预涂晶种诱导法Al2O3 陶瓷管载体上合成ZIF-8 膜

第27卷 第10期 无 机 材 料 学 报

Vol. 27

No. 10

2012年10月

Journal of Inorganic Materials Oct., 2012

收稿日期: 2011-11-29; 收到修改稿日期: 2012-01-06

基金项目: 国家自然科学基金(21076030, 21036006); 辽宁省高等学校优秀人才支持计划项目(LR201008); 辽宁省自然科

学基金(201202027)

National Natural Science Foundation of China (21076030, 21036006); Program for Liaoning Excellent Talents in Univer-sity (LR201008); Natural Science Foundation of Liaoning Province (201202027)

作者简介: 杜淑慧(1985−), 女, 硕士研究生. E-mail: hmilyqzd@ 文章编号: 1000-324X(2012)10-1105-07 DOI: 10.3724/SP.J.1077.2012.11739

预涂晶种诱导法在α-Al 2O 3陶瓷管载体上合成ZIF-8膜

杜淑慧, 刘亚光, 孔令寅, 张 健, 刘海鸥, 张雄福

(大连理工大学 化工学院, 精细化工国家重点实验室, 大连116024)

摘 要: 以纳米级ZIF-8晶体粒子为晶种, 利用晶种诱导二次生长法在α-Al 2O 3陶瓷管载体上制备出连续的ZIF-8膜, 并详细考察了晶种涂层液中晶种含量、成膜温度和添加剂PEI 、甲酸钠用量等参数对ZIF-8成膜的调控影响. 经SEM 、XRD 和气体渗透分析结果表明: 制备的ZIF-8纳米粒子的粒径约为100~150 nm, 粒度分布较均匀, 适宜作为成膜的晶种; 在晶种液中添加适量的PEI 作为偶联剂有利于连续ZIF-8晶种层及膜的形成; 在成膜液中添加适量的甲酸钠能有效阻止载体表面晶种层的溶解脱落. SEM 显示所得ZIF-8膜的晶体粒径均一、晶粒间连接紧密且无明显裂痕, 膜层厚度约为18 μm. 单组分气体渗透测试可知, H 2/CO 2的分离因数为5.4, H 2/CH 4的分离因数为2.56, 气体通过ZIF-8膜均属于努森扩散范围.

关 键 词: 金属有机骨架材料; MOFs 膜; ZIF-8膜; 气体分离 中图分类号: O614 文献标识码: A

Seeded Secondary Growth Synthesis of ZIF-8 Membranes Supported on α-Al 2O 3 Ceramic Tubes

DU Shu-Hui, LIU Ya-Guang, KONG Ling-Yin, ZHANG Jian, LIU Hai-Ou, ZHANG Xiong-Fu

(State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China)

Abstract: A seeded growth procedure was used to successfully prepare continuous and well inter-grown zeolitic imi-dazolate framework-8 (ZIF-8) membranes on porous α-alumina tubes. The effects of some parameters including the content of seeds and PEI in seeding solution, the concentration of sodium formate in synthesis solution and synthesis temperature on the formation of ZIF-8 membranes were investigated in detail. The characterization of SEM, XRD and single gas permeation showed that PEI added in the seeding solution can improve the adhesion between the seed crys-tals and the support surface. Moreover, sodium formate used in synthesis solution could prevent the seed layer from peeling off during the membrane growing process. The as-synthesized ZIF-8 membrane is well inter-grown and con-tinuous. Single gas permeation shows that the separation factors of H 2/CO 2 and H 2/CH 4 are 5.4 and 2.56, respectively, indicating that Knudsen diffusion plays a controlling role in the gas permeation through the ZIF-8 membrane.

Key words: metal-organic frameworks; MOFs membrane; ZIF-8 membrane; gas separation

金属有机骨架化合物(MOFs)是一种由过渡金属离子与含氧、氮等多齿有机配体通过配位作用自

组装形成的新型有机–无机杂化多孔材料. MOFs 材料具有多孔性、比表面积大、骨架结构多样性以及