Ladder type covalent organic frameworks constructed with natural units for the oxygen and carbon dioxide reduction reactions.

[Display omitted] • The ladder covalent organic frameworks showed high electrocatalytic performance. • The ladder π-conjugation contributed to electronic conductivity. • The natural phenolic molecule improved CO 2 uptakes and reductive capacity. • The theoretical calculation revealed the phenolic molecule enhance the activity. Covalent organic frameworks (COFs) constructed with metallocyclophane units and organic linkers have found application as electrocatalytic systems. Nevertheless, the majority of linkers within COFs necessitate intricate design and synthesis. Conversely, the potential utilization of natural building blocks in COF construction remains largely unexplored. In this study, we constructed a natural COF (CoPc-EA-COF) by employing a natural phenolic molecule (ellagic acid (EA)) as the linker and Co-hexadecafluorophthalocyanine (CoPc) as blocks. This framework serves as an electrocatalyst for both the oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO 2 RR). The incorporation of EA units imparts the CoPc-EA-COF with elevated electronic conductivity, enhanced CO 2 binding affinity, and superior reductive capacity compared to the controlled COF lacking EA units. The CoPc-EA-COF demonstrated enhanced performance in the ORR, as evidenced by a half-wave potential of 0.80 V. Moreover, it showcased elevated activity and selectivity in the CO 2 RR, achieving a maximum CO faradic efficiency of 97.32 % at − 0.8 V, along with turnover frequency (TOF) values reaching 2092 h−1. Theoretical calculations revealed that the presence of EA units facilitated the generation of OOH* and COOH* species, which are pivotal in the rate-determining stages of both ORR and CO 2 RR processes. The contribution of EA units significantly bolstered the overall catalytic activity. [ABSTRACT FROM AUTHOR]