Heterointerface of Monodispersed Ultrathin-MnO2@Amorphous Carbon to Attain Durable Lattice Oxygen Redox Chemistry through Creation of Dual Lattice Oxygens

Lattice oxygen (O_L) redox chemistry is a key to alleviating the energy and environmental crisis, but it faces challenges in activating the O_L while ensuring structural stability. We disclosed herein that engineering a heterogeneous interface between ultrathin oxide and amorphous carbon can attain the durable O_L redox chemistry without introducing catalytically impure sites. To this end, we proposed a green strategy to grow ∼3.9 nm-thickness wrinkled δ-MnO₂ nanosheets that are rich in defects and are vertically aligned on amorphous carbon spheres. Experiments and calculations reveal that the electrons can easily migrate from the amorphous carbon to MnO₂ at the δ-MnO₂@C heterointerface. The heterogeneous interfaces can not only regulate the Mn-O bond and create oxygen defects in δ-MnO₂ but also introduce lattice oxygen with varying reactivities. Specifically, the δ-MnO₂@C structure carries more activated lattice oxygen that contributes to the enhanced activity on catalytic oxidation of bioderived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), with a high FDCA formation rate of 1759 μmol gcat^-1 h^-1 and a high selectivity of 95%. The heterogeneous interface of MnO₂@C also brings inert lattice oxygen, so that it manifests high structural stability during the oxidation reactions. This work deepens the fundamental understandings in the engineering of lattice oxygen for durable lattice oxygen redox chemistry and showcases an effective interface technique in creating advanced catalysts for clean sustainable energy.