Density functional study of formate decomposition on NiO(111) surface

Citation
T. Miura et al., Density functional study of formate decomposition on NiO(111) surface, J PHYS CH B, 105(41), 2001, pp. 10001-10006
Citations number
37
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY B
ISSN journal
1520-6106 → ACNP
Volume
105
Issue
41
Year of publication
2001
Pages
10001 - 10006
Database
ISI
SICI code
1520-6106(20011018)105:41<10001:DFSOFD>2.0.ZU;2-7
Abstract
The mechanism of formate decomposition on a NiO(111) surface is investigate d using the density functional method and (NiO)(x) cluster models. The reac tion consists of three steps: (1) configuration change from bidentate to mo nodentate, (2) HCOO rotation around the CO axis, and (3) H atom transfer fr om the formate to the surface O atom. The bidentate form is more stable by 21 kJ/mol than the monodentate one, and the energy barrier measured from th e former is 25 kJ/mol, which is consistent with the recent experimental fin ding that the mutual conversion is an equilibrium reaction. There is no ess ential reaction barrier during the HCOO rotation about the CO axis. The mig ration of H atoms from formate to the surface O atom is the rate-limiting s tep, and the activation energy is estimated to be 73 kJ/mol. The product is the surface OH groups and adsorbed CO2 molecule, which is consistent with the recent experimental stidies.