Revealing Significant Electronic Effects on the Oxygen Reduction Reaction with Iron Porphyrins
Understanding electronic effects on catalysis from a mechanism point of view is of fundamental significance but is also challenging. We herein report on electronic effects on the oxygen reduction reaction (ORR) with Fe porphyrins. By using Fe<sup>III</sup> tetraphenylporphyrin (TPP-Fe) and Fe<sup>III</sup> tetra(pentafluorophenyl)porphyrin (TPFP-Fe), we showed their different electrochemical and chemical behaviors for ORR. Mechanism studies revealed that the Fe<sup>III</sup>-superoxo species of TPP-Fe can undergo smooth protonation with trifluoroacetic acid (TFA) but the electron-deficient Fe<sup>III</sup>-superoxo species of TPFP-Fe cannot be protonated with TFA. The Fe<sup>III</sup>-superoxo reactivity difference between TPP-Fe and TPFP-Fe is the origin of their different catalytic ORR behaviors.
Authors
- Rui Cao (ORCID: https://orcid.org/0000-0002-1821-9583)
- Haonan Qin (ORCID: https://orcid.org/0000-0002-1272-858X)
- Haitao Lei (ORCID: https://orcid.org/0000-0003-2572-6011)
- Jiafan Kong (ORCID: https://orcid.org/0009-0006-0647-6503)
- Zhimeng Wang
- Xinyang Peng
- Xialiang Li
- Wei Zhang (ORCID: https://orcid.org/0000-0003-4813-211X)
Institutions
- Shaanxi Normal University (CN)
Publication Details
- Journal
- ChemSusChem
- Published
- 2024-08-30
- DOI
- https://doi.org/10.1002/cssc.202401739
- Citations
- 18
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 1.84
Funders
- National Natural Science Foundation of China
- Shaanxi Normal University
- Fundamental Research Funds for the Central Universities