Reaction path for dissociative chemisorption of CO2 on Ni(111) and Pt(111)

ALEJANDRA E. MARTÍNEZ; GIULIA N. SEMINARA; BOCAN, GISELA; BUSNENGO, H. FABIO

Conferencia; VI San Luis Conference on Surfaces, Interfaces and Catalysis; 2018

The dissociative adsorption of CO2 on surfaces plays a central role in many important catalyzed reactions (i.e. the water-gas shift CO+H2O ↔ CO2+H2). What is more, given the connection between atmospheric CO2 and global warming much effort is being focused on carbon management and the conversion of CO2 into useful products (i.e. dry reforming of methane, CO2+CH4↔2CO+2H2). In this context, the reaction of CO2 on metal surfaces has been addressed by various groups. However, the dynamics of its dissociative chemisorption has seldom been considered. In this contribution we present a comparative theoretical study of the reaction path to dissociative adsorption for CO2 on Ni(111) and on Pt(111) (both group 10 elements). We make use of DFT calculations as implemented in the VASP code. We analyze the energetics as well as the configurational evolution of both systems. Physisorbed CO2 reacts with the surface giving way to a molecular chemisorbed state, precursor to the final dissociative adsorption configuration. We address the role of van der Waals (vdW) interactions in the reaction by comparing PBE and vdW calculations. For the case of Ni we use the vdW-DF2 approach, while for Pt we opt for BEEF-vdW due to its reported good performance for this system. Nudged Elastic Band calculations are currently under way to find the transition states and energy barriers along the presented reaction paths.