title: Ruthenium Metal-Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties.
abstract: By employing the mixed-component, solid-solution approach, various functionalized ditopic isophthalate (ip) defect-generating linkers denoted 5-X-ipH2 , where X=OH (1), H (2), NH2 (3), Br (4), were introduced into the mixed-valent ruthenium analogue of [Cu3 (btc)2 ]n (HKUST-1, btc=benzene-1,3,5-tricarboxylate) to yield Ru-DEMOFs (defect-engineered metal-organic frameworks) of the general empirical formula [Ru3 (btc)2-x (5-X-ip)x Yy ]n . Framework incorporation of 5-X-ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh-vacuum IR spectroscopy, thermogravimetric analysis, (1) H NMR spectroscopy, N2 sorption, and X-ray absorption near edge structure. Interestingly, Ru-DEMOF 1 c with 32 % framework incorporation of 5-OH-ip shows the highest BET surface area (≈1300 m(2)  g(-1) , N2 adsorption, 77 K) among all materials (including the parent framework [Ru3 (btc)2 Yy ]n ). The characterization data are consistent with two kinds of structural defects induced by framework incorporation of 5-X-ip: modified paddlewheel nodes featuring reduced ruthenium sites (Ru(δ+) , 0<δ<2, type A) and missing nodes leading to enhanced porosity (type B). Their relative abundances depend on the choice of the functional group X in the defect linkers. Defects A and B also appeared to play a key role in sorption of small molecules (i.e., CO2 , CO, H2 ) and the catalytic properties of the materials (i.e., ethylene dimerization and the Paal-Knorr reaction).
authors.affiliation: Chair of Inorganic Chemistry II, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Wenhua
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Chair of Inorganic Chemistry II, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Max
authors.initials: M
authors.lastname: Kauer
authors.affiliation: Chair of Inorganic Chemistry II, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Olesia
authors.initials: O
authors.lastname: Halbherr
authors.affiliation: Chair of Inorganic and Metal-Organic Chemistry, Technical University Munich, Lichtenbergstrasse 4, 85748, Garching, (Germany).
authors.forename: Konstantin
authors.initials: K
authors.lastname: Epp
authors.affiliation: Laboratory of Industrial Chemistry, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Penghu
authors.initials: P
authors.lastname: Guo
authors.affiliation: Department of Chemistry, University of California, Berkeley, 94720, California, USA.
authors.forename: Miguel I
authors.initials: MI
authors.lastname: Gonzalez
authors.affiliation: Department of Chemistry, University of California, Berkeley, 94720, California, USA.
authors.forename: Dianne J
authors.initials: DJ
authors.lastname: Xiao
authors.affiliation: Chair of Inorganic Chemistry II, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Wiktor
authors.affiliation: Instituto deTecnología Química (ITQ), Universitat Politècnica de València, Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n, 46022, Valencia, Spain.
authors.forename: Francesc X
authors.initials: FX
authors.lastname: LIabrés I Xamena
authors.affiliation: Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany.
authors.forename: Christof
authors.initials: C
authors.lastname: Wöll
authors.affiliation: Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany. yuemin.wang@kit.edu.
authors.forename: Yuemin
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Laboratory of Industrial Chemistry, Ruhr University Bochum, Universitätsstrasse 150, 44801, Bochum, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Muhler
authors.affiliation: Chair of Inorganic and Metal-Organic Chemistry, Technical University Munich, Lichtenbergstrasse 4, 85748, Garching, (Germany). roland.fischer@tum.de.
authors.forename: Roland A
authors.initials: RA
authors.lastname: Fischer
keywords: defect engineering; heterogeneous catalysis; hydrothermal synthesis; metal-organic frameworks; ruthenium