Issue 35, 2024

Computational insights into aqueous speciation of metal-oxide nanoclusters: an in-depth study of the Keggin phosphomolybdate

Abstract

Herein, we present a new computational methodology that unlocks the prediction of the complex multi-species multi-equilibria processes involved in the formation of complex metal-oxo nanoclusters. Relying on our recently introduced method named POMSimulator, we extended its capabilities and challenged its accuracy with the well-known phosphomolybdate [PMo12O40]3− Keggin anion system. We show how the use of statistical techniques enabled the processing of a vast number of speciation models and their associated systems of non-linear equations efficiently and in a scalable manner. Subsequently, this approach is applied to generate statistically averaged speciation diagrams and their associated error bars. Then, we unveil the previously unreported speciation phase diagram under varying [Mo]/[P] ratios vs. pH. Our findings align well with experimental data, indicating the prevalence of the Keggin {PMo12} as the primary species at low pH, but the lacunary {PMo11}and Strandberg {P2Mo5} anions also emerge as major species at other concentration ratios. Finally, from 7 × 104 speciation models we inferred a plausible reaction network across the diverse nuclearities present within the system, which underlines the role of trimers as key intermediate building blocks.

Graphical abstract: Computational insights into aqueous speciation of metal-oxide nanoclusters: an in-depth study of the Keggin phosphomolybdate

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Article information

Article type
Edge Article
Submitted
20 maj 2024
Accepted
23 jul 2024
First published
27 jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 14218-14227

Computational insights into aqueous speciation of metal-oxide nanoclusters: an in-depth study of the Keggin phosphomolybdate

J. Buils, D. Garay-Ruiz, M. Segado-Centellas, E. Petrus and C. Bo, Chem. Sci., 2024, 15, 14218 DOI: 10.1039/D4SC03282A

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