金属离子掺杂TiO_2纳米管制备及光催化还原CO_2性能研究
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摘要
近年来,工业迅速发展的同时,人们面临着两大问题,可再生能源的日益匮乏及化工生产对环境造成重污染。然而,利用光催化反应制备一系列化工产品正好解决了上述问题。TiO_2因其具有无毒、廉价、催化活性高等优点被广泛的应用于光催化反应中。但是,颗粒状的纳米TiO_2对可见光利用率不高是光催化反应一直不能工业化的原因。因此,学者们尝试采用物理和化学方法改变TiO_2的颗粒状结构,例如将其制备成纳米管、纳米棒、纳米线和纳米薄膜,并对其进行金属掺杂,期望提高TiO_2的光催化反应效率。
本文以钛酸四丁酯为钛源,采用改良溶胶-凝胶法制备了纳米TiO_2颗粒。设计了单因素实验研究了原料配比、反应温度、反应时间和煅烧温度等因素对制备纳米TiO_2催化剂的影响。经XRD、BET、SEM、TG/DSC和Uv-Vis等仪器表征催化剂得知,纳米TiO_2颗粒平均粒径为94.2 nm、锐钛矿晶型、比表面积为54.31 m2/g、最佳煅烧温度为500℃、对紫外光有较强吸收,对可见光响应较弱。
本文以纳米TiO_2颗粒为前驱体,采用水热法制备出TiO_2纳米管,并对其进行金属离子(Fe3+、Cu2+、Cr3+、Co2+、Al3+)掺杂,得到了金属离子掺杂的TiO_2纳米管。研究了水热反应时间、水热反应温度、煅烧温度及前驱体用量对TiO_2纳米管光催化活性的影响,通过正交试验对TiO_2纳米管的制备条件进行了优化。经SEM检测得知纳米TiO_2颗粒经水热处理后形成了管状物,管径均小于30 nm,管长大于500 nm；经XRD检测得知未掺杂的TiO_2纳米管为锐钛矿；BET测试得知其比表面积为154.3 m2/g；经TG/DSC检测得知最佳煅烧温度为300℃; Uv-Vis检测发现TiO_2纳米管催化剂对紫外和可见光均有较大提高。
本文以TiO_2纳米管为催化剂、紫外灯为光源,在自行设计的光催化反应装置中进行还原CO2制备CH3OH实验。以单因素实验和正交实验结合确定了光催化还原CO2的最佳反应条件。实验结果表明Fe3+、Cu2+、Al3+离子掺杂TiO_2纳米管反应制得CH3OH产量较高,Co2+、Cr3+离子掺杂的TiO_2纳米管虽然对紫外光和可见光有较好的吸收,但其光催化反应能力一般。
本文还进行了光催化还原CO2制备CH3OH反应动力学研究,结果表明反应温度为30℃、40℃时产物CH3OH浓度与时间的关系分别为C=29.94t0.043、C=13.7t0.54。计算活化能得知TiO_2催化剂的加入降低了光催化还原CO2制备CH3OH反应的能垒,使反应更易进行。
In recent years, with rapidly industrial development, people are faced two problems:the increasing shortage of renewable energy and the environment are seriously polluted by chemical production. However, these problems could be solved by using a series of chemical products which prepared by photocatalytic reaction. With the merits of non-toxic, low-cost and High-performance catalytic activity, Nano-TiO2 catalyst are widely used in the photocatalytic reaction. However, due to the lower utilization rate of Nano-TiO2 for visible light, photocatalytic reaction hve been unable to industrialization. Therefore,the granular structure of TiO2 have been changed to improve the photocatalysis by physical or chemical methods, for example, nanotubes, nanotubes, nanowire and nanofilm.
In this work, the nanoparticle TiO2 was prepared with tetrabutyl titanate (TNB) by modified sol-gel method. The effect of the ratio of reactants, reaction time, reaction temperature and calcination temperature on preparation of nano-TiO2 were investigated in the single factor experiment The Nano-TiO2 catalysts were characterized by XRD, BET, SEM, TG/DSC and UV-Vis spectroscopy. The results showed that structure of nano-TiO2 was anatase, average diameter size was 94.2 nm, surface area was 54.31 m2/g and the optimal calcinations temperature was 500℃. Moreover, the ultraviolet absorbability of nano-TiO2 was more significant than visible light.
The TiO2 nanotube was prepared with TiO2 doped with metal ions:Fe3+, Cu2+, Cr3+, Co2+, Al3+ by hydrothermal method. The influence of calcinations temperature, dosage of raw material, synthesis temperature and time on photocatalytic performance of TiO2 nanotube was investigated. Result of SEM showed that TiO2 nanoparticle transformed into nanotube with hydrothermal treatment, the diameter of nanotube was smaller than 30 nm, the length of nanotube was more than 500 nm. XRD showed that the structure of TiO2 nanotube was anatase. The surface area was 154.3 m2/g by BET characteristic, and the optimal calcinations temperature was 300℃by TG/DSC, Uv-Vis spectroscopy showed that TiO2 nanotube had better photocatalytic performance than the TiO2 nanoparticle.
In the experiment of photocatalysis, methanol were prepared by photoreduction of CO2 with TiO2 catalysts in self-designed reactor under ultraviolet. The optical reaction conditions were studied by single factor combined with orthogonal design experiments. The results showed that TiO2 nanotube doped with Fe3+, Cu2+, Al3+ possessed remarkable photocatalytic activity. TiO2 nanotube doped with Co2+, Cr3+ had more significant absorption of ultraviolet than visible light, however, it had weaker photocatalytic performance.
The reaction kinetics of photocatalytic reduction of CO2 was also discussed. The results showed that the photocatalytic reaction rate equation were C=29.94t0.443 or C=13.7t0.54 when reaction temperature was 30℃or 40℃, respectively. Photoreduction of CO2 was more likely occured upon the addition of TiO2, the energy barrier of reaction of photocatalytic reduction of CO2 was decreased, which made the photoreduction of CO2 be more likely occurred.
本文以钛酸四丁酯为钛源,采用改良溶胶-凝胶法制备了纳米TiO_2颗粒。设计了单因素实验研究了原料配比、反应温度、反应时间和煅烧温度等因素对制备纳米TiO_2催化剂的影响。经XRD、BET、SEM、TG/DSC和Uv-Vis等仪器表征催化剂得知,纳米TiO_2颗粒平均粒径为94.2 nm、锐钛矿晶型、比表面积为54.31 m2/g、最佳煅烧温度为500℃、对紫外光有较强吸收,对可见光响应较弱。
本文以纳米TiO_2颗粒为前驱体,采用水热法制备出TiO_2纳米管,并对其进行金属离子(Fe3+、Cu2+、Cr3+、Co2+、Al3+)掺杂,得到了金属离子掺杂的TiO_2纳米管。研究了水热反应时间、水热反应温度、煅烧温度及前驱体用量对TiO_2纳米管光催化活性的影响,通过正交试验对TiO_2纳米管的制备条件进行了优化。经SEM检测得知纳米TiO_2颗粒经水热处理后形成了管状物,管径均小于30 nm,管长大于500 nm；经XRD检测得知未掺杂的TiO_2纳米管为锐钛矿；BET测试得知其比表面积为154.3 m2/g；经TG/DSC检测得知最佳煅烧温度为300℃; Uv-Vis检测发现TiO_2纳米管催化剂对紫外和可见光均有较大提高。
本文以TiO_2纳米管为催化剂、紫外灯为光源,在自行设计的光催化反应装置中进行还原CO2制备CH3OH实验。以单因素实验和正交实验结合确定了光催化还原CO2的最佳反应条件。实验结果表明Fe3+、Cu2+、Al3+离子掺杂TiO_2纳米管反应制得CH3OH产量较高,Co2+、Cr3+离子掺杂的TiO_2纳米管虽然对紫外光和可见光有较好的吸收,但其光催化反应能力一般。
本文还进行了光催化还原CO2制备CH3OH反应动力学研究,结果表明反应温度为30℃、40℃时产物CH3OH浓度与时间的关系分别为C=29.94t0.043、C=13.7t0.54。计算活化能得知TiO_2催化剂的加入降低了光催化还原CO2制备CH3OH反应的能垒,使反应更易进行。
In recent years, with rapidly industrial development, people are faced two problems:the increasing shortage of renewable energy and the environment are seriously polluted by chemical production. However, these problems could be solved by using a series of chemical products which prepared by photocatalytic reaction. With the merits of non-toxic, low-cost and High-performance catalytic activity, Nano-TiO2 catalyst are widely used in the photocatalytic reaction. However, due to the lower utilization rate of Nano-TiO2 for visible light, photocatalytic reaction hve been unable to industrialization. Therefore,the granular structure of TiO2 have been changed to improve the photocatalysis by physical or chemical methods, for example, nanotubes, nanotubes, nanowire and nanofilm.
In this work, the nanoparticle TiO2 was prepared with tetrabutyl titanate (TNB) by modified sol-gel method. The effect of the ratio of reactants, reaction time, reaction temperature and calcination temperature on preparation of nano-TiO2 were investigated in the single factor experiment The Nano-TiO2 catalysts were characterized by XRD, BET, SEM, TG/DSC and UV-Vis spectroscopy. The results showed that structure of nano-TiO2 was anatase, average diameter size was 94.2 nm, surface area was 54.31 m2/g and the optimal calcinations temperature was 500℃. Moreover, the ultraviolet absorbability of nano-TiO2 was more significant than visible light.
The TiO2 nanotube was prepared with TiO2 doped with metal ions:Fe3+, Cu2+, Cr3+, Co2+, Al3+ by hydrothermal method. The influence of calcinations temperature, dosage of raw material, synthesis temperature and time on photocatalytic performance of TiO2 nanotube was investigated. Result of SEM showed that TiO2 nanoparticle transformed into nanotube with hydrothermal treatment, the diameter of nanotube was smaller than 30 nm, the length of nanotube was more than 500 nm. XRD showed that the structure of TiO2 nanotube was anatase. The surface area was 154.3 m2/g by BET characteristic, and the optimal calcinations temperature was 300℃by TG/DSC, Uv-Vis spectroscopy showed that TiO2 nanotube had better photocatalytic performance than the TiO2 nanoparticle.
In the experiment of photocatalysis, methanol were prepared by photoreduction of CO2 with TiO2 catalysts in self-designed reactor under ultraviolet. The optical reaction conditions were studied by single factor combined with orthogonal design experiments. The results showed that TiO2 nanotube doped with Fe3+, Cu2+, Al3+ possessed remarkable photocatalytic activity. TiO2 nanotube doped with Co2+, Cr3+ had more significant absorption of ultraviolet than visible light, however, it had weaker photocatalytic performance.
The reaction kinetics of photocatalytic reduction of CO2 was also discussed. The results showed that the photocatalytic reaction rate equation were C=29.94t0.443 or C=13.7t0.54 when reaction temperature was 30℃or 40℃, respectively. Photoreduction of CO2 was more likely occured upon the addition of TiO2, the energy barrier of reaction of photocatalytic reduction of CO2 was decreased, which made the photoreduction of CO2 be more likely occurred.
引文
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