以钛酸丁酯为原料,乙酸为有机配体,甲酰胺为干燥控制化学添加剂(DCCA),采用溶胶一凝胶法和溶剂置换等后续工艺,实现了块状TiO2气凝胶催化剂的常压干燥法制备,并考察了有机配体对气凝胶结构性能的影响。采用XRD、BET、SEM、EDS及DSC-TG对样品进行表征。结果表明:当有机配体与钛酸丁酯物质的量之比为0.9时,制备的样品性能最佳,该TiO2气凝胶样品为非晶态,表观密度为0.25g·cm^-3,比表面积716.5m^2·g^-1,平均孔径19.1nm;在850℃大气气氛下热处理2h后,比表面积为122.4m^2·g^-1,平均孔径23.4nm,具有较高光催化活性;经1000℃热处理后,TiO2晶型仍为锐钛矿相,热稳定性较好,光催化活性有所降低。未采用有机配体制备的TiO2气凝胶表观密度为0.57g·cm^-3,比表面积为482.2m^2·g^-1。有机配体的使用更有利于制备出表观密度较小、比表面积较高的TiO2气凝胶。
Monolithic TiO2 aerogels have been prepared by sol- gel method and subsequent process such as solvent replacement with ambient pressure drying using titanate tetrabutoxide, formamide and acetic acid as raw material. The influences of organic ligand on the structure of aerogels were investigated. The microstructure and properties of samples were characterized by means of XRD, BET, SEM, EDS and DSC - TG. The results indicate that when the mole ratio of organic ligand to titanate tetrabutoxide is 0.9, the property of prepared TiO2 aerogel is the best, with the apparent density of 0. 25 g. cm^-3 , the specific surface area of 716. 5 m^2 . g^-1, and the average pore size of 19.1 nm. After calcined at 850 ℃ for 2 h in air, the sample has high photocatalytic activity, while it's specific surface area reduces to 122.4 m^2 . g^-1 and average pore size increases to 23.4 nm. After calcined at 1000℃, anatase is still the main crystalling phase, and shows low photocatalytic activity. The apparent density of TiO2 aerogel (not using organic ligand) is 0.57 g .cm^-3 , and itts specific surface area is 482.2 m2. g^-1. TiO2 aerogels prepared using organic ligand present less dense and higher specific surface area.
参考文献
[1] | Baia L, Peter A, Cosoveanu V, et al. Synthesis and nanostructural characterization of TiOz aerogels for photovoltaic devices [J]. Thin Solid Films, 2006, 511/512: 512-516. |
[2] | 付乌有,杨海滨,刘冰冰,等.锐钛矿型TiO2/MnFe2O4核壳结构复合纳米颗粒的制备及其光催化特性[J].复合材料学报,2007,24(3):136-140. |
[3] | 胡久刚,陈启元,李洁,等.常压干燥法制备TiO2气凝胶光催化剂[J].无机材料学报,2009,24(4):685-689. |
[4] | 王勇,张吴,张军,等.纳米TiO2/再生纤维素复合薄膜的制备及光催化性能[J].复合材料学报,2007,24(3):35-39. |
[5] | Zhu J J, Xie J M, Lu X M, et al. Synthesis and characterization of superhydrophobic silica and silica/titania aerogels by sol - gel method at ambient pressure [J]. Colloids and Surfaces, 2009, 342: 97-101. |
[6] | Malinowska B, Walendziewski J, Robert D, et al. The study of pbotocatalytic activities of titania and titania-silica aerogels [J]. Applied Catalysis B: Environmental, 2003, 46: 441-451. |
[7] | Aravind P R, Shajesh P, Mukundan P, et al. Silica- titania aerogel monoliths with large pore volume and surface area by ambient pressure drying [J].Sol - Gel Sci Technol, 2009, 52 328-344. |
[8] | Smitha S, Shajesh P, Aravind P R, et al. Effect of aging time and concentration of aging solution on the porosity characteristics of subcritically dried silica aerogels [J]. Microporous and Mesoporous Materials, 2006, 91: 286-292. |
[9] | 冷小威,刘敬肖,史非,等.TiO2/SiO2复合气凝胶常压干燥制备及性能表征[J].无机化学学报,2009,25(10):1791-1796. |
[10] | Michael K S, Reenamole G, Patrick F, et al. Silver doped titanium dioxide nanomaterials for enhanced visible light photoeatalysis [J]. Photochemistry and Photobiology A:Chemistry, 2007, 189: 258-263. |
[11] | 高濂,郑珊,张青红.纳米氧化钛光催化材料及其应用[M].北京:化学工业出版社,2002:26. |
[12] | 张青红,高濂,孙静.氧化硅对二氧化钛纳米晶相变和晶粒生长的抑制作用[J].无机材料学报,2002,17(3):415-421. |
[13] | Periyat P, Baiju K V, Mukundan P, et al. High temperature stable mesoporous anatase TiO2 photocatalyst achieved by silica addition [J]. Applied Catalysis A, 2008, 349:13-19. |
[14] | RajeshKS, Suresh C, Vasudevan A K, et al. Phase transformation in sol - gel titania containing silica [J ]. Materials Letters, 1999, 38: 161-166. |
[15] | XuZJ, Gan L H, Jia Y Y, et al. Preparation and characterization of silica- titania aerogel-like balls by ambient pressure drying [J]. Sol- Gel Science Technology, 2007, 41: 203-207. |
[16] | Gregg S J,Sing K S W.吸附、比表面与空隙率[M].高敬琮,刘希尧,译.北京:化学工业出版社,1989:118-132 |
[17] | De Bore J H. The structure and properties of porous materials [M]. London: Butterworth, 1958: 68. |
[18] | Dutoit D C M, Schneider M, Baiker A. A influence of sol - gel and drying conditions on structural properties [J]. Journal of Catalysis, 1995, 153(1): 165-176. |
[19] | 孙奉玉,吴呜,李文钊,等.二氧化钛表面光学特性与光催化活性的关系[J].催化学报,1998,19(2):121-124. |
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