High-Performance Binary Mo–Ni Catalysts for Efficient Carbon Removal during Carbon Dioxide Reforming of Methane

Dry reforming of methane (DRM) can convert greenhouse gases (CO2 and CH4) into value-added syngas (CO and H2), which is one of the promising approaches to achieve carbon neutrality. Designing coking resistant catalysts is still a challenge for an efficient DRM reaction. Here, we developed an efficient binary Mo–Ni catalyst through elucidating the promotional role of Mo in boosting the coking resistance of Ni-based catalysts during the DRM. Mo-modified ZSM-5 served as the "smart support", which provided the dynamic variation between MoOx and MoOxCy, enabling efficient carbon removal during the DRM reaction. Furthermore, the introduction of Mo maintained more active Ni0 species and enhanced the activity. A more effective pathway via a formate intermediate driven by the Mo-modified Ni/ZSM-5 further suppressed coking during DRM. This work discovered that both activity and coking resistance of traditional Ni catalysts can be simultaneously improved due to the addition of Mo through restraining Ni oxidation and a unique MoOx ↔ MoCxOy redox cycle.