Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal-Organic Framework

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• 作者：Benjamin S. Gelfand ; Racheal P. S. Huynh ; Roger K. Mah and Prof. George K. H. Shimizu
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：November 14, 2016
• 年：2016
• 卷：55
• 期：47
• 页码：14614-14617
• 全文大小：1938K
• ISSN：1521-3773

文摘

A crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000 m² g⁻¹, as measured by N₂ sorption, the highest reported for a phosphonate-based metal–organic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO₂ and low calculated selectivity for CO₂ over N₂ and CH₄ in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO₂ giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO₂ over both N₂ and CH₄. Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.