三乙胺改性TiO_2薄膜的常温制备及光催化性能研究
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摘要
TiO_2半导体光催化材料以其廉价、无毒、催化效率高、操作简单等优点得到广泛的研究。但是,由于其可见光响应能力差、光生电子-空穴易复合等缺点造成它在实际应用上的限制,因此对于提高TiO_2可见光催化活性成为光催化研究领域的一个重点。虽然经过N掺杂改性TiO_2具有很强可见光活性,但是关于掺N的制备均须采用后续煅烧处理,经此处理后所得的TiO_2便成为固体状态,不利其在不耐热或难于热处理的基材上的使用,因此本文开展了用三乙胺改性制备免热处理工序的可见光响应TiO_2及其性能研究。
以钛酸丁酯为前驱体、乙醇为溶剂、盐酸为催化剂,采用溶胶-凝胶法在室温下制备了具有锐钛矿晶型的TiO_2溶胶,以三乙胺为改性剂,在磁力搅拌下滴加三乙胺制备后滴加改性TiO_2溶胶,作为对比将改性剂三乙胺与钛酸丁酯混合一起作为前驱体制备三乙胺前滴加改性TiO_2溶胶;调整改性剂的用量来研究不同三乙胺的量对改性TiO_2性能的影响;在此基础上用恒温水浴加热来制备不同温度下的三乙胺改性TiO_2溶胶;研究三乙胺改性对提高TiO_2可见光催化性能的作用。溶胶陈化后采用浸渍提拉法在普通载玻片上涂膜,室温晾干,采用X射线衍射、扫描电镜、透射电镜、粒度分析仪、紫外-可见分光光度计、傅立叶红外光谱分析仪等测试手段对溶胶及薄膜结构性能进行研究。结果表明:
1、三乙胺后添加改性的TiO_2及三乙胺与前驱体混合滴加改性的TiO_2溶胶都为锐钛矿晶型,但是后添加改性TiO_2的性能更优异些。
2、当三乙胺的量使得溶胶pH值接近中性时,溶胶稳定性能最差;三乙胺的量增多有利于溶胶重新稳定,但量增多后会使溶胶中TiO_2的相对量减少,不利于薄膜可见光催化性能提高,实验所得最适宜的三乙胺用量是m(三乙胺):m(钛酸丁酯)为1:1。而不同水浴温度下添加三乙胺改性时,随着温度升高改性TiO_2颗粒有所长大,薄膜的表面吸附能力减弱,但同时由于薄膜的可见光吸收能力增强,使得可见光催化性能提高。65℃下制备的改性TiO_2薄膜具有最高的降解速率常数。
3、TiO_2薄膜的紫外可见吸收光谱显示,经过三乙胺改性的TiO_2显示出比纯TiO_2好的多的可见光吸收能力,同时降解罗丹明B的过程中也表现出了更好的可见光催化性能,改性后的TiO_2薄膜可见光催化降解速率常数比未经改性TiO_2高出7倍多,并且在重复的使用后,改性TiO_2薄膜仍具有稳定的催化性能。
The problem of environment and energy become more and more serious now.All over the world focus the problem and try to deal it.Titanium dioxide,as an excellent photocatalytic materials is researched thoroughly because of low price,non-toxic,high catalytic efficiency and easy to operate.However,weak visible spectral response and fast recombination rate of photo-generated electron-hole pair limits its application in practice.So the research to enhance the visible light activity is very important in this field.N-doped was a possible method to improve its' visible light activity.The process of high-heat treatment limited the application of TiO_2.Based on the actuality,the preparation and properties of triethylamine modified titanium dioxide film in room-temperature was posed in this paper.
The TiO_2-sol in anatase phase was synthesized at room temperature through sol-gel method.In this study,butyl titanate was used as precursor,ethanol as impregnate and HCl as catalyzer.Then under violent agitating,the triethylamine was used as modifying agent to be doped into the TiO_2 solution.The dosage and temperature were changed to look for the optimum.Triethylamine with butyl titanate was used as a precursor to prepare Triethylamine modified TiO_2-sol.The TiO_2 films were prepared by the dip-coating for thrice used the solutions prepared as above.After that,the crystal structure and the photocatalytic efficiency of the samples completed were tested through XRD,SEM,TEM,Volume analyzer,UV-Vis,FT-IR.The research results were shown below:
Firstly,the modified TiO_2 sol remained be anatase crystalline,the difference is that the TiO_2 modified as Triethylamine doped later has a better property than the one doped with butyl titanate.
Secondly,when the pH of sol was change to neutral as Triethylamine doped the TiO_2-sol show out worst stability.Then it will re-stable as Triethylamine being kept on doping.But it won't improve the visible light photocatalytic ability.The mass ratio of m (Triethylamine):m(butyl titanate)reaches to 1:1 show out to be the best.As the temperature rises,the modified TiO_2 displays better visible-light absorptivity even though the volume of particle growth quite fast because of the high temperature,which weaken the photocatalytic ability.From above,the optimum temperature was 65℃and modified TiO_2 flims showd the best photodecomposition performance.
The modified TiO_2 perform better visible-light absorptive than the pure TiO_2.At the same time,the modified TiO_2 has better photocatalytic activity than the pure one from the degradation of Rhodamine B under visible-light.The degradation speed constant is seven times more than the pure one.The modified TiO_2 remind has a steady catalytic activity in long-last experiment.
以钛酸丁酯为前驱体、乙醇为溶剂、盐酸为催化剂,采用溶胶-凝胶法在室温下制备了具有锐钛矿晶型的TiO_2溶胶,以三乙胺为改性剂,在磁力搅拌下滴加三乙胺制备后滴加改性TiO_2溶胶,作为对比将改性剂三乙胺与钛酸丁酯混合一起作为前驱体制备三乙胺前滴加改性TiO_2溶胶;调整改性剂的用量来研究不同三乙胺的量对改性TiO_2性能的影响;在此基础上用恒温水浴加热来制备不同温度下的三乙胺改性TiO_2溶胶;研究三乙胺改性对提高TiO_2可见光催化性能的作用。溶胶陈化后采用浸渍提拉法在普通载玻片上涂膜,室温晾干,采用X射线衍射、扫描电镜、透射电镜、粒度分析仪、紫外-可见分光光度计、傅立叶红外光谱分析仪等测试手段对溶胶及薄膜结构性能进行研究。结果表明:
1、三乙胺后添加改性的TiO_2及三乙胺与前驱体混合滴加改性的TiO_2溶胶都为锐钛矿晶型,但是后添加改性TiO_2的性能更优异些。
2、当三乙胺的量使得溶胶pH值接近中性时,溶胶稳定性能最差;三乙胺的量增多有利于溶胶重新稳定,但量增多后会使溶胶中TiO_2的相对量减少,不利于薄膜可见光催化性能提高,实验所得最适宜的三乙胺用量是m(三乙胺):m(钛酸丁酯)为1:1。而不同水浴温度下添加三乙胺改性时,随着温度升高改性TiO_2颗粒有所长大,薄膜的表面吸附能力减弱,但同时由于薄膜的可见光吸收能力增强,使得可见光催化性能提高。65℃下制备的改性TiO_2薄膜具有最高的降解速率常数。
3、TiO_2薄膜的紫外可见吸收光谱显示,经过三乙胺改性的TiO_2显示出比纯TiO_2好的多的可见光吸收能力,同时降解罗丹明B的过程中也表现出了更好的可见光催化性能,改性后的TiO_2薄膜可见光催化降解速率常数比未经改性TiO_2高出7倍多,并且在重复的使用后,改性TiO_2薄膜仍具有稳定的催化性能。
The problem of environment and energy become more and more serious now.All over the world focus the problem and try to deal it.Titanium dioxide,as an excellent photocatalytic materials is researched thoroughly because of low price,non-toxic,high catalytic efficiency and easy to operate.However,weak visible spectral response and fast recombination rate of photo-generated electron-hole pair limits its application in practice.So the research to enhance the visible light activity is very important in this field.N-doped was a possible method to improve its' visible light activity.The process of high-heat treatment limited the application of TiO_2.Based on the actuality,the preparation and properties of triethylamine modified titanium dioxide film in room-temperature was posed in this paper.
The TiO_2-sol in anatase phase was synthesized at room temperature through sol-gel method.In this study,butyl titanate was used as precursor,ethanol as impregnate and HCl as catalyzer.Then under violent agitating,the triethylamine was used as modifying agent to be doped into the TiO_2 solution.The dosage and temperature were changed to look for the optimum.Triethylamine with butyl titanate was used as a precursor to prepare Triethylamine modified TiO_2-sol.The TiO_2 films were prepared by the dip-coating for thrice used the solutions prepared as above.After that,the crystal structure and the photocatalytic efficiency of the samples completed were tested through XRD,SEM,TEM,Volume analyzer,UV-Vis,FT-IR.The research results were shown below:
Firstly,the modified TiO_2 sol remained be anatase crystalline,the difference is that the TiO_2 modified as Triethylamine doped later has a better property than the one doped with butyl titanate.
Secondly,when the pH of sol was change to neutral as Triethylamine doped the TiO_2-sol show out worst stability.Then it will re-stable as Triethylamine being kept on doping.But it won't improve the visible light photocatalytic ability.The mass ratio of m (Triethylamine):m(butyl titanate)reaches to 1:1 show out to be the best.As the temperature rises,the modified TiO_2 displays better visible-light absorptivity even though the volume of particle growth quite fast because of the high temperature,which weaken the photocatalytic ability.From above,the optimum temperature was 65℃and modified TiO_2 flims showd the best photodecomposition performance.
The modified TiO_2 perform better visible-light absorptive than the pure TiO_2.At the same time,the modified TiO_2 has better photocatalytic activity than the pure one from the degradation of Rhodamine B under visible-light.The degradation speed constant is seven times more than the pure one.The modified TiO_2 remind has a steady catalytic activity in long-last experiment.
引文
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