孔道型微孔和介孔分子筛的改性及超级绝热性能

doi:10.7503/cjcu20140096

摘要/Abstract

摘要：

在水热体系中合成了具有规则孔道结构的微孔分子筛ZSM-5和介孔分子筛MCM-41, SBA-15, MAS-5, 通过改变材料表面的电性对介孔材料进行了化学修饰. 采用X射线衍射(XRD)和扫描电子显微镜(SEM)对样品的结构、形貌进行了表征; 通过氮气吸附-脱附测试了产物的比表面积, 采用BJH法计算孔分布和孔容; 将制得的样品压制成绝热材料后, 进行导热性质测定. 常温(25 ℃)常压下, 有序介孔分子筛MCM-41的导热系数为0.038 W·m^-1·K^-1, 具有少量微孔结构的MAS-5的导热系数为0.035 W·m^-1·K^-1, 二者均为超级绝热材料. 材料经改性后, 绝热性能有所提高: MCM-41的导热系数降至0.028 W·m^-1·K^-1, MAS-5的导热系数降至0.017 W·m^-1·K^-1. 结合纳米介孔材料导热理论模型进行分析, 发现纳米孔绝热材料的孔径越小, 孔隙率越大, 绝热性能好; 介孔分子筛的导热系数与其孔壁厚度、孔径大小以及孔隙率有关.

关键词: 介孔分子筛, 微孔分子筛, 纳米绝热材料, 热导

Abstract:

Microporous aluminosilicates ZSM-5, ordered mesostructured materials MCM-41, SBA-15, MAS-5 were synthesized in hydrothermal system. Then, these nanoparticles were electrostatically modified with linear cationic polymer agent. The as-synthesized samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and N₂ adsorption-desorption isotherms. Surface area was determined by Brunauer-Emmett-Teller(BET) equation; pore size distribution and pore volume were measured by Barrett-Joyner-Halonda(BJH) method. Samples for thermal conductivity measurements were prepared by pressing powders into disks. The thermal conductivity of well-ordered mesoporous MCM-41 is as low as 0.038 W·m^-1·K^-1. The thermal conductivity of MAS-5 is 0.035 W·m^-1·K^-1. The thermal conductivities of modified MCM-41 and MAS-5 deereased to 0.028 and 0.017 W·m^-1·K^-1 respectively. Theoretical analysis and experimental results simultaneously explain that materials with smaller pore size or higher porosity demonstrate better properties of thermal insulation; thermal conductivities of ordered mesoporous materials associate with wall thickness, pore size and porosity.

Key words: Mesoporous molecular sieve, Microporous molecular sieve, Nano thermal insulation material, Thermal conductivity

中图分类号:

O614

TrendMD:

张涛, 董雪, 张宗弢. 孔道型微孔和介孔分子筛的改性及超级绝热性能. 高等学校化学学报, 2014, 35(4): 689.

ZHANG Tao, DONG Xue, ZHANG Zongtao. Surface Modification of Microporous and Mesoporous Molecular Sieves and Their Super Insulation Properties^†. Chem. J. Chinese Universities, 2014, 35(4): 689.

图/表 4

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Sample	Pore size/nm	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	Pore type	n(Si)/n(Al)
SBA-15	7.56	790	1.08	Meso	∞
MCM-41	2.48	904	0.84	Meso	∞
MAS-5	2.70	1150	1.17	Micro & Meso	30
ZSM-5	0.55	440	0.16	Micro	30
Silica aerogel^[3,9]	2—5	600—1000		Meso	∞

Sample	Pore size/nm	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	Pore type	n(Si)/n(Al)
SBA-15	7.56	790	1.08	Meso	∞
MCM-41	2.48	904	0.84	Meso	∞
MAS-5	2.70	1150	1.17	Micro & Meso	30
ZSM-5	0.55	440	0.16	Micro	30
Silica aerogel^[3,9]	2—5	600—1000		Meso	∞

Sample	Density^*/ (g·cm^-3)	Thermal conductivity/ (W·m^-1·K^-1)
SBA-15	0.623	0.040
MCM-41	0.652	0.038
MAS-5	0.612	0.035
SBA-15-P	0.642	0.035
MCM-41-P	0.680	0.028
MAS-5-P	0.674	0.017
ZSM-5	0.745	0.022
Silica aerogels^[3]	0.003—0.35	0.020

Sample	Density^*/ (g·cm^-3)	Thermal conductivity/ (W·m^-1·K^-1)
SBA-15	0.623	0.040
MCM-41	0.652	0.038
MAS-5	0.612	0.035
SBA-15-P	0.642	0.035
MCM-41-P	0.680	0.028
MAS-5-P	0.674	0.017
ZSM-5	0.745	0.022
Silica aerogels^[3]	0.003—0.35	0.020