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.