Cu single atoms supported on crystalline graphdiyne porphyrin analogs with dual active sites for enhanced C2 product formation

Developing advanced catalysts for efficient electrochemical CO 2 reduction has long been a sought-after objective, but designing catalysts with open porous structures, metal sites, high atom utilization, nanoporosity, and electrical conductivity, remains challenging. Downsizing metal sites to single atoms and supporting them on conductive Covalent Organic Frameworks (COFs) offers a strategic solution to these challenges. Herein, we report a novel catalyst with a combination of copper single-atom sites supported by a highly crystalline graphdiyne porphyrin analog (Cu-SGPA). Computational analysis reveals the presence of 2.34 nm open pores with conducting π-conjugated graphdiyne linkages. The joint action of the dual active sites of Cu single atoms and the adjacent carbon atoms facilitates carbon product formation through uniquely achieved intermediate species. Cu-SGPA demonstrates a remarkable faradaic efficiency (FE) of 70 % at optimized potentials of −1.0 V vs RHE, with over 45 % FE for C 2 products, surpassing FE for single-atom catalysts supported on COFs. This study introduces a promising catalyst design that will inspire future efforts in developing and optimizing similar single-atom catalysts supported on conductive COFs for enhanced CO 2 utilization. • A novel Cu-SGPA structure with copper single atoms supported on graphdiyne porphyrin analogs was fabricated. • Computational analysis revealed an open porous structure with 2.34 nm pore size and π-conjugated linkages. • Detailed DFT simulations revealed the synergetic action of dual active sites that facilitate C-C bonding. • As a result, Cu-SGPA showed a high performance of 45 % FE for C2 products in CO2R which surpasses other single atoms on COF supports.