Zirconium Carbide Mediates Coke‐Resistant Methane Dry Reforming on Nickel‐Zirconium Catalysts

Abstract

Graphitic deposits anti-segregate into Ni⁰ nanoparticles to provide restored CH₄ adsorption sites and near-surface/dissolved C atoms, which migrate to the Ni⁰ /ZrO₂ interface and induce local Zr_x C_y formation. The resulting oxygen-deficient carbidic phase boundary sites assist in the kinetically enhanced CO₂ activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO₂ support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni-CeZr_x O_y catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.