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 [M-3(II,II)(btc)(2)] (M= Cu, Mo, Cr, Ni, Zn; btc= benzene-1,3,5-tricarboxylate), with partly missing carbox...

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Detalles Bibliográficos
Autores: Kozachuk, O., Luz Mínguez, Ignacio, Noei, H., Kauer, M., Albada, H.B., Bloch, E.D., Marler, B., Wang, Y.M., Muhler, M., Fischer, R.A., Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
Tipo de recurso: artículo
Fecha de publicación:2014
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/63867
Acceso en línea:https://riunet.upv.es/handle/10251/63867
Access Level:acceso abierto
Palabra clave:CO2 reduction
Heterogeneous Catalysis
Hydrogen splitting
Metal-Organic Frameworks
Structural defects
Descripción
Sumario: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 [M-3(II,II)(btc)(2)] (M= Cu, Mo, Cr, Ni, Zn; btc= benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru-2 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.