Constructing Molybdenum-Stabilized Nickel-Oxo Sites for Boosting Low-Temperature Dry Reforming of Methane

Dry reforming of methane (DRM) converts methane (CH 4 ) and carbon dioxide (CO 2 ) into syngas (H 2 and CO), which serves as a crucial feedstock for the production of high-value chemicals. However, traditional DRM requires high temperatures (>800 °C) to effectively activate the C–H and C=O bonds, resulting in significant energy demands. Herein, we present a NiMo/MgO catalyst to promote DRM reactions at significantly lower temperatures (465 °C). Molybdenum stabilizes nickel-oxo species within surface chemistry that lower the energy required for bond dissociation, enabling efficient DRM at reduced temperatures. Using in situ steady-state isotopic transient kinetic analysis (SSITKA), Fourier transform diffuse reflectance infrared spectroscopy (DRIFTS), and isotopic analysis ( 13 CO 2 –CD 4 ), we identified the formation rate of hydroxymethyl groups involving C–H bonds to preferentially occur before the dehydrogenation process, thereby efficiently regulating the aggregation of hydroxyl groups dissociated during CO 2 hydrogenation on the surface. Results showed specific yield rates of 2.49 mmol g cat –1 min –1 for H 2 and 2.34 mmol g cat –1 min –1 for CO at 465 °C. These results demonstrate that the “hydroxyl-mediated” DRM mechanism operating at mild temperatures is effective in enhancing syngas production. This research provides insights into low-temperature DRM kinetics and catalyst design for enhanced energy efficiency.