Thèse de doctorat en Chimie - Physique
Sous la direction de Laurent Ruhlmann.
Soutenue le 04-06-2013
Le président du jury était Pierre Audebert.
Synthèse et applications d’hybrides de porphyrine-POM pour la dépollution de l'eau par photocatalyse et production d'énergie solaire
The dissertation is presented on 252 content pages which has been framed in five chapters and two annexures while the title page opens into a list of abbreviations followed by a foreword on the work. The core theme of the research work is to validate the extended photocatalytic properties of porphyrin-POM materials in evolving from UV to visible light range of solar spectrum. Which describing additional modes for synthesis of hybrid materials (i) electrostatic multilayer’s comprising of Dawson , sandwich Dawson type and preyssler,s POM in combination with free base tetracationic porphyrin [H₂TPhN(Me)₃P⁴⁺] (ii) an easy method of synthesis of two dimers with a pyridinium spacer (abbreviated 4-H₂–Zn and 3-H₂–Zn) (iii) Langmuir Schafer approach for hybrid monolayer. The prepared photoactive thin layers have been characterized by UV-visible spectroscopy and fluorescence spectroscopy for optical properties. Cyclic voltammetry for electrochemistry and ionic permeability studies. Atomic force microscopy (AFM) for surface morphology and its role in physical mechanism of reduction process and shape of nanostructures obtained. Transmission electron microscopy (TEM) has been used to interpret size and shape of dendritic silver nanoparticles obtained as photoreduction product. Although ,the ultimate goal is the photoreduction of heavy metals (Cr(VI), Hg(II), Cd(II), Pb(II) ), reduction of a simpler system like Ag⁺ ion has been chosen as a model system due to single electron simpler oxidation reduction process. A novel application of photocurrent generation from these hybrid films has been demonstrated in the fifth chapter of the manuscript as an initial studies which has enhanced the significance of all previously fabricated systems upto by many folds .The foresaid development of photovoltaic application has paved the way for future studies to enhance the photocurrent yield further by tuning the electron donor-acceptor system. Both components porphyrin and POM can be tuned with different axial substituent’s and stereo chemical properties to achieve maximum yield of solar energy as well as diversified metal nanostructure for nanoelectronics, e.g. silver dendrites for sensor applications. At the end of the manuscript, three appendices describe successively the experimental techniques used to carry out this work, the Job method used to determine the stoichiometry and formation constants of complex electrostatic and coordination, and then finally the origin or Protocols for the synthesis of various compounds used.
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