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Las superposiciones nanoscópicas de dióxido de titanio mejoran la durabilidad de los electrocatalizadores moleculares

Patrick O Aghadiuno¹, W Wilson McNeary², William D H Stinson¹

¹Department of Chemical Engineering, Columbia Electrochemical Engineering Center, Lenfest Center for Sustainable Energy Columbia University in the City of New York, New York, New York 10027, United States.

ACS applied materials & interfaces

|August 30, 2025

Resumen

Las capas de dióxido de titanio (TiO2) estabilizan los catalizadores moleculares como el cobalto (III) meso-tetra (4-carboxifenilo) cloruro de porfirina (CoTCPP) para la división del agua. La encapsulación por TiO2 mejora significativamente la adhesión y la estabilidad del catalizador durante las reacciones de evolución del hidrógeno.

Área de la Ciencia:

Ciencias de los materiales
La electroquímica
Catálisis

Sus antecedentes:

Los catalizadores moleculares, como las porfirinas metálicas, son prometedores para la división fotocatalítica del agua.
Sin embargo, su aplicación está limitada por la escasa estabilidad, incluida la desmetalización y el desprendimiento de los soportes.

Objetivo del estudio:

Mejorar la estabilidad y la adhesión de los catalizadores moleculares de cobalto (III) meso-tetra (4-carboxifeno) cloruro (CoTCPP) en las superficies de los electrodos.
Investigar el efecto de las capas de dióxido de titanio (TiO2) sobre la estabilidad y el rendimiento de CoTCPP.

Principales métodos:

Se utilizó la deposición de capas atómicas (ALD) para crear capas de TiO2 nanoscópicas que encapsulaban CoTCPP.
Se emplearon espectroscopias de Raman y ultravioleta visible para confirmar la estructura de la metaloporfirina.
Se realizaron mediciones electroquímicas, incluida la cronoamperometría, para evaluar la estabilidad y la actividad del catalizador.

Principales resultados:

La encapsulación de TiO2 mejoró significativamente la adhesión de CoTCPP a las superficies de los electrodos en un amplio rango de potenciales.
Hasta el 97% del CoTCPP encapsulado permaneció atado después de las pruebas de reacción de evolución del hidrógeno (HER), en comparación con <36% para los catalizadores no encapsulados.
El CoTCPP encapsulado mantuvo una actividad redox parcial para las capas de TiO2 hasta 8 nm, suprimiendo las reacciones secundarias no deseadas.

Conclusiones:

Las capas de TiO2 depositadas con ALD estabilizan eficazmente los catalizadores moleculares CoTCPP para aplicaciones electroquímicas.
Esta estrategia de encapsulación mejora la longevidad y el rendimiento del catalizador en la división del agua y las reacciones relacionadas.
Los hallazgos ofrecen una vía para desarrollar electrocatalizadores moleculares más robustos y eficientes.

Palabras clave:

deposición de la capa atómica (ALD)electrocatálisis el hidrógeno electrocatalizador encapsulado con óxido Porfirina y sus derivados Espectroelectroquímica Estabilidad

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