Computational study of CO₂ methanation over two-dimensional molybdenum carbide catalysts

Two-dimensional molybdenum carbide (2D-Mo₂C) is thought to be promising for catalytic hydrogenation of CO₂ to CH₄, but little is known about its catalytic reaction mechanism. In this work, we investigate the hydrogenation of CO₂ to CH₄ on 2D-Mo₂C using density functional theory. Our calculations show that Mo on the surface can efficiently decompose CO₂ to CO and O, and also H₂ to H. The hydrogenation of CO produces CHO that is readily deoxygenated to CH, and CH is selectively hydrogenated to produce CH₄. Interestingly, the embedded Ir₁ on 2D-Mo₂C can act as a single-atom promoter to improve the performance of CO₂ methanation, while on the other hand maintaining its high selectivity for CH₄. This work provides insight into the mechanism of 2D-Mo₂C-catalyzed CO₂ methanation reactions and suggests a strategy to improve the performance of such catalysts through single-atom promoters.