Fabrication and Photoelectrochemical Properties of Ag/g-C3N4 Co-Sensitized TiO2 Nanotube Composite Film on Ti Substrate

doi:10.11900/0412.1961.2024.00099

Acta Metall Sin

2025, Vol. 61

Issue (12): 1769-1780 DOI: 10.11900/0412.1961.2024.00099

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Fabrication and Photoelectrochemical Properties of Ag/g-C₃N₄ Co-Sensitized TiO₂ Nanotube Composite Film on Ti Substrate

GUAN Zichao¹^,², HU Juan¹^,³, SHI Haiyan¹, DONG Shigang⁴(

), Liu Ya'an⁵, WANG Xia¹, JIN Piao¹, DU Ronggui¹(

)

1 State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
2 CNOOC Changzhou Paint and Coatings Industry Research Institute Co. Ltd. , Changzhou 213016, China
3 National Center of Inspection on Additive Manufacturing Product Quality, Wuxi 214101, China
4 College of Energy, Xiamen University, Xiamen 361102, China
5 School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China

Cite this article:

GUAN Zichao, HU Juan, SHI Haiyan, DONG Shigang, Liu Ya'an, WANG Xia, JIN Piao, DU Ronggui. Fabrication and Photoelectrochemical Properties of Ag/g-C₃N₄ Co-Sensitized TiO₂ Nanotube Composite Film on Ti Substrate. Acta Metall Sin, 2025, 61(12): 1769-1780.

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Abstract

Photoelectrochemical cathodic protection for metals, leveraging the unique photoelectrochemical properties of TiO₂ semiconductor films, represents an innovative approach to corrosion protection with promising potential. However, pure TiO₂ films exhibit limitations, including low visible light absorption, rapid recombination of photogenerated electrons and holes, and low photoelectric conversion efficiency. To enhance the photoelectrochemical properties of TiO₂ film photoanodes, composite films are essential. In this study, a g-C₃N₄ layer and Ag nanoparticles were sequentially deposited onto an anodized TiO₂ nanotube array film on a Ti foil via simplified chemical vapor deposition and chemical bath deposition, respectively, to enhance the TiO₂ composite film's photoelectrochemical performance for metal cathodic protection applications. The results demonstrated substantial improvements in light absorption and photoelectrochemical performance for the Ag/g-C₃N₄ co-sensitized TiO₂ nanotube composite film compared to the pure TiO₂ nanotube array film. The Ag/g-C₃N₄/TiO₂ composite film's light absorption was extended into the visible light spectrum, enhancing the separation efficiency of photogenerated electrons and holes. Under white light irradiation, the photocurrent density of the composite film in an aqueous solution containing 50% (volume fraction) ethylene glycol and 0.2 mol/L NaOH reached 135 μA/cm², approximately 11 times that of the pure TiO₂ film. Furthermore, when employed as a photoanode, the composite film on the Ti surface reduced the electrode potential of 403 stainless steel in a 0.5 mol/L NaCl solution by 530 mV relative to the steel's free corrosion potential, demonstrating a notably enhanced photoelectrochemical cathodic protection effect.

Key words: Ti anodic oxidation chemical vapor deposition chemical bath deposition TiO₂ nanotube g-C₃N₄ Ag photocathodic protection

Received: 08 April 2024

ZTFLH:

TG174.41

Fund: National Natural Science Foundation of China(21573182)

Corresponding Authors: DU Ronggui, professor, Tel: 13959276526, E-mail: rgdu@xmu.edu.cn; DONG Shigang, senior engineer, Tel: 13696994309, E-mail: sgdong@xmu.edu.cn

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	GUAN Zichao
	HU Juan
	SHI Haiyan
	DONG Shigang
	Liu Ya'an
	WANG Xia
	JIN Piao
	DU Ronggui

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https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00099 OR https://www.ams.org.cn/EN/Y2025/V61/I12/1769

Fig.1 Schematic for the preparation of TiO₂ nanotube composite films (CVD—chemical vapor deposition)

Fig.2 SEM images of the prepared films of TiO₂ (a), g-C₃N₄/TiO₂ (b), Ag/TiO₂ (c), and Ag/g-C₃N₄/TiO₂ (d) (Insets show the corresponding cross-sectional morphologies, NP—nanoparticle)

Fig.3 EDS of the prepared films of TiO₂ (a), g-C₃N₄/TiO₂ (b), Ag/TiO₂ (c), and Ag/g-C₃N₄/TiO₂ (d)

Table 1 Chemical compositions of the prepared films

Fig.4 XPS of the TiO₂ nanotube film and the Ag/g-C₃N₄/TiO₂ composite film
(a) full spectra
(b-f) high-resolution spectra of Ti2p (b), Ag3d (c), C1s (d), N1s (e), and O1s (f)

Fig.5 UV-Vis absorption spectra of the TiO₂, g-C₃N₄/TiO₂, Ag/TiO₂, and Ag/g-C₃N₄/TiO₂ films

Fig.6 Photoluminescence spectra of the TiO₂, g-C₃N₄/TiO₂, Ag/TiO₂, and Ag/g-C₃N₄/TiO₂ films

Fig.7 Transient photocurrent responses of the TiO₂, g-C₃N₄/TiO₂, Ag/TiO₂, and Ag/g-C₃N₄/TiO₂ films under intermittent white light illumination (i—current density, t—time)

Fig.8 Potential changes of 403 stainless steel (403SS) under different conditions (Curves a, b, and c represent uncoupled, coupled to the pure TiO₂ film, and coupled to the Ag/g-C₃N₄/TiO₂ composite film, respectively, E—potential, ΔE—potential fall)

Fig.9 Nyquist plots (a), Bode-phase plots (b), and Bode-modulus plots (c) of 403SS in the 0.5 mol/L NaCl solution under different conditions (Z—impedance,Z'—real component of the impedance, Z"—imaginary component of the impedance, f—frequency)

Fig.10 Equivalent circuit models for 403SS in the 0.5 mol/L NaCl solution (R_s—solution resistance, R_ct—charge transfer resistance, R—film resistance, CPE and CPE₁—constant phase elements)
(a) uncoupled (b) coupled to the illuminated film

Table 2 Fitting results of EIS for 403SS in the 0.5 mol/L NaCl solution

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