title: Metal Insertion in a Methylamine-Functionalized Zirconium Metal-Organic Framework for Enhanced Carbon Dioxide Capture.
abstract: The reaction of ZrCl4with 2',3',5',6'-tetramethylamino-p-terphenyl-4,4″-dicarboxylic acid (H2tpdc-4CH2NH2·3HCl) in the presence of NaF affords Zr6O4(OH)2.1F1.9(tpdc-4CH2NH2·3HCl)6(1), which is a new member of the Zr6O4(OH)4(dicarboxylate linker)12or UiO-68 family, and exhibits high porosity with BET and Langmuir surface areas of 1910 m2/g and 2220 m2/g, respectively. Remarkably, fluoride ion incorporation in the zirconium clusters results in increased thermal stability, marking the first example of enhancement in the stability of a UiO framework by this defect-restoration approach. Although material 1 features four alkylamine groups on each organic linker, the framework does not exhibit the high CO2uptake that would be expected for reaction between CO2and the amine groups to form carbamic acid or ammonium carbamate species. The absence of strong CO2adsorption can likely be attributed to protonation at some of the amine sites and the presence of counterions. Indeed, exposure of material 1 to acetonitrile solutions of the organic bases 1,8-bis(dimethylamino)naphthalene (DMAN) or trimethylamine, affords a partially deprotonated material, which exhibits enhanced CO2uptake. Exposure of basic amine sites also facilitates the postsynthetic chelation of copper(I) ([Cu(MeCN)4]·CF3SO3) to yield material 2 with an enhanced CO2uptake of 4 wt % at 0.15 bar, which is double that of the parent framework 1.
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.|División de Ingeniería en Ciencias de la Tierra, Facultad de Ingeniería, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria , 04510, Ciudad de México, México.
authors.forename: A Paulina
authors.identifier: http://orcid.org/0000-0003-1487-8204
authors.initials: AP
authors.lastname: Gómora-Figueroa
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Jarad A
authors.initials: JA
authors.lastname: Mason
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Miguel I
authors.initials: MI
authors.lastname: Gonzalez
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Eric D
authors.initials: ED
authors.lastname: Bloch
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Katie R
authors.initials: KR
authors.lastname: Meihaus