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Pd@UiO‐66‐Type MOFs Prepared by Chemical Vapor Infiltration as Shape‐Selective Hydrogenation Catalysts
Author(s) -
Luz Ignacio,
Rösler Christoph,
Epp Konstantin,
Llabrés i Xamena Francesc X.,
Fischer Roland A.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500299
Subject(s) - chemistry , catalysis , steric effects , adsorption , heterogeneous catalysis , palladium , metal organic framework , ferrocene , octahedron , nanoparticle , inorganic chemistry , photochemistry , chemical engineering , crystallography , stereochemistry , crystal structure , organic chemistry , electrode , electrochemistry , engineering
Host‐guest inclusion properties of UiO‐66 and UiO‐67 metal‐organic frameworks have been studied using ferrocene (FeCp 2 ) as probe molecule. According to variable‐temperature solid‐state 1 H and 13 C CP‐MAS‐NMR, two different environments exist for adsorbed FeCp 2 inside UiO‐66 and UiO‐67, which have been assigned to octahedral and tetrahedral cavities. At room temperature, a rapid exchange between these two adsorption sites occurs in UiO‐67, while at –80 °C the intracrystalline traffic of FeCp 2 through the triangular windows is largely hindered. In UiO‐66, FeCp 2 diffusion is already impeded at room temperature, in agreement with the smaller pore windows. Palladium nanoparticles (Pd NPs) encapsulated inside UiO‐66 and UiO‐67 have been prepared by chemical vapor infiltration of (allyl)Pd(Cp) followed by UV light irradiation. Infiltration must be carried out at low temperature (–10 °C) to avoid uncontrolled decomposition of the organometallic precursor and formation of Pd NPs at the external surface of the MOF. The resulting Pd‐MOFs are shape selective catalysts, as shown for the hydrogenation of carbonyl compounds with different steric hindrance.