Reaction Pathways in Acrolein Oxidation over a Mixed‐Oxide Catalyst

Abstract A reaction network detailing the mechanistic origins of 17 C 1 −C 7 byproducts in acrolein oxidation over a vanadium molybdate mixed oxide catalyst doped with antimony and copper is proposed based on measurements of acrolein oxidation rates with co‐feeds of C 1 −C 7 organics formed as byproducts, acrylic acid 13 C isotopic tracer experiments, and probe molecule reactions. C 1 and C 2 products form via C−C bond scission of either the single or double C−C bond in acrolein and acrylic acid. C 4 −C 7 products form by addition of one or two acrolein or acrylic acid molecules to a C 2 surface species coupled with decarbonylation or decarboxylation events. Two‐carbon ethyl and vinyl surface species and three‐carbon acrolein‐derived surface species are involved in all pathways that lead to byproduct formation; controlling the relative abundance and reactivity of such intermediates is integral to prescribing process conditions and material compositions for selective oxidation of acrolein.