Control of pore size in Hf-based metal-organic frameworks and exploration of their adsorption properties

doi:10.3969/j.issn.0438-1157.2014.05.020

Abstract

Abstract: By incorporating three organic carboxylic acids with different lengths, fumaric (FUM), 1,4-benzene- dicarboxylate (BDC) and 4,4'-biphenyl-dicarboxylate (BPDC) acids, three novel Hf-based metal-organic frameworks (MOFs), Hf-FUM, Hf-BDC and Hf-BPDC, were synthesized using a solvothermal method combined with conventional electric heating. These MOFs were characterized by various experimental techniques including PXRD, N₂ adsorption, TG and SEM. Moreover, the stabilities of these materials were examined by soaking the samples in water. The PXRD results reveal that all of these Hf-based MOFs have a topology similar to that of UiO-66(Zr), and Hf-FUM is stable up to 400 ℃ while Hf-BDC and Hf-BPDC remain stable at 500 ℃. The structures of Hf-FUM and Hf-BDC are water-resistant, while that of Hf-BPDC will decompose after water treatment. On the basis of the adsorption isotherms of CO₂, N₂ and CH₄ at 298 K, the effect of pore size on the separation of CO₂/N₂and CO₂/CH₄ systems were also investigated. It is found that Hf-FUM with the smallest pore size possesses the highest adsorption selectivity for CO₂ over N₂and CH₄. This is the first study on the performance of Hf-based MOFs for gas separation, and the knowledge obtained in this work provides a foundation for the design of new nanoporous materials towards CO₂ capture from various gas mixtures.

Key words: metal-organic frameworks, hafnium, pore-size regulation, stability, adsorption, CO₂ capture

摘要： 利用三种不同长度的有机配体——反丁烯二酸（H₂FUM）、对苯二甲酸（H₂BDC）和联苯二甲酸（H₂BPDC），合成了一系列具有不同孔尺寸的新型铪（Hf）金属-有机骨架（MOF）材料（Hf-FUM、Hf-BDC和Hf-BPDC），并考察了CO₂、N₂和CH₄三种气体在这些材料中吸附分离行为。研究结果表明，这三种材料具有和UiO-66（Zr）相同的拓扑结构，且具有很好的热稳定性。Hf-FUM和Hf-BDC的结构在水中能够保持稳定，而Hf-BPDC在水中会发生降解。同时，具有最小孔尺寸的Hf-FUM材料对CO₂/N₂以及CO₂/CH₄体系具有最好的分离性能。这为以后设计用于CO₂分离的新型纳微结构材料提供了参考依据。

关键词: 金属-有机骨架材料, 铪, 孔尺寸调控, 稳定性, 吸附, 二氧化碳捕集

CLC Number:

TQ028.1

WANG Keke, LI Liangsha, HUANG Hongliang, YANG Qingyuan, ZHANG Yi, WANG Shaohua, WU Pingyi, LAN Ling, LIU Dahuan, ZHONG Chongli. Control of pore size in Hf-based metal-organic frameworks and exploration of their adsorption properties[J]. CIESC Journal, DOI: 10.3969/j.issn.0438-1157.2014.05.020.

王可可, 李亮莎, 黄宏亮, 阳庆元, 张轶, 王少华, 吴平易, 兰玲, 刘大欢, 仲崇立. 铪金属-有机骨架材料的孔尺寸调控及其吸附性能[J]. 化工学报, DOI: 10.3969/j.issn.0438-1157.2014.05.020.

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