具有高活性(001)晶面的TiO2纳米方块的制备及光催化性能

doi:10.15541/jim20160012

摘要/Abstract

摘要：

采用水热法制备了尺寸为70~100 nm, 具有高活性(001)晶面的锐钛矿相TiO₂纳米方块, 利用FE-SEM、TEM、XRD和UV-Vis DRS等手段对催化剂结构和光吸收性能进行分析, 同时考察了水热反应温度和溶液pH对TiO₂形貌和(001)晶面暴露率的影响。以酸性红染料为目标污染物, 对催化剂的光催化活性进行研究。实验结果表明, 合成TiO₂纳米方块的最佳条件为水热温度180℃、溶液pH=4~5。(001)晶面的光催化活性优于(101)晶面, 具有33%(001)晶面暴露率的TiO₂纳米方块的光催化活性是普通TiO₂的1.6倍。

关键词: TiO2, 水热法, (001)晶面, 光催化

Abstract:

Anatase TiO₂ single crystals with exposed (001) facets were successfully synthesized by a one-step hydrothermal route using TiF₄ as raw material. The crystal phase, morphology, microstructure, and photoabsorption of the samples were analyzed by field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS). The influences of hydrothermal temperature and pH of solution on morphology of TiO₂and exposure of (001) facets were also investigated. Photocatalytic catalysts was evaluated by degradation of acid red dye. Experimental results demonstrated that exposure of (001) facets was beneficial for improving photocatalytic performance. Under ultraviolet light irradiation, TiO₂ nanocube with exposure of (001) facets ca. 33% exhibited significantly higher activity than the common TiO₂ without exposed (001) facets. The photocatalytic efficiency of the former was 1.6 times as high as that of the latter. The sample with the highest exposure of (001) facets was obtained at hydrothermal temperature of 180℃ and pH of solution 4-5. The corrosion of crystal surface would occur at hydrothermal temperature higher than 180℃. In addition, the pH of solution higher than 6 was unfavorable for the adsorption of F^- ions on TiO₂ crystals and the stabilization of (001) facets, which led to the disappearance of (001) facets.

Key words: TiO2, hydrothermal treatment, (001) facet, photocatalysis

中图分类号:

O643

万建风, 胡德圣, 卢朋辉, 林碧洲, 陈亦琳, 高碧芬. 具有高活性(001)晶面的TiO₂纳米方块的制备及光催化性能[J]. 无机材料学报, 2016, 31(8): 845-849.

WAN Jian-Feng, HU De-Sheng, LU Peng-Hui, LIN Bi-Zhou, CHEN Yi-Lin, GAO Bi-Fen. Preparation of Anatase TiO₂ Nanocube with Exposed (001) Facet and Its Photocatalytic Properties[J]. Journal of Inorganic Materials, 2016, 31(8): 845-849.

图/表 6

图1 不同水热温度下合成的TiO2样品的XRD图谱

Fig. 1 XRD patterns of TiO2 samples synthesized at various hydrothermal temperatures(a) 160℃, (b) 180℃ and (c) 200℃. The hydrothermal treatment was kept for 20 h at pH 4

图2 TiO2纳米方块的SEM(a, b)、TEM(c)照片及电子衍射图(d)

Fig. 2 SEM (a, b) and TEM (c, d) images of TiO2 nanocubes Inset of (d) shows the angle between (001) and (101) facets of the nanocube. The sample was obtained by hydrothermal treatment at 180℃ for 20 h at pH 4

图3 不同水热温度下合成的TiO2样品的SEM照片

Fig. 3 FE-SEM images of anatase TiO2 synthesized at different hydrothermal temperatures(a) 160℃, (b) 180℃ and (c) 200℃. The hydrothermal treatment was kept for 20 h at pH 4

图4 不同pH条件下合成的TiO2样品的SEM照片

Fig. 4 SEM images of TiO2 obtained with different pH(a) pH=3, (b) pH=6. The hydrothermal experiments were carried out at 180℃ for 20 h

图5 TiO2样品的紫外-可见漫反射谱

Fig. 5 Diffuse reflectance spectra of TiO2 samples with different morphologiesMorphologies of sample A, tetragonal-dipyramid, and sample B, nanocube

图6 (a)TiO2样品光催化降解酸性红染料曲线和(b)不同水热温度下合成的TiO2样品以及P25表观活性的比较

Fig. 6 (a) Photodegradation of acid red dye by TiO2 samples with different morphologies and (b) specific photocatalytic activity of P25 and TiO2 synthesized at different hydrothermal temperaturesMorphologies of sample A, tetragonal-dipyramid, and sample B, nanocube

参考文献 25

[1]	REN L, LI Y Z, HOU J G, et al.Preparation and enhanced photocatalytic activity of TiO2 nanocrystals with internal pores.ACS Appl. Mater. Interfaces., 2014, 6(3): 1608-1615.
[2]	TONG T Z, HILL A N, ALSINA M A.Spectroscopic characterization of TiO2 polymorphs in wastewater treatment and sediment samples.Environ. Sci. Technol. Lett., 2015, 2(1): 12-18.
[3]	WENG Z G, GUO H, LIU X G, et al.Nanostructured TiO2 for energy conversion and storage.RSC Adv., 2013, 3(47): 24758-24775.
[4]	DUAN Y D, ZHENG J X, XU M, et al.Metal and F dual-doping to synchronously improve electron transport rate and lifetime for TiO2 photoanode to enhance dye-sensitized solar cells performances.J. Mater. Chem. A, 2015, 3(10): 5692-5700.
[5]	HIRAYAMA J, KAMIYA K.Combining the photocatalyst Pt/TiO2 and the nonphotocatalyst SnPd/Al2O3 for effective photocatalytic purification of groundwater polluted with nitrate.ACS Catal., 2014, 4(7): 2207-2215.
[6]	KAMEGAWA T, ISHIGURO Y, SETO H, et al.Enhanced photocatalytic properties of TiO2-loaded porous silica with hierarchical macroporous and mesoporous architectures in water purification.J. Mater. Chem. A, 2015, 3(5): 2323-2330.
[7]	YANG J L, WU Q L, HE S M, et al.Completely <001> oriented anatase TiO2 nanoarrays: topotactic growth and orientationrelated efficient photocatalysis.Nanoscale, 2015, 7(33): 13888-13897.
[8]	XU T Z, ZHENG H, SEKIGUCHI Y, et al.Hydrothermal preparation of nanoporous TiO2 films with exposed {001} facets and superior photocatalytic activity.J. Mater. Chem. A, 2015, 3(37): 19115-19122.
[9]	YANG H G, SUN C H, QIAO S Z, et al.Anatase TiO2 single crystals with a large percentage of reactive facets.Nature, 2008, 453(7195): 638-642.
	YANG H G, LIU G, QIAO S Z, et al.Solvothermal synthesis and photoreactivity of anatase TiO2 nanosheets with dominant {001} facets.J. Am. Chem. Soc., 2009, 131(11): 4078-4083.
[10]	HAN X G, KUANG Q, JIN M S, et al.Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties.J. Am. Chem. Soc., 2009, 131(9): 3152-3153.
[11]	LI H M, ZENG Y S, LIU M, et al.Controlled synthesis of anatase tio2 single crystals with dominant {001} facets from TiO2 powders.Chem Plus Chem., 2012, 77(11): 1017-1021.
[12]	LIU M, PIAO L G, WANG W J, et al.Anatase TiO2 single crystals with exposed {001} and {110} facets: facile synthesis and enhanced photocatalysis.Chem. Commun., 2010, 46(10): 1664-1666.
[13]	KIM J Y, LEE D, KIM H J, et al.Annealing-free preparation of anatase TiO2 nanopopcorns on Ti foil via a hydrothermal process and their photocatalytic and photovoltaic applications.J. Mater. Chem. A, 2013, 1(19): 5982-5988.
[14]	GAO B F, LUO X Z, GU Z J, et al.Facile synthesis of TiO2 microspheres with reactive (001) facets for improved photocatalytic performance.J. Nanosci. Nanotechnol., 2014, 14(5): 3969-3975.
[15]	JUN Y W, CASULA M F, SIM J H, et al.Surfactant-assisted elimination of a high energy facets as a means of controlling the shapes of TiO2 nanocrystals.J. Am. Chem. Soc., 2003, 125(51): 15981-15985.
[16]	DAI Y, COBLEY C M, SUN Y M, et al.Synthesis of anatase TiO2 nanocrystals with exposed {001} facets.Nano Lett., 2009, 9(6): 2455-2459.
[17]	SELCUK S, SELLONI A.Surface structure and reactivity of anatase TiO2 crystals with dominant {001} facets.J. Phys. Chem. C, 2013, 117(12): 6358-6362.
[18]	ZHOU Y, WANG X Y, WANG H.Enhanced dye-sensitized solar cells performance using anatase TiO2 mesocrystals with the Wulff construction of nearly 100% exposed {101} facets as effective light scattering layer.Dalton Trans., 2014, 43(12): 4711-4719.
[19]	ZHANG H M, WANG Y, ZHAO H J, et al.Anatase TiO2 crystal facet growth: mechanistic role of hydrofluoric acid and photoelectrocatalytic activity.ACS Appl. Mater. Interfaces., 2011, 3(7): 2472-2478.
[20]	RYU J, CHOI W.Substrate-specific photocatalytic activities of TiO2 and multiactivity test for water treatment application.Environmental Science & Technology, 2007, 42(1): 294-300.
[21]	PRINGUET A, PAGNOUX C, VIDECOQ A, et al.Granulating titania powder by colloidal route using polyelectrolytes.Langmuir, 2008, 24(19): 10702-10708.
[22]	GAO Y, WAHI R, KAN A T, et al.Adsorption of cadmium on anatase nanoparticles effect of crystal size and pH.Langmuir., 2004, 20(22): 9585-9593.
[23]	WU GUO-TAO, ZHENG SHU-KAI, LÜ XIAO.First-principles calculation of Bi-doped anatase TiO2.Chinese J. Inorg. Chem., 2013, 29(1): 9-14.
[24]	YUAN X, GAO B F, SHI J X, et al.Morphologically-tunable anatase TiO2 with exposed (001) facet and related photocatalytic performance.Materials Letters., 2014, 128: 167-169.
[25]	LIU G, SUN C, WANG L Z, et al.Nanosized anatase TiO2 single crystals for enhanced photocatalytic activity.Chem Commun., 2010, 46(5): 755-757.

具有高活性(001)晶面的TiO₂纳米方块的制备及光催化性能

Preparation of Anatase TiO₂ Nanocube with Exposed (001) Facet and Its Photocatalytic Properties

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