Preparation of SrTiO3/TiO2 composite film for photoelectrochemical cathodic protection
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摘要: 由于TiO2存在禁带宽度大、光生载流子分离率低等缺点，限制了其光电化学阴极保护性能。为解决此问题，首先采用水热法制备TiO2纳米阵列，然后通过超声喷雾热解法制备了SrTiO3/TiO2复合薄膜。通过XRD、SEM、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)对样品物相结构、微观形貌、光吸收性能等特征进行表征。最后以304不锈钢(304 SS)为被保护基体，考察了SrTiO3/TiO2复合薄膜的光电化学阴极保护性能。结果表明，通过超声喷雾热解法制备得到的SrTiO3/TiO2复合薄膜，其光吸收范围为415 nm以下，进入可见光区；SrTiO3/TiO2复合薄膜相比于TiO2纳米阵列，具有更好的光吸收特性；光生电子-空穴对分离率提高，且光生电子迁移率提高；在3.5wt%NaCl溶液中，SrTiO3/TiO2复合薄膜使304不锈钢腐蚀电位负移至–0.45 V，负移了近270 mV，而TiO2纳米阵列仅能负移210 mV，性能提升了28.5%。经过四次开光与闭光循环测试，SrTiO3/TiO2复合薄膜性能稳定。Abstract: Due to the presence of large band gap TiO2, photogenerated carriers disadvantage low rate of separation, which limits the photoelectrochemical cathodic protection. To solve this problem, TiO2 nanoarrays were prepared by hydrothermal method, and then SrTiO3/TiO2 composite films were prepared by ultrasonic spray pyrolysis. XRD, SEM, UV-visible diffuse reflectance spectrum (UV-Vis DRS), fluorescence spectra (PL) were used to characterize the phase structure, microscopic morphology, and light absorption properties of the samples. Finally, using 304 stainless steel (304 SS) as the protected substrate, the photoelectrochemical cathodic protection performance of the SrTiO3/TiO2 composite film was investigated. The results show that the SrTiO3/TiO2 composite film prepared by the ultrasonic spray pyrolysis method has a light absorption range of light below 415 nm, which enters the visible light region. The SrTiO3/TiO2 composite film has better light absorption than the TiO2 nanoarray. The separation rate of photogenerated electron-hole pairs is increased, and the mobility of photogenerated electrons is improved. In 3.5wt%NaCl solution, the SrTiO3/TiO2 composite film makes the corrosion potential of 304 stainless steel negatively shift to −0.45 V, and the negative shift is nearly 270 mV. While the TiO2 nanoarray can only move 210 mV negatively, and the performance is improved by 28.5%. The performance of the SrTiO3/TiO2 composite film is stable after four open and closed light cycle tests.
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Key words:
- TiO2 /
- SrTiO3 /
- composite film /
- ultrasonic spray pyrolysis /
- photoelectrochemical cathodic protection
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图 1 SrTiO3/TiO2复合薄膜制备流程图
Figure 1. Flow chart of preparation for SrTiO3/TiO2 composite film
FTO—Fluorine-doped tin oxide
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
图 3 TiO2纳米阵列和SrTiO3/TiO2复合薄膜的XRD图谱
Figure 3. XRD patterns of TiO2 nanoarray and SrTiO3/TiO2 composite film
图 4 TiO2纳米阵列 (a) 和SrTiO3/TiO2复合薄膜材料表面 (b) 及截面 (c) 的SEM图像
Figure 4. SEM images of TiO2 nanoarray (a), SrTiO3/TiO2 composite film with surface (b) and section morphology (c)
图 5 TiO2纳米阵列和SrTiO3/TiO2复合薄膜紫外-可见漫反射光谱(UV-Vis DRS)图谱及Tauc图
Figure 5. UV-visible diffuse reflectance spectrum (UV-Vis DRS) and Tauc of TiO2 nanoarray and SrTiO3/TiO2 composite film
图 6 TiO2纳米阵列和SrTiO3/TiO2复合薄膜荧光光谱图谱
Figure 6. Fluorescence spectra of TiO2 nanoarray and SrTiO3/TiO2 composite film
图 7 TiO2纳米阵列和SrTiO3/TiO2复合薄膜电化学阻抗谱
Figure 7. Electrochemical impedance test results of TiO2 nanoarray and SrTiO3/TiO2 composite film
图 8 TiO2纳米阵列和SrTiO3/TiO2复合薄膜开路电位-时间曲线
Figure 8. Open circuit potential-time curves of TiO2 nanoarray and SrTiO3/TiO2 composite film
E304 SS—Potential of 304 stainless steel
图 9 TiO2纳米阵列和SrTiO3/TiO2复合薄膜的光电流密度-时间曲线
Figure 9. Photocurrent density-time curves of TiO2 nanoarray and SrTiO3/TiO2 composite film
图 10 TiO2纳米阵列和SrTiO3/TiO2复合薄膜塔菲尔极化曲线
Figure 10. Tafel polarization curves of TiO2 nanoarray and SrTiO3/TiO2 composite film
304 SS—304 Stainless steel
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