钛基纳米管的制备工艺及光催化性能研究
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摘要
钛基纳米管薄膜因其独特的管式结构、较大的比表面积及方便回收再利用的特点,在光催化降解有机物方面有着广阔的应用前景。本论文采用水热法和阳极氧化法分别制备出了钛酸盐纳米管薄膜和TiO2纳米管阵列薄膜,并利用XRD、TEM、SEM、UV-Vis等手段对制备出样品的结构、表面形貌以及光催化降解MO的性能进行了研究。
以钛片和NaOH为原料,采用水热法成功制备出了钛酸盐纳米管薄膜。TEM和SEM结果表明,此薄膜由无序缠绕的纳米管组成,管径约为10nm。XRD结果表明,水热产物经水洗处理得到的是Na_2Ti_3O_7纳米管,而经酸洗处理后则变为H_2Ti_4O_9·H_2O纳米管。随着煅烧温度的提高,两种纳米管薄膜经历了不同的结构和形貌演变过程,最终Na_2Ti_3O_7纳米管转变成由Na_2Ti_6O_(13)和金红石相组成的纳米棒,而H_2Ti_4O_9·H_2O纳米管则转变为由纯金红石相组成的纳米片。光催化降解MO的实验结果表明,随着煅烧温度的升高,H_2Ti_4O_9·H_2O纳米管薄膜的光催化活性呈现先增加后减小的趋势,其中在500℃下煅烧的H_2Ti_4O_9·H_2O纳米管薄膜具有最高的光催化降解甲基橙(MO)的活性。
以钛片为阴、阳极,在含氟的有机电解液中,采用阳极氧化法成功制备出微观形貌均一、与基体结合牢固、有序的TiO_2纳米管阵列薄膜。结合SEM的测试结果,简单分析了有机两步法制备TiO_2纳米管阵列薄膜的机理;分析发现,脱膜处理有利于提高Ti基体的平整度,同时第二次阳极氧化制备纳米管阵列是以原位生长的方式进行的。光催化降解MO的实验结果表明,有机两步法制备的纳米管阵列薄膜的光催化活性高于有机一步法制备的纳米管阵列薄膜的光催化活性;随着煅烧温度的升高,TiO_2纳米管阵列薄膜的光催化活性也呈现先增加后减小的趋势,其中在700℃下煅烧的TiO_2纳米管阵列薄膜具有最高的光催化活性。此外,本文还采用水浴加热、电镀和光致还原等三种不同的方法分别将Fe、Cu、Ag三种元素成功的负载到纳米管薄膜上。
TiO_2-based nanotube thin films show a wide application prospect in the filed of photocatalytic degradation of organic due to their special tubular structure, larger specific surface areas and convenient for recycling. In this paper, titanate nanotube thin films and TiO_2 nanotube thin films were prepared by hydrothermal method and anodization technique, respectively. The samples were characterized by X-ray diffraction(XRD), Transmission electron microscopy(TEM), Scanning electron microscopy(SEM) and UV-Vis spectroscopy(UV-Vis), while their properties for photocatalytic degradation of methyl orange(MO) were also investigated.
Titanate nanotube thin films were successfully prepared by hydrothermal method using titanium plate and sodium hydroxide as the source materials. TEM and SEM images show that titanate nanotube thin films were composed of nanotubes with a diameter of 10nm which twisted together in a disordered way. XRD results indicate that hydrothermal products washed with distilled water result in Na2Ti3O7 nanotubes, while H_2Ti_4O_9·H2O nanotubes were obtained after washing with acid. As the calcination temperature increased, the two kinds of nanotube thin films experienced different structure and morphology evolution process. Finally, Na_2Ti_3O_7 nanotubes were transformed into nanorods which were composed of Na_2Ti_6O_(13) and rutile, while H_2Ti_4O_9·H2O nanotubes turned into nanosheets constituted of pure rutile. The experiment results of photocatalytic degradation of MO suggest that the photocatalytic activity of H_2Ti_4O_9·H2O nanotube thin films increased first and then decreased with the increasing calcination temperature. And the films calcined at 500℃show the highest photocatalytic activity for degradation of MO.
Using titanium plates as cathode and anode, ordered TiO_2 nanotube array thin films with uniform morphology were successfully prepared by anodization technique in organic solution containing F-, which combined with substrste firmly. Based on the SEM results, we simply analysed the mechanism of TiO_2 nanotube array thin films prepared by two step anodization. It was found that the film-wiped off treatment was helpful for improving the surface smoothness of titanium substrate, and the nanotube arrays growed in-situ during second anodiation process. The experiment results of photocatalytic degradation of MO indicate that the photocatalytic activity of the film prepared by two step anodation is higher than that of the films prepared by one step anodation. Moreover, as the calcination temperature increased, the photocatalytic activity of TiO_2 nanotube array thin films increased first and then decreased. And the films calcined at 700℃show -the highest photocatalytic activity. In this paper, Fe, Cu and Ag elements were successfully loaded onto TiO_2 nanotube array thin films by water heated process, electroplating method and photoinduced reduction technique, respectively.
以钛片和NaOH为原料,采用水热法成功制备出了钛酸盐纳米管薄膜。TEM和SEM结果表明,此薄膜由无序缠绕的纳米管组成,管径约为10nm。XRD结果表明,水热产物经水洗处理得到的是Na_2Ti_3O_7纳米管,而经酸洗处理后则变为H_2Ti_4O_9·H_2O纳米管。随着煅烧温度的提高,两种纳米管薄膜经历了不同的结构和形貌演变过程,最终Na_2Ti_3O_7纳米管转变成由Na_2Ti_6O_(13)和金红石相组成的纳米棒,而H_2Ti_4O_9·H_2O纳米管则转变为由纯金红石相组成的纳米片。光催化降解MO的实验结果表明,随着煅烧温度的升高,H_2Ti_4O_9·H_2O纳米管薄膜的光催化活性呈现先增加后减小的趋势,其中在500℃下煅烧的H_2Ti_4O_9·H_2O纳米管薄膜具有最高的光催化降解甲基橙(MO)的活性。
以钛片为阴、阳极,在含氟的有机电解液中,采用阳极氧化法成功制备出微观形貌均一、与基体结合牢固、有序的TiO_2纳米管阵列薄膜。结合SEM的测试结果,简单分析了有机两步法制备TiO_2纳米管阵列薄膜的机理;分析发现,脱膜处理有利于提高Ti基体的平整度,同时第二次阳极氧化制备纳米管阵列是以原位生长的方式进行的。光催化降解MO的实验结果表明,有机两步法制备的纳米管阵列薄膜的光催化活性高于有机一步法制备的纳米管阵列薄膜的光催化活性;随着煅烧温度的升高,TiO_2纳米管阵列薄膜的光催化活性也呈现先增加后减小的趋势,其中在700℃下煅烧的TiO_2纳米管阵列薄膜具有最高的光催化活性。此外,本文还采用水浴加热、电镀和光致还原等三种不同的方法分别将Fe、Cu、Ag三种元素成功的负载到纳米管薄膜上。
TiO_2-based nanotube thin films show a wide application prospect in the filed of photocatalytic degradation of organic due to their special tubular structure, larger specific surface areas and convenient for recycling. In this paper, titanate nanotube thin films and TiO_2 nanotube thin films were prepared by hydrothermal method and anodization technique, respectively. The samples were characterized by X-ray diffraction(XRD), Transmission electron microscopy(TEM), Scanning electron microscopy(SEM) and UV-Vis spectroscopy(UV-Vis), while their properties for photocatalytic degradation of methyl orange(MO) were also investigated.
Titanate nanotube thin films were successfully prepared by hydrothermal method using titanium plate and sodium hydroxide as the source materials. TEM and SEM images show that titanate nanotube thin films were composed of nanotubes with a diameter of 10nm which twisted together in a disordered way. XRD results indicate that hydrothermal products washed with distilled water result in Na2Ti3O7 nanotubes, while H_2Ti_4O_9·H2O nanotubes were obtained after washing with acid. As the calcination temperature increased, the two kinds of nanotube thin films experienced different structure and morphology evolution process. Finally, Na_2Ti_3O_7 nanotubes were transformed into nanorods which were composed of Na_2Ti_6O_(13) and rutile, while H_2Ti_4O_9·H2O nanotubes turned into nanosheets constituted of pure rutile. The experiment results of photocatalytic degradation of MO suggest that the photocatalytic activity of H_2Ti_4O_9·H2O nanotube thin films increased first and then decreased with the increasing calcination temperature. And the films calcined at 500℃show the highest photocatalytic activity for degradation of MO.
Using titanium plates as cathode and anode, ordered TiO_2 nanotube array thin films with uniform morphology were successfully prepared by anodization technique in organic solution containing F-, which combined with substrste firmly. Based on the SEM results, we simply analysed the mechanism of TiO_2 nanotube array thin films prepared by two step anodization. It was found that the film-wiped off treatment was helpful for improving the surface smoothness of titanium substrate, and the nanotube arrays growed in-situ during second anodiation process. The experiment results of photocatalytic degradation of MO indicate that the photocatalytic activity of the film prepared by two step anodation is higher than that of the films prepared by one step anodation. Moreover, as the calcination temperature increased, the photocatalytic activity of TiO_2 nanotube array thin films increased first and then decreased. And the films calcined at 700℃show -the highest photocatalytic activity. In this paper, Fe, Cu and Ag elements were successfully loaded onto TiO_2 nanotube array thin films by water heated process, electroplating method and photoinduced reduction technique, respectively.
引文
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