Anupam Bera, Ratnadip De, Heiner Schmidt, Desirée Leistenschneider, Turkan Gamze Ulusoy Ghobadi, Martin Oschatz, Ferdi Karadaş, Benjamin Dietzek-Ivanšić
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Structural and compositional changes of the Prussian blue layer during electrochemical oxidation are studied by monitoring the stretching vibration of the CN group. At open circuit potential, VSFG reveals a non-homogeneous distribution of oxidation states of metal sites: Fe<sup>III</sup>–CN–Co<sup>II</sup> and Fe<sup>II</sup>–CN–Co<sup>III</sup> coordination motifs are dominantly observed at the Co-PBA|TiO<sub>2</sub> interface, while it is only the Fe<sup>II</sup>–CN–Co<sup>II</sup> unit at the electrolyte interface. Upon increasing the potential applied to the electrode, the partial oxidation of Fe<sup>II</sup>–CN–Co<sup>II</sup> to Fe<sup>III</sup>–CN–Co<sup>II</sup> is observed followed by its transformation to Fe<sup>II</sup>–CN–Co<sup>III</sup> via charge transfer and, finally, the formation of Fe<sup>III</sup>–CN–Co<sup>III</sup> species at the interface with TiO<sub>2</sub> and the electrolyte.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202400009","citationCount":"0","resultStr":"{\"title\":\"Probing the Interfacial Molecular Structure of a Co-Prussian Blue In Situ\",\"authors\":\"Anupam Bera, Ratnadip De, Heiner Schmidt, Desirée Leistenschneider, Turkan Gamze Ulusoy Ghobadi, Martin Oschatz, Ferdi Karadaş, Benjamin Dietzek-Ivanšić\",\"doi\":\"10.1002/admi.202400009\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Molecular-level insight into the interfacial composition of electrodes at the solid-electrolyte and the solid-electrode interface is essential to understanding the charge transfer processes, which are vital for electrochemical (EC) and photoelectrochemical (PEC) applications. However, spectroscopic access to both interfaces, particularly upon application of an external bias, remains a challenge. Here, in situ surface sensitive vibrational sum-frequency generation (VSFG) spectroscopy is used for the first time to directly access the interfacial structure of a cobalt-containing Prussian blue analog (Co-PBA) in contact with the electrolyte and TiO<sub>2</sub>/Au surface. Structural and compositional changes of the Prussian blue layer during electrochemical oxidation are studied by monitoring the stretching vibration of the CN group. At open circuit potential, VSFG reveals a non-homogeneous distribution of oxidation states of metal sites: Fe<sup>III</sup>–CN–Co<sup>II</sup> and Fe<sup>II</sup>–CN–Co<sup>III</sup> coordination motifs are dominantly observed at the Co-PBA|TiO<sub>2</sub> interface, while it is only the Fe<sup>II</sup>–CN–Co<sup>II</sup> unit at the electrolyte interface. Upon increasing the potential applied to the electrode, the partial oxidation of Fe<sup>II</sup>–CN–Co<sup>II</sup> to Fe<sup>III</sup>–CN–Co<sup>II</sup> is observed followed by its transformation to Fe<sup>II</sup>–CN–Co<sup>III</sup> via charge transfer and, finally, the formation of Fe<sup>III</sup>–CN–Co<sup>III</sup> species at the interface with TiO<sub>2</sub> and the electrolyte.</p>\",\"PeriodicalId\":115,\"journal\":{\"name\":\"Advanced Materials Interfaces\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-04-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202400009\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Materials Interfaces\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/admi.202400009\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Materials Interfaces","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/admi.202400009","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Probing the Interfacial Molecular Structure of a Co-Prussian Blue In Situ
Molecular-level insight into the interfacial composition of electrodes at the solid-electrolyte and the solid-electrode interface is essential to understanding the charge transfer processes, which are vital for electrochemical (EC) and photoelectrochemical (PEC) applications. However, spectroscopic access to both interfaces, particularly upon application of an external bias, remains a challenge. Here, in situ surface sensitive vibrational sum-frequency generation (VSFG) spectroscopy is used for the first time to directly access the interfacial structure of a cobalt-containing Prussian blue analog (Co-PBA) in contact with the electrolyte and TiO2/Au surface. Structural and compositional changes of the Prussian blue layer during electrochemical oxidation are studied by monitoring the stretching vibration of the CN group. At open circuit potential, VSFG reveals a non-homogeneous distribution of oxidation states of metal sites: FeIII–CN–CoII and FeII–CN–CoIII coordination motifs are dominantly observed at the Co-PBA|TiO2 interface, while it is only the FeII–CN–CoII unit at the electrolyte interface. Upon increasing the potential applied to the electrode, the partial oxidation of FeII–CN–CoII to FeIII–CN–CoII is observed followed by its transformation to FeII–CN–CoIII via charge transfer and, finally, the formation of FeIII–CN–CoIII species at the interface with TiO2 and the electrolyte.
期刊介绍:
Advanced Materials Interfaces publishes top-level research on interface technologies and effects. Considering any interface formed between solids, liquids, and gases, the journal ensures an interdisciplinary blend of physics, chemistry, materials science, and life sciences. Advanced Materials Interfaces was launched in 2014 and received an Impact Factor of 4.834 in 2018.
The scope of Advanced Materials Interfaces is dedicated to interfaces and surfaces that play an essential role in virtually all materials and devices. Physics, chemistry, materials science and life sciences blend to encourage new, cross-pollinating ideas, which will drive forward our understanding of the processes at the interface.
Advanced Materials Interfaces covers all topics in interface-related research:
Oil / water separation,
Applications of nanostructured materials,
2D materials and heterostructures,
Surfaces and interfaces in organic electronic devices,
Catalysis and membranes,
Self-assembly and nanopatterned surfaces,
Composite and coating materials,
Biointerfaces for technical and medical applications.
Advanced Materials Interfaces provides a forum for topics on surface and interface science with a wide choice of formats: Reviews, Full Papers, and Communications, as well as Progress Reports and Research News.