Citation: WANG Haipeng, GUAN Zichao, WANG Xia, JIN Piao, XU Hui, CHEN Lifang, SONG Guangling, DU Ronggui. Fabrication of a ZnSe/MoO₃/TiO₂ Composite Film Exhibiting Photocathodic Protection Effect[J]. Acta Physico-Chimica Sinica, ;2019, 35(11): 1232-1240. doi: 10.3866/PKU.WHXB201901025 shu

Fabrication of a ZnSe/MoO₃/TiO₂ Composite Film Exhibiting Photocathodic Protection Effect

WANG Haipeng ¹ ,
GUAN Zichao ¹ ,
WANG Xia ¹ ,
JIN Piao ¹ ,
XU Hui ¹ ,
CHEN Lifang ¹ ,
SONG Guangling ^2,, ,
DU Ronggui ^1,,

1.
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
2.
Center for Marine Materials Corrosion and Protection, College of Materials, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Corresponding author: SONG Guangling, guangling.song@hotmail.com DU Ronggui, rgdu@xmu.edu.cn
Received Date: 9 January 2019
Revised Date: 25 February 2019
Accepted Date: 26 February 2019
Available Online: 14 November 2019
Fund Project: the National Natural Science Foundation of China J1310024the National Natural Science Foundation of China 51731008The project was supported by the National Natural Science Foundation of China (21573182, 51731008, 51671163, 21621091, J1310024)the National Natural Science Foundation of China 21573182the National Natural Science Foundation of China 51671163the National Natural Science Foundation of China 21621091

TiO₂ is a semiconductor material with excellent photoelectrochemical properties that can provide photocathodic protection for metals. However, TiO₂ can only absorb ultraviolet (UV) light at wavelengths of < 380 nm because of its wide band gap. In addition, photo-induced electron-hole pairs in the TiO₂ semiconductor easily recombine, which leads to a low photoelectric conversion efficiency. Another shortcoming is that pure TiO₂ semiconductors cannot sustain photocathodic protection in the dark, which may limit their practical applications to provide photocathodic protection. To address these shortcomings, various modification methods have been established by preparing TiO₂ composite materials to improve their photoelectrochemical properties. In this study, a ZnSe- and MoO₃-modified TiO₂ nanotube composite film with charge storage ability was prepared to enhance its photocathodic protection effect on stainless steel. A TiO₂ nanotube array film was prepared on a Ti foil via anodic oxidation and then MoO₃ and ZnSe particles were deposited onto the film by cyclic voltammetry and pulse electrodeposition, respectively, to afford a ZnSe/MoO₃/TiO₂ nanotube composite film having a cascade band structure. Scanning electron microscopy observations showed that the TiO₂ film consisted of ordered nanotubes with an average inner diameter of approximately 100 nm and wall thickness of approximately 15 nm. This nanotube structure remained intact after MoO₃ and ZnSe particle deposition on the film. Energy dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses indicated that the prepared nanotube composite film was composed of ZnSe, MoO₃, and TiO₂. The UV-Vis absorption and photoluminescence spectra showed that the photoresponse of the composite film was extended to the visible light region and the photo-induced electron-hole pair recombination was reduced. Photoelectrochemical and electrochemical measurements indicated that the photocurrent intensity of the composite film in a 0.5 mol·L⁻¹ KOH solution was two-fold higher than that of the pure TiO₂ film. Under white light illumination, the ZnSe/MoO₃/TiO₂ composite film decreased the potential of the coupled 403 stainless steel (403SS) in a 0.5 mol·L⁻¹ NaCl solution by 470 mV (relative to the corrosion potential), demonstrating an effective photocathodic protection effect. It should be noted that the composite film exhibited a charge storage capability and could continuously provide cathodic protection for 22.5 h after illumination was stopped. In addition, electrochemical impedance spectroscopy results indicated that the composite film significantly decreased the charge transfer resistance of the coupled 403SS, highlighting the photocathodic protection effect on 430SS.
- Anodic oxidation,
- Electrochemical deposition,
- TiO₂ nanotube,
- Stainless steel,
- Photoelectrochemical property,
- Photocathodic protection
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Fabrication of a ZnSe/MoO3/TiO2 Composite Film Exhibiting Photocathodic Protection Effect

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Fabrication of a ZnSe/MoO₃/TiO₂ Composite Film Exhibiting Photocathodic Protection Effect