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Ruthenium Metal–Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties
Author(s) -
Zhang Wenhua,
Kauer Max,
Halbherr Olesia,
Epp Konstantin,
Guo Penghu,
Gonzalez Miguel I.,
Xiao Dianne J.,
Wiktor Christian,
LIabrés i Xamena Francesc X.,
Wöll Christof,
Wang Yuemin,
Muhler Martin,
Fischer Roland A.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602641
Subject(s) - sorption , porosity , ruthenium , catalysis , metal organic framework , materials science , metal , chemical engineering , inorganic chemistry , chemistry , organic chemistry , metallurgy , composite material , adsorption , engineering
By employing the mixed‐component, solid‐solution approach, various functionalized ditopic isophthalate (ip) defect‐generating linkers denoted 5‐X‐ipH 2 , where X=OH ( 1 ), H ( 2 ), NH 2 ( 3 ), Br ( 4 ), were introduced into the mixed‐valent ruthenium analogue of [Cu 3 (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 [Ru 3 (btc) 2− x (5‐X‐ip) x Y y ] n . Framework incorporation of 5‐X‐ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh‐vacuum IR spectroscopy, thermogravimetric analysis, 1 H NMR spectroscopy, N 2 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 , N 2 adsorption, 77 K) among all materials (including the parent framework [Ru 3 (btc) 2 Y y ] 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., CO 2 , CO, H 2 ) and the catalytic properties of the materials (i.e., ethylene dimerization and the Paal–Knorr reaction).