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Estudio teórico de la oxidación de CO con O2 usando catalizadores de Au-Pd y Au-Pt
Theoretical study of the CO Oxidation with O2 using Au-Pd and Au-Pt catalysts
Estudo teórico da oxidação de CO com O2 usando catalisadores de Au-Pd e Au-Pt
Palabras clave:
Clústeres bimetálicos, oxidación selectiva de CO, índices de reactividad, adsorción (es)Clústers bimetálicos, oxidação seletiva de CO, índices de reatividade, adsorção (pt)
Bimetallic clusters, selective oxidation of CO, reactivity index, adsorption (en)
En el presente estudio se realizaron cálculos con base en la Teoría del Funcional de la Densidad Electrónica (DFT) con la aproximación B3PW91/LANL2DZ para optimizar los sistemas monometálicos y bimetálicos Au9, Au8Pd, Au8Pt, AuPd8, AuPt8, Pd9 y Pt9. Los materiales fueron teóricamente evaluados como catalizadores para la oxidación de monóxido de carbono (CO) y se determinó el sistema más favorable para la adsorción de esta molécula. La sustitución de átomos de Pt y Pd por átomos de Au en los nonámeros generó un cambio en la estructura tridimensional del sistema. El análisis de reactividad global mostró que el clúster más reactivo es 𝑃𝑡9, seguido por 𝐴𝑢𝑃𝑡8. Los índices de Fukui identificaron los sitios más susceptibles para un ataque nucleofílico de ambos clústeres. La adsorción de CO generó una cascada de oxidación que liberó ~4,5 eV, indicando que la reacción es altamente exotérmica y exergónica. Los clústeres 𝐴𝑢𝑃𝑡8 y 𝑃𝑡9 mostraron los valores más bajos de energía de activación de la etapa determinante del mecanismo. En general, la sustitución de un átomo de platino (o paladio) por un átomo de oro no afecta la reactividad de los nonámeros y, por tanto, se infiere que el clúster 𝐴𝑢𝑃𝑡8 podría ser un catalizador promisorio en la oxidación de CO.
In the current study were development calculations based on Density Functional Theory (DFT) with the B3PW91/LANL2DZ approach for optimizing both monometallic and bimetallic systems: Au9, Au8Pd, Au8Pt, AuPd8, AuPt8, Pd9 y Pt9. Such materials were theoretically tested as catalyst for the oxidation of carbon monoxide (CO) and the most favorable system for its further adsorption was determined. The substitution of Pt and Pd by Au atoms in the nonamers generated a change in the tridimensional structure of the system. The global reactivity analysis showed that the most reactive cluster is Pt9 and AuPt8. On the other hand, the Fukui indexes identified the most susceptible sites for a nucleophilic attack of both clusters. The CO adsorption generated an oxidation cascade which liberated 4,5 eV, indicating that the reaction is highly exothermic and exergonic. Both AuPt8 and Pt9 showed the lowest values of activation energy in the determining step of the mechanism. In general, the substitution of a Pt (Pd) atom by an Au atom does not affect the reactivity of the nonamers and then it was evident that the AuPd8 cluster could be a promissory catalyst in the CO oxidation.
No presente estudo, cálculos baseados na Teoria do Funcional da Densidade Eletrônica (DFT) com a abordagem B3PW91/LANL2DZ foram realizados para otimizar sistemas monometálicos e bimetálicos Au9, Au8Pd, Au8Pt, AuPd8, AuPt8, Pd9 y Pt9. Tais materiais foram teoricamente avaliados como catalisadores para a oxidação do monóxido de carbono (CO) e foi determinado o sistema mais favorável para a adsorção desta molécula. A substituição dos átomos de Pt e Pd por átomos de Au nós não-nomes gerou uma mudança na estrutura tridimensional do sistema. A análise de reatividade global mostrou que o cluster mais reativo é 𝑃𝑡9, seguido por 𝐴𝑢𝑃𝑡8. Os índices de Fukui identificaram os sítios mais suscetíveis ao ataque nucleofílico de ambos os clusters. A adsorção de CO gerou uma cascata de oxidação que liberou ~4,5 eV, indicando que a reação é altamente exotérmica e exergônica. Os aglomerados 𝐴𝑢𝑃𝑡8 𝑦 𝑃𝑡9 apresentaram os menores valores de energia de ativação do estágio determinante do mecanismo. Em geral, a substituição de um átomo de platina (ou paládio) por um átomo de ouro não afeta a reatividade dos não-nomes e, portanto, infere-se que o aglomerado 𝐴𝑢𝑃𝑡8 pode ser um catalisador promissor na oxidação do CO.
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Derechos de autor 2022 Andrés Felipe Forero Garzón, Sergio Joya Rodríguez, Kevin Nicolás Sebastián Cachón Osorio, Andrés Fernando Bernal Escobar, Badhin Gómez; Julián E. Sánchez-Velandia; Sol Milena Mejía Chica
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