CdS/TiO2纳米晶薄膜的原位法制备及光电化学性能研究

doi:10.15541/jim20180126

无机材料学报 ›› 2018, Vol. 33 ›› Issue (12): 1343-1348.DOI: 10.15541/jim20180126

CdS/TiO₂纳米晶薄膜的原位法制备及光电化学性能研究

刘灿军¹, 陈述¹, 李洁²

1. 湖南科技大学化学化工学院, 理论有机化学与功能分子教育部重点实验室, 湘潭 411201;
2. 中南大学化学化工学院, 长沙 410083

收稿日期:2018-03-22 修回日期:2018-06-21 出版日期:2018-12-20 网络出版日期:2018-11-27
作者简介:刘灿军(1985-), 男, 讲师. E-mail: liucanjun@hnust.edu.cn
基金资助:
国家自然科学基金 (51502088);湖南省自然科学基金(2017JJ3079);湖南省教育厅科学研究基金(17C0628)

CdS/TiO₂ Nanocrystalline Films: In-situ Synthesis and Photoelectrochemical Performance

LIU Can-Jun¹, CHEN Shu¹, LI Jie²

1. Key Laboratory of Theoretical Chemistry and Molecular Simulation, Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;
2. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

Received:2018-03-22 Revised:2018-06-21 Published:2018-12-20 Online:2018-11-27
About author:LIU Can-Jun. E-mail: liucanjun@hnust.edu.cn
Supported by:
National Natural Science Foundation of China (51502088);Hunan Provincial Natural Science Foundation (2017JJ3079);Scientific Research Fund of Hunan Provincial Education Department (17C0628)

摘要/Abstract

摘要：

CdS/TiO₂异质结薄膜因其优异的可见光催化性能, 在光催化领域引起了广泛关注。然而, 目前传统方法制备的CdS/TiO₂薄膜可能存在交界面结合不紧密的问题, 不利于光生载流子在交界面处的传输。因此, 本研究基于原位转换的原理(TiO₂→CdTiO₃→CdS), 将TiO₂纳米晶表层原位转换成CdS, 制备了CdS/TiO₂纳米晶薄膜。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)手段对样品薄膜的形貌和结构进行了表征。由表征结果可知, 在TiO₂纳米晶表面形成了CdS, 构成了交界面结合紧密的CdS/TiO₂异质结薄膜。光电化学性能研究表明, 与传统的连续离子层吸附反应法(SILAR)制备的薄膜相比, 原位法制备的CdS/TiO₂薄膜的光电流密度更高, 达到9.8 mA·cm^-2(V=0.4 V (vs. RHE)); 交流阻抗谱(EIS)结果表明, 原位法制备的CdS/TiO₂薄膜具有更小的电荷传输电阻, 说明原位法形成的CdS/TiO₂异质结结合更紧密, 能减小光生载流子在CdS/TiO₂界面处的传输阻力, 降低光生载流子在传输过程中的复合几率, 进而提高CdS/TiO₂薄膜的光电化学性能。

关键词: CdS/TiO₂, 光电化学性能, 原位法, 光阳极, 异质结

Abstract:

CdS/TiO₂ heterojunction films have attracted much attention in the field of photocatalysis due to their excellent photocatalytic performance under visible light irradiation. However, the CdS/TiO₂ films prepared by the conventional methods may exhibit loose interface, leading to poor transport of photogenerated carriers in the interface. In this study, CdS/TiO₂ heterojunction films were successfully prepared by in-situ transformation (TiO₂→CdTiO₃→CdS). Morphologies and structures of as-prepared films were characterized by XRD, SEM and TEM. Results show that CdS formed on the surface of TiO₂ nanoparticle, and the interface of CdS/TiO₂ heterojunction was compact. Their photoelectrochemical (PEC) performance was investigated by electrochemical working station．Results indicate that the CdS/TiO₂ films prepared by in-situ method, whose photocurrent density was as high as 9.8 mA∙cm^-2 at 0.4 V (vs. RHE), present higher PEC activity than those prepared by successive ionic layer adsorption and reaction (SILAR). The electrochemical impedance spectroscopy (EIS) results show that the in-situ synthesized CdS/TiO₂ films own lower charge transfer resistance, which reveals that the in-situ formed compact interface can reduce the charge transfer resistance in the CdS/TiO₂interface, restrict the recombination of photo-induced carriers, and further enhance the PEC performance.

Key words: CdS/TiO₂, photoelectrochemical performance, in-situ synthesis, photoanode, heterojunction

中图分类号:

O644

刘灿军, 陈述, 李洁. CdS/TiO₂纳米晶薄膜的原位法制备及光电化学性能研究[J]. 无机材料学报, 2018, 33(12): 1343-1348.

LIU Can-Jun, CHEN Shu, LI Jie. CdS/TiO₂ Nanocrystalline Films: In-situ Synthesis and Photoelectrochemical Performance[J]. Journal of Inorganic Materials, 2018, 33(12): 1343-1348.

图/表 13

图1 (a) 原位合成CdS/TiO2薄膜的制备技术路线示意图以及(b) TiO2、CdTiO3/TiO2和2-CdS/TiO2薄膜的XRD图谱

Fig. 1 The synthetic process (a) and XRD patterns (b) of TiO2, CdTiO3/TiO2 and 2-CdS/TiO2 films

图2 TiO2(a)~(b)和2-CdS/TiO2 (c)~(d)薄膜的SEM照片

Fig. 2 SEM images of TiO2 (a-b) and 2-CdS/TiO2 (c-d) films(b, d): Magnified images of (a, b); Inset in (a) showing cross sectional image of (a)

图S1 2-CdS/TiO2薄膜的EDS图谱

Fig. S1 EDS of the 2-CdS/TiO2 films

图3 2-CdS/TiO2薄膜的TEM(a)和HRTEM(b)照片

Fig. 3 TEM (a) and HRTEM (b) images of 2-CdS/TiO2 films

图4 TiO2、CdTiO3/TiO2和2-CdS/TiO2薄膜的UV-Vis吸收光谱图

Fig. 4 UV-Vis absorption spectra of TiO2, CdTiO3/TiO2 and 2-CdS/TiO2 films

图5 TiO2和CdS/TiO2薄膜的光电流密度曲线

Fig. 5 Photocurrent density curves of TiO2 and CdS/TiO2 films

图S2 1-CdS/TiO2和2-CdS/TiO2薄膜的UV-Vis吸收光谱图

Fig. S2 (a) UV-Vis absorption spectra of 1-CdS/TiO2 and 2-CdS/TiO2 films

图6 1-CdS/TiO2和2-CdS/TiO2薄膜的交流阻抗图谱, 插图为等效电路图

Fig. 6 EIS plots of 1-CdS/TiO2 and 2-CdS/TiO2 films with the inset showing equivalent circuit

表1 交流阻抗图谱的等效电路中Rs与R1的拟合值

Table 1 Simulated values of resistance (Rs) and charge transfer resistance (R1) of EIS plots calculated by equivalent circuit

Sample	R_s/(Ω·cm^-2)	R₁/(Ω·cm^-2)
1-CdS/TiO₂	20.43	1424.0
2-CdS/TiO₂	14.72	629.4

图S3 TiO2、1-CdS/TiO2和2-CdS/TiO2薄膜的IPCE曲线

Fig. S3 IPCE curves of TiO2, 1-CdS/TiO2 and 2-CdS/TiO2 films

图S4 2-CdS/TiO2薄膜的I-t 曲线

Fig. S4 I-t curves of 2-CdS/TiO2 films

图S5 TiO2、CdTiO3/TiO2、2-CdS/TiO2和CdS电极的肖特基曲线

Fig. S5 Mott-Schottky plots of TiO2, CdTiO3/TiO2, 2-CdS/TiO2 and CdS electrodes

图7 CdS/TiO2电极中光生电子和空穴的传输机理示意图

Fig. 7 Schematic diagram of the photogenerated charge transport mechanism in the CdS/TiO2 electrode

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CdS/TiO₂纳米晶薄膜的原位法制备及光电化学性能研究

CdS/TiO₂ Nanocrystalline Films: In-situ Synthesis and Photoelectrochemical Performance

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