TY - JOUR
T1 - Ruthenium Metal–Organic Frameworks with Different Defect Types
T2 - Influence on Porosity, Sorption, and Catalytic Properties
AU - Zhang, Wenhua
AU - Kauer, Max
AU - Halbherr, Olesia
AU - Epp, Konstantin
AU - Guo, Penghu
AU - Gonzalez, Miguel I.
AU - Xiao, Dianne J.
AU - Wiktor, Christian
AU - LIabrés i Xamena, Francesc X.
AU - Wöll, Christof
AU - Wang, Yuemin
AU - Muhler, Martin
AU - Fischer, Roland A.
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/9/26
Y1 - 2016/9/26
N2 - 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)xYy]n. Framework incorporation of 5-X-ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh-vacuum IR spectroscopy, thermogravimetric analysis,1H NMR spectroscopy, N2sorption, 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 m2g−1, N2adsorption, 77 K) among all materials (including the parent framework [Ru3(btc)2Yy]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 (Ruδ+, 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).
AB - 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)xYy]n. Framework incorporation of 5-X-ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh-vacuum IR spectroscopy, thermogravimetric analysis,1H NMR spectroscopy, N2sorption, 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 m2g−1, N2adsorption, 77 K) among all materials (including the parent framework [Ru3(btc)2Yy]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 (Ruδ+, 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).
KW - defect engineering
KW - heterogeneous catalysis
KW - hydrothermal synthesis
KW - metal–organic frameworks
KW - ruthenium
UR - http://www.scopus.com/inward/record.url?scp=84981725611&partnerID=8YFLogxK
U2 - 10.1002/chem.201602641
DO - 10.1002/chem.201602641
M3 - Article
AN - SCOPUS:84981725611
SN - 0947-6539
VL - 22
SP - 14297
EP - 14307
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 40
ER -