Molybdenum Oxide Cluster Anion Reactions with C2H4 and H2O: Cooperativity and Chemifragmentation.

To probe the mechanism of sacrificial reagents in catalytic processes, product distributions from MoxOy- clusters reacting individually with C2H4 and H2O are compared with those from reactions with a C2H4 + H2O mixture, with the thermodynamics explored computationally. These molecules were chosen to model production of H2 from H2O via H2O + C2H4 → H2 + CH3CHO, mediated by MoxOy- clusters. H2O is known to sequentially oxidize MoxOy- suboxide clusters while producing H2, resulting in less reactive clusters. MoxOy- (y ∼ x) clusters undergo chemi-fragmentation reactions with C2H4, with MoxOyC2Hz- complexes forming as the cluster oxidation state increases. Unique species observed in reactions with the C2H4 + H2O mixture, Mo2O5C2H2- and MoO3C2H4-, suggest that the internal energy gained in new Mo-O bond formation from oxidation by H2O opens additional reaction channels. C2H3O- is observed uniquely in reactions with the C2H4 + H2O mixture, giving indirect evidence of CH3CHO formation via the cluster mediated H2O + C2H4 → H2 + CH3CHO reaction; C2H3O- can form via dissociative electron attachment to CH3CHO. Calculations support mechanisms that invoke participation of two ethylene molecules on thermodynamically favorable pathways leading to experimentally observed products.