The reaction mechanism of the CO2 hydration on copper alkoxide functionalization in Metal-Organic Frameworks is investigated by employing the density functional theory, M06L method. The reaction is proposed in a three-step process. It commences from the O-H bond of water dissociation leading to the formation of the surface OH species which is followed by the C-O bond formation between the O of the OH species and the incoming CO2 molecule to produce a hydrogen carbonate. Finally, this carbonate species is converted to carbonic acid via a hydrogen abstraction. The activation energy for the first step, which is considered to be rate-determining step, is computed to be 19.4 kcal/mol and for the subsequent reactions, second and third reaction steps, are 6.4 and 7.0 kcal/mol, respectively. The effect of Cu-MOF-5 is highlighted by comparing it with the bare system where the reaction takes place in one step with a barrier of 48.9 kcal/mol, which is higher than the Cu-MOFs system. It can be suggested that the Cu-MOFs might be an active material to use to capture and hydrate the CO2 molecule.

Structures and energetics of carbon dioxide hydration over copper alkoxide functionalization in metal-organic frameworks: A DFT study

248th National Meeting (2014)

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