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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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. |
doi_str_mv | 10.1002/anie.202413673 |
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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.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>ISSN: 1521-3773</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202413673</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>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</subject><ispartof>Angewandte Chemie International Edition, 2025-01, Vol.64 (1), p.e202413673-n/a</ispartof><rights>2024 Wiley-VCH GmbH</rights><rights>2025 Wiley-VCH GmbH</rights><rights>2024 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-1649-942X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202413673$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202413673$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids></links><search><creatorcontrib>Wang, Xiang</creatorcontrib><creatorcontrib>Yi, Zhen‐Yu</creatorcontrib><creatorcontrib>Wang, Yu‐Qi</creatorcontrib><creatorcontrib>Wang, Dong</creatorcontrib><title>Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction</title><title>Angewandte Chemie International Edition</title><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.</description><subject>axial coordination effect</subject><subject>Chemical reduction</subject><subject>Coordination</subject><subject>electrochemical scanning tunneling microscopy</subject><subject>Electrochemistry</subject><subject>Electron spin</subject><subject>Electronic structure</subject><subject>Gold</subject><subject>Iodine</subject><subject>Iron</subject><subject>Ligands</subject><subject>Oxygen</subject><subject>oxygen reduction reaction</subject><subject>Oxygen reduction reactions</subject><subject>Scanning tunneling microscopy</subject><subject>Self-assembly</subject><subject>single-atom catalysis</subject><issn>1433-7851</issn><issn>1521-3773</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2025</creationdate><recordtype>article</recordtype><recordid>eNpdkctOAjEUhhujiYhuXTdx42awnXYuXU7IoCQICeq6Ke0ZLRmmOBeFnY_gM_okFjAsXJ3bdy45P0LXlAwoIeGdqiwMQhJyyuKEnaAejUIasCRhp97njAVJGtFzdNE0S8-nKYl7qHl0JeiuVDXOP6yBSgMuXI3bN8DZxqoSD52rja1Ua12F86IA3WJX4Kx1K6vx2PkaYF8awc_X95TjJ9tCg22FZ5vtK1R4DqbT--Y5qL1zic4KVTZw9Wf76GWUPw8fgsnsfjzMJsGaipgFMVcRVUooo40hhsVaK79dRUJzn9bcpJxHsVkwkaSgeaRZIQAWlCgCXHDWR7eHuevavXfQtHJlGw1lqSpwXSMZJREXu8949OYfunRdXfnrPBXRlBFCiafEgfq0JWzlurYrVW8lJXIngNwJII8CyGw6zo8R-wV9o32Q</recordid><startdate>20250102</startdate><enddate>20250102</enddate><creator>Wang, Xiang</creator><creator>Yi, Zhen‐Yu</creator><creator>Wang, Yu‐Qi</creator><creator>Wang, Dong</creator><general>Wiley Subscription Services, Inc</general><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-1649-942X</orcidid></search><sort><creationdate>20250102</creationdate><title>Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction</title><author>Wang, Xiang ; Yi, Zhen‐Yu ; Wang, Yu‐Qi ; Wang, Dong</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p1963-64a51aa9adcdd0d36ccafeca59c4aa9c4d84456db3978ec45c3f9eeb10a0e4943</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2025</creationdate><topic>axial coordination effect</topic><topic>Chemical reduction</topic><topic>Coordination</topic><topic>electrochemical scanning tunneling microscopy</topic><topic>Electrochemistry</topic><topic>Electron spin</topic><topic>Electronic structure</topic><topic>Gold</topic><topic>Iodine</topic><topic>Iron</topic><topic>Ligands</topic><topic>Oxygen</topic><topic>oxygen reduction reaction</topic><topic>Oxygen reduction reactions</topic><topic>Scanning tunneling microscopy</topic><topic>Self-assembly</topic><topic>single-atom catalysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wang, Xiang</creatorcontrib><creatorcontrib>Yi, Zhen‐Yu</creatorcontrib><creatorcontrib>Wang, Yu‐Qi</creatorcontrib><creatorcontrib>Wang, Dong</creatorcontrib><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wang, Xiang</au><au>Yi, Zhen‐Yu</au><au>Wang, Yu‐Qi</au><au>Wang, Dong</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction</atitle><jtitle>Angewandte Chemie International Edition</jtitle><date>2025-01-02</date><risdate>2025</risdate><volume>64</volume><issue>1</issue><spage>e202413673</spage><epage>n/a</epage><pages>e202413673-n/a</pages><issn>1433-7851</issn><issn>1521-3773</issn><eissn>1521-3773</eissn><abstract>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.</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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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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