Abstract : We investigated the oxidation of formaldehyde, one of the major indoor air pollutants, into
CO2 and H2O over Fe atoms trapped in defects on graphene by first-principles based calculations.
These trapped Fe atoms are not only stable to withstand interferences with the reaction
environments but are also efficient to catalyze the reactions between coadsorbed O2 and
formaldehyde. The oxidation of formaldehyde starts with the formation of a peroxide-like
intermediate and continues by its dissociation into a η1-OCHO coadsorbed with an OH radical.
Then, the adsorbed OCHO undergoes conformational changes and hydride transfer, leading to
the formation of H2O and CO2. Subsequent adsorption of O2 or formaldehyde facilitates
desorption of H2O and a new reaction cycle initiates. The calculated barriers for formation and
dissociation of the peroxide-like intermediate are 0.43 and 0.40 eV, respectively, and those for
conformation changes and hydride transfer are 0.47 and 0.13 eV, respectively. These relatively
low barriers along the reaction path suggest the potential high catalytic performance of these
trapped Fe atoms for formaldehyde oxidation.
