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La importancia de las reacciones de tipo Cannizzaro durante la reducción electrocatalítica de dióxido de carbono
Yuvraj Y Birdja1, Marc T M Koper1
1Leiden Institute of Chemistry, Leiden University , P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Journal of the American Chemical Society
|January 19, 2017
Resumen
Los electrodos de diamante dopados con boro pueden reducir el dióxido de carbono (CO2) y el monóxido de carbono (CO) a formaldehído y metano. La formación inesperada de ácido y alcohol es el resultado de un entorno alcalino localizado, no de la reducción directa de CO2.
Área de la Ciencia:
- La electroquímica
- Ciencias de los materiales
- Reacciones químicas
Sus antecedentes:
- Los electrodos de diamante dopados con boro (BDD) se consideran típicamente inactivos catalíticamente para la reducción de CO2 y CO.
- La comprensión de la selectividad del producto en la reducción electroquímica de CO2 es crucial para el desarrollo de tecnologías energéticas sostenibles.
Objetivo del estudio:
- Investigar la reducción electroquímica de CO2 y CO mediante el uso de electrodos BDD.
- Para aclarar el mecanismo detrás de la formación de subproductos inesperados como ácidos y alcoholes.
Principales métodos:
- Experimentos de reducción electroquímica con electrodos BDD en varios potenciales.
- Análisis de los productos de reacción mediante técnicas analíticas.
- Investigación de la influencia del pH de los electrolitos y de la capacidad tampón.
Principales resultados:
- Los electrodos BDD reducen activamente el CO2 y el CO a formaldehído y metano.
- El ácido fórmico y el metanol se forman a través de la desproporción de tipo Cannizzaro catalizada por base del formaldehído.
- Esta desproporción es impulsada por un entorno alcalino localizado generado por la reacción de evolución del hidrógeno.
Conclusiones:
- La formación de ácidos y alcoholes durante la reducción de CO2 es a menudo un artefacto de reacciones secundarias, no la formación directa de productos.
- El pH del electrolito y la capacidad de amortiguación influyen significativamente en estas reacciones secundarias.
- El fenómeno observado es generalizable a otros materiales de electrodos y aldehídos.
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