三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性能

引用本文: 洪志发, 韦奇, 李国华, 王学伟, 聂祚仁, 李群艳. 三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性能[J]. 无机化学学报, 2013, 29(5): 941-947. doi: 10.3969/j.issn.1001-4861.2013.00.161 shu

Citation: HONG Zhi-Fa, WEI Qi, LI Guo-Hua, WANG Xue-Wei, NIE Zuo-Ren, LI Qun-Yan. Preparation, H₂ Separation and Hydrothermal Stability of Trifluoropropyl-Modified Silica Membranes[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(5): 941-947. doi: 10.3969/j.issn.1001-4861.2013.00.161 shu

三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性能

洪志发 ^1, ,
韦奇 ^{1,
,} ,
李国华 ^2, ,
王学伟 ^1, ,
聂祚仁 ^1, ,
李群艳 ^1,

通讯作者: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

基金项目:
国家自然科学基金(No.21171014,50502002) (No.21171014,50502002)

国家863计划课题(No.2009AA03Z213) (No.2009AA03Z213)

浙江省绿色化学合成技术国家重点实验室培育基地开放基金(No.GCTKF2012016)资助项目。 (No.GCTKF2012016)

摘要: 以三氟丙基三甲氧基硅烷(TFPTMS)和正硅酸乙酯(TEOS)作为前驱体,通过溶胶-凝胶法制备三氟丙基修饰的SiO₂膜材料,研究了三氟丙基修饰对膜材料孔结构和疏水性的作用、疏水膜材料的氢气渗透和分离性能以及水热稳定性能。结果表明三氟丙基修饰后的膜材料仍保持良好的微孔结构,孔径狭窄分布在0.45～0.7 nm之间。修饰后膜材料疏水性明显提高,当n_TFPTMS/n_TEOS=0.6时,对水的接触角达到(102.7°±0.1°)。H₂在修饰后膜材料的输运遵循微孔扩散机理,在300 ℃时,H₂的单组份渗透率达到4.77×10^-7 mol·m^-2·s^-1·Pa^-1,H₂/CO₂的理想分离系数以及双组份分离系数分别达到6.99和6.93,均高于其Knudsen扩散分离因子。在200 ℃水蒸气物质的量含量为5%的环境中陈化220 h后,H₂的单组份渗透率仅在前3 h有轻微下降,然后基本保持不变,说明三氟丙基修饰的SiO₂膜具有良好的水热稳定性。

关键词:

二氧化硅膜;溶胶-凝胶法;疏水性;气体分离;水热稳定性

English

Preparation, H₂ Separation and Hydrothermal Stability of Trifluoropropyl-Modified Silica Membranes

1.
1. College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;

Corresponding author: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

Received Date: 10 October 2012
Fund Project:
国家自然科学基金(No.21171014,50502002)

国家863计划课题(No.2009AA03Z213)

浙江省绿色化学合成技术国家重点实验室培育基地开放基金(No.GCTKF2012016)资助项目。

Abstract: Trifluoropropyl-modified silica membranes were prepared by sol-gel technique using tetraethyl orthosilicate (TEOS) and (trifluoropropyl)trimethoxysilane (TFPTMS) as precursors. The effect of trifluoropropyl modification on the hydrophobic pore structure, properties, hydrogen permeation and separation properties and long-term hydrothermal stability of the modified silica membranes were investigated in detail. The results show that the modified membranes retain a desirable microporous structure with a pore size distributed from 0.45 to 0.7 nm. The hydrophobic property of silica membranes has been considerably enhanced after modification, with a water contact angle of (102.7°±0.1°) at a TFPTMS/TEOS molar ratio of 0.6. The hydrogen transport in the modified silica membranes complies with a micropore diffusion mechanism, with a single H₂ permeance of 4.77×10^-7 mol·m^-2·s^-1·Pa^-1, a H₂/CO₂ permselectivity of 6.99 and a H₂/CO₂ binary gas mixture separation factor of 6.93 at 300 ℃, higher than Knudsen permselectivity (4.69). Under a humid condition with a temperature of 200 ℃ and a water vapor molar ratio of 5%, the single H₂ permeance slightly decrease in the first 3 hours and then almost remain constant for at least 220 hours, indicating that the modified membranes are more hydrothermally stable than pure SiO₂ membranes.

Key words:

silica membrane;sol-gel technique;hydrophobic property;gas separation;hydrothermal stability

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沈阳化工大学材料科学与工程学院沈阳 110142

三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性能

通讯作者: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

English

Preparation, H₂ Separation and Hydrothermal Stability of Trifluoropropyl-Modified Silica Membranes

Corresponding author: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性能

通讯作者: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

English

Preparation, H2 Separation and Hydrothermal Stability of Trifluoropropyl-Modified Silica Membranes

Corresponding author: 韦奇,通讯联系人,E-mail:qiwei@bjut.edu.cn;会员登记号:S06N6731M1006,

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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