New catalyst design tackles methane and CO2 conversion without fouling up

<p>Dry reforming of methane (DRM) enables the simultaneous conversion of CH₄ and CO₂, yet rapid coking severely restricts the stability of Ni-based catalysts. In this study, Co was incorporated into Ce-, La-, and Zr-promoted Ni catalysts to construct Ni-Co alloy active sites, and their catalytic behavior was systematically evaluated. While single-promoter modification partially suppressed coke deposition at the expense of activity, Ni-Co alloy formation maintained high reforming performance and significantly enhanced stable catalytic performance within the 20 h evaluation period, with the Ce-promoted Ni-Co catalyst exhibiting the most durable anti-coking performance. CO₂-TPD and coke characterization results indicate that promoter species enhance medium-strength basicity and oxygen mobility, thereby facilitating CO₂ adsorption and accelerating the oxidation of surface coke intermediates; in particular, Ce supplies mobile active oxygen species through its oxygen storage-release capacity. DFT calculations further reveal that Co incorporation modulates the electronic structure of Ni sites, optimizing the balance between CH₄ dissociation and CO₂ activation and thus suppressing excessive methane cracking. These findings elucidate the synergistic effect of Ni-Co alloying and promoter modification in DRM and provide mechanistic insight for the rational design of coke-resistant Ni-based catalysts.</p>