[2,1,3]-Benzothiadiazole-Spaced Co-Porphyrin-Based Covalent Organic Frameworks for O₂ Reduction

Designing N-coordinated porous single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) is a promising approach to achieve enhanced energy conversion due to maximized atom utilization and higher activity. Here, we report two Co(II)-porphyrin/ [2,1,3]-benzothiadiazole (BTD)-based covalent organic frameworks (COFs; Co@rhm-PorBTD and Co@sql-PorBTD), which are efficient SAC systems for O₂ electrocatalysis (ORR). Experimental results demonstrate that these two COFs outperform the mass activity (at 0.85 V) of commercial Pt/C (20%) by 5.8 times (Co@rhm-PorBTD) and 1.3 times (Co@sql-PorBTD), respectively. The specific activities of Co@rhm-PorBTD and Co@sql-PorBTD were found to be 10 times and 2.5 times larger than that of Pt/C, respectively. These COFs also exhibit larger power density and recycling stability in Zn-air batteries compared with a Pt/C-based air cathode. A theoretical analysis demonstrates that the combination of Co-porphyrin with two different BTD ligands affords two crystalline porous electrocatalysts having different d-band center positions, which leads to reactivity differences toward alkaline ORR. The strategy, design, and electrochemical performance of these two COFs offer a pyrolysis-free bottom-up approach that avoids the creation of random atomic sites, significant metal aggregation, or unpredictable structural features.