In:
Chemistry – A European Journal, Wiley, Vol. 22, No. 40 ( 2016-09-26), p. 14297-14307
Abstract:
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).
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201602641
Language:
English
Publisher:
Wiley
Publication Date:
2016
detail.hit.zdb_id:
1478547-X
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