Catalysis Letters

, Volume 143, Issue 12, pp 1354–1361 | Cite as

Topological and Electronic Structure of Heterocyclic Compounds Adsorbed on Hydrotreating Catalysts

  • Diego Valencia
  • Roberto Olivares-Amaya
  • Jorge Aburto
  • Isidoro García-Cruz


We studied the electronic structure of the adsorption of S- and N-containing aromatic compounds present in crude oils on MoS2 and WS2 clusters by means of all-electron DFT methods. The aim of this work is to understand results related to the hydrotreating catalyst poisoning by quinoline. We studied the adsorption of the organic compounds by flat (π) and perpendicular (σ) adsorption on each cluster catalyst. The calculated adsorption energies indicated that π-adsorption was more favorable over σ-adsorption. In the σ mode, quinoline presented the largest adsorption energy, which led to understand the poisoning of the catalysts. We performed electron localization function (ELF) studies on the molecules adsorbed on a perpendicular orientation. We showed methyl-substituted compounds had a weaker S-{Mo,W} bond due to steric hindrance. Furthermore, atoms-in-molecules (AIM) calculations at the critical points (i.e. {S,N}-{Mo,W} interfaces) revealed a correlation between electron density and Laplacian of the electron density at this region and the adsorption energy. Ellipticity (ε) studies revealed structural information of binding at these sites, as well as the competition between S- and N-containing compounds. Similarly, ε showed that methyl-containing compounds had a very distinct character than non-substituted ones, thus revealing the importance of steric effects. Analytic tools such as ELF and AIM provide correlations between the experimental observations and properties. We find these studies can be further used to understand other catalytic phenomena.

Graphical Abstract


DFT ELF Ellipticity DBT Quinoline Hydrodesulfurization Poisoning 



The authors wish to thank Departamento de Supercómputo de la Dirección General de Cómputo y de Tecnologías de la Información y Comunicación (DGTIC) de la UNAM and LUFAC Computación S. A. de C. V. for CPU time. Proyecto Universitario de Nanotecnología Ambiental (PUNTA) IMPULSA is gratefully acknowledged. D.V. also acknowledges Instituto Mexicano del Petróleo for their kind hospitality. R.O.A. is thankful for the support of CONACYT and Fundación México en Harvard A.C.


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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  1. 1.Facultad de QuímicaUniversidad Nacional Autónoma de MéxicoMexicoMexico
  2. 2.Programa de Ingeniería MolecularInstituto Mexicano del PetróleoMexicoMexico
  3. 3.Department of Chemistry and Chemical BiologyHarvard UniversityCambridgeUSA
  4. 4.Department of ChemistryPrinceton UniversityPrincetonUSA
  5. 5.Programa de Procesos de TransformaciónInstituto Mexicano del PetróleoMexicoMexico

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