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Propan-2-ol dehydration on H-ZSM-5 and H-Y zeolite: a DFT study

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Abstract

The catalytic dehydration of propan-2-ol over H-Y and H-ZMS-5 aluminated zeolite models, mimicking both internal cavities and external surfaces, was studied by DFT calculations to investigate the reaction mechanism. After the adsorption of propan-2-ol on the zeolite, the dehydration mechanism starts with alcohol protonation, occurring by one acidic –OH group of the zeolite fragment, followed by a concerted β-elimination to give propene. The catalytic activity is affected by the size of the zeolite cavity, which is larger in the H-Y than in the H-ZMS-5 zeolite. The adsorption energy of the reagent, as an example, decreases in the order: H-Y cavity ≃ H-ZMS-5 surface > H-ZMS-5 cavity, pointing that the adsorption process should preferentially occur either on open surface or inside larger cavity. More interestingly, confinement effects play a twofold role in driving the reaction pathway, resulting in two different effects on the reaction outcomes. The thermodynamic stability, evaluated by the standard free energy difference of the products (water and propene) with respect to the reactant (propan-2-ol), would indeed suggest that the reaction more smoothly could occur for the systems: H-ZMS-5 surface > non-catalyzed > H-Y cavity > H-ZMS-5 cavity. The activation standard free energy of the process conversely decreases in the order: non-catalyzed > H-ZMS-5 surface > H-ZMS-5 cavity > H-Y cavity, suggesting that the reaction is faster inside zeolite cavities. Experimental and computational results are in agreement, giving confidence on the atomistic-level insights provided.

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Notes

  1. T represents one tetrahedral unit, singly including Si or Al and four O atoms.

  2. Non-concerted mechanisms were also attempted, without being successful.

  3. The enthalpy value is ca. 125 kJ mol−1 at concentrations of propan-2-ol per H-ZSM-5 grams larger than 600 μmol g−1. The latter correspond to the concentrations mimicked by the 22T and 26T H-ZSM-5 systems.

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Acknowledgments

This work was supported by the University of Palermo and by the Italian Ministero dell’Istruzione, dell’Università à e della Ricerca.

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  1. Dipartimento di Chimica dell’Università di Palermo, Viale delle Scienze Ed. 17, 90128, Palermo, PA, Italy

    Antonio Prestianni, Remedios Cortese & Dario Duca

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  1. Antonio Prestianni
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Correspondence to Dario Duca.

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Prestianni, A., Cortese, R. & Duca, D. Propan-2-ol dehydration on H-ZSM-5 and H-Y zeolite: a DFT study. Reac Kinet Mech Cat 108, 565–582 (2013). https://doi.org/10.1007/s11144-012-0522-5

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