Chemical Fixation of CO₂ Using Highly Dispersed Cu on Hierarchically Porous N-Doped Carbon

Chemical transformation of carbon dioxide (CO2) into fine chemicals such as oxazolidinones and carbamates is mainly reported using transition-metal complexes as homogeneous catalysts. Herein, we demonstrate that a heterogeneous catalyst of highly dispersed Cu (Cu/NHPC) supported on hierarchically porous N-doped carbon (NHPC) can efficiently promote CO2 fixations to oxazolidinones and β-oxopropylcarbamates. The obtained NHPC, assembled by ultrathin nitrogen-doped carbon nanosheets with a three-dimensional (3D) structure, is readily prepared by pyrolysis of a nitrogen-containing polymer gel (NPG) in the presence of an activator of potassium bicarbonate (KHCO3). The resulting NHPC shows specific Brunauer–Emmet–Teller (BET) surface areas up to 2054 m2 g–1 with a mean micro/mesopore size of 0.55/3.2 nm and a broad macropore size distribution from 50 to 230 nm. The Cu/NHPC can efficiently promote three-component coupling of CO2, amines, and propargyl alcohols for syntheses of various oxazolidinones and β-oxopropylcarbamates with yields up to 99% and a wide substrate scope. Moreover, the Cu/NHPC exhibits excellent recyclability in CO2-to-oxazolidinone transformation during nine-time recycling. The research thus develops an NHPC-based heterogeneous Cu catalyst for green transformation of CO2.