
[25]	ZHANG QING-HONG, GAO LIAN.Preparation of nanocrystalline titanium oxide by decomposition of molecular precursor alpha- (NH4)2TiO(SO4)2.Chemistry Letters, 2003, 32(5): 461-462.
[26]	ARNOUT I.Preparation and characterization of titania-coated polystyene spheres and hollow titania shells.Langmuir, 2001, 17(12): 3579-3585.
[27]	ANTHONY J P, WAYNE L, JAMES M N.Dispersion polymerization of styrene in polar solvents.Macromolecules, 1990, 23(12): 3104-3109.
[28]	SUN XIAO-MING, LI YA-DONG.Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles.Angewandte Chemie, 2004, 43(5): 597-601.
[29]	SPURR R A, HOWARD MYERS.Quantitative analysis of anatase- rutile mixtures with an X-ray diffractometer.Analytical Chemistry, 1957, 29(5): 760-762
[30]	JAMES L GOLE, JOHN D STOUT.Highly efficient formation of visible light tunable TiO2-xNx photocatalysts and their transformation at the nanoscale.The Journal of Physical Chemistry, B, 2004, 108(4): 1230-1240.
[31]	MONA SAIF, ABDEL-MOTTALEB M S A. Titanium dioxide nanomaterial doped with trivalent lanthanide ions of Tb, Eu and Sm: Preparation, characterization and potential applications.Inorg. Chim . Acta, 2007, 360(9): 2863-2874.
[32]	XIE YI-BING, YUAN CHUN-WEI.Characterizationand photocatalysis of Eu3+-TiO2 sol in the hydrosol reaction system.Materials Research Bulletin, 2004, 39(4-5): 533-543.
[33]	AN XIAO-SHA, CHEN JUN-DE, ZHOU ZHI-YOU, et al.Rare earth Eu doped PtRu/C catalysts and their properties for methanol electrooxidation.Acta Physico-Chimica Sinica, 2010, 26(5): 1207-1213.
[34]	LI JING-HONG, KANG WAN-LIN, YAN WEN-HUA, et al.Preparation of Eu3+ doped titania nanocrystals and photocatalytic degradation partially hydrolyzed polyacrylamide.Acta Physico-Chimica Sinica, 2008, 24(6): 1030-1034.

铕掺杂的TiO₂空心微球的制备及光催化性能

Preparation, Characterization and Photocatalytic Property of Eu-doped TiO₂ Hollow Microspheres

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