纳米二氧化钛粒子的可控制备、表征及其对甲醛降解反应的光催化性能的研究
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摘要
纳米二氧化钛的附加值高,在环境、信息、材料、能源、医疗与卫生等领域有着广阔的应用前景,在近20年来引起极大关注,并得到了蓬勃发展,其生产地区主要集中在西欧和北美,亚洲的日本与韩国也有较大的生产量,我国也进行了大规模的研究。
本文以制备出质量好、成本低、效率高、光催化性能好的纳米二氧化钛为目标,研究内容涉及到二氧化钛纳米粒子制备过程的各影响因素分析、最佳制备工艺条件的确定、二氧化钛纳米粒子的主要物化性能表征、在静态和动态条件下光催化降解甲醛的光催化性能。
采用控制水解法制备纳米二氧化钛,并通过分析四氯化钛浓度、反应温度、滴加速度、加水量、碳酸铵用量、锻烧温度等因素对制备过程及最终产物粒径的影响,确定了最佳制备工艺条件。即:四氯化钛对正辛醇的质量浓度为20%,反应温度为50℃,反应物的滴加速度为3s/滴,溶液加水量为80mL,碳酸铵用量为30g,煅烧温度为350℃。
表征结果显示,所得二氧化钛粒子的粒径在30nm左右,晶型为纯锐钛矿结构,纯度在98.7%以上,比表面积为229.77m~2/g,水溶性盐含量在1.6%以下,灼烧失重为0.61%左右,水浸pH值为6,表观密度在0.46 g/mL以下。
在静态和动态条件下,测定了所得纳米二氧化钛和购买的P25对光催化降解甲醛的效果。结果表明,两者均有很好的降解效果,而且静态条件下的降解率要高于动态条件下的,所得纳米二氧化钛对甲醛的降解效果与P25的降解效果比较接近,但还是P25对甲醛的降解效果更好一些。
Because of highly increased value, nanosized TiO_2 particles have been extensively applied in environment, information, materials, energy sources, medical treatments and hygiene, etc. Great concern and striking development have been made in the world in the past 20 years. Their production focuses in Western Europeand the northern America, and another bigger output in Japan and Korea. A wide range of research has been carried out in our country.
The purpose of this disquisition is to produce Nanometer TiO_2 particles with good qulity,low cost,high efficiency.The contents of research include the study of the optimal reaction condition, the test and analysis of the major property of the self-producted nanometer TiO_2, the study of formaldehyde photocatalyze in the static experiment system and the continuous flow system.
Nanometer TiO_2 particles were prepared by controled liquid phase methods The effect of reaction temperature, the dipping speed, the water dosage and the calcining temperature have been studied systematically. From the results of experiments, we draw the conclusions that the optimal reaction temperature is 50℃,the ration of tetrachloride is 20%, the dipping speed is 3s/drop, the water dosage is 80mL, the weight of salvolatile is 30g, the optimal calcining temperature is 350℃
By choosing and analyzing the major property of self-producted nanometer TiO_2, the particle size is about 30nm, the crystal form is anatase, the purity is above 98.7%, the specific surface area is 229.77m~2/g, the impurity content is below 1.6%, the water content is about 0.61%, the pH value is about 6, the apparent density is about 0.46 g/mL.
The self-producted nanometer TiO_2 and P25 were used for the experiment of formaldehyde photocatalyze in the static experiment system and the continuous flow system, By choosing and analyzing, the photocatalyze decomposition effect of two catalyzers is good and the photo-catalytic efficiency of the static experiment system is higher than the continuous flow system. the photo-catalytic efficiency of two catalyzers is very close,but the effect of P25 is better than the self-producted nanometer TiO_2.
本文以制备出质量好、成本低、效率高、光催化性能好的纳米二氧化钛为目标,研究内容涉及到二氧化钛纳米粒子制备过程的各影响因素分析、最佳制备工艺条件的确定、二氧化钛纳米粒子的主要物化性能表征、在静态和动态条件下光催化降解甲醛的光催化性能。
采用控制水解法制备纳米二氧化钛,并通过分析四氯化钛浓度、反应温度、滴加速度、加水量、碳酸铵用量、锻烧温度等因素对制备过程及最终产物粒径的影响,确定了最佳制备工艺条件。即:四氯化钛对正辛醇的质量浓度为20%,反应温度为50℃,反应物的滴加速度为3s/滴,溶液加水量为80mL,碳酸铵用量为30g,煅烧温度为350℃。
表征结果显示,所得二氧化钛粒子的粒径在30nm左右,晶型为纯锐钛矿结构,纯度在98.7%以上,比表面积为229.77m~2/g,水溶性盐含量在1.6%以下,灼烧失重为0.61%左右,水浸pH值为6,表观密度在0.46 g/mL以下。
在静态和动态条件下,测定了所得纳米二氧化钛和购买的P25对光催化降解甲醛的效果。结果表明,两者均有很好的降解效果,而且静态条件下的降解率要高于动态条件下的,所得纳米二氧化钛对甲醛的降解效果与P25的降解效果比较接近,但还是P25对甲醛的降解效果更好一些。
Because of highly increased value, nanosized TiO_2 particles have been extensively applied in environment, information, materials, energy sources, medical treatments and hygiene, etc. Great concern and striking development have been made in the world in the past 20 years. Their production focuses in Western Europeand the northern America, and another bigger output in Japan and Korea. A wide range of research has been carried out in our country.
The purpose of this disquisition is to produce Nanometer TiO_2 particles with good qulity,low cost,high efficiency.The contents of research include the study of the optimal reaction condition, the test and analysis of the major property of the self-producted nanometer TiO_2, the study of formaldehyde photocatalyze in the static experiment system and the continuous flow system.
Nanometer TiO_2 particles were prepared by controled liquid phase methods The effect of reaction temperature, the dipping speed, the water dosage and the calcining temperature have been studied systematically. From the results of experiments, we draw the conclusions that the optimal reaction temperature is 50℃,the ration of tetrachloride is 20%, the dipping speed is 3s/drop, the water dosage is 80mL, the weight of salvolatile is 30g, the optimal calcining temperature is 350℃
By choosing and analyzing the major property of self-producted nanometer TiO_2, the particle size is about 30nm, the crystal form is anatase, the purity is above 98.7%, the specific surface area is 229.77m~2/g, the impurity content is below 1.6%, the water content is about 0.61%, the pH value is about 6, the apparent density is about 0.46 g/mL.
The self-producted nanometer TiO_2 and P25 were used for the experiment of formaldehyde photocatalyze in the static experiment system and the continuous flow system, By choosing and analyzing, the photocatalyze decomposition effect of two catalyzers is good and the photo-catalytic efficiency of the static experiment system is higher than the continuous flow system. the photo-catalytic efficiency of two catalyzers is very close,but the effect of P25 is better than the self-producted nanometer TiO_2.
引文
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2 陶宁, 康斌, 王兰武. 纳米 TiO_2 制备及应用技术开发. 四川冶金, 2002, 14(2):17~19.
3 姚超, 朱毅青, 成庆堂, 顾力新. 纳米 TiO_2 粉体的制备方法和发展趋势. 现代化工, 2000, 17(10):126~132.
4 张立德, 牟秀美. 纳米材料科学. 辽宁科技出版社, 1994:378~429.
5 金寿日, 赵新洛译. 金属烟粒子结晶学. 西南师范大学出版社, 1993:23~35.
6 Halperin W P. Quantum size effects in metal particles. Modern. Phys, 1986, 58 (3):533~605.
7 张立德, 牟秀美. 纳米材料和纳米结构. 科技出版社, 2001:101~131.
8 Birringer R, Gleiten H, Klein HP. Synthesis of n-metals. Phys.Lett, 1984,102(8):365~369.
9 苏品书. 超微粒子材料技术. 复汉出版社, 1989:460~478.
10 梅滨, 王晓兰. 纳米材料的应用和进展, 煤炭技术, 2002, 12(5):3~7.
11 Abram T. Advanceded ceramic powder arid nano-sized ceramic powder:An Industry and market overiew. Ceramic Trans, 1996, 62(2):3~13.
12 Linsebiger A. L, Lu G. Q. Photo-catalysis is on TiO_2 Surface: Principles, Mechanism and Selected Results. Chem Rev, 1995(3):735.
13 Keichi T., Mario C., Teruaki H. Effect of Crystallinity of TiO_2 on its Photocatalytic Action. Chemical Physical Letters, 1991, 187(2):73~76.
14 霍爱群, 谭欣, 丛培君. 纳米 TiO_2 光催化膜中的缺陷结构与性能关系初探. 化学通报, 1998,11(3):31~32.
15 Kumar K. N., Keizer P. K. Densification of Nanostructured Titania Assisted by a Phase Transformation. Nature, 1992, 358(2):48~51.
16 逗俊峰, 邹振扬, 郑泽根. 纳米 TiO_2 的光催化特性及其在环境科学中的应用. 材料导报, 2000, 14(6):35~37.
17 曾维勇, 李秋珍. 纳米 TiO_2 的应用. 矿冶工程, 2000, 20 (2):5.
18 Feng D. Metal Physics. Vol 2 Structure and Defect. Science Press, 1987:408.
19 Goswami D. Y. A Review of Engineering Developments of Aqueouos Phase Solar Photocatalytic Detoxification and Disinfection Processes. Journal of Solar Energy Engineering, 1997:119~107.
20 罗菊仙, 赵中一. 半导体多相光催化技术在环境保护中的应用研究进展. 中国地质大学学报, 2000, 25(5):526-541.
21 高铁, 钱朝勇. TiO_2 表面超亲水性.材料导报, 2000, 14 (7):29.
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