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3D atomic-scale imaging of mixed Co-Fe spinel oxide nanoparticles during oxygen evolution reaction.

ABSTRACT: The three-dimensional (3D) distribution of individual atoms on the surface of catalyst nanoparticles plays a vital role in their activity and stability. Optimising the performance of electrocatalysts requires atomic-scale information, but it is difficult to obtain. Here, we use atom probe tomography to elucidate the 3D structure of 10 nm sized Co₂FeO₄ and CoFe₂O₄ nanoparticles during oxygen evolution reaction (OER). We reveal nanoscale spinodal decomposition in pristine Co₂FeO₄. The interfaces of Co-rich and Fe-rich nanodomains of Co₂FeO₄ become trapping sites for hydroxyl groups, contributing to a higher OER activity compared to that of CoFe₂O₄. However, the activity of Co₂FeO₄ drops considerably due to concurrent irreversible transformation towards Co^IVO₂ and pronounced Fe dissolution. In contrast, there is negligible elemental redistribution for CoFe₂O₄ after OER, except for surface structural transformation towards (Fe^III, Co^III)₂O₃. Overall, our study provides a unique 3D compositional distribution of mixed Co-Fe spinel oxides, which gives atomic-scale insights into active sites and the deactivation of electrocatalysts during OER.

SUBMITTER: Xiang W

PROVIDER: S-EPMC8748757 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Spinel iron oxide nanoparticles of different mean sizes in the range 10-25 nm have been prepared by surfactant-free up-scalable near- and super-critical hydro-thermal synthesis pathways and characterized using a wide range of advanced structural characterization methods to provide a highly detailed structural description. The atomic structure is examined by combined Rietveld analysis of synchrotron powder X-ray diffraction (PXRD) data and time-of-flight neutron powder-diffraction (NPD) data. The local atomic ordering is further analysed by pair distribution function (PDF) analysis of both X-ray and neutron total-scattering data. It is observed that a non-stoichiometric structural model based on a tetragonal γ-Fe2O3 phase with vacancy ordering in the structure (space group P43212) yields the best fit to the PXRD and total-scattering data. Detailed peak-profile analysis reveals a shorter coherence length for the superstructure, which may be attributed to the vacancy-ordered domains being smaller than the size of the crystallites and/or the presence of anti-phase boundaries, faulting or other disorder effects. The intermediate stoichiometry between that of γ-Fe2O3 and Fe3O4 is confirmed by refinement of the Fe/O stoichiometry in the scattering data and quantitative analysis of Mössbauer spectra. The structural characterization is complemented by nano/micro-structural analysis using transmission electron microscopy (TEM), elemental mapping using scanning TEM, energy-dispersive X-ray spectroscopy and the measurement of macroscopic magnetic properties using vibrating sample magnetometry. Notably, no evidence is found of a Fe3O4/γ-Fe2O3 core-shell nanostructure being present, which had previously been suggested for non-stoichiometric spinel iron oxide nanoparticles. Finally, the study is concluded using the magnetic PDF (mPDF) method to model the neutron total-scattering data and determine the local magnetic ordering and magnetic domain sizes in the iron oxide nanoparticles. The mPDF data analysis reveals ferrimagnetic collinear ordering of the spins in the structure and the magnetic domain sizes to be ∼60-70% of the total nanoparticle sizes. The present study is the first in which mPDF analysis has been applied to magnetic nanoparticles, establishing a successful precedent for future studies of magnetic nanoparticles using this technique.

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3D atomic-scale imaging of mixed Co-Fe spinel oxide nanoparticles during oxygen evolution reaction.

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