Investigating the Mars-van Krevelen Mechanism for CO Capture on the Surface of Carbides.

Electrochemical reduction processes enable the CO to be converted into a useful chemical fuel. Our study employs density functional theory calculations to analyze the (110) facets of the transition metal carbide surfaces for CO capture, incorporating the Mars-van Krevelen (MvK) mechanism. All the possible adsorption sites on the surface, including carbon, metal, and bridge sites, were fully investigated. The findings indicate that the carbon site is more active relative to the other adsorption sites examined. The CO hydrogenation paths have been comprehensively investigated on all the surfaces, and the free energy diagrams have been constructed towards the product. The results conclude that the TiC is the most promising candidate for the formation of methane, exhibiting an onset potential of -0.44 V. The predicted onset potential for CrC, MoC, NbC, VC, WC, ZrC, and HfC are -0.86, -0.61, -0.61, -0.93, -0.87, -0.61, and -0.81 V, respectively. Our calculated results demonstrate that MvK is selectively relevant to methane synthesis. Additionally, we investigated the stability of these surfaces against decomposition and conversion to pure metals concerning thermodynamics and kinetics. It was found that these carbides could remain stable under ambient conditions. The exergonic adsorption of hydrogen on carbon sites, requiring smaller potential values for product formation, and stability against decomposition indicate that these surfaces are highly suitable for CO reduction reactions using the MvK mechanism.