Amino-Modified Copper Catalysts with Dual Geometric–Electronic Regulation for the Mild and Efficient Hydrogenation of Oxalates to Ethanol

The conventional process for producing ethanol through hydrogenation of diethyl oxalate (DEO) derived from coal-based synthesis gas requires operation under severe reaction conditions, including high temperatures, high pressures, and high H 2 /DEO ratios. This results in substantial energy consumption and necessitates the use of high-cost equipment, hindering the industrialization of this hydrogenation process. This study achieved dual electronic and structural regulation of copper-based catalysts through amine modification. This enhanced interactions between copper species and the functionalized support, strengthened metal-amine coordination, and significantly improved hydrogen adsorption. Consequently, the Cu sites became both conducive to H 2 activation and resistant to deactivation, enabling highly efficient and stable hydrogenation reactions. Compared to other copper–ammonia catalysts, this catalyst achieves deep hydrogenation of DEO to ethanol under mild conditions (low temperature─the lowest reported─and low H 2 /DEO molar ratio), enabling near-complete conversion of DEO while maintaining high selectivity for ethanol, and shows no significant deactivation after 260 h of continuous reaction. Furthermore, the catalyst demonstrated exceptional performance in the hydrogenation of other substrates containing C–O bonds, providing a novel strategy for designing efficient catalysts for broad C–O bond hydrogenation processes.