Relationships of Structural, Electronic and Energy Properties of Free and Adsorbed Molecules Over MoS₂ Model Clusters, Involved in the DDS and HYDS Pathways for the HDS Of 4,6-DMDBT. A CDFT Study
DOI:
https://doi.org/10.29356/jmcs.v70i1.2498Keywords:
DFT, CDFT, HDS, 4,6-DMBT, Catalizador de MoS2Abstract
Abstract. The reaction pathways, direct desulfurization (DDS) and hydrogenation-desulfurization (HYDS), in the HDS of 4,6-DMDBT on MoS2 clusters representing different models of coordinatively unsaturated sites (CUS) and brim active sites are analyzed using Density Functional Theory (DFT) and related concepts (CDFT). Reactivity indices of free molecule are related to the structural and energy properties of the chemisorbed molecules in model clusters. The results show that the bond lengths between the S atom of the adsorbed organic molecules and the Mo atom at CUS are multilinearly related to nucleophilic indices of nucleophilic centers of free molecules. In the DDS pathway, the high adsorption energy and the large S-Mo bond length of 3,3'-dimethyl-biphenyl-2-thiol suggest that the controlling reaction step is the hydrogenolysis of its S-C bond. It was found that a multilinear relationship exists between surface reaction energies (hydrogenation, hydrogen transfer, and hydrogenolysis) and reaction energies calculated for free molecules, electrophilicity global indices, and HOMO-LUMO gaps of free sulfur-containing molecules. Similarly, multilinear relationships were found between adsorption energies of the molecules on CUS and brim sites of model clusters and the nucleophilic indices of the different nucleophilic centers in free molecule.
Resumen. Se analizan las rutas de reacción, desulfuración directa (DDS) e hidrogenación-desulfuración (HYDS), en la HDS de 4,6-DMDBT en cúmulos modelos de MoS2 que representan diferentes sitios coordinativamente insaturados (CUS) y sitios activos brim mediante la Teoría del Funcional de la Densidad (DFT) y los conceptos relacionados (CDFT). Los índices de reactividad de moléculas libres son relacionados con las propiedades estructurales y de energía de las moléculas quimisorbidas en los cúmulos modelo. Los resultados muestran que las longitudes de enlace entre el átomo de S de las moléculas orgánicas adsorbidas y el átomo de Mo en un CUS están relacionadas multilinealmente con los índices nucleofílicos de los centros nucleofílicos de las moléculas libres. En la ruta DDS, la alta energía de adsorción y la gran longitud de enlace S-Mo del 3,3'-dimetil-bifenil-2-tiol sugieren que el paso de reacción controlante es la hidrogenólisis de su enlace S-C. Se encontró una relación multilínea entre las energías de reacción superficial (hidrogenación, transferencia de hidrógeno e hidrogenólisis) y las energías de reacción calculadas para moléculas libres, los índices globales de electrofilicidad y las brechas HOMO-LUMO de las moléculas libres que contienen azufre. De igual manera, se encontraron relaciones multilíneas entre las energías de adsorción de las moléculas en los sitios brim y CUS de los cúmulos modelo y los índices nucleofílicos de los diferentes centros nucleofílicos en las moléculas libres.
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