Approach to Chemically Durable Nickel and Cobalt Lanthanum-Nitride-Based Catalysts for Ammonia Synthesis

摘要

Metal nitride complexes have recently been proposed as an efficient noble-metal-free catalyst for ammonia synthesis utilizing a dual active site concept. However, their high sensitivity to air and moisture has restricted potential applications. We report that their chemical sensitivity can be improved by introducing Al into the LaN lattice, thereby forming La-Al metallic bonds (La-Al-N). The catalytic activity and mechanism of the resulting TM/La-Al-N (TM=Ni, Co) are comparable to the previously reported TM/LaN catalyst. Notably, the catalytic activity did not degrade after exposure to air and moisture. Kinetic analysis and isotopic experiment showed that La-Al-N is responsible for N2 absorption and activation despite substantial Al being introduced into its lattice because the local coordination of the lattice N remained largely unchanged. These findings show the effectiveness of metallic bond formation, which can support the chemical stability of rare-earth nitrides with retention of catalytic functionality.