Title: Molybdate- and tungstate-exchanged layered double hydroxides as catalysts for O-1(2) formation: Characterization of reactive oxygen species and a critical evaluation of O-1(2) detection methods
Authors: Sels, Bert ×
De Vos, Dirk
Grobet, Pierre
Pierard, F
Kirsch-De Mesmaeker, F
Jacobs, Pierre #
Issue Date: 1999
Publisher: American Chemical Society
Series Title: Journal of Physical Chemistry B, Materials, Surfaces, Interfaces & Biophysical vol:103 issue:50 pages:11114-11123
Abstract: Layered double hydroxides (LDHs) with the formula [Mg0.7Al0.3(OH)(2)] (NO3)(0.3) were partially exchanged with MoO42- and WO42- and were used as heterogeneous catalysts for the decomposition of H2O2 into singlet molecular oxygen (O-1(2)). The oxometalate anions are present on the LDH as monomeric, tetrahedral MO42- anions. With LDH-MoO42- and H2O2, O-1(2) is by far the prevailing reactive oxygen species. EPR trapping detected a minor amount of free OH. radicals, but these do not appreciably contribute to product formation in olefin oxygenation. LDH-WO42- transforms H2O2 into O-1(2) about 4 times slower than the Mo catalyst, and additionally effects mono-oxygen transfer to electron-rich substrates such as amines and olefins. Only for alkenes with very low beta values, the Schenck hydroperoxidation dominates over the epoxidation in the W-catalyzed reactions. While most tests for O-1(2) detection were designed for photosensitized reactions, the applicability of these methods to dark catalytic reactions is not always clear. Therefore, a series of common O-1(2) detection methods was critically evaluated in the LDH-WO42- or LDH-MoO42- + H2O2 reactions. Isomer distributions in the olefin hydroperoxidation and detection of NIR luminescence are the most reliable and sensitive methods. Quenching or trapping methods that involve amines should not be used when the catalyst also effects mono-oxygenation.
ISSN: 1089-5647
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Centre for Surface Chemistry and Catalysis
× corresponding author
# (joint) last author

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