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

Subhajit Bhunia, Armando Peña-Duarte, Huifang Li, Hong Li, Mohamed Fathi Sanad, Pranay Saha, Matthew A. Addicoat, Kotaro Sasaki, T. Amanda Strom, Miguel José Yacamán, Carlos R. Cabrera, Ram Seshadri, Santanu Bhattacharya, Jean Luc Brédas, Luis Echegoyen

Research output: Contribution to journalArticlepeer-review

21 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)3492-3505
Number of pages14
JournalACS Nano
Issue number4
StatePublished - Feb 28 2023


  • alkaline oxygen reduction
  • benzothiadiazole based
  • covalent organic framework
  • donor−acceptor
  • porphyrin-benzothiadiazole
  • porphyrinic framework

ASJC Scopus subject areas

  • General Materials Science
  • General Engineering
  • General Physics and Astronomy


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