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Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments

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Abstract

Molecular modeling in combination with powder X-ray diffraction (XRD) provided new information on the organization of the interlayer space of Mg-Al layered double hydroxide (LDH) containing intercalated porphyrin anions [5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS)]. Anion-exchange and rehydration procedures were used for the preparation of TPPS-containing LDH with an Mg/Al molar ratio of 2. Molecular modeling was carried out in the Cerius2 and Materials Studio modeling environment. Three types of models were created in order to simulate the experimental XRD patterns of LDH intercalates with a TPPS loading of 70–80% with respect to the theoretical anion exchange capacity (AEC). The models represent single-phase systems with a 100% TPPS loading in the interlayer space (Type 1) and models represent the coexistence of two phases corresponding to the total exchange from 75 to 92% (Type 2). To cover other possible arrangements, models with the coexistence of both TPPS and NO −3 anions in the same interlayer space were calculated (Type 3). The models are described and compared with experimental data. In all cases, guest TPPS anions are tilted with respect to the hydroxide layers, and are horizontally shifted to each other by up to one-half of the TPPS diameter. According to the energy characteristics and simulated XRD, the most probable arrangement is of Type 2, where some layers are saturated with TPPS anions and others are filled with original NO −3 anions.

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Acknowledgments

This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic (MSM 0021620835 and MSM 6046137302), the Czech Science Foundation (203/06/1244, 202/05/H003 and 205/08/0869), and the Grant Agency of the Academy of Sciences of the Czech Republic (KAN 100500651). The authors thank Petr Bezdička (Institute of Inorganic Chemistry AS CR, v.v.i.) for measuring the powder XRD patterns of the prepared samples.

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Authors and Affiliations

  1. Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 3, 121 16, Prague, Czech Republic

    Petr Kovář & Miroslav Pospíšil

  2. Institute of Inorganic Chemistry, v.v.i, Academy of Sciences of the Czech Republic, 250 68, Řež, Czech Republic

    Eva Káfuňková & Kamil Lang

  3. Faculty of Sciences, Charles University in Prague, 2030 Hlavova, 128 43, Prague, Czech Republic

    Eva Káfuňková

  4. Department of Solid State Chemistry, Institute of Chemical Technology, Prague, Technická, 5 166 28, Prague, Czech Republic

    František Kovanda

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  1. Petr Kovář
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  2. Miroslav Pospíšil
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  3. Eva Káfuňková
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  4. Kamil Lang
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  5. František Kovanda
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Correspondence to Petr Kovář.

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Kovář, P., Pospíšil, M., Káfuňková, E. et al. Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments. J Mol Model 16, 223–233 (2010). https://doi.org/10.1007/s00894-009-0537-7

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