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Adsorption of H2O, NH3 and C6H6 on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

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Abstract

Adsorption of H2O, NH3 and C6H6 on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH3) > E(H2O) > E(C6H6). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li+ cation, and (3) steric hindrances of the flat C6H6 molecule adsorbed on the cation in the cage of zeolite.

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Acknowledgments

This work has been supported by the Austrian Science Fund under Project P17020-PHYS and by the German Research Foundation, priority program SPP 1315, Project GE 1676/1-1. We are grateful to Pascal Boulet and one anonymous reviewer for useful comments and suggestions.

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Authors and Affiliations

  1. Faculty of Physics and Center for Computational Materials Science, Vienna University, Sensengasse 8, 1090, Vienna, Austria

    Lubomir Benco

  2. Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, 84536, Bratislava, Slovak Republic

    Lubomir Benco & Daniel Tunega

  3. University of Natural Resources and Applied Life Sciences, Peter Jordan Strasse 82, 1190, Vienna, Austria

    Daniel Tunega

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  1. Lubomir Benco
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Correspondence to Lubomir Benco.

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Benco, L., Tunega, D. Adsorption of H2O, NH3 and C6H6 on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study. Phys Chem Minerals 36, 281–290 (2009). https://doi.org/10.1007/s00269-008-0276-9

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