Computational investigation of the kinetics and mechanism of the initial steps of the Fischer–Tropsch synthesis on cobalt

Abstract

A multi-site microkinetic model for the Fischer–Tropsch synthesis (FTS) reaction up to C₂ products on a FCC cobalt catalyst surface is presented. This model utilizes a multi-faceted cobalt nanoparticle model for the catalyst, consisting of the two dominant cobalt surface facets Co(111) and Co(100), and a step site represented by the Co(211) surface. The kinetic parameters for the intermediates and transition states on these sites were obtained using plane-wave, periodic boundary condition density functional theory. Using direct DFT data as is, the microkinetic results disagree with the expected experimental results. Employing an exploratory approach, a small number of microkinetic model modifications were tested, which significantly improved correspondence to the expected experimental results. Using network flux and sensitivity analysis, an in-depth discussion is given on the relative reactivity of the various sites, CO activation mechanisms, the nature of the reactive chain growth monomer, the probable C₂ formation mechanism, the active site ensemble interplay and the very important role of CO* surface coverage. The findings from the model scenarios are discussed with the aim of guiding future work in understanding the FTS mechanism and subsequent controlling kinetic parameters.