Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: sorption and catalytic properties.
A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru(II/III) structural analogue of the well-known MOF family [M3(II,II)(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the "defective" variants in the dissociative chemisorption of CO2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins.
Chair of Inorganic Chemistry II, Ruhr-University Bochum, Universitätsstrasse 150, 44801 Bochum (Germany).
Olesia
O
Kozachuk
Ignacio
I
Luz
Francesc X
FX
Llabrés i Xamena
Heshmat
H
Noei
Max
M
Kauer
H Bauke
HB
Albada
Eric D
ED
Bloch
Bernd
B
Marler
Yuemin
Y
Wang
Martin
M
Muhler
Roland A
RA
Fischer
D002245:Carbon Dioxide / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D006865:Hydrogenation; D009930:Organic Chemicals / Q000737:chemistry*; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*
D056831:Coordination Complexes; D009930:Organic Chemicals; D002245:Carbon Dioxide; D002248:Carbon Monoxide; D012428:Ruthenium
CO2 reduction; heterogeneous catalysis; hydrogen splitting; metal-organic frameworks; structural defects