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Estabilización mediada por redox en nitritos de molibdeno y zinc

Elisabetta Arca¹, Stephan Lany¹, John D Perkins¹

¹National Renewable Energy Laboratory , Golden , Colorado 80401 , United States.

Journal of the American Chemical Society

|March 2, 2018

Resumen

Descubrimos nuevos compuestos de nitruro de molibdeno y zinc, Zn3MoN4 y ZnMoN2, con una estructura única derivada de la wurtcita. Esta "estabilización mediada por redox" permite propiedades optoelectrónicas ajustables, allanando el camino para nuevas aplicaciones de materiales.

Área de la Ciencia:

Ciencias de los materiales
Química del estado sólido
Ciencias de los materiales computacionales

Sus antecedentes:

Los nitritos ternales son cruciales para las aplicaciones de materiales avanzados.
La comprensión de las relaciones estructura-propiedad en nuevos compuestos es esencial.
Los sistemas de zinc-molibdeno-nitrógeno (Zn-Mo-N) ofrecen potencial para el descubrimiento de nuevos materiales.

Objetivo del estudio:

Predecir teóricamente y realizar experimentalmente nuevos compuestos ternários de nitruro de molibdeno y zinc.
Para analizar el entorno de unión y la estabilidad estructural de estos compuestos.
Investigar la relación entre estequiometría, estados de oxidación y propiedades optoelectrónicas.

Principales métodos:

Cálculos teóricos para predecir compuestos ternários estables en el sistema Zn-Mo-N.
Síntesis experimental de aleaciones de Zn-Mo-N en una amplia gama de composiciones.
Difracción de rayos X y otras técnicas de caracterización para determinar la estructura y la estabilidad del cristal.
Análisis de los estados de oxidación y de la unión utilizando datos teóricos y experimentales.

Principales resultados:

Identificación y realización experimental de los compuestos Zn3MoN4 y ZnMoN2.
Formación de aleaciones de Zn-Mo-N en una estructura derivada de la wurtcita con una estoiquiometría significativa.
Descubrimiento de la "estabilización mediada por redox" habilitada por la electronegatividad intermedia del zinc y los estados de oxidación variables del molibdeno (+VI a +IV).
El Zn3MoN4 exhibe una estructura de wurtzita estable, mientras que el ZnMoN2 es metastable.
Ajuste continuo de las propiedades optoelectrónicas desde resistivas/semitransparentes (Zn3MoN4) a conductivas/absorbentes (ZnMoN2) con cambio de estequiometría.

Conclusiones:

El sistema Zn-Mo-N alberga compuestos ternários novedosos estabilizados por procesos redox.
La estabilización mediada por redox ofrece una vía para crear materiales con propiedades sintonizables.
Este principio puede guiar el descubrimiento de nuevos compuestos ternários con características deseables.

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