Theoretical study of the catalytic performance of Fe and Cu single-atom catalysts supported on Mo(2)C toward the reverse water–gas shift reaction

The reverse water–gas shift (RWGS) is an attractive process using CO(2) as a chemical feedstock. Single-atom catalysts (SACs) exhibit high catalytic activity in several reactions, maximizing the metal use and enabling easier tuning by rational design than heterogeneous catalysts based on metal nanoparticles. In this study, we evaluate, using DFT calculations, the RWGS mechanism catalyzed by SACs based on Cu and Fe supported on Mo(2)C, which is also an active RWGS catalyst on its own. While Cu/Mo(2)C showed more feasible energy barriers toward CO formation, Fe/Mo(2)C presented lower energy barriers for H(2)O formation. Overall, the study showcases the difference in reactivity between both metals, evaluating the impact of oxygen coverage and suggesting Fe/Mo(2)C as a potentially active RWGS catalyst based on theoretical calculations.