摘要
In this article, we report the preparation of a three-dimensional（3D） interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional（2D） hexagonal mesoporous anatase 70 TiO2-30 SiO2-950 nanocomposite（crystallized at 950 °C for 2 h） as a precursor, NaO H as an etchant of SiO2 via a ＂creating mesopores in the pore walls＂ approach. Our strategy adopts mild conditions of creating pores such as diluted NaO H solution, appropriate temperature and solid/liquid ratio, etc. aiming at ensuring the integrities of mesopores architecture and anatase nanocrystals. XRD, TEM and N2 sorption techniques have been used to systematically investigate the physico-chemical properties of the nanocomposites. The results show that the intrawall mesopores are highly dense and uniform（average pore size 3.6 nm）, and highly link the initial mesochannels in a 3D manner while retaining mesostructural integrity. There is no significant change to either crystallinity or size of the anatase nanocrystals before and after creating the intrawall mesopores. The photocatalytic degradation rates of rhodamine B（RhB, 0.303 min^–1） and methylene blue（MB, 0.757 min^–1） dyes on the resultant nanocomposite are very high, which are 5.1 and 5.3 times that of the precursor; even up to 16.5 and 24.1 times that of Degussa P25 photocatalyst, respectively. These results clearly demonstrate that the 3D interconnected mesopores structure plays an overwhelming role to the increments of activities. The 3D mesoporous anatase TiO2-SiO2 nanocomposite exhibits unexpected-high degradation activities to RhB and MB in the mesoporous metal oxide-based materials reported so far. Additionally, the nanocomposite is considerably stable and reusable. We believe that this method would pave the way for the preparation of other 3D highly interconnected mesoporous metal oxide-based materials with ultra-high performance.
本文报道一种孔道三维相互连通锐钛矿TiO_2-SiO_2纳米复合介孔材料的制备.该介孔材料是以两维六方有序结构、直孔道、锐钛矿70TiO_2-30SiO_2-950纳米复合介孔材料(于950oC晶化2 h)为前驱体,NaOH为SiO_2的刻蚀剂,通过"在孔壁内造孔"的方法获得.我们的策略是采用温和的造孔条件,如稀NaOH溶液,合适的温度与固/液比等.采用X射线衍射(XRD),透射电镜(TEM)和低温N_2吸附等技术对样品的介孔结构进行了系统表征.结果表明,墙内孔的密度非常高,孔径均一(平均尺寸3.6 nm),且在三维网络高度连通原孔道,但介孔结构仍保持其完整性.锐钛矿纳米晶粒的结晶度和大小在墙内造孔前后基本保持不变.该材料光催化降解罗丹明B(0.303 min^(–1))与亚甲基蓝(0.757 min^(–1))的活性相当高,此活性分别是其母体材料的5.1和5.3倍,甚至是Degussa P25光催化剂的16.5和24.1倍.这充分表明三维连通孔道结构对活性的大幅提高起了关键作用.孔道三维连通式锐钛矿TiO_2-SiO_2纳米复合介孔材料对上述污染物展现出意想不到的高降解活性,显著高于迄今已报道的金属氧化物基介孔材料对上述污染物的降解活性.更重要的是,该光催化剂具有相当高的稳定性和重复使用性.相信,本方法将为具有超高性能的孔道三维相互连通其它金属氧化物基介孔材料的制备铺平了道路.小角XRD结果表明,母体材料的孔道是两维六方有序结构,在孔壁内造孔之后,样品原有的介孔结构仍保持其规整性.宽角XRD结果显示,二氧化钛的晶相是锐钛矿,晶粒尺寸为10.8 nm.造新孔之后,锐钛矿纳米晶粒的结晶度和大小与母体样品的相比变化不大.TEM结果显示,母体样品的孔壁内没有孔.孔道是两维六方有序排列的直孔道,孔径大小均一(平均尺寸4.1 nm).高分辨透射电镜(TEM)观察揭示,锐钛矿纳米晶粒(平均大小11.3 nm)在孔壁内随机排列,并与无定形SiO_2纳米颗�
基金
supported by the National Natural Science Foundation of China(21373056)
the Science and Technology Commission of Shanghai Municipality(13DZ2275200)~~
