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

Graphitic deposits anti‐segregate into Ni(0) nanoparticles to provide restored CH(4) adsorption sites and near‐surface/dissolved C atoms, which migrate to the Ni(0)/ZrO(2) interface and induce local Zr( x )C( y ) formation. The resulting oxygen‐deficient carbidic phase boundary sites assist in the kinetically enhanced CO(2) activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO(2) 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.