Methanol formation from CO2 catalyzed by Fe3S4{111}: formate versus hydrocarboxyl pathways

We have carried out a systematic study of the adsorption and selective reduction of CO2 on the Fe3S4{111} surface. We have considered both formate and hydrocarboxyl key intermediates leading to different reaction pathways via Eley-Rideal and Langmuir-Hinshelwood mechanisms and we have built a kinetic model considering the wide range of intermediates in the reaction network. Our results show that the mechanism to produce formic acid takes place via a formate intermediate mostly on FeA sites, while methanol is formed via hydrocarboxyl intermediates on FeB sites. From the kinetic model we have derived a reaction constant comparison and determined the limiting step rates.The data comprises energies (in eV) of all reactants, intermediaries and transition states.Results based upon these data are published at http://dx.doi.org/10.1039/c5fd00186b