电还原MoSe2修饰TiO2纳米管光电化学性能研究

doi:10.15541/jim20180463

摘要/Abstract

摘要：

通过阳极氧化法在乙二醇电解液中制备TiO₂纳米管阵列, 以钼酸钠和亚硒酸为原料, 改变原料的浓度配比以及沉积电压, 电化学还原沉积MoSe₂对TiO₂纳米管阵列进行修饰, 以半导体复合的方式提高TiO₂的光电化学性能。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)对复合物进行物相、形貌分析, 通过电化学工作站测试复合材料的线性伏安曲线、交流阻抗。结果表明, MoSe₂与TiO₂形成了p-n异质结, 降低了光生电子和空穴的复合以及电荷转移电阻显著降低, 使载流子浓度、光电流密度明显增大。沉积电压为-0.5 V, 2 mmol/L H₂SeO₃沉积30 s, 经过300 ℃热处理的MoSe₂/TiO₂复合材料具有优异的光电化学性能, 在0 V偏压条件下光响应电流密度为1.17 mA/cm ², 是空白样品的3倍, 电荷转移电阻从331.6 Ω/cm ²下降到283.9 Ω/cm ²。当热处理温度为330 ℃时, MoSe₂会发生团聚, 堵塞TiO₂基底, 使得MoSe₂/TiO₂吸光能力减弱, 综合性能变差。

关键词: TiO₂纳米管阵列, MoSe₂, 电化学沉积, 光电化学性能

Abstract:

MoSe₂ was deposited by electrochemical reduction method on TiO₂ nanotube arrays which were prepared by anodic oxidation in ethylene glycol electrolyte, in which sodium molybdate and seleninic acid were used as raw materials. The composites were characterized by X-ray diffraction and scanning electron microscope, and I-V plot and electrochemical impedance spectroscopy were measured by electrochemical workstation. The results show that a p-n heterojunction is formed between molybdenum diselenide and titanium dioxide, which can reduce the combination of photo-generated electron-hole pairs and charge transfer resistance, and can increase its carrier concentration and light response current density. The composite deposited at -0.5 V in the electrolyte containg 2 mmol/L seleninic acid for 30 s exhibits optimum photo-electrochemical performance after 300 ℃ heat treatment, with a high photocurrent density of 1.17 mA/cm ² without bias, which is approximately three times higher than that of blank sample. And the charge transfer resistance decreased from 331.6 Ω/cm ² to 283.9 Ω/cm ². Selenide molybdenum agglomerates seriously to block the TiO₂nanotube once heat treatment over 330 ℃, resulting in a lower performance.

Key words: TiO₂ nanotube arrays, MoSe₂, electrochemical deposition, photoelectrochemical property

中图分类号:

TQ174

张亚萍, 丁文明, 朱海丰, 黄承兴, 于濂清, 王永强, 李哲, 徐飞. 电还原MoSe₂修饰TiO₂纳米管光电化学性能研究[J]. 无机材料学报, 2019, 34(8): 797-802.

ZHANG Ya-Ping, DING Wen-Ming, ZHU Hai-Feng, HUANG Cheng-Xing, YU Lian-Qing, WANG Yong-Qiang, LI Zhe, XU Fei. Photoelectrochemical Properties of MoSe₂ Modified TiO₂ Nanotube Arrays[J]. Journal of Inorganic Materials, 2019, 34(8): 797-802.

图/表 7

图1 MoSe2/TiO2样品的XRD图谱

Fig. 1 XRD patterns of MoSe2/TiO2

图2 MoSe2/TiO2样品的SEM照片(a~d)及图(b)样品的EDS分析结果(e)

Fig. 2 SEM images of MoSe2/TiO2 (a-d) and EDS analysis (e) of sample in (b) Sampls deposited at -0.5 V with H2SeO3 concentration of (a) 0.5, (b) 4 mmol/L; Sampls deposited at (c) -0.45, (d) -0.7 V with H2SeO3 concentration of 2 mmol/L

图3 沉积电压为-0.5 V,不同浓度H2SeO3沉积的 MoSe2/ TiO2的(a)线性扫描伏安曲线, (b)电化学阻抗图谱和(c)莫特-肖特基曲线

Fig. 3 (a) Linear sweep voltammol/Lograms, (b) Nyquist diagrams and (c) Mott-Schottky plots for MoSe2/TiO2 samples deposited at -0.5 V with different H2SeO3 concentrations

图4 H2SeO3浓度为2 mmol/L, 不同沉积电压下沉积的MoSe2/TiO2的(a)线性扫描伏安曲线, (b)电化学阻抗图谱和(c)莫特-肖特基曲线

Fig. 4 (a) Linear sweep voltammol/Lograms, (b) Nyquist diagrams and (c) Mott-Schottky plots for MoSe2/TiO2 samples deposited at different voltages with 2 mmol/L H2SeO3

图5 不同温度热处理MoSe2/TiO2样品的SEM照片

Fig. 5 SEM images of MoSe2/TiO2 heat-treated at different temperatures (a) 270 ℃; (b) 300 ℃; (c) 330 ℃ (MoSe2/TiO2 deposited at -0.5 V in 2 mmol/L H2SeO3 for 30 s)

图6 不同温度热处理MoSe2/TiO2样品的(a)线性扫描伏安曲线, (b)莫特-肖特基曲线, (c)光电流-时间曲线, (d)电化学阻抗图谱(插图为等效电路图)以及(e)界面载流子迁移示意图

Fig. 6 (a) Linear sweep voltammol/Lograms, (b) Mott-Schottky, (c) Amperometric i-t curves, (d) Nyquist diagrams With insert showing Insert is equivalent circuit, and (e) schematic diagram of carrier for MoSe2/TiO2 heat-treated at different temperatures MoSe2/TiO2 deposited at -0.5 V in 2 mmol/L H2SeO3 for 30 s

表1 等效电路得到热处理后MoSe2/TiO2的参数值

Table 1 Equivalent circuit parameters of MoSe2/TiO2

Sample	R_b/(Ω?cm^-2)	C_sc/ (F?cm^-2)	R_sc/(Ω?cm^-2)	C_dl/(F?cm^-2)	R_ct/(Ω?cm^-2)
330 ℃	2.11	1.60×10^-3	11.67	1.3×10^-3	345.4
300 ℃	0.60	7.64×10^-4	61.67	8.0×10^-2	283.9
270 ℃	0.85	1.37×10^-3	19.74	1.6×10^-1	305.5
Unheated	1.94	2.49×10^-3	0.53	1.1×10^-3	331.6

参考文献 18

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电还原MoSe₂修饰TiO₂纳米管光电化学性能研究

Photoelectrochemical Properties of MoSe₂ Modified TiO₂ Nanotube Arrays

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