Highly Dispersed Molybdenum Carbide Clusters Enable Efficient CO 2 Hydrogenation

The reverse water-gas shift (RWGS) offers a promising route to convert CO2 into CO, a vital feedstock for chemical synthesis. However, the reaction is strongly endothermic and only driven by marginal entropy increasing, requiring high temperature to achieve appreciable CO yields. At such conditions, non-noble metal catalysts suffer from low activity, and noble metals, though being more active, are prone to deactivation. Here, we report that sub-nanometer molybdenum carbide (MoC) clusters supported on carbon enable highly efficient and stable RWGS catalysis without noble metals. The catalyst achieves CO formation rate of 1.26 molCO molMo -1 s-1 and mass-specific activity of 1028 µmolCO gcat -1 s-1, with near 100% CO selectivity and exceptional stability. Characterizations reveal that MoC spontaneously disperses as sub-nanometer clusters on support, maximizing the density of coordinatively unsaturated surface sites. These sites facilitate efficient CO2 adsorption/activation, enabling rapid removal of surface oxygen species. Density functional theory calculations show that highly dispersed MoC sites exhibit distinct local environment, which accounts for weak Mo-O binding and enhances overall catalytic power. This work demonstrates a noble-metal-free catalyst that couples high activity, selectivity, and stability with exceptional atom efficiency, offering robust and sustainable strategy for CO2 valorization.