金属硒化物修饰的TiO2纳米材料对304不锈钢的光生阴极保护
韦秦怡
学位类型硕士
导师王秀通
2017-05
学位授予单位中国科学院大学
学位授予地点北京
学位专业海洋腐蚀与防护
关键词金属硒化物 二氧化钛 阴极保护 304不锈钢 纳米材料
其他摘要TiO2纳米薄膜因具有优良的光电性能、光催化性能、环境友好性和化学稳定性而备受关注,其对金属材料优良的阴极保护性能也展现出了诱人的发展前景,近年来,越来越多的科研工作者将TiO2纳米薄膜应用于金属腐蚀防护的研究中。然而,一方面,TiO2对太阳光的光响应范围较窄,仅局限于紫外光区(仅占太阳光谱的5%),因而对太阳能的有效利用效率极低;另一方面,光照下TiO2产生的光生电子-空穴对复合率较高,光电转换效率不高,无光照条件下光生阴极保护性能不佳。为了获得解决上述问题的有效途径,研究者们做了大量的研究工作。
本研究侧重于探究金属硒化物修饰的二氧化钛纳米材料对304不锈钢的光生阴极保护性能及作用机理。本文以纯的钛箔作为基底,采用阳极氧化法在它的表面制备出排列整齐有序的TiO2纳米管阵列薄膜,再在TiO2纳米管阵列薄膜表面用电化学沉积的方法分别修饰上NiSe2和WSe2两种金属硒化物。所制试样的表面形貌特征、物相结构组成和紫外、可见光区的光响应性能分别通过扫描电子显微镜(SEM)、X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)等表征手段来观测。TiO2纳米管阵列薄膜和经金属硒化物修饰后的复合纳米薄膜对304不锈钢的光生阴极保护性能则采用腐蚀电化学测试技术和光电技术相结合的方式来探究。
(1)通过改变电化学沉积的循环周期在TiO2纳米管阵列薄膜表面修饰上不同量的NiSe2纳米颗粒,通过性能测试优选出可见光下对304不锈钢具有最佳光生阴极保护性能的NiSe2/TiO2纳米复合膜。试验结果表明,NiSe2纳米颗粒的存在将TiO2的光响应范围拓宽到了可见光区域,对304不锈钢的光生阴极保护性能也得到了极大的提高;当电化学沉积的周期为2时制备得到的NiSe2/TiO2纳米复合膜对304不锈钢具有最优的光生阴极保护性能,304不锈钢偶联制备得到的复合膜在可见光照下产生的光生电流密度可以达到283 µA/cm2,开路电位的值可以负移达到-730 mV。
(2)以二氧化钛为基底,采用恒电流电沉积的方法通过改变沉积液中SeO2的加入量制备获得不同的WSe2/TiO2纳米复合薄膜材料,观测SeO2加入量与复合薄膜材料的光响应和光生阴极保护性能的影响。结果表明,WSe2修饰后的TiO2纳米管薄膜相比纯TiO2纳米管薄膜在可见光区的光响应性能和对304不锈钢的光生阴极保护性能均有明显提升。当SeO2的加入量为20 mg时制备得到的WSe2/TiO2纳米复合膜对304不锈钢具有最优的光生阴极保护性能, 304不锈钢偶联此复合膜在可见光照射下的光生电流密度可以达到206 µA/cm2,开路电位的值可以负移达到-800 mV。
; TiO2 nanometer film shows attractive prospects in the field of metal corrosion protection, because it owns good photoelectric property, photocatalytic performance, environmental friendliness and chemical stability, attracts extensive attention. However, TiO2 as a wide bandgap semiconductor can only effectively response to ultraviolet light (only accounts for 5% of the solar spectrum) so that its solar energy utilization is extremely low. Moreover, the recombination rate of photogenerated electron-hole pairs in TiO2 is high and the photoelectric conversion efficiency is low, which limits its photogenerated cathodic protection performance for 304 stainless steel (304SS). Lots of research has been carried out to solve these problems.
The main goal and motivation of this dissertation is to explore the photogenerated cathodic protection performance and mechanism of titanium dioxide nanomaterial modified with metal selenide for 304SS. The arranged orderly TiO2 nanotube arrays film was prepared on the surface of titanium substrate via anodic oxidation. Then NiSe2 and WSe2 metal selenide semiconductor nanomaterials were modified on the TiO2 nanotube arrays film through electrochemical deposition, respectively. The surface morphology, phase structure and optical response performance of prepared samples were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and UV-Vis diffuse reflection spectroscopy (UV-Vis DRS). The photogenerated cathodic protection properties of TiO2 nanotube arrays film and modified nanocomposite films for 304SS were tested by a combined technology of the corrosion electrochemistry testing technology and photoelectric technology in 3.5 wt.% NaCl solution.
(1) Different amount of NiSe2 nanoparticles were modified on the surface of TiO2 nanotube arrays film via changing the cycle number of electrochemical deposition. The NiSe2/TiO2 nanocomposite with the optimal photogenerated cathodic protection performance for 304SS was selected. It turns out that the existence of NiSe2 nanoparticles promoted visible light response of TiO2 nanotube arrays film, enhanced its photogenerated cathodic protection property for 304SS. NiSe2/TiO2 nanocomposite owned the optimal photogenerated cathodic protection for 304SS while the cycle number of electrochemical deposition was 2. The photogenerated current density and open circuit potential of 304SS coupled with this nanofilm were 283 µA/cm2 and -730 mV, respectively.
(2) Different WSe2/TiO2 nanocomposite films was prepared through changing the additive amount of SeO2 in electrolyte. The effects of SeO2 content on the visible light response and photogenerated cathodic protection properties of as-prepared WSe2/TiO2 nanocomposite films were investigated. The results showed that the visible light response and photogenerated cathodic protection properties of WSe2/TiO2 nanocomposites were better than pure TiO2 nanotube arrays film. WSe2/TiO2 nanocomposite film prepared in the electrolyte with 20 mg SeO2 exhibited the optimal photogenerated cathodic protection performance for 304SS. The photogenerated current density of 304SS coupling with this composite under visible light irradiation can reach 206 µA/cm2, and the open circuit potential negatively shifted to -800mV.
语种中文
文献类型学位论文
条目标识符http://ir.qdio.ac.cn/handle/337002/136553
专题海洋环境腐蚀与生物污损重点实验室
作者单位中国科学院海洋研究所
第一作者单位中国科学院海洋研究所
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韦秦怡. 金属硒化物修饰的TiO2纳米材料对304不锈钢的光生阴极保护[D]. 北京. 中国科学院大学,2017.
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