Studium struktury a delaminace podvojných vrstevnatých hydroxidů interkalovaných organickými molekulami metodami molekulárních simulací s upravenými parametry silových polí

• Thesis title in Czech: Studium struktury a delaminace podvojných vrstevnatých hydroxidů interkalovaných organickými molekulami metodami molekulárních simulací s upravenými parametry silových polí
• Thesis title in English: Study of structure and delamination of layered double hydroxides intercalated with organic molecules by molecular simulation methods with modified force field parameters
• Key words: molekulární simulace|podvojné vrstevnaté hydroxidy|interkalace|delaminace
• English key words: molecular simulation|layered double hydroxides|intercalation|delamination
• Academic year of topic announcement: 2022/2023
• Thesis type: dissertation
• Thesis language: čeština
• Department: Department of Chemical Physics and Optics (32-KCHFO)
• Supervisor: doc. RNDr. Miroslav Pospíšil, Ph.D.
• Author: hidden - assigned and confirmed by the Study Dept.
• Date of registration: 08.02.2023
• Date of assignment: 08.02.2023
• Confirmed by Study dept. on: 13.02.2023

Guidelines

Teoretické základy molekulárně mechanických a dynamických simulací.
Krystalochemie, chemické a fyzikální vlastnosti podvojných vrstevnatých hydroxidů, způsoby interkalace, modifikace a delaminace.
Provést aktuální rešerši současně dosažených výsledků o typech interkalovaných podvojných vrstevnatých hydroxidů jak z hlediska prvků ve vrstvě tak možností jejich interkalace organickými molekulami.
Možnosti řešení interkalovaných struktur, určení vhodných nových parametrů pro silové pole, jejich charakterizace a porovnání vypočtených výsledků s dostupnými experimentálními daty.
Vlastní modelování možných postupů delaminace jednotlivých vrstev a ověření správnosti výpočtů vzhledem k dostupným experimentálním výsledkům.
Prezentace dosažených výsledků modelování na seminářích a konferencích.

References

M. O. Steinhauser: Computational Multiscale Modeling of Fluids and Solids, Springer, Verlag, 2008
W. Gans, A. Amann, J. C. A. Boeyens: Fundamental Principles of Molecular Modeling, Plenum Publishing Corporation, New York, 1996.
V. A. Drits, C. Tchoubar: X Ray Diffraction by Disordered Lamellar Structures, Mineralogical Society Monograph No.5, 1990.
V. Rives, (Ed.), Layered Double Hydroxides: Present and Future. Nova Science Publishers, Inc., New York, 2006.
R. Cygan, J. Greathouse, H. Heinz, A. Kalinichev: Molecular models and simulations of layered materials. Journal of Materials Chemistry 2009, 19(17), 2470.
P. Kovář, M. Pospíšil, E. Káfuňková, K. Lang, F. Kovanda: Mg-Al layered double hydroxides intercalated with porphyrin anions: molecular simulations and experiments. Journal of Molecular Modeling 2010, 16, 223-233.
P. Sideris, U. Nielsen, Z. Gan, C. Grey: Mg/Al Ordering in Layered Double Hydroxides Revealed by Multinuclear NMR Spectroscopy. Science, 2008, 321(5885), 113-117.
M. Pouvreau, J. A. Greathouse, R. T. Cygan, A. G. Kalinichev: Structure of Hydrated Gibbsite and Brucite Edge Surfaces: DFT Results and Further Development of the ClayFF Classical Force Field with Metal−O−H Angle Bending Terms. Journal of Physical Chemistry C, 2017, 121, 1457-14771.
M. Pouvreau, J. A. Greathouse, R. T. Cygan, A. G. Kalinichev: Structure of Hydrated Kaolinite Edge Surfaces: DFT Results and Further Development of the ClayFF Classical Force Field with Metal−O−H Angle Bending Terms. Journal of Physical Chemistry C, 2019, 123(18), 11628-11638.

Preliminary scope of work

Předpokládané znalosti uchazeče na úrovni ukončeného magisterského studia v přírodních oborech zaměřených na mineralogii nebo strukturní analýzu nebo chemickou fyziku, popř. biofyziku.

Preliminary scope of work in English

Based on our previous experiences with various types of layered materials and their structure analysis and delamination, this work will be focused to describe the interlayer of selected layered double hydroxides (LDH)-organic intercalates and consequently basal spacing increasing, and delamination processes in dispersant by large scale molecular dynamic (MD) simulations using Material Studio and LAMMPS software packages, where the newly developed parametrization of interface (IFF), clay force field (ClayFF) and their mutual modification will be used. This process is strongly dependent on the structure of the surfactant guests, where for example benzene sulfonate ‘head groups’ are stabilising the delaminated material but the sulphate functionalised surfactants are not. The more general goal is to determine the minimum alkyl chain length required to delaminate selected LDH in specific solvent and moreover to explore if there is any correlation between chain length and stability of the suspension formed, where we will follow the similar approach as in our previously published works on the different types of layered materials (A: Jan Demel, Jan Hynek, Petr Kovář, Yan Dai, Christine Taviot-Gueho, Ondřej Demel, Miroslav Pospíšil, Kamil Lang, Insight into the Structure of Layered Zinc Hydroxide Salts Intercalated with Dodecyl Sulfate Anions, J. Phys. Chem. C, 2014, 118, no. 46, p. 27131-27141, DOI: 10.1021/jp508499g; B: Jan Svoboda, Klára Melánová, Vítězslav Zima. Ludvík Beneš, Milan Pšenička, Miroslav Pospíšil, Petr Kovář, Influence of 1,2-alkanediols on the structure of their intercalates with strontium phenylphosphonate solved by molecular simulation and experimental methods, J. Mol. Model. 2016, 22, 143, DOI:10.1007/s00894-016-3014-0). The calculated results will be used as validation of newly developed force field parameters and moreover, as a suitable guide for experimentalists for selection of appropriate dispersants and organic interlayer anions for specific types of LDH.
The resultant basal spacing d003 as well as calculated XRD patterns will be directly compared to experimental data in order to obtain detailed description of LDH interlayer galleries. The simulation of delamination processes itself will be based on MD simulation with NPT statistical ensemble on nanosecond time scale. As supporting analysis the PDF (Pair Distribution Function), diffusion coefficients and interaction energies will be calculated for all interlayer species.
Ph.D. work is planned to be potentially a part of our mutual project between Miroslav Pospíšil (MFF UK) and Dr. Piotr Kowalski (IEK-13, Forschungszentrum Jülich, Germany) and Prof. Dr. Eckhard Spohr (ES) (University of Duisburg-Essen, Germany) with support of founders IFF - H. Heinz and ClayFF - A. Kalinichev, which allow us fellowship on their laboratories.