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Rapid removal of fluoride from water using core@shell and @shell nanoparticles of SiO2@ZrO2 and @ZrO2. Investigation of the mechanisms involved and impact of elemental leaching

Authors: Iván Maisuls; Yolanda Castro; Alicia Durán; Dominic Larivière; Pablo M. Arnal;

Rapid removal of fluoride from water using core@shell and @shell nanoparticles of SiO2@ZrO2 and @ZrO2. Investigation of the mechanisms involved and impact of elemental leaching

Abstract

[ES] El fluoruro es un contaminante natural del agua, el cual pone en peligro a muchas personas en todo el mundo cuando está presente en concentraciones superiores a 2 ppm. Aquí, la eliminación de fluoruro por cuatro partículas coloidales nanoestructuradas diferentes (SiO2@ZrO2nc, SiO2@ZrO2c, @ZrO2nc y @ZrO2c) se midió en sistemas estancos en un período de 24 h. Sorprendentemente, estos materiales eliminaron el fluoruro de las soluciones acuosas y alcanzaron el equilibrio en menos de 10 minutos. La combinación de una superficie específica alta y una rápida eliminación de fluoruro colocó a estos materiales entre los mejores actualmente conocidos en la eliminación de fluoruro. Además, se midió y cuantificó el impacto de la lixiviación de elementos. La influencia del tiempo, el pH y la concentración de fluoruro en la lixiviación de Zr y Si se evaluó con una metodología de superficie de respuesta. La lixiviación de Zr y Si continuó durante varias horas y dependió de coeficientes de primer orden, cuadráticos y de productos cruzados. Los estudios previos de eliminación de fluoruro con óxido de circonio a menudo asumían que una disminución en la concentración de fluoruro en la solución indicaba que el fluoruro estaba unido a la superficie del óxido. La solubilidad del óxido de circonio en agua es baja, pero no nula. Por tanto, Zr podría haber formado complejos fluorados solubles. Este es el primer reporte de eliminación de fluoruro con óxido de circonio que estudió la lixiviación del sólido para excluir la formación de fluorocomplejos solubles.

[EN] Fluoride is a natural contaminant of water – that endangers many people worldwide when present in concentrations higher than 2 ppm. Here, fluoride removal by four different nanostructured colloidal particles (SiO2@ZrO2nc, SiO2@ZrO2c, @ZrO2nc, and @ZrO2c) was measured in batch systems within a period of 24 h. Surprisingly, these materials removed fluoride from the water solutions and reached equilibrium in less than 10 min. The combination of high specific surface and fast fluoride removal placed these materials among the top materials currently known in fluoride removal. Also, the impact of element leaching was measured and quantified. The influence of time, pH, and fluoride concentration on leaching of Zr and Si was evaluated with a response surface methodology. Leaching of Zr and Si continued for several hours and depended on first-order, quadratic and cross-product coefficients. Previous studies of fluoride removal with zirconium oxide often assumed that a decrease in fluoride concentration in the solution indicated that fluoride was bound to the surface of the oxide. Zirconium oxide's solubility in water is low, but not zero. Hence, Zr might have formed soluble fluorocomplexes. This is the first report of fluoride removal with zirconium oxide that studied the leaching of the solid to exclude the formation of soluble fluorocomplexes.

This study was partially supported by CONICET (PIP-2013-0105) and PICT-2014-2583, and by Comisión de Investigaciones Científicas de la Provincia de Buenos Aires (fellowship for undergraduate students for Iván Maisuls). Authors thank Dr. Pablo Lebed for performing leaching experiments.

Appendix A. Supplementary data

Peer reviewed

Countries
Argentina, Spain
Keywords

Clay industries. Ceramics. Glass, LEACHING, Core@shell, fluorocomplex, Eliminación de fluoruro del agua, @cáscara, CORE@SHELL, Sílice, https://purl.org/becyt/ford/1.4, @SHELL, ZIRCONIUM OXIDE, Zirconium oxide, SILICA, https://purl.org/becyt/ford/1, Lixiviación fluorocomplejo, Lixiviación, RSM, Óxido de circonio, FLUOROCOMPLEX, Silica, @shell, FLUORIDE REMOVAL FROM WATER, Fluorocomplejo, TP785-869, Carcaza del núcleo, Leaching, Fluoride removal from water

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