Jrb. Gomes et Janf. Gomes, A theoretical study of dioxymethylene, proposed as intermediate in the oxidation of formaldehyde to formate over copper, SURF SCI, 446(3), 2000, pp. 283-293
The density functional theory-based hybrid method B3LYP was used to study t
he interaction of the dioxymethylene species with the copper(lll) surface.
This species has been proposed experimentally as one possible intermediate
in the oxidation of methanol catalysed by metal surfaces. The H2CO2 species
is very unstable, and this makes the experimental study too difficult. As
far as we know, there are no direct theoretical or experimental studies of
H2CO2 adsorption on metal surfaces in the literature. The experimental know
ledge is limited to the IR frequencies obtained for adsorption on metal oxi
des.
In this study, two different clusters and two different adsorption sites ha
ve been studied. A two-layer Cu-7 cluster was used to model the H2CO2 and [
H2CO2](2-) adsorption on a small copper island, and a large three-layer Cu-
30 cluster was used to model the H2CO2 adsorption on a copper (111) surface
. These clusters were used to extract information concerning the energetics
, geometry and IR frequencies for the dioxymethylene adsorption. When compa
red with a similar species, formate, dioxymethylene is stabilized more effi
ciently on the cross-bridge site than on the aligned-bridge site, which is
the preferred orientation for formate. However, the oxygen-to-surface dista
nces are similar, and the same is observed for the bonding type, which is m
ainly ionic. A bridge-bonded conformation is predicted for adsorption on th
e two sites considered. The comparison of the adsorption energy of the diox
ymethylene species and the adsorption energy of atomic oxygen and free form
aldehyde yields an interesting result: H2CO2(ads) is energetically more sta
ble than adsorbed (C)((ads)) and H2CO(g). The IR frequencies are in good ag
reement with experimental data obtained for dioxymethylene adsorption on se
veral oxide surfaces. (C) 2000 Published by Elsevier Science B.V. All right
s reserved.