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Electrogenerated Mesoporous Silica Thin Films : Thickness Control and Electroanalytical Applications

Abstract : The combination of rich surface chemistry of silica and ordered perpendicularly-standing hexagonal mesostructure of films generated by EASA makes this material a perfect choice for use as the electrode coatings. In this light, improvement of film design is a constant challenge in order to benefit from porous layer and to increase the efficiency of electrochemical sensors. The first part of project was centred around the optimisation of the film thickness towards the thinnest with preservation of the beneficial hexagonal structure. The mesoporous silica film (MSF) thickness is a parameter that can affect the mass transport through the silica coating to the electrode specifically because of the reactivity of surface silanol groups. Thinning of the MSF can facilitate the diffusion of species, while keeping the presence of the beneficial silica layer can increase the electrochemical response, hence, the sensitivity of analysis. Two approaches were used in order to decrease thickness. The first was a study of the effect of the deposition time during the modification of the electrode (EASA process). The second one was the wet etching of film after its deposition. The thinnest uniform MSFs, which can be generated on indium tin oxide (ITO) surface, require minimum 10 seconds deposition with an applied potential equal to -1.3 V and a 100 mM silane-containing sol. This gave rise to 80 ± 9 nm coating. Post-synthesis etching with the soft fluoride solution of ammonium fluoride, NH4F, allowed to control the decrease of the MSF thickness. By keeping the surfactant inside the silica pores, template agent for the synthesis, the kinetic of the etching reaction was faster, but with a more homogeneous dissolution. It was possible to obtain the thinnest ordered MSF in comparison with an etching procedure conducted on MSF after the extraction of the template. The profilometry determined thickness of well-structured film with vertical pore orientation was respectively of 28 ± 9 nm for the templated silica films and 57 ± 11 nm for films without surfactant inside their pores. In the second part of the study, MSFs were applied to modify ITO electrodes for the development of electrochemiluminescence platform for detection of amine-containing herbicide glyphosate using co-reactant system with Ru(bpy)₃²⁺. Comparison between physical and chemical immobilisation of the organometallic agent was studied. Covalent functionalisation was achievable due to introduction of azide functions on co-condensation step with their further coupling with propargyl-functionalised derivative of Ru(bpy)₃²⁺ complex by Huisgen 1,3-cycloaddition reaction. The effect of the herbicide addition was investigated using electrodes with immobilised by two approaches Ru(bpy)₃²⁺ complex as well as in solution of Ru(bpy)₃²⁺, operating bare ITO electrode and ITO electrode covered with unmodified MSF. The evolution of electrochemical signal was used to conclude on the possibility to detect glyphosate.
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Submitted on : Wednesday, May 19, 2021 - 5:54:16 PM
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Taisiia Sikolenko. Electrogenerated Mesoporous Silica Thin Films : Thickness Control and Electroanalytical Applications. Chemical Sciences. Université de Lorraine, 2020. English. ⟨NNT : 2020LORR0242⟩. ⟨tel-03230348⟩

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