Graphene Chainmail Shelled Dilute Ni─Cu Alloy for Selective and Robust Aqueous Phase Catalytic Hydrogenation

Abstract Cost‐effective non‐noble metal‐based catalysts for selective hydrogenation with excellent activity, selectivity, and durability are still the holy grail. Herein, an oxygen‐doped carbon (OC) chainmail encapsulated dilute Cu–Ni alloy is developed by simple pyrolysis of Cu/Ni‐metal–organic framework. The CuNi 0.05 @OC catalyst displays superior performance for atmospheric pressure transfer hydrogenation of p ‐chloronitrobenzene and p ‐nitrophenol, and for hydrogenation of furfural, all in water and with exceptional durability. Comprehensive characterizations confirm the close interactions between the diluted Ni sites, the base Cu, and optimized three‐layered graphene chainmail. Theoretical calculations demonstrate that the properly tuned lattice strain and Schottky junction can adjust electron density to facilitate specific adsorption on the active centers, thus enhancing the catalytic activity and selectivity, while the OC shell also offers robust protection. This work provides a simple and environmentally friendly strategy for developing practical heterogeneous catalysts that bring the synergistic effect into play between dilute alloy and functional carbon wrapping.