Modulation of Co spin state at Co₃O₄ crystalline-amorphous interfaces for CO oxidation and N₂O decomposition.

Abstract

Modulation of electronic spin states in cobalt-based catalysts is an effective strategy for molecule activations. Crystalline-amorphous interfaces often exhibit unique catalytic properties due to disruptions of long-range order and alterations in electronic structure. However, the mechanisms of molecule activation and spin states at interfaces remain elusive. Herein, we present a Co₃O₄ spinel-based catalyst featuring crystalline-amorphous interfaces. Characterization analyses confirm that tetrahedral Co²⁺ is selectively etched from bulk spinel, forming amorphous CoO islands on the surface. The resultant symmetry breaking in the coordination field induces a reconstruction of the Co³⁺ 3 d orbitals, leading to high-spin states. In CO oxidation, the interface serves as novel active sites with a lower energy barrier, facilitated by lattice oxygen activation. In N₂O decomposition, the interface promotes reassociation of dissociated oxygen through quantum spin exchange interactions. This work provides a straightforward approach to modulating the spin state of interfaces and elucidates their role in molecule activations.