Greatly Enhanced Stability of Supported Copper Nanocatalyst with a Thin Nitrogen‐Doped Carbon Overlayer for Transfer Dehydrogenation

Abstract In the present study, we report a facile synthetic approach for supported copper nanocatalysts with a thin nitrogen‐doped carbon (CN) overlayer. This Cu@CN catalyst was directly generated by a thermal decomposition of Cu‐Al layered double hydroxide (CuAl‐LDH)/melamine hybrid precursor, and employed in the liquid‐phase transfer dehydrogenation of primary aliphatic alcohols. The strategy was found to be useful for the formation of a very thin in situ formed CN overlayer of 0.5–0.7 nm in thickness on copper nanoparticles of about 8.5 nm in diameter. Compared with uncoated copper‐based catalyst derived from pristine CuAl‐LDH, as‐fabricated Cu@CN catalyst showed significantly enhanced catalytic activity, which was attributed to the surface cooperative effect among strong Lewis base sites originating from the CN layer, well‐dispersed Cu⁰ nanoparticles and Cu⁺ species, thereby greatly promoting the activation of hydroxyl group in primary aliphatic alcohols and the following abstraction and transfer of hydrogen. Most importantly, the thin CN overlayer could successfully stabilize copper nanoparticles, thus preventing the leaching and the growth of copper species over the course of the reaction. This work offers a new strategy for fabricating cost‐effective, highly efficient and extremely stable supported copper catalysts for the transfer dehydrogenation of primary aliphatic alcohols.