Pt负载中空TiO_2纳米管的制备及其光催化活性研究
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摘要
以TiO_2(Degussa P25)和NaOH为起始原料,采用传统水热法制备了钛酸盐纳米管,此纳米管经进一步水热“碳化”和溶胶-凝胶包覆SiO_2层的化学形貌冻结与高温煅烧处理后制得形貌得以保持的锐钛矿相核壳中空结构TiO_2纳米管(titania nanotube,简称TiNTs)。一方面,以该锐钛矿型TiNTs为载体,H_2PtCl6·6H_2O为Pt源,采用光沉积法制得载铂TiO_2纳米管(Pt/TiNTs);其次,又以钛酸盐纳米管为基体,H_2PtCl_6·6H_2O为Pt源,通过热还原法制备了Pt/TiNTs。借助透射电子显微镜(TEM)、场发射电子显微镜(FESEM)、X射线衍射(XRD)及电子能谱(EDS)等表征手段对制得纳米管的形貌、结构及组成进行分析,并研究了它们的光催化性能。主要研究内容和结论如下:
水热反应制得的钛酸盐纳米管为无定形态,且组成为H_2Ti_2O_5·H_2O。纳米管形貌和尺寸分布均一,具有突出的大比表面积和高长径比结构性能;随着煅烧温度的提高,纳米管虽相转变为锐钛矿TiO_2,但管状形貌易发生形变,其结构长度迅速缩短,表现为许多聚结在一起的纳米棒状粒子,团聚情况较严重;在原来水热反应制得的钛酸盐纳米管基础上,作包碳包硅的化学形貌冻结后处理,然后500℃高温煅烧制得了热稳定性的且纳米管形貌完好的锐钛相TiNTs,它在物理性能参数上保持了大比表面积及高孔隙体积等的优势。在高温600℃煅烧后形貌有部分破坏,达到700℃则会导致结构几乎完全坍塌;在有空气参与的情况下光催化分解乙酸溶液的测试表明,随着煅烧温度的升高,纳米管的光催化活性也在增强,600℃煅烧的纳米管光催化性能较好。
对于光沉积制得的Pt/TiNTs,Pt纳米颗粒以单质形式在纳米管表面均匀分散,且载Pt后纳米管的晶型结构没有发生明显变化;光还原条件如光照时间、光照强度及前躯体预处理条件等对Pt/TiNTs的性能和结构有较大影响,光还原时间以1.5h为佳;纳米管担载Pt后其光催化性能有了不同程度的提高,而且纳米管煅烧温度与Pt负载量共同决定Pt/TiNTs催化剂的活性,其中以Pt/TiNTs-600℃-1.5wt%为最佳;纳米管表面过量沉积Pt会降低其光催化活性。
水热还原法制备的较低载Pt量Pt/TiNTs,Pt粒子可在纳米管表面均匀分散且粒径较小,此时Pt的负载对纳米管表面形貌没有大的影响;当载Pt量偏高时,Pt粒子在纳米管表面形成尺寸较大的球形颗粒或団聚体，造成纳米管晶型结构发生明显变化,甚至Pt的晶相覆盖过锐钛矿相,损害了催化剂的形貌和结构;而材料催化性能则受比表面积大小、晶相组成及Pt粒子存在形式等几方面因素影响,水热载Pt后纳米管的催化性能有不同程度提高,其中理论担载量为2.0wt%且经600℃热处理制备的Pt/TiNTs光催化效率较高,过量担载会显著损害Pt/TiNTs的活性。
Titanate nanotubes were synthesized via a typical hydrothermal method taking TiO_2 (Degussa P25) and NaOH as raw materials, and further core-shell titania nanotube (TiNTs) with intact morphology and anatase phase were obtained by chemical morphology freezing routes which consisted of carbon injection and silica-coated processes and high-temperature calcination treatment. On the one hand, Pt nanoparticles loaded titania nanotubes were prepared by photodeposition method using H_2PtCl6·6H_2O as a platinum source and methanol as a sacrificial electron donor and the finally obtained samples were referred as Pt/TiNTs; secondly, a combination processes of hydrothermal reactions and chemical morphology freezing method were also employed to synthesize Pt/TiNTs catalysis with titanate nanotubes as carriers and H_2PtCl6·6H_2O as a platinum source. The morphology, structures and compositions of the as-prepared TiNTs and Pt/TiNTs were investigated by TEM, FESEM, XRD and EDS spectrum; furthermore, the photo-catalytic activities of the samples were studied. The main content and key conclusions were summarized below:
The titanate nanotubes were amorphous, and the structural formula was H_2Ti2O5·H_2O. With a unified shape and well-balanced size distribution, the nanotubes possessed an outstanding property of specific surface area and high length-diameter ratio structures; the nanotubes gradually transformed into anatase occurred as elevating the calcination temperature, however, the morphology of the nanotubes could easily be damaged with a rapid cut of structures in length, and finally became a mess of agglomerated nanorods or particles; But the thermally stable anatase TiNTs with undamaged morphology after 500℃calcination treatment could be achieved by adopting chemical morphology freezing method to protect the primary nanotubes against the possible shape deformation, and thus the prepared TiNTs maintained its advantages of large specific surface area and high pore volume. Calcinating at a higher temperature of 600℃, the TiNTs happened to be partially damaged, and the tube structure can hardly be found when the calcination temperature arrived at 700℃; the photo-catalytic activity tests were carried out with the participation of oxygen for the degradation of AcOH, and the increase of calcination temperature could significantly improve the catalytic performance of the samples, and the TiNTs calcined at 600℃acquired a better performance.
For the catalysts prepared by photo-deposition method, the Pt nanoparticles on the surface of Pt/TiNTs were Pt metal and dispersed uniformly on the nanotubes, and the crystalline constitution of Pt/TiNTs was not apparently changed after a certain amounts of Pt loaded on the nanotubes; the photoreduction conditions such as irradiation time, intensity and pretreatment had a great impact on the performance and structures of the catalysts, and the optimal loading time were 1.5h; otherwise, the thermal treatment temperature also distinctively affected their photo-catalytic ability, and together with Pt loading amount determined the activities of the as-prepared Pt/TiNTs catalysts, among which Pt/TiNTs-600℃-1.5wt% exhibited the best performance, however, the excessive loading content of Pt particles would lower the photo-activities of the Pt/TiNTs.
The Pt nanoparticles in the form of Pt metal deposited on the surface of Pt/TiNTs (low Pt loading amounts) neatly when a new hydrothermal-reduction method was employed to prepare the catalysts, and thereby the crystalline phase of Pt/TiNTs was not evidently changed; But the Pt particles started to appear even in the form of large spherical particles or agglomerations when the TiNTs loaded with a large quantity of Pt content which led to a pronounced variation of the phase composition of Pt/TiNTs and to damage catalyst’s shape and microstructures; the specific surface area, phase composition as well as the form of Pt particle state jointly decided the photo-catalytic ability of the prepared materials. The Pt/TiNTs had a certain degree of photo-catalytic activity improvement after being loaded with an appropriate amount of Pt and results showed that Pt/TiNTs-600℃with a theoretical loading content of 2.0wt% Pt had the most satisfactory catalytic performance. In addition, it was also found that the activities of the Pt/TiNTs with excessive Pt loading amounts would be significantly reduced.
水热反应制得的钛酸盐纳米管为无定形态,且组成为H_2Ti_2O_5·H_2O。纳米管形貌和尺寸分布均一,具有突出的大比表面积和高长径比结构性能;随着煅烧温度的提高,纳米管虽相转变为锐钛矿TiO_2,但管状形貌易发生形变,其结构长度迅速缩短,表现为许多聚结在一起的纳米棒状粒子,团聚情况较严重;在原来水热反应制得的钛酸盐纳米管基础上,作包碳包硅的化学形貌冻结后处理,然后500℃高温煅烧制得了热稳定性的且纳米管形貌完好的锐钛相TiNTs,它在物理性能参数上保持了大比表面积及高孔隙体积等的优势。在高温600℃煅烧后形貌有部分破坏,达到700℃则会导致结构几乎完全坍塌;在有空气参与的情况下光催化分解乙酸溶液的测试表明,随着煅烧温度的升高,纳米管的光催化活性也在增强,600℃煅烧的纳米管光催化性能较好。
对于光沉积制得的Pt/TiNTs,Pt纳米颗粒以单质形式在纳米管表面均匀分散,且载Pt后纳米管的晶型结构没有发生明显变化;光还原条件如光照时间、光照强度及前躯体预处理条件等对Pt/TiNTs的性能和结构有较大影响,光还原时间以1.5h为佳;纳米管担载Pt后其光催化性能有了不同程度的提高,而且纳米管煅烧温度与Pt负载量共同决定Pt/TiNTs催化剂的活性,其中以Pt/TiNTs-600℃-1.5wt%为最佳;纳米管表面过量沉积Pt会降低其光催化活性。
水热还原法制备的较低载Pt量Pt/TiNTs,Pt粒子可在纳米管表面均匀分散且粒径较小,此时Pt的负载对纳米管表面形貌没有大的影响;当载Pt量偏高时,Pt粒子在纳米管表面形成尺寸较大的球形颗粒或団聚体，造成纳米管晶型结构发生明显变化,甚至Pt的晶相覆盖过锐钛矿相,损害了催化剂的形貌和结构;而材料催化性能则受比表面积大小、晶相组成及Pt粒子存在形式等几方面因素影响,水热载Pt后纳米管的催化性能有不同程度提高,其中理论担载量为2.0wt%且经600℃热处理制备的Pt/TiNTs光催化效率较高,过量担载会显著损害Pt/TiNTs的活性。
Titanate nanotubes were synthesized via a typical hydrothermal method taking TiO_2 (Degussa P25) and NaOH as raw materials, and further core-shell titania nanotube (TiNTs) with intact morphology and anatase phase were obtained by chemical morphology freezing routes which consisted of carbon injection and silica-coated processes and high-temperature calcination treatment. On the one hand, Pt nanoparticles loaded titania nanotubes were prepared by photodeposition method using H_2PtCl6·6H_2O as a platinum source and methanol as a sacrificial electron donor and the finally obtained samples were referred as Pt/TiNTs; secondly, a combination processes of hydrothermal reactions and chemical morphology freezing method were also employed to synthesize Pt/TiNTs catalysis with titanate nanotubes as carriers and H_2PtCl6·6H_2O as a platinum source. The morphology, structures and compositions of the as-prepared TiNTs and Pt/TiNTs were investigated by TEM, FESEM, XRD and EDS spectrum; furthermore, the photo-catalytic activities of the samples were studied. The main content and key conclusions were summarized below:
The titanate nanotubes were amorphous, and the structural formula was H_2Ti2O5·H_2O. With a unified shape and well-balanced size distribution, the nanotubes possessed an outstanding property of specific surface area and high length-diameter ratio structures; the nanotubes gradually transformed into anatase occurred as elevating the calcination temperature, however, the morphology of the nanotubes could easily be damaged with a rapid cut of structures in length, and finally became a mess of agglomerated nanorods or particles; But the thermally stable anatase TiNTs with undamaged morphology after 500℃calcination treatment could be achieved by adopting chemical morphology freezing method to protect the primary nanotubes against the possible shape deformation, and thus the prepared TiNTs maintained its advantages of large specific surface area and high pore volume. Calcinating at a higher temperature of 600℃, the TiNTs happened to be partially damaged, and the tube structure can hardly be found when the calcination temperature arrived at 700℃; the photo-catalytic activity tests were carried out with the participation of oxygen for the degradation of AcOH, and the increase of calcination temperature could significantly improve the catalytic performance of the samples, and the TiNTs calcined at 600℃acquired a better performance.
For the catalysts prepared by photo-deposition method, the Pt nanoparticles on the surface of Pt/TiNTs were Pt metal and dispersed uniformly on the nanotubes, and the crystalline constitution of Pt/TiNTs was not apparently changed after a certain amounts of Pt loaded on the nanotubes; the photoreduction conditions such as irradiation time, intensity and pretreatment had a great impact on the performance and structures of the catalysts, and the optimal loading time were 1.5h; otherwise, the thermal treatment temperature also distinctively affected their photo-catalytic ability, and together with Pt loading amount determined the activities of the as-prepared Pt/TiNTs catalysts, among which Pt/TiNTs-600℃-1.5wt% exhibited the best performance, however, the excessive loading content of Pt particles would lower the photo-activities of the Pt/TiNTs.
The Pt nanoparticles in the form of Pt metal deposited on the surface of Pt/TiNTs (low Pt loading amounts) neatly when a new hydrothermal-reduction method was employed to prepare the catalysts, and thereby the crystalline phase of Pt/TiNTs was not evidently changed; But the Pt particles started to appear even in the form of large spherical particles or agglomerations when the TiNTs loaded with a large quantity of Pt content which led to a pronounced variation of the phase composition of Pt/TiNTs and to damage catalyst’s shape and microstructures; the specific surface area, phase composition as well as the form of Pt particle state jointly decided the photo-catalytic ability of the prepared materials. The Pt/TiNTs had a certain degree of photo-catalytic activity improvement after being loaded with an appropriate amount of Pt and results showed that Pt/TiNTs-600℃with a theoretical loading content of 2.0wt% Pt had the most satisfactory catalytic performance. In addition, it was also found that the activities of the Pt/TiNTs with excessive Pt loading amounts would be significantly reduced.
引文
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