Our recent computational investigations modeling small transition metal oxide cluster anion (Mo2O4−/Mo2O5−cluster couple) reactions with dual reactants (CO + H2O or C2H2 + H2O) suggest possible completion of a catalytic cycle of H2 production using molybdenum oxide cluster anions. Calculations on the Mo2O4−/Mo2O5− cluster couple reactions with CO + H2O or C2H2 + H2O or C2H4 + H2O using Density Functional Theory (DFT) predict that non-dissipation of internal energy in the cluster-H2O complex during reaction will play a key role in the completion of the catalytic step. The calculations have been followed up by experimental reactivity studies on these systems using Time-of-flight mass spectrometry. The reaction products suggest addition, double addition and also some promising fragmentation reactions (where higher metal oxide cluster products fragment to produce lower oxide clusters) in addition to the formation of some CnHn− species as observed in the mass spectra. The fragmented products and the presence of CnHn− species indicate possible regeneration of lower metallic oxide clusters in these dual reactant experiments with Mo-Oxide clusters. Detailed description of the observed products, their possible formation reactions and their reaction kinetics will be discussed in this talk to analyze any possible catalytic cycle that was shown previously using DFT calculations. Finally, the study of these local interactions between C2H4/C2H2 +H2O and Mo-oxide clusters will help in elucidating the relevance of these interactions to heterogeneous catalysis.

Gas phase catalytic cycle of hydrogen production from water using small Mo-oxide cluster anions

253rd National Meeting (2017)

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