Atomic-level insight into the carburization process of iron-based catalysts: A ReaxFF molecular dynamics study

Abstract

Transition metal carbide catalysts have garnered widespread attention due to their outstanding catalytic performance. The carbide catalysts, such as FexC and MoxC are typically obtained from their oxide carburization. The reduction and carburization processes are key steps during the activation of oxide precursors, which determine the activity and stability. An understanding of the carburization process mechanism is very important for the optimization of carbide catalysts. Iron-based catalysts are widely used in the large-scale coal-to-liquid industry because of their low price and high activity. In this paper, the carburization process of iron oxide nanoparticles was simulated by the Reactive force field (ReaxFF) molecular dynamics method. The results illustrate that the competition between CO dissociation and reduction of oxides occurs at the 100 ps time scale, which can be tuned by particle size and oxygen vacancy. We have explained the counter-intuitive finding that small oxide particles are more difficult to achieve fully carburization than larger ones; this is because rapid carbon accumulation on the surface blocks the oxygen diffusion channels from bulk to surface. The atomic distribution heat map was carried out to demonstrate the carbon and oxygen penetration processes. Meanwhile, the volumetric strain analysis reveals the driving force comes from the strong tendency to form Fe-C bonds. The dependence on surface orientation was further systematically investigated. This work provides microscopic insights into the carburization process of iron-based materials and the fundamental knowledge for the optimization of catalyst synthesis procedures.