Assessing the Impact of Adlayer Description Fidelity on Theoretical Predictions of Coking on Ni(111) at Steam Reforming Conditions

[Image: see text] Methane steam reforming is an important industrial process for hydrogen production, employing Ni as a low-cost, highly active catalyst, which, however, suffers from coking due to methane cracking. Coking is the accumulation of a stable poison over time, occurring at high temperatures; thus, to a first approximation, it can be treated as a thermodynamic problem. In this work, we developed an Ab initio kinetic Monte Carlo (KMC) model for methane cracking on Ni(111) at steam reforming conditions. The model captures C–H activation kinetics in detail, while graphene sheet formation is described at the level of thermodynamics, to obtain insights into the “terminal (poisoned) state” of graphene/coke within reasonable computational times. We used cluster expansions (CEs) of progressively higher fidelity to systematically assess the influence of effective cluster interactions between adsorbed or covalently bonded C and CH species on the “terminal state” morphology. Moreover, we compared the predictions of KMC models incorporating these CEs into mean-field microkinetic models in a consistent manner. The models show that the “terminal state” changes significantly with the level of fidelity of the CEs. Furthermore, high-fidelity simulations predict C–CH island/rings that are largely disconnected at low temperatures but completely encapsulate the Ni(111) surface at high temperatures.