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Mechanistic Study on the Selective Oxidation of Acrolein to Acrylic Acid: Identification of the Rate‐Limiting Step via Perdeuterated Acrolein
Author(s) -
Knoche Stefan,
Heid Maurice,
Gora Niklas,
Ohlig Dominik,
Drochner Alfons,
Hess Christian,
Etzold Bastian,
Vogel Herbert
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201900549
Subject(s) - acrolein , chemistry , photochemistry , selectivity , hydrogen atom abstraction , context (archaeology) , acrylic acid , rate determining step , hydrogen , organic chemistry , catalysis , polymer , monomer , paleontology , biology
Gas phase oxidation of acrolein to acrylic acid on hydrothermally prepared Mo/V/W mixed oxides was investigated by isotopic labeling of acrolein. In this context, perdeuterated acrolein was synthesized for the first time and subsequently used for mechanistic studies. A clear kinetic isotopic effect (KIE) is observed referring to the α ‐hydrogen‐abstraction as the rate‐determining step in the selective acrolein oxidation. Furthermore, no change in the selectivity patterns is observed due to the perdeuteration, which confirms that the α ‐hydrogen‐abstraction also acts as the rate‐limiting step in the total oxidation of acrolein. Based on these KIE studies combined with additional experiments including D 2 O‐SSITKA and temperature‐programmed desorption, a detailed reaction mechanism for acrolein oxidation is proposed.