Active‐Site Shifting on the Ni‐FeO _x Interface Bridges Metallic and Oxidative Catalysis for Efficient Methane Partial Oxidation

Abstract Partial oxidation reforming of methane provides stoichiometrically optimal syngas as an alternative feedstock for the chemical industry currently relying on coal and petroleum resources. However, effective catalysis at moderate temperatures has been challenging. We report an active‐site shifting mechanism that inherently couples metallic and oxidative catalysis for efficient methane reforming, achieving a syngas yield of 9.7 millimoles per gram of the developed Ni‐FeO x catalyst at 89.9% methane conversion below 700 °C. The discovered mechanism features the ongoing transfer of CH 3 * species from metallic Ni to FeO x , enabling both superior reaction kinetics by prompt liberation of occupied Ni sites and intrinsic avoidance of the intractable carbon deposition. Charge orientational distribution due to the electronic interaction between metallic Ni and FeO x induces the fundamental force driving active‐site shifting. This study substantiates an efficient methane partial oxidation pathway that is distinct from those based on the prevailing tandem‐reaction hypothesis in the coupled catalysis, offering new insights into the catalyst design by active‐site modulation.