title: A computational modelling study of oxygen vacancies at LaCoO3 perovskite surfaces.
abstract: Atomistic computational modelling of the surface structure of the catalytically-active perovskite LaCoO(3) has been undertaken in order to develop better models of the processes involved during catalytic oxidation processes. In particular, the energetics of creating oxygen ion vacancies at the surface have been investigated for the three low index faces (100), (110) and (111). Two mechanisms for vacancy creation have been considered involving dopant Sr(2+) cations at the La(3+) site and reduction of Co(3+) to Co(2+). For both mechanisms, there is a general tendency that the smaller the cation defect separation, the lower the energy of the cluster, as would be expected from simple electrostatic considerations. In addition, there are clear indications that oxygen vacancies are more easily created at the surface than in the bulk. The results also confirm that the presence of defects strongly influences crystal morphology and surface chemistry. The importance of individual crystal surfaces in catalysis is discussed in terms of the energetics for the creation of oxygen vacancies.
authors.affiliation: Davy Faraday Research Laboratory, The Royal Institution of Great Britain, 21 Albemarle Street,, London, UKW1S 4BS.
authors.forename: S
authors.initials: S
authors.lastname: Khan
authors.forename: R J
authors.initials: RJ
authors.lastname: Oldman
authors.forename: F
authors.initials: F
authors.lastname: Corà
authors.forename: C R A
authors.initials: CR
authors.lastname: Catlow
authors.forename: S A
authors.initials: SA
authors.lastname: French
authors.forename: S A
authors.initials: SA
authors.lastname: Axon
mesh_terms: D001665:Binding Sites; D017610:Calcium Compounds / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D003198:Computer Simulation; D007811:Lanthanum / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*
chemical_list: D017610:Calcium Compounds; D010087:Oxides; C059910:perovskite; D003035:Cobalt; D007811:Lanthanum; D014025:Titanium; D010100:Oxygen; C060728:cobalt oxide