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Nucleation mechanisms and speciation of metal oxide clusters

The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. We present a new computational methodology that identifies the reaction mechanism for the formation of metal-oxide clus...

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Detalles Bibliográficos
Autores principales: Petrus, Enric, Segado, Mireia, Bo, Carles
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8163382/
https://www.ncbi.nlm.nih.gov/pubmed/34123104
http://dx.doi.org/10.1039/d0sc03530k
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author Petrus, Enric
Segado, Mireia
Bo, Carles
author_facet Petrus, Enric
Segado, Mireia
Bo, Carles
author_sort Petrus, Enric
collection PubMed
description The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. We present a new computational methodology that identifies the reaction mechanism for the formation of metal-oxide clusters and provides a speciation model from first-principles and in an automated manner. As a first example, we apply our method to the formation of octamolybdate. In our model, we include variables such as pH, temperature and ionic force because they have a determining effect on driving the reaction to a specific product. Making use of graphs, we set up and solved 2.8 × 10(5) multi-species chemical equilibrium (MSCE) non-linear equations and found which set of reactions fitted best with the experimental data available. The agreement between computed and experimental speciation diagrams is excellent. Furthermore, we discovered a strong linear dependence between DFT and empirical formation constants, which opens the door for a systematic rescaling.
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spelling pubmed-81633822021-06-11 Nucleation mechanisms and speciation of metal oxide clusters Petrus, Enric Segado, Mireia Bo, Carles Chem Sci Chemistry The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. We present a new computational methodology that identifies the reaction mechanism for the formation of metal-oxide clusters and provides a speciation model from first-principles and in an automated manner. As a first example, we apply our method to the formation of octamolybdate. In our model, we include variables such as pH, temperature and ionic force because they have a determining effect on driving the reaction to a specific product. Making use of graphs, we set up and solved 2.8 × 10(5) multi-species chemical equilibrium (MSCE) non-linear equations and found which set of reactions fitted best with the experimental data available. The agreement between computed and experimental speciation diagrams is excellent. Furthermore, we discovered a strong linear dependence between DFT and empirical formation constants, which opens the door for a systematic rescaling. The Royal Society of Chemistry 2020-08-03 /pmc/articles/PMC8163382/ /pubmed/34123104 http://dx.doi.org/10.1039/d0sc03530k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Petrus, Enric
Segado, Mireia
Bo, Carles
Nucleation mechanisms and speciation of metal oxide clusters
title Nucleation mechanisms and speciation of metal oxide clusters
title_full Nucleation mechanisms and speciation of metal oxide clusters
title_fullStr Nucleation mechanisms and speciation of metal oxide clusters
title_full_unstemmed Nucleation mechanisms and speciation of metal oxide clusters
title_short Nucleation mechanisms and speciation of metal oxide clusters
title_sort nucleation mechanisms and speciation of metal oxide clusters
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8163382/
https://www.ncbi.nlm.nih.gov/pubmed/34123104
http://dx.doi.org/10.1039/d0sc03530k
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