Methane autothermal reforming with CO2 and O2 to synthesis gas at the boundary between Ni and ZrO2

A series of different amount ZrO2-promoted SiO2 supported Ni catalysts were prepared and used for methane autothermal reforming with CO2 and O2 [MATR] to synthesis gas in a fluidized bed reactor. Pulse-injected surface reactions and in situ XRD characterizations disclosed that CO2 dissociated exclusively at the boundary between Ni and ZrO2. O species derived from CO2 dissociation overflowed to metallic Ni and accelerated the activation of methane. Ni/5ZrO2–SiO2 catalyst with larger Ni–ZrO2 boundary exhibited the best activity and stability for MATR even at an extremely space velocity 90,000 h−1.