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Raman spectroscopic study of anhydrous and hydrous REE phosphates, oxides, and hydroxides

Authors

Hurtig,  Nicole C.
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Gysi,  Alexander P.
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Smith-Schmitz,  Sarah E.
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/persons/resource/dharlov

Harlov,  D. E.
3.6 Chemistry and Physics of Earth Materials, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

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Citation

Hurtig, N. C., Gysi, A. P., Smith-Schmitz, S. E., Harlov, D. E. (2024): Raman spectroscopic study of anhydrous and hydrous REE phosphates, oxides, and hydroxides. - Dalton Transactions, 53, 23, 9964-9978.
https://doi.org/10.1039/D4DT01086H


Cite as: https://gfzpublic.gfz-potsdam.de/pubman/item/item_5026288
Abstract
Rare earth elements (REE) include the lanthanides (La–Lu), Y, and Sc which are critical elements for the green energy transition. The REE show a decrease in ionic radii with increased atomic numbers, which results in a so-called lanthanide contraction systematically affecting crystal structures and mineral properties. Here we present a compilation of reference Raman spectra of ten REE sesquioxides (A-, B- and C-type), five REE hydroxides, eight xenotime-structured REE phosphate endmembers and two solid solutions, seven monazite-structured REE phosphate endmembers and two solid solutions and seven rhabdophane endmembers with up to five Ce1−xLREEx rhabdophane solid solutions (LREE = La–Gd). Raman mode assignment is based on a detailed literature review summarizing existing analytical work and theoretical calculations and systematic trends observed in this study by analyzing different REE-bearing solids. The wavenumbers of the main REE-O Raman band systematically increase with decreasing ionic radii forming discrete linear trends within isostructural mineral groups, that can be used to estimate the REE-O mode in other solids with known REE-O coordination numbers. Photoluminescence using 266 nm, 532 nm and 633 nm excitation laser wavelengths for REE-bearing oxides, hydroxides, anhydrous and hydrous phosphates is also presented providing a new framework for identifying REE-phases in phosphate-bearing natural mineral deposits.