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Design of Porous Materials for Electrochemical Applications

Abstract : The development of porous materials has been one of the most fascinating research topics in the frame of a wide variety of applications ranging from chemical analysis to separation and catalysis. Among the huge amount of different porous materials, nanoporous metals are one of the most interesting candidates because of their outstanding properties such as a high surface area, a large pore volume and a high accessibility for guest molecules which have to diffuse into the internal matrix where catalytically active sites are located. In order to synthesize such materials, a templating approach, including hard and soft templating is typically used to generate uniform porous structures, depending on the shape of the templates. In the present dissertation thesis, the elaboration of various porous metal electrodes via a soft templating approach and their potential applications in the field of enantioselective analysis, synthesis and separation are discussed. Several chiral imprinted metals such as platinum and nickel with a significantly increased internal electroactive surface area are studied. Subsequently, these chiral imprinted mesoporous metals can be used to improve the electrochemical performance with respect to several tasks, including electrochemical synthesis of chiral compounds, chiral separation and actuation, which are important for pharmaceutical applications. The first part of the present work is devoted to the elaboration of chiral imprinted metals for asymmetric synthesis. The prepared electrode surfaces show a surprisingly high selectivity in terms of chiral synthesis when they are combined with the concept of pulsed electrochemistry. The second part of the manuscript is dedicated to their use for the separation of racemic mixtures with the opportunity to fine-tune the separation efficiency by applying a potential to the metal matrix in order to adjust the electrostatic interactions between the chiral compounds and the designer surfaces. Under the most suitable conditions, complete baseline separation of both enantiomers can be observed. The third part of this thesis deals with chiral detection, for which a hybrid film of chiral imprinted Pt and polypyrrole is used as a selective actuator under bipolar electrochemical conditions. The synergistic properties of both materials, wireless actuation and chiral recognition, have been successfully combined for wireless chiral analysis. Apart from the design and application of chiral mesoporous metal films, the last chapter is dedicted to the elaboration of hierarchically structured metals containing macro- and mesoporous features, obtained by using simultaneously hard and soft templating approaches for electrocatalytic oxygen evolution in basic media. Multiporous nickel nanosheets were prepared via a two-step electrodeposition process in the presence of silica beads and surfactant as templates to control the macro- and mesoporous structure, respectively. The resulting synergistic effect of combined macroporous and mesoporous cavities allows fine tuning structural properties, electrocatalytic performance and stability for water splitting applications. In conclusion, our findings open interesting perspectives for development of new porous materials, which are of potential interest for various applications, such as chiral analysis, asymmetric synthesis, chemical separation, as well as energy conversion and storage.
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Submitted on : Wednesday, October 28, 2020 - 5:38:06 PM
Last modification on : Thursday, October 29, 2020 - 3:04:27 AM


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  • HAL Id : tel-02982697, version 1



Sunpet Assavapanumat. Design of Porous Materials for Electrochemical Applications. Other. Université de Bordeaux; Vidyasirimedhi Institute of Science and Technology, 2020. English. ⟨NNT : 2020BORD0092⟩. ⟨tel-02982697⟩



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