Lattice Nitrogen-Mediated Amination via an N ₂ -Rechargeable Cycle over the Co–Mo Nitride

Harnessing lattice nitrogen for the direct conversion of dinitrogen (N 2 ) 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 N 2 /H 2 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 H 2 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 N 2 activation and conversion to valuable organic N -containing compounds via the Co–Mo bimetallic nitride.