In situ uncovering the catalytic cycle of electrochemical and chemical oxygen reduction mediated by iron porphyrin

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

As one of the critical reactions in biotransformation and energy conversion processes, oxygen reduction reaction (ORR) catalyzed by iron porphyrins has been widely explored electrochemical, spectroscopic, theoretical methods. However, experimental identification all proposed intermediates catalytic cycle is rather challenging mechanistic studies ORR driven electrochemical or chemical Herein, we report application mass spectrometry (EC-MS) (CR-MS) to situ uncover ORRs mediated an porphyrin molecular catalyst. Five crucial iron-oxygen detected both EC-MS CR-MS help build whole indicate details 4e-/4H+ pathway produce H2O ORRs. By combining MS methods with spectroscopic characterize study selectivities, this work provides a comparison model porphyrin.

Language: Английский

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Enhancing oxygen evolution over a highly fluorinated porphyrin-based COF covalently anchored on graphene oxide

Applied Surface Science, Journal Year: 2025, Volume and Issue: unknown, P. 163089 - 163089

Published: March 1, 2025

Language: Английский

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Oxygen Reduction Intermediates‐Mediated Electron Transport in Single‐Molecule Junctions

Small, Journal Year: 2025, Volume and Issue: unknown

Published: May 30, 2025

Abstract Single‐molecule electrical measurements have recently emerged as a unique platform for exploring single‐molecule physical chemistry and reaction processes. Herein, the electrochemical technique has been first oxygen reduction (ORR) in junctions of iron porphyrins modified with pyridine groups (Fe‐TPyP). conductance O 2 ‐saturated solutions clearly show that FeTPyP binds to form ferric‐superoxide porphyrin complex ((Fe‐O • − )‐TPyP) intermediate molecular junctions. This is further supported by observed evidence Fe─O FeO─O stretching vibrations (Fe‐O )‐TPyP during situ Raman ex electron paramagnetic resonance (EPR) experiments. DFT calculations also reveal potential determining step ORR protonation )‐TPyP, resulting highest probability forming Au‐(Fe‐O )‐TPyP‐Au process. work reveals impact on transport provides new way explore electrocatalytic processes catalysts at level using break junction method.

Language: Английский

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分子电催化：金属卟啉催化析氢、析氧和氧还原反应研究

Chinese Science Bulletin (Chinese Version), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

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