Hierarchical Porous Carbon Nitride-Crumpled Nanosheet-Embedded Copper Single Atoms: An Efficient Catalyst for Carbon...

Rational design of metal single-site embedded porous graphitic carbon nitride (P-g-C₃N₄) nanostructures exploiting maximum atom utilization is warranted to enhance the thermal CO oxidation (CO_Ox) reaction. Herein, a facile, green, one-pot, and template-free approach is developed to fabricate the hierarchical porous P-g-C₃N₄-crumpled ultrathin nanosheets atomically doped with copper single atoms (Cu-P-g-C₃N₄). Mechanistically, the quick protonation of melamine and pyridine under acidic conditions induces deamination to form melem, which is polycondensed under heating. The interconnected pores, high surface area (240 m²g^-1), and maximized exposed isolated Cu atomic active sites (1.8 wt %) coordinated with nitrogen atom P-g-C₃N₄ are the salient features of Cu- P-g-C₃N₄ that endowed complete conversion to CO₂ at 184 °C. In contrast, P-g-C₃N₄ only converted 3.8% of CO even at 350 °C, implying the electronic effect of Cu single atoms. The abundant Cu-nitrogen moieties can drastically weaken the binding affinity of the CO-oxidation (CO_Ox) intermediates and products, thus accelerating the reaction kinetics at a low temperature. This study may promote the fabrication of P-g-C₃N₄ doped with various single atoms for the oxidation of CO.