In Situ Construction of High-Performance Molybdenum-Based Multicomponent Catalysts with Metal Carbide/Metal Nitride-Support Interactions

Abstract

The development of nonprecious metal supported catalysts is crucial for advancing the chemical industry. In this study, we successfully synthesized molybdenum-based three-component catalysts (Mo-BMC) by in situ loading β-Mo₂C and γ-Mo₂N onto the reducible MoO_2-x through the thermal decomposition method of metal complexes. Notably, XPS revealed a significant electronic transfer from β-Mo₂C and γ-Mo₂N to MoO_2–x in Mo-BMC, reflecting the presence of strong metal carbide/metal nitride-support interactions. Using the reverse water gas shift reaction (RWGS) as a model, the Mo-BMC demonstrated outstanding catalytic performance, achieving a CO₂ conversion of 43.07% and over 99.7% CO selectivity at 500 °C, outperforming 5% Pt/MoO_2–x with a CO₂ conversion (12.61%) 3.42 times higher. Mechanistic studies reveal that in the Mo-BMC, the reducible MoO_2–x primarily facilitates CO₂ activation, while the Pt-like β-Mo₂C and γ-Mo₂N effectively activate H₂. The RWGS reaction proceeds via the formate mechanism. By replacing active metals in traditional metal-supported catalysts with β-Mo₂C and γ-Mo₂N, Mo-BMC not only retains high activity but also significantly reduces costs and improves sintering resistance. This study provides a new approach for the development of novel high-performance catalysts, effectively advancing the industrial application of low-cost, high-activity, and highly stable catalysts.