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Spatially and Chemically Resolved Visualization of Fe Incorporation into NiO Octahedra during the Oxygen Evolution Reaction

[Image: see text] The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the natur...

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Detalles Bibliográficos
Autores principales: Yang, Fengli, Lopez Luna, Mauricio, Haase, Felix T., Escalera-López, Daniel, Yoon, Aram, Rüscher, Martina, Rettenmaier, Clara, Jeon, Hyo Sang, Ortega, Eduardo, Timoshenko, Janis, Bergmann, Arno, Chee, See Wee, Roldan Cuenya, Beatriz
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10557136/
https://www.ncbi.nlm.nih.gov/pubmed/37726200
http://dx.doi.org/10.1021/jacs.3c07158
Descripción
Sumario:[Image: see text] The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the nature of the catalyst surface under reaction conditions remains unclear. Here, using a combination of electrochemical cell and conventional transmission electron microscopy, we show how the surface of NiO electrocatalysts, with initially well-defined surface facets, restructures under applied potential and forms an active NiFe layered double (oxy)hydroxide (NiFe-LDH) when Fe(3+) ions are present in the electrolyte. Continued OER under these conditions, however, leads to the creation of additional FeO(x) aggregates. Electrochemically, the NiFe-LDH formation correlates with a lower onset potential toward the OER, whereas the formation of the FeO(x) aggregates is accompanied by a gradual decrease in the OER activity. Complementary insight into the catalyst near-surface composition, structure, and chemical state is further extracted using X-ray photoelectron spectroscopy, operando Raman spectroscopy, and operando X-ray absorption spectroscopy together with measurements of Fe uptake by the electrocatalysts using time-resolved inductively coupled plasma mass spectrometry. Notably, we identified that the catalytic deactivation under stationary conditions is linked to the degradation of in situ-created NiFe-LDH. These insights exemplify the complexity of the active state formation and show how its structural and morphological evolution under different applied potentials can be directly linked to the catalyst activation and degradation.