Identifying Highly Active and Selective Cobalt X‐Ides for Electrocatalytic Hydrogenation of Quinoline

Earth-abundant Co X-ides are emerging as promising catalysts for the electrocatalytic hydrogenation of quinoline (ECHQ), yet challenging due to the limited fundamental understanding of ECHQ mechanism on Co X-ides. This work identifies the catalytic performance differences of Co X-ides in ECHQ and provides significant insights into the catalytic mechanism of ECHQ. Among selected Co X-ides, the Co₃O₄ presents the best ECHQ performance with a high conversion of 98.2% and 100% selectivity at ambient conditions. The Co₃O₄ sites present a higher proportion of 2-coordinated hydrogen-bonded water at the interface than other Co X-ides at a low negative potential, which enhances the kinetics of subsequent water dissociation to produce H*. An ideal 1,4/2,3-H* addition pathway on Co₃O₄ surface with a spontaneous desorption of 1,2,3,4-tetrahydroquinoline is demonstrated through operando tracing and theoretical calculations. In comparison, the Co₉S₈ sites display the lowest ECHQ performance due to the high thermodynamic barrier in the H* formation step, which suppresses subsequent hydrogenation; while the ECHQ on Co(OH)F and CoP sites undergo the 1,2,3,4- and 4,3/1,2-H* addition pathway respectively with the high desorption barriers and thus low conversion of quinoline. Moreover, the Co₃O₄ presents a wide substrate scope and allows excellent conversion of other quinoline derivatives and N-heterocyclic substrates.