The Vital Role of Step-Edge Sites for Both CO Activation and Chain Growth on Cobalt Fischer–Tropsch Catalysts Revealed through First-Principles-Based Microkinetic Modeling Including Lateral Interactions

Microkinetic modeling is employed to predict catalytic turnover rates, product distributions, preferred mechanistic pathways, and rate- and selectivity-controlling elementary reaction steps for the Fischer-Tropsch (FT) reaction. We considered all relevant elementary reaction steps on Co(112̅1) step-edge and Co(0001) terrace sites as well as such important aspects as coverage-related lateral interactions, different chain-growth mechanisms, and the migration of adsorbed species between the two surfaces in the dual-site model. CH x –CH y coupling pathways relevant to the carbide mechanism have favorable barriers in comparison to the overall barriers for the CO insertion mechanism. A comparison of reaction barriers indicates why cobalt is such a good FT catalyst: CO bond scission and chain growth compete, while termination to olefins has a slightly higher barrier. The predicted kinetic parameters correspond well with experimental kinetic data. The Co(112̅1) model surface is highly active and selective for the FT reaction. Adding terrace Co­(0001) sites in a dual-site model approach leads to a substantially higher CH4 selectivity at the expense of the C2+-hydrocarbons selectivity. The chain-growth probability decreases with increasing temperature and H2/CO ratio, caused by faster hydrogenation of the hydrocarbon chains. The elementary reaction steps for O removal and CO dissociation significantly control the overall CO consumption rate. Chain growth occurs almost exclusively at step-edge sites, while additional CH4 stems from CH and CH3 migration from step-edge to terrace sites. Replacing CO by CO2 as the reactant shifts the product distribution nearly completely to CH4, which is related to the much higher H/CO coverage ratio during CO2 hydrogenation in comparison to CO hydrogenation. These findings highlight the importance of a proper balance of CO and H surface species during the FT reaction and pinpoint step-edge sites as the locus of the FT reaction with low-reactive terrace sites near step-edge sites being the origin of unwanted CH4.