The synthesis of primary amines from renewable biomass and its derivatives through reductive amination has garnered significant attention. How to construct efficient non-noble-metal catalysts that enable low-temperature catalysis still remains challenging. Herein, we report a Cu-doped Co@CoO x heterostructure catalyst that features structural Co-CoCuO x bifunctional sites, which enable room temperature reductive amination of various aldehydes with 1.57-45 times higher efficiency than Co@CoO x , outperforming many reported non-noble and even noble metal catalysts. Experiments and DFT calculations indicate that Cu doping leads to a phase transition of Co from hcp to fcc, while electrons are transferred from Cu to Co, forming a dual active site with electron-rich Co closely interacting with CoCuO x . These electron-rich Co sites demonstrate excellent activity in the activation and dissociation of hydrogen, while the CuO x component facilitates hydrogen spillover at the CoCuO x interface, thus resulting in a highly efficient cooperative effect for the furfural (FAL) reductive amination. This work provides general guidance for the rational design of high-performance reductive amination catalysts for biomass upgrading.
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