Evidence for spontaneous CO2 activation on cobalt surfaces

Density functional calculations carried out for the interaction of CO2 with the low index faces of Co(fcc) using periodic slab models predict that the interaction is structure sensitive and that the molecular structure of CO2 on the Co( 100) and Co( 110) faces is highly distorted and reminiscent of CO2-. This is interpreted as spontaneous activation of the adsorbed molecule. These results are at variance for the interaction of CO2 on most metal surfaces, strongly suggest that Co( 100) and Co( 110) oriented surfaces of the Co( fcc) nanoparticles in supported catalysts are likely to trigger CO2 activation and hence to ease CO2 dissociation; in agreement with recent experimental observations. (c) 2008 Elsevier B. V. All rights reserved.