Au纳米粒子/双层TiO2周期结构的制备及其对乙醇的电催化性质

doi:10.15541/jim20150380

摘要/Abstract

摘要：

利用二次阳极氧化法成功制备了双层TiO₂纳米管周期结构。通过改变氧化电压可以有效地调整双层TiO₂纳米管的管径, 从而控制样品的形貌。通过实验优化确定双层TiO₂周期结构的制备条件为一次氧化电压60 V, 二次氧化电压40 V。利用原位光还原法, 在TiO₂周期结构表面负载了Au纳米粒子并研究了前驱体溶液浓度与光照时间对样品的影响。在0.05 mmol/L HAuCl₄溶液中光照90 min后得到的Au纳米粒子具有最优的形貌与分布。这种绿色的原位光还原法因为避免使用保护剂与还原剂而有效提高了Au纳米粒子的催化活性。制备所得的Au/TiO₂周期异质结构可以直接作为工作电极用于乙醇的电催化氧化, 并表现出了良好的催化活性与稳定性。除了Au纳米粒子, 其他金属纳米粒子如Ag、Pd、Cu等均可通过该方法成功负载于双层TiO₂纳米管周期结构上。这种新型的异质结纳米结构作为燃料电池的阳极材料表现出了巨大的潜力。

关键词: TiO₂纳米管, Au纳米粒子, 光还原, 乙醇, 电催化氧化

Abstract:

The bilayer TiO₂ nanotube periodical structure was fabricated by a two-step anodization method. The morphology of this bilayer TiO₂ nanotube could be controlled by adjusting the tube diameter under different anodizing voltages. The optimized bilayer periodical nanostructure was obtained under a first voltage of 60 V and second voltage of 40 V. Au nanoparticles were then decorated onto the periodical TiO₂ nanotube surface by using in-situ photoreduction. The influences of precursor concentration and irradiation time were investigated. The best morphology and distribution of Au NPs on TiO₂ were obtained in 0.05 mmol/L HAuCl₄solution accompanied by irradiation for 90 min. This green method of in-situ photoreduction greatly enhanced the catalytic activity of Au nanoparticles due to the fact of avoiding reducing and protective agents. As-prepared Au/TiO₂ periodical hetero-nanostructures could be directly used as working electrode and showed good catalytic activity and stability for electrocatalytic oxidation of ethanol. Except for Au nanoparticles, other metal nanoparticles such as Ag, Pd, and Cu could also be decorated onto the bilayer TiO₂ nanotube periodical structure by using this method. This novel hetero-nanostructure shows great potential in application for preparing high efficient anode materials for fuel cell.

Key words: TiO₂ nanotube, Au nanoparticle, photoreduction, ethanol, electrocatalytic oxidation

中图分类号:

O646

金朝, 陈其汉, 郑梦佳, 赵鹏, 李倩, 崔小强. Au纳米粒子/双层TiO₂周期结构的制备及其对乙醇的电催化性质[J]. 无机材料学报, 2016, 31(3): 241-247.

JIN Zhao, CHEN Qi-Han, ZHENG Meng-Jia, ZHAO Peng, LI Qian, CUI Xiao-Qiang. Fabrication of Au Nanoparticles / Bilayer TiO₂ Nanotube Periodical Structure and Electrocatalytic Oxidation of Ethanol[J]. Journal of Inorganic Materials, 2016, 31(3): 241-247.

图/表 8

表1 制备TiO2纳米管所使用的氧化电压

Table 1 Anodization voltages for TiO2 nanotube fabrication

First time/V	40		50		60
Second time/V	10	20	30	40	50	60

表2 负载Au纳米粒子时使用的溶液浓度与光照时间

Table 2 Concentration and irradiation time for Au nanoparticles decoration

HAuCl₄ concentration/(mmol·L^-1)	0.01	0.05	0.09
Irradiation time/min	30	90	150

图1 不同一次氧化电压下所得TiO2纳米管的SEM照片及XRD表征结果

Fig. 1 SEM images (a-c) of TiO2 nanotubes after first anodizing under different voltages and corresponding XRD patterns(a) 40 V; (b) 50 V; (c) 60 V; (d) XRD pattern of Ti and TiO2 nanotubes after annealing

图2 不同二次氧化电压下, 所得TiO2纳米管的SEM照片及管径统计结果

Fig. 2 SEM images (a-f) of TiO2 nanotubes after second anodizing under different voltages and histogram of nanotube diameter (g)(a) 10 V; (b) 20 V; (c) 30 V; (d) 40 V; (e) 50 V; (f) 60 V

图3 使用不同浓度HAuCl4溶液所得样品的SEM照片及其XRD表征结果

Fig. 3 SEM images (a-c) of TiO2 photoreduced in different concentrations of HAuCl4 and corresponding XRD patterns (d)(1) 0.01 mmol/L; (2) 0.05 mmol/L; (3) 0.09 mmol/L

图4 不同光照时间所得样品的SEM照片及CV表征结果

Fig. 4 SEM images (a-c) of TiO2 nanotubes photoreduced in different time and the corresponding CV characterization(a) 30 min; (b) 90 min; (c) 150 min; (d) CV measured in 0.5 mol/L H2SO4; (e) CV measured in KOH and ethanol

图5 光照90 min样品的CV稳定性表征, 循环圈数为50

Fig. 5 Stability characterization of CV with cycle number of 50 The inset shows the change of peak current vs. the cycle number

图6 TiO2在不同金属盐溶液中进行光还原后的SEM照片

Fig. 6 SEM images of TiO2 nanotubes photoreduced in different solutions(a) AgNO3; (b) PdCl2; (c) CuCl2

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Au纳米粒子/双层TiO₂周期结构的制备及其对乙醇的电催化性质

Fabrication of Au Nanoparticles / Bilayer TiO₂ Nanotube Periodical Structure and Electrocatalytic Oxidation of Ethanol

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