Molybdenum carbide clusters for thermal conversion of CO2 to CO via reverse water-gas shift reaction

Molybdenum carbides are highly active for COconversion to CO via the reverse water-gas shift（RWGS）reaction, however the large grain size up to micrometers renders its relatively lower active sites utilization efficiency while generating CHas a by-product. In this work, a homogeneously dispersed molybdenum carbide hybrid catalyst with sub-nanosized cluster（the average size as small as 0.5 nm） is prepared via a facile carbothermal treatment for highly selective CO-CO reduction. The partially disordered MoC clusters are characterized by synchrotron high-resolution XRD and atomic resolution HAADF-STEM analysis, for which the source cause of the disorder is pinpointed by XAFS analysis to be the nitrogen intercalants from the carbonaceous precursor. The partially disordered MoC clusters show a RWGS rate as high as 184.4 μmol gsat 400 ℃ with a superior selectivity toward CO（> 99.5%）. This work 2 highlights a facile strategy for fabricating highly dispersed and partially disordered MoC clusters at a sub-nano size with beneficial N-doping for delivering high catalytic activity and operational stability.