铜掺杂二氧化硅膜的制备及孔结构研究

doi:10.3724/SP.J.1077.2010.01047

无机材料学报 ›› 2010, Vol. 25 ›› Issue (10): 1047-1052.DOI: 10.3724/SP.J.1077.2010.01047 CSTR: 32189.14.SP.J.1077.2010.01047

铜掺杂二氧化硅膜的制备及孔结构研究

魏娜娜, 韦奇, 李振杰, 李群艳, 聂祚仁

(北京工业大学材料科学与工程学院, 北京 100124)

收稿日期:2010-01-26 修回日期:2010-03-19 出版日期:2010-10-20 网络出版日期:2010-09-26
基金资助:
国家863计划(2009AA03Z213); 国家自然科学基金(50502002); 北京工业大学自然科学基础研究项目

Preparation and Pore Structure of Copper-doped Silica Membranes

WEI Na-Na, WEI Qi, LI Zhen-Jie, LI Qun-Yan, NIE Zuo-Ren

(College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China)

Received:2010-01-26 Revised:2010-03-19 Published:2010-10-20 Online:2010-09-26
Supported by:
863 Programe(2009AA03Z213); National Nature Science Foundation (50502002); Natural Science Program for Key Basic Research of Beijing University of Technology

摘要/Abstract

摘要： 以正硅酸乙酯和硝酸铜为前驱体, 通过溶胶-凝胶法制备了铜掺杂的二氧化硅膜, 通过FT-IR、XPS、XRD等测试方法研究了铜元素在膜材料中的存在形态, 并利用N₂吸附对膜材料的孔结构进行表征, 讨论了铜掺杂量以及水/正硅酸乙酯的化学计量比对膜材料孔结构的影响, 最后初步研究了铜掺杂二氧化硅膜在水热环境下的孔结构稳定性. 结果表明, 当n(H₂O):n(TEOS)= 0.5:1.0时能获得微孔结构, 铜掺杂后的二氧化硅膜仍然保持良好的微孔结构,当n(Cu):n(Si)=0.8:1.0时膜材料的孔容达到0.155 cm³/g, 孔径狭窄分布在0.5nm. 铜元素除了进入二氧化硅骨架外主要以晶态Cu单质和Cu₂O存在. 铜掺杂的膜材料在水热环境下短期内能保持微孔结构, 但长期的水热环境导致膜材料孔结构的崩溃.

关键词: 二氧化硅膜, 铜掺杂, 孔结构, 溶胶-凝胶法

Abstract: Copper-doped silica membranes were prepared via Sol-Gel process with tetraethylorthosilicate(TEOS) and copper nitrate as precursors. The status of copper in the membranes was detected by means of FT-IR, XPS, XRD and the pore structure was determined by N₂ adsorption. The effects of copper dopant and H₂O/TEOS molar ratio on the pore structure were investigated and the stability of the pore structure under hydrothermal conditions was studied in detail. The results show that when the molar ratio of TEOS to H₂O is 0.5, it leads to microporous structure, with a pore volume of 0.155 cm³/g and a sharp pore size distribution centered at 0.5nm for the sample with a Cu/Si molar ratio of 0.8. A faction of copper is incorporated into silica framework by replacing silicon atoms, and the residual mainly exists as crystalline phase such as Cu and Cu₂O outside the framework. The microporous structure of the doped samples could be preserved for a short time (240h) under hydrothermal conditions but finally collapsed after further hydrothermal treatment.

Key words: silica membranes, copper-doped, pore structure, Sol-Gel process

中图分类号:

O484

魏娜娜, 韦奇, 李振杰, 李群艳, 聂祚仁. 铜掺杂二氧化硅膜的制备及孔结构研究[J]. 无机材料学报, 2010, 25(10): 1047-1052.

WEI Na-Na, WEI Qi, LI Zhen-Jie, LI Qun-Yan, NIE Zuo-Ren. Preparation and Pore Structure of Copper-doped Silica Membranes[J]. Journal of Inorganic Materials, 2010, 25(10): 1047-1052.

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铜掺杂二氧化硅膜的制备及孔结构研究

Preparation and Pore Structure of Copper-doped Silica Membranes

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