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Oxidative dissolution of synthetic vivianites as a method for the crystallization of molecular structural motifs

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Abstract

Isolation of structural motifs from minerals can be used to improve the understanding of fundamental processes such as catalytic mechanisms and spectroscopic vibrations. In this study, we designed an oxidative dissolution reaction using 2,2′-bipyridine in combination with minerals from the vivianite family. Vivianites are structurally similar to amorphous cobalt oxide water oxidation catalysts (CoCat). Specifically, we used pakhomovskyite (Pak: Co3(PO4)2•8H2O) and erythrite (Ery: Co3(AsO4)2•8H2O)). Through the designed synthetic route, we crystallized two mononuclear isostructural complexes containing phosphate or arsenate and a cobalt-arsenate trinuclear cluster. We observed three main binding modes from the anions: (i) both arsenates or phosphates bind to cobalt forming an O-μ2-bridge, (ii) arsenate forms a bridge between two cobalt atoms, and (iii) arsenate binds between three cobalt atoms expanding its coordination sphere to five. This structural information allows us to propose an updated structural model for amorphous cobalt oxide catalysts containing arsenate.

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Acknowledgments

We thank Dr. Leslie W. Pineda for data collection and Dr. Mauricio Gutiérrez and Ravyn Malatesta for productive discussion.

Funding

This work was funded by Vicerrectoría de Investigación (UCR).

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Authors and Affiliations

  1. Centro de Investigación en Ciencia e Ingeniería de Materiales (CICIMA), Universidad de Costa Rica San José, San Pedro, San José, 11501 2060, Costa Rica

    Esteban Rojas-Gatjens, Christian Viales-Montero, Roberto Urcuyo, Diego González-Flores & Mavis L. Montero

  2. Centro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica San José, San Pedro, San José, 11501 2060, Costa Rica

    Esteban Rojas-Gatjens, Roberto Urcuyo & Diego González-Flores

  3. Escuela de Química, Universidad de Costa Rica San José, San Pedro, San José, 11501 2060, Costa Rica

    Esteban Rojas-Gatjens, Christian Viales-Montero, Roberto Urcuyo, Diego González-Flores & Mavis L. Montero

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  1. Esteban Rojas-Gatjens
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  2. Christian Viales-Montero
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Correspondence to Mavis L. Montero.

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Rojas-Gatjens, E., Viales-Montero, C., Urcuyo, R. et al. Oxidative dissolution of synthetic vivianites as a method for the crystallization of molecular structural motifs. Struct Chem 32, 445–455 (2021). https://doi.org/10.1007/s11224-020-01644-3

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