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Catalytically Active Silicon Oxide Nanoclusters Stabilized in a Metal–Organic Framework
Author(s) -
Rimoldi Martino,
Gallington Leighanne C.,
Chapman Karena W.,
MacRenaris Keith,
Hupp Joseph T.,
Farha Omar K.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701902
Subject(s) - nanoclusters , x ray photoelectron spectroscopy , catalysis , silicon , oxide , atomic layer deposition , materials science , metal , zirconium , inorganic chemistry , silicon oxide , silicon dioxide , infrared spectroscopy , aluminium , chemical engineering , layer (electronics) , nanotechnology , chemistry , organic chemistry , metallurgy , silicon nitride , engineering
Post‐synthetic modification of the zirconium‐based metal–organic framework (MOF) NU‐1000 by atomic layer deposition (ALD), using tetramethoxysilane (Si(OMe) 4 ) as a precursor, led to the incorporation and stabilization of silicon oxide clusters composed of only a few silicon atoms in the framework's pores. The resulting SiO x functionalized material (Si‐NU‐1000) was found to be catalytically active despite the inactivity of related bulk silicon dioxide (SiO 2 ), thus demonstrating the positive effects of having nanosized clusters of SiO x . Moreover, Si‐NU‐1000 showed activity greater than that found for aluminum oxide based catalysts—oxides known for their high acidity—such as an aluminum oxide functionalized MOF (Al‐NU‐1000) and bulk γ‐Al 2 O 3 . X‐ray photoelectron spectroscopy and infrared spectroscopy measurements unmasked the electron donating nature of Si‐NU‐1000, explaining the unusual electronic properties of the nanosized SiO x clusters and supporting their high catalytic activity.