Cooperative Redox Catalysis of N₂O Decomposition by Short-Range RhO_x and CeO_x Anchored to Co₃O₄

Hybrid materials based upon mixed metal oxides provide an effective strategy to boost catalytic performance through redox-induced interfacial engineering. Herein, we present an efficient catalyst toward N₂O decomposition containing short-range ordered RhO_x and CeO_x species anchored to the Co₃O₄ spinel. The activity enhancement relative to Co₃O₄ is non-additive with respect to the RhO_x/Co₃O₄ and CeO_x/Co₃O₄ interfaces and is uniquely linked to the modulation of the Co and Rh oxidation states at a synergistic Rh-O-Co-O-Ce interface. This ensemble provides increased redox flexibility and facilitated lattice oxygen activation, resulting in markedly enhanced N₂O decomposition. Kinetic analysis and operando modulated excitation x-ray absorption spectroscopy (ME-XAS) provide direct mechanistic evidence that N₂O decomposition proceeds via a multi-site, cooperative Mars-van Krevelen pathway, in which Co₃O₄-CeO₂ acts as an oxygen reservoir enabling the redox cycling of RhO_x species. This study highlights the ability of mixed metal oxide catalysts to exploit interfacial effects to achieve improved activity in redox-mediated reactions and offers a rationale for the engineering of metal oxide-metal oxide catalysts guided by operando spectroscopy.