孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料的制备及其高光催化活性

doi:10.1016/S1872-2067(15)61081-6

催化学报 ›› 2016, Vol. 37 ›› Issue (6): 846-854.DOI: 10.1016/S1872-2067(15)61081-6

孔道三维相互连通锐钛矿TiO₂-SiO₂纳米复合介孔材料的制备及其高光催化活性

董维阳^a, 姚有为^a, 孙尧俊^b, 华伟明^c, 庄国顺^a

a 复旦大学环境科学与工程系, 上海 200433;
b 复旦大学分析测试中心, 上海 200433;
c 复旦大学化学系, 上海 200433

收稿日期:2016-01-21 修回日期:2016-03-03 出版日期:2016-05-30 发布日期:2016-05-30
通讯作者: Weiyang Dong
基金资助:
国家自然科学基金(21373056); 上海市科学技术委员会(13DZ2275200).

Preparation of three-dimensional interconnected mesoporous anatase TiO₂-SiO₂nanocomposites with high photocatalytic activities

Weiyang Dong^a, Youwei Yao^a, Yaojun Sun^b, Weiming Hua^c, Guoshun Zhuang^a

a Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China;
b Center for Analysis and Measurement, Fudan University, Shanghai 200433, China;
c Department of Chemistry, Fudan University, Shanghai 200433, China

Received:2016-01-21 Revised:2016-03-03 Online:2016-05-30 Published:2016-05-30
Contact: Weiyang Dong
Supported by:
This work was supported by the National Natural Science Foundation of China (21373056), and the Science and Technology Commission of Shanghai Municipality (13DZ2275200)

摘要/Abstract

摘要：

本文报道一种孔道三维相互连通锐钛矿TiO₂-SiO₂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70TiO₂-30SiO₂-950纳米复合介孔材料(于950 oC晶化2 h)为前驱体, NaOH为SiO₂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N₂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TiO₂-SiO₂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SiO₂纳米颗粒相互连接, 相间共存, 形成类似“砖块-水泥砂浆”砌成的孔壁, 这种独特的复合骨架结构赋予其很高的稳定性. 当一些SiO₂纳米颗粒被去除之后, TEM观察显示, 孔壁内有密集分布的孔, 这些孔取向随机, 并在三维方向连通原孔道, 但介孔骨架结构仍保持其完整性. 墙内孔的大小范围很窄(3.1-4.3 nm), 平均大小为3.6 nm. 高分辨TEM观察显示, 锐钛矿晶粒大小与母体材料内的相比基本未变. 上述结果与XRD结果一致. 低温N₂吸附表征结果显示, 母体样品内只有一种孔道, 孔径为4.0 nm. 去除部分SiO₂后的样品内有两种孔道, 孔径分别是3.4和4.1 nm. 这些结果与TEM的观察吻合. 罗丹明B与亚甲基蓝在造孔前后样品内扩散速率评价结果显示, 其在三维连通孔道内的扩散速率很高, 大约是其母体材料内的5倍以上. 这表明相互连通的孔道网络结构非常有利于客体分子在其内扩散. 光催化降解性能评价结果显示, 罗丹明B与亚甲基蓝在相互连通孔道内降解的速率相当高, 分别是其在不连通孔道内的5.1和5.3倍. 这充分证明孔道三维相互连通对活性的大幅提高起了关键作用. 我们对材料的稳定性和重复使用性作了评价, 经过10次循环使用孔道三维相互连通锐钛矿TiO₂-SiO₂纳米复合介孔材料, 其吸附与光催化降解罗丹明B的性能变化不大. 这充分证明本文制备的孔道连通复合介孔材料的性能是相当稳定的和可重复使用的. 该方法可用于制备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, 如Nb₂O₅, Ta₂O₅等.

关键词: 二氧化钛, 二氧化硅, 纳米复合介孔材料, 三维连通式介孔结构, 光催化降解, 有机污染物

Abstract:

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 70TiO₂-30SiO₂-950 nanocomposite (crystallized at 950 ℃ for 2 h) as a precursor, NaOH 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 NaOH 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.

Key words: Preparation, Mesoporous anatase crystal-silica nanocomposite, Three dimensional interconnected mesopores architecture, Photocatalytic degradation, Organic pollutants

董维阳, 姚有为, 孙尧俊, 华伟明, 庄国顺. 孔道三维相互连通锐钛矿TiO₂-SiO₂纳米复合介孔材料的制备及其高光催化活性[J]. 催化学报, 2016, 37(6): 846-854.

Weiyang Dong, Youwei Yao, Yaojun Sun, Weiming Hua, Guoshun Zhuang. Preparation of three-dimensional interconnected mesoporous anatase TiO₂-SiO₂nanocomposites with high photocatalytic activities[J]. Chinese Journal of Catalysis, 2016, 37(6): 846-854.

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孔道三维相互连通锐钛矿TiO₂-SiO₂纳米复合介孔材料的制备及其高光催化活性

Preparation of three-dimensional interconnected mesoporous anatase TiO₂-SiO₂nanocomposites with high photocatalytic activities

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