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Nucleation Mechanisms and Speciation of Metal Oxide Clusters

preprint
submitted on 10.07.2020 and posted on 13.07.2020 by Enric Petrus, Mireia Segado, Carles Bo

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 2.8·105 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.

Funding

2017SGR00290

CTQ2017-88777-R

History

Email Address of Submitting Author

cbo@iciq.cat

Institution

Institute of Chemical Research of Catalonia, ICIQ

Country

Spain

ORCID For Submitting Author

0000-0001-9581-2922

Declaration of Conflict of Interest

No conflict of interest

Version Notes

version submitted under reviewing

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in Chemical Science

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