Coordination modulation of MoNx catalysts for an enhanced CO2 hydrogenation reaction

The reverse water-gas shift (RWGS) reaction represents a central strategy for CO 2 utilization, yet conventional catalysts often require high temperatures and exhibit poor selectivity due to complex mechanisms. Here, we report a carbon-doped molybdenum nitride (Mo–N–C) catalyst that enables a redox-dominated RWGS pathway under mild conditions. Structural and electronic analyses reveal that carbon incorporation modulates the Mo oxidation state and induces the coexistence of Mo–N and Mo–C coordination, creating an optimized electronic environment for CO 2 activation. In-situ DRIFTS and quasi-in-situ XPS, supported by DFT calculations, demonstrate that CO formation proceeds via CO 2 direct dissociation rather than hydrogen-assisted dissociation, confirming a redox-mediated mechanism. This unique electronic configuration allows MoNC to achieve 21.7% CO 2 conversion and 98.4% CO selectivity at 400 °C, with outstanding stability over 100 h. The findings establish C–N synergistic coordination as a broadly applicable design principle for electronic-state tuning in non-noble metal catalysts for CO 2 reduction. A carbon-doped molybdenum nitride catalyst exhibits excellent performance in the reverse water gas shift reaction by following a redox reaction pathway. Download: Download high-res image (82KB) Download: Download full-size image