It is desirable to use CO2 as a C1 feedstock to convert low-value chemicals into value-added products. Coupling CO2with ethylene can produce acrylic acid, which is crucial for manufacturing various industrial compounds. Currently, this reaction is catalyzed by d-metal molecular complexes, limiting its industrial application. Mechanistically, C-C coupling, β-H transfer, and desorption of acrylic acid (depending on the catalyst) hinder the overall kinetics of the process. Therefore, development of heterogeneous catalysts with high reactivity for this reaction is highly desirable. In this study, we investigated the CO2-ethylene coupling reaction on N3M-MN3 (where M = Ir, Ni, Pd, Rh, Cu, Co, Ru, Zn, and Os) dimers anchored in graphene using density functional theory calculations. We found that the β-H transfer is the rate-limiting step over Pd, Zn, Cu, Ru, and Os dimers. In contrast, the C-C coupling step is rate-limiting on Ir, Rh, Ni, and Co dimers. This study identifies Cu, Ni, Pd, Rh, and Ir dimers as promising catalysts for CO2-ethylene coupling. Furthermore, descriptors for C-C coupling and β-H transfer steps are also identified.
