Terminal Amines, Nitriles, and Olefins through Catalytic CO Hydrogenation in the Presence of Ammonia

We report on the "one step-one pot" synthesis of chain-lengthened aliphatic amines and nitriles from CO/H-2/NH3 gas feeds using potassium-promoted Co/MnOx catalysts prepared via MOF-type (metal organic framework) mixed-metal Co-Mn oxalates. We show that the reaction can be tuned via adjustments of the H-2/ CO ratio so as to favor the production of either terminal amines or nitriles. Besides regioselective nitrogen functionalization, ammonia addition to CO/H-2 strongly favors chain-lengthened olefin formation at the expense of alkanes. Linear Anderson-Schulz-Flory behavior, independent of the H-2/CO ratio, is found for the sum of C4+ nitrogen-containing compounds and olefins but not for alkanes. X-ray diffraction reveals Co to Co2C bulk reconstruction to occur for CO/H-2 feeds in either the presence or absence of ammonia. X-ray photoelectron spectroscopy provides evidence for nitrogen to modify the near-surface composition by forming Co-C-N chemical structures.