BaTiO<sub>3</sub>/SrTiO<sub>3</sub>复合薄膜的制备及其光电化学阴极保护性能

庆达; 王建省; 苏新悦; 赵英娜; 曾雄丰

doi:10.13801/j.cnki.fhclxb.20230817.003

BaTiO₃/SrTiO₃复合薄膜的制备及其光电化学阴极保护性能

doi: 10.13801/j.cnki.fhclxb.20230817.003

庆达^{1, 2},
王建省^{1, 2, ,},
苏新悦^{1, 2},
赵英娜^{1, 2},
曾雄丰^{1, 2}

1.
华北理工大学　材料科学与工程学院，河北省无机非金属材料实验室，唐山 063210
2.
河北省(唐山)陶瓷产业技术研究院，唐山 063007

基金项目: 河北省自然科学基金钢铁联合基金(E2021209002)；唐山市科技局项目(21130211D；22130215H)

详细信息

通讯作者:
王建省，博士，副教授，研究方向为光催化、光电催化、光电化学腐蚀防护　E-mail: wangjiansheng@ncst.edu.cn

中图分类号: O643；TB332
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出版历程
- 收稿日期: 2023-05-30
- 修回日期: 2023-07-28
- 录用日期: 2023-08-03
- 网络出版日期: 2023-08-18
- 刊出日期: 2024-04-01

Preparation of BaTiO₃/SrTiO₃ composite film and its photoelectrochemical cathodic protection performance

QING Da^{1, 2},
WANG Jiansheng^{1, 2
, ,},
SU Xinyue^{1, 2},
ZHAO Yingna^{1, 2},
ZENG Xiongfeng^{1, 2}

1.
Hebei Inorganic Nonmetallic Materials Laboratory, School of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China
2.
Hebei (Tangshan) Ceramic Industry Technology Research Institute, Tangshan 063007, China

Funds: Natural Science Foundation—Steel and Iron Foundation of Hebei Province (E2021209002); Tangshan Science and Technology Bureau Project (21130211D; 22130215H)

摘要

摘要: 提高光生载流子的分离效率是提高光电化学阴极保护性能的有效途径，为弥补SrTiO₃禁带宽度大、光生载流子分离效率低等缺点，通过两步超声喷雾热解工艺在氟掺杂氧化锡导电玻璃(FTO)上制备了BaTiO₃/SrTiO₃复合薄膜。通过XRD、SEM、UV-vis DRS、PL对样品物相成分、表面形貌、光学性能等进行观测。随后以304不锈钢(304 SS)为被保护金属，观测了BaTiO₃/SrTiO₃复合薄膜遮蔽光条件下的光电化学阴极保护性能。其中BaTiO₃/SrTiO₃的相对位置由Mott-Schottky曲线确定。结果表明：通过两步超声喷雾热解工艺制备得到的 BaTiO₃/SrTiO₃复合薄膜，光吸收范围拓宽至400 nm；BaTiO₃/SrTiO₃ 复合薄膜相比于SrTiO₃薄膜，光吸收性能增强；光生载流子分离效率提高；在3.5wt%NaCl 溶液中，BaTiO₃/SrTiO₃ 复合薄膜使304 SS的开路电位负移至−0.38 V，负移程度约230 mV，而纯SrTiO₃薄膜仅能负移100 mV。其性能提升主要归因于BaTiO₃与SrTiO₃ 复合形成了异质结，促进了光生载流子的分离。
- BaTiO₃ /
- SrTiO₃ /
- 复合薄膜 /
- 超声喷雾热解 /
- 光电化学阴极保护
Abstract: Improving the separation efficiency of photogenerated carriers is an effective way to improve the protection performance of photoelectrochemical cathode. In order to make up for the shortcomings of SrTiO₃, such as large band gap and low separation efficiency of photogenerated carriers, BaTiO₃/SrTiO₃ composite films were prepared on fluorine-doped tin oxide conductive glass (FTO) by two-step ultrasonic spray pyrolysis process. The phase composition, surface morphology and optical properties of the samples were observed by XRD, SEM, UV-vis DRS and PL. Then, 304 stainless steel (304 SS) was used as the protected metal, and the photoelectrochemical cathodic protection performance of BaTiO₃/SrTiO₃ composite film was observed under the condition of shading light. The relative position of BaTiO₃/SrTiO₃ is determined by Mott-Schottky curve. The results show that the light absorption range of BaTiO₃/SrTiO₃ composite films prepared by two-step ultrasonic spray pyrolysis process is broadened to 400 nm. Compared with SrTiO₃ film, BaTiO₃/SrTiO₃ composite film has better light absorption performance. The separation efficiency of photo-generated carriers is improved. In 3.5wt%NaCl solution, BaTiO₃/SrTiO₃ composite film negatively shifts the open circuit potential of 304 SS to −0.38 V, with a negative shift degree of about 230 mV, while pure SrTiO₃ film can only negatively shift by 100 mV. The performance improvement is mainly attributed to the heterojunction formed by BaTiO₃ and SrTiO₃, which promotes the separation of photogenerated carriers.
- BaTiO₃ /
- SrTiO₃ /
- composite film /
- ultrasonic spray pyrolysis /
- photoelectrochemical cathodic protection

HTML全文

图 1 BaTiO₃/SrTiO₃复合薄膜制备流程图

Figure 1. Flowchart of preparation of BaTiO₃/SrTiO₃ composite film

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图 2 光电化学阴极保护测试装置图

Figure 2. Test device diagram for photoelectrochemical cathodic protection

GW—Ground wire; CE—Counter electrode; RE—Reference electrode; WE—Working electrode; CHI660E—Electrochemical workstation; AM 1.5G—Air mass 1.5 global, 100 W/cm²; hν—Photon energy

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图 3 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的XRD图谱

Figure 3. XRD patterns of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

FTO—Fluorine-doped tin oxide conductive glass

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图 4 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜表面((a)~(c))与截面((d)~(f))的微观形貌

Figure 4. Microstructure of surface ((a)-(c)) and cross section ((d)-(f)) of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite films

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图 5 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的UV-vis DRS图(a)及Tauc图(b)

Figure 5. UV-vis DRS diagram (a) and Tauc diagram (b) of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

α—Absorption coefficient

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图 6 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的光致发光光谱图

Figure 6. Photoluminescent spectrum of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

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图 7 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的电化学阻抗谱图

Figure 7. Electrochemical impedance spectra of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

Z'—Real part of impedance ; Z''—Imaginary part of impedance; Q₁, Q₂—Electrochemical capacitor; R_s—Electrolyte resistance; R₁—Depletion layer resistance; R₂—Charge-transfer resistance

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图 8 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的光电流密度-时间曲线

Figure 8. Photocurrent density-time curves of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

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图 9 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的开路电位(OCP)-时间曲线

Figure 9. Open-circuit potential (OCP)-time curves of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

E_{304 SS}—Potential of 304 stainless steel

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图 10 SrTiO₃、BaTiO₃和BaTiO₃/SrTiO₃复合薄膜的塔菲尔极化曲线

Figure 10. Tafel polarization curves of SrTiO₃, BaTiO₃ and BaTiO₃/SrTiO₃ composite film

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图 11 SrTiO₃、BaTiO₃的莫特-肖特基曲线

Figure 11. Mott-Schottky curves of SrTiO₃ and BaTiO₃ film

C—Capacitance density

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图 12 BaTiO₃/SrTiO₃复合薄膜光电化学阴极保护机制

Figure 12. Photoelectrochemical cathodic protection mechanism of BaTiO₃/SrTiO₃ composite film

NHE—Normal hydrogen electrode

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