Anchoring Ultrafine β‐Mo₂C Clusters Inside Porous Co‐NC Using MOFs for Electric‐Powered Coproduction of Valuable Chemicals

Abstract Electroredox of organics provides a promising and green approach to producing value‐added chemicals. However, it remains a grand challenge to achieve high selectivity of desired products simultaneously at two electrodes, especially for non‐isoelectronic transfer reactions. Here a porous heterostructure of Mo₂C@Co‐NC is successfully fabricated, where subnanometre β‐Mo₂C clusters (<1 nm, ≈10 wt%) are confined inside porous Co, N‐doped carbon using metalorganic frameworks. It is found that Co species not only promote the formation of β‐Mo₂C but also can prevent it from oxidation by constructing the heterojunctions. As noted, the heterostructure achieves >96% yield and 92% Faradaic efficiency (FE) for aldehydes in anodic alcohol oxidation, as well as >99.9% yield and 96% FE for amines in cathodal nitrocompounds reduction in 1.0 M KOH. Precise control of the reaction kinetics of two half‐reactions by the electronic interaction between β‐Mo₂C and Co is a crucial adjective. Density functional theory (DFT) gives in‐depth mechanistic insight into the high aldehyde selectivity. The work guides authors to reveal the electrooxidation nature of Mo₂C at a subnanometer level. It is anticipated that the strategy will provide new insights into the design of highly effective bifunctional electrocatalysts for the coproduction of more complex fine chemicals.