Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction

We present a molecular‐scale investigation of the axial coordination effect of atomic iodine on Fe‐N4 sites in the oxygen reduction reaction (ORR) by electrochemical scanning tunneling microscopy (ECSTM). A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites...

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Veröffentlicht in:Angewandte Chemie International Edition 2025-01, Vol.64 (1), p.e202413673-n/a
Hauptverfasser: Wang, Xiang, Yi, Zhen‐Yu, Wang, Yu‐Qi, Wang, Dong
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Wang, Yu‐Qi
Wang, Dong
description We present a molecular‐scale investigation of the axial coordination effect of atomic iodine on Fe‐N4 sites in the oxygen reduction reaction (ORR) by electrochemical scanning tunneling microscopy (ECSTM). A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites was constructed facilely by the self‐assembly of iron(II) phthalocyanine (FePc) on an I‐modified Au(111) surface. The electrocatalytic activity of FePc for the ORR shows notable enhancement with axial iodine ligands. The modulation of the electronic structure of Fe sites to evoke a higher spin configuration by axial iodine was evidenced. The interaction strength between oxygen‐containing species and active centers becomes weaker due to the presence of iodine ligands, and the reaction is thermodynamically preferable. Furthermore, the reaction dynamics of FePc on I/Au(111) were explicitly determined via in situ ECSTM potential pulse experiments. In contrast, axial atomic iodine was found inefficacious for improving the activity of Co‐N4 sites, and electron rearrangement was found to be marginal, demonstrating that adequate interactions between axial ligands and metal sites for optimizing electronic structures and catalytic behaviors are prerequisites for the impactful role of axial ligands. The axial coordination effect of atomic iodine on Fe‐N4 sites in oxygen reduction reaction is deciphered at the molecular scale. The electronic structure of the 3d orbital of Fe centers and the binding of the reactant/intermediate species on active sites are modulated exquisitely by the adequate interactions between Fe‐N4 moiety and axial iodine, which is determined as an important factor for the improved performance.
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A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites was constructed facilely by the self‐assembly of iron(II) phthalocyanine (FePc) on an I‐modified Au(111) surface. The electrocatalytic activity of FePc for the ORR shows notable enhancement with axial iodine ligands. The modulation of the electronic structure of Fe sites to evoke a higher spin configuration by axial iodine was evidenced. The interaction strength between oxygen‐containing species and active centers becomes weaker due to the presence of iodine ligands, and the reaction is thermodynamically preferable. Furthermore, the reaction dynamics of FePc on I/Au(111) were explicitly determined via in situ ECSTM potential pulse experiments. In contrast, axial atomic iodine was found inefficacious for improving the activity of Co‐N4 sites, and electron rearrangement was found to be marginal, demonstrating that adequate interactions between axial ligands and metal sites for optimizing electronic structures and catalytic behaviors are prerequisites for the impactful role of axial ligands. The axial coordination effect of atomic iodine on Fe‐N4 sites in oxygen reduction reaction is deciphered at the molecular scale. 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A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites was constructed facilely by the self‐assembly of iron(II) phthalocyanine (FePc) on an I‐modified Au(111) surface. The electrocatalytic activity of FePc for the ORR shows notable enhancement with axial iodine ligands. The modulation of the electronic structure of Fe sites to evoke a higher spin configuration by axial iodine was evidenced. The interaction strength between oxygen‐containing species and active centers becomes weaker due to the presence of iodine ligands, and the reaction is thermodynamically preferable. Furthermore, the reaction dynamics of FePc on I/Au(111) were explicitly determined via in situ ECSTM potential pulse experiments. In contrast, axial atomic iodine was found inefficacious for improving the activity of Co‐N4 sites, and electron rearrangement was found to be marginal, demonstrating that adequate interactions between axial ligands and metal sites for optimizing electronic structures and catalytic behaviors are prerequisites for the impactful role of axial ligands. The axial coordination effect of atomic iodine on Fe‐N4 sites in oxygen reduction reaction is deciphered at the molecular scale. 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A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites was constructed facilely by the self‐assembly of iron(II) phthalocyanine (FePc) on an I‐modified Au(111) surface. The electrocatalytic activity of FePc for the ORR shows notable enhancement with axial iodine ligands. The modulation of the electronic structure of Fe sites to evoke a higher spin configuration by axial iodine was evidenced. The interaction strength between oxygen‐containing species and active centers becomes weaker due to the presence of iodine ligands, and the reaction is thermodynamically preferable. Furthermore, the reaction dynamics of FePc on I/Au(111) were explicitly determined via in situ ECSTM potential pulse experiments. In contrast, axial atomic iodine was found inefficacious for improving the activity of Co‐N4 sites, and electron rearrangement was found to be marginal, demonstrating that adequate interactions between axial ligands and metal sites for optimizing electronic structures and catalytic behaviors are prerequisites for the impactful role of axial ligands. The axial coordination effect of atomic iodine on Fe‐N4 sites in oxygen reduction reaction is deciphered at the molecular scale. The electronic structure of the 3d orbital of Fe centers and the binding of the reactant/intermediate species on active sites are modulated exquisitely by the adequate interactions between Fe‐N4 moiety and axial iodine, which is determined as an important factor for the improved performance.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/anie.202413673</doi><tpages>8</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-1649-942X</orcidid></addata></record>
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source Wiley Online Library Journals Frontfile Complete
subjects axial coordination effect
Chemical reduction
Coordination
electrochemical scanning tunneling microscopy
Electrochemistry
Electron spin
Electronic structure
Gold
Iodine
Iron
Ligands
Oxygen
oxygen reduction reaction
Oxygen reduction reactions
Scanning tunneling microscopy
Self-assembly
single-atom catalysis
title Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction
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