热处理工艺对TiO2纳米管阵列结构及其光电性能的影响

doi:10.3724/SP.J.1077.2012.00054

摘要/Abstract

摘要：

通过阳极氧化法在钛箔上制备了TiO₂纳米管阵列, 在不同热处理工艺下使其晶化. 利用扫描电子显微镜(SEM)和X射线衍射(XRD)对TiO₂纳米管阵列的形貌和结构进行了表征. 结果表明, 阳极氧化法制备的TiO₂纳米管经450~750℃热处理后为纳米晶结构, 平均晶粒尺寸随退火温度升高而增大, 相同温度下氮气气氛中热处理的TiO₂平均晶粒尺寸小于空气气氛中热处理的TiO₂. 氮气气氛下退火可拓宽TiO₂由锐钛矿型(Anatase)向金红石型(Rutile)结构转变的热处理温度范围, 650℃以上退火处理后, TiO₂纳米管中掺杂有少量的氮. 光照开路电位测试和稳态极化曲线测试结果表明, 在氮气气氛中、经650℃退火处理2 h制备的TiO₂纳米管阵列电极光电响应性能最佳, 此时TiO₂为锐钛矿型和金红石型的混晶结构.

关键词: TiO₂纳米管, 退火, 晶体结构, 光电响应

Abstract:

TiO₂ nanotube arrays were made on the titanium foil by the method of anodic oxidation, and then crystallized by different heat-treatment processes. The morphology and structure of the TiO₂ nanotube arrays were characterized by SEM and XRD. The results showed that the TiO₂ nanotube arrays prepared by anodic oxidation and annealed at the temperature range of 450-750℃ were nanocrystalline structure, and the average measurement of the crystal particle grew with the increasing of the annealing temperature. The average crystal size of TiO₂ nanotube arrays annealed in the nitrogen atmosphere is smaller than that annealed in the air atmosphere at the same temperature. Annealing in the nitrogen atmosphere can widen the limit of the transformation temperature from Anatase to Rutile. Annealed above 650℃, the TiO₂ nanotube arrays can be doped into a small amount of nitrogen. The results of light open-circuit potential tests and the steady-state polarization curves tests show that the TiO₂ namotube arrays electrode has the best photoelectric response properties after being annealed in the nitrogen atmosphere at 650℃ for 2 h. The arrays have mixed crystal structure of Anatase and Rutile.

Key words: TiO₂ nanotubes, anneal, crystal structure, photoelectric response

中图分类号:

O649

金冲, 张卫国, 姚素薇, 王宏智. 热处理工艺对TiO₂纳米管阵列结构及其光电性能的影响[J]. 无机材料学报, 2012, 27(1): 54-58.

JIN Chong, ZHANG Wei-Guo, YAO Su-Wei, WANG Hong-Zhi. Effect of Heat-treatment Process on the Structure and Photoelectric Performance of TiO₂ Nanotube Arrays[J]. Journal of Inorganic Materials, 2012, 27(1): 54-58.

图/表 8

图1 钛基TiO2纳米管阵列表面(a)和断面(b)的SEM照片

Fig. 1 Surface(a)and cross-section(b)SEM images of Ti-based TiO2 nanotube arrays

图2 空气气氛下不同温度退火处理后TiO2纳米管阵列的XRD图谱

Fig. 2 XRD patterns of TiO2 nanotube arrays annealed in air at different temperatures

图3 氮气气氛下不同温度退火处理后TiO2纳米管阵列的XRD图谱

Fig. 3 XRD patterns of TiO2 nanotube arrays annealed in N2 atmosphere at different temperatures

Table 1 Average grain size and phase composition of the TiO2 nanotube arrays calain under different conditions

Sample	Calcination temperature /℃	Crystallite size of anatase / nm	Crystallite size of rutile / nm	Rutile by XRD / %
a	450	15.6	-	0
b	550	17.2	23.3	24.25
c	650	18.2	28.2	47.70
d	750	-	32.3	100
e	450	14.9	19.8	2.12
f	550	16.3	21.6	21.39
g	650	17.6	23.5	29.53
h	750	25.1	28.0	95.33

图4 空气气氛中不同温度退火后TiO2纳米管阵列电极的光照开路电位

Fig. 4 Open-circuit potential of TiO2 nanotube arrays electrodes annealed in air

图5 氮气气氛中不同温度退火后TiO2纳米管阵列电极的光照开路电位表2 不同退火条件下TiO2纳米管阵列电极的光照开路电位

Fig. 5 Open-circuit potential of TiO2 nanotube arrays electrodes annealed in N2 atmosphere

Table 2 Open-circuit potentials of TiO2 nanotube arrays electrodes annealed in different conditions

Heat temperature	/mV
Heat temperature	N₂	Air
450℃	180	150
550℃	240	220
650℃	330	180
750℃	230	120

图6 不同气氛中退火处理后TiO2纳米管阵列电极暗态与光照下的稳态极化曲线

Fig. 6 Dark and irradiation polarization curves of TiO2 nanotube arrays electrodes annealed at different atmosphere

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热处理工艺对TiO₂纳米管阵列结构及其光电性能的影响

Effect of Heat-treatment Process on the Structure and Photoelectric Performance of TiO₂ Nanotube Arrays

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