title: Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal-Organic Framework.
abstract: 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 m2g-1, as measured by N2sorption, 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 CO2and low calculated selectivity for CO2over N2and CH4in 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 CO2giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO2over both N2and CH4. Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
authors.forename: Benjamin S
authors.initials: BS
authors.lastname: Gelfand
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
authors.forename: Racheal P S
authors.initials: RP
authors.lastname: Huynh
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
authors.forename: Roger K
authors.initials: RK
authors.lastname: Mah
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
authors.forename: George K H
authors.initials: GK
authors.lastname: Shimizu
keywords: gas capture; metal-organic frameworks; phosphonate monoester; phosphonates; porous solids