Lattice Nitrogen-Mediated Amination via an N₂-Rechargeable Cycle over the Co-Mo Nitride

Harnessing lattice nitrogen for the direct conversion of dinitrogen (N₂) into organonitrogen compounds remains a grand challenge in heterogeneous catalysis. Herein, we report a nitride-mediated looping strategy for alcohol amination, enabled by a Co-Mo bimetallic nitride operating as a rechargeable nitrogen carrier. The nitrogen carrier interacts with alcohol substrates to generate amines, followed by regeneration in a N₂/H₂ atmosphere to achieve a rechargeable cycle. Using 1-octanol as the substrate to produce trioctylamine (TOA), this process enables stable amine production of 42.2 μmolTOA·g_carrier^-1 at 250 °C and 10 bar H₂ for 5 cycles. Electron microscopy and spectroscopy studies demonstrate that lattice N release occurs within nanoscale regions over the Co-Mo nitride surface, while the bulk structure remains stable. This unique quasi-topological flexible structural transition concurrently attains reaction and regeneration capabilities, facilitating easy turnover of N-related species. Kinetic analysis indicates that the nucleophilic attack of lattice N on aldehyde intermediates constitutes the rate-determining step. The TOA exhibits a product-assisted promotion effect, modulating the electronic structure of the nitride surface to promote the lattice N reactivity and desorption of the amine product. This work provides an approach for the N₂ activation and conversion to valuable organic N-containing compounds via the Co-Mo bimetallic nitride.