Cargando…
Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite
Ferrihydrite is a poorly crystalline iron oxyhydroxide nanomineral that serves a critical role as the most bioavailable form of ferric iron for living systems. However, its atomic structure and composition remain unclear due in part to ambiguities in interpretation of X-ray scattering results. Preva...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814694/ https://www.ncbi.nlm.nih.gov/pubmed/36697713 http://dx.doi.org/10.1038/s42004-021-00562-7 |
_version_ | 1784864192806780928 |
---|---|
author | Sassi, Michel Chaka, Anne M. Rosso, Kevin M. |
author_facet | Sassi, Michel Chaka, Anne M. Rosso, Kevin M. |
author_sort | Sassi, Michel |
collection | PubMed |
description | Ferrihydrite is a poorly crystalline iron oxyhydroxide nanomineral that serves a critical role as the most bioavailable form of ferric iron for living systems. However, its atomic structure and composition remain unclear due in part to ambiguities in interpretation of X-ray scattering results. Prevailing models so far have not considered the prospect that at the level of individual nanoparticles multiple X-ray indistinguishable phases could coexist. Using ab initio thermodynamics we show that ferrihydrite is likely a nanocomposite of distinct structure types whose distribution depends on particle size, temperature, and hydration. Nanoparticles of two contrasting single-phase ferrihydrite models of Michel and Manceau are here shown to be thermodynamically equivalent across a wide range of temperature and pressure conditions despite differences in their structural water content. Higher temperature and water pressure favor the formation of the former, while lower temperature and water pressure favor the latter. For aqueous suspensions at ambient conditions, their coexistence is maximal for particle sizes up to 12 nm. The predictions inform and help resolve different observations in various experiments. |
format | Online Article Text |
id | pubmed-9814694 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-98146942023-01-10 Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite Sassi, Michel Chaka, Anne M. Rosso, Kevin M. Commun Chem Article Ferrihydrite is a poorly crystalline iron oxyhydroxide nanomineral that serves a critical role as the most bioavailable form of ferric iron for living systems. However, its atomic structure and composition remain unclear due in part to ambiguities in interpretation of X-ray scattering results. Prevailing models so far have not considered the prospect that at the level of individual nanoparticles multiple X-ray indistinguishable phases could coexist. Using ab initio thermodynamics we show that ferrihydrite is likely a nanocomposite of distinct structure types whose distribution depends on particle size, temperature, and hydration. Nanoparticles of two contrasting single-phase ferrihydrite models of Michel and Manceau are here shown to be thermodynamically equivalent across a wide range of temperature and pressure conditions despite differences in their structural water content. Higher temperature and water pressure favor the formation of the former, while lower temperature and water pressure favor the latter. For aqueous suspensions at ambient conditions, their coexistence is maximal for particle sizes up to 12 nm. The predictions inform and help resolve different observations in various experiments. Nature Publishing Group UK 2021-09-20 /pmc/articles/PMC9814694/ /pubmed/36697713 http://dx.doi.org/10.1038/s42004-021-00562-7 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Sassi, Michel Chaka, Anne M. Rosso, Kevin M. Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title | Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title_full | Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title_fullStr | Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title_full_unstemmed | Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title_short | Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
title_sort | ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814694/ https://www.ncbi.nlm.nih.gov/pubmed/36697713 http://dx.doi.org/10.1038/s42004-021-00562-7 |
work_keys_str_mv | AT sassimichel abinitiothermodynamicsrevealsthenanocompositestructureofferrihydrite AT chakaannem abinitiothermodynamicsrevealsthenanocompositestructureofferrihydrite AT rossokevinm abinitiothermodynamicsrevealsthenanocompositestructureofferrihydrite |