able conditions oxidation of the thiophene results in proton loss followed by polymerization, where the polymerization step is believed to proceed through radical-radical or radical-monomer coupling [198]. Proton loss followed by coupling of the monomers results in a lower reaction free energy, and is thus energetically more favorable than simple monomer oxidation. Generally, elec- tropolymerization of thiophene is carried out in non-aqueous solutions. How- ever, thiophene have been shown to polymerize at Pt electrodes from aqueous solutions, where it has been solubilized by surfactants, to overcome the low aqueous solubility [199].
In this study, a shoulder was found in the UV-Vis spectrum at the wave- lengths corresponding to poly(thiophene-3-acetic acid),i.e. 340-400 nm, and also the absorption peak of thiophene-3-acetic acid has been shifted to longer wavelengths. The XPS spectra shows that the thiophene ring is present at the particle surface and that sulfur is present only in thiophene. A possible reaction mechanism involves the formation of a precursor complex, which by bringing the thiophene moieties close together favors polymerization. The evidence supporting polymerization in this study is not conclusive, and thus, other reaction mechanisms also should be considered.
6 Conclusions
The aim of this thesis was to study the formation, growth and properties of metal nanoparticles. Special emphasis was placed on reactivity and formation of such particles at liquid|liquid interfaces. Based on the results obtained in this work, the following conclusions can be drawn:
The electrodeposition studies presented in publications I-III show that the electrified liquid|liquid interface is suitable to study the initial steps of nucleation, with the advantage of controlling the growth reaction with the applied potential, while not suffering from the presence of strong interactions between the electrode and the new phase. In publication I, a novel model based on the concept of planar diffusion fields was presented. It was shown that this approach is inconsistent and therefore, not generally applicable to the liquid|liquid interface, since the overlap and hence current are dependent on the species under consideration.
In publication II, a new model based on average interfacial concentra- tions was developed. This model overcomes the problems encountered in the first publication. Additionally, it was shown that the mean interfacial concentration can be used as a good approximation for the overlap of the diffusion zones. The interpretation of the experimental results indicates that the particles formed at the interface agglomerate.
In publication III, the adsorption of particles at liquid|liquid was consid- ered. A thermodynamic model was developed based on macroscopic surface and line tensions. It was shown in the experimental work that the addition of phospholipids destabilizes the embryonic clusters at the initial stages of growth, and thereby, decreases the nucleation rate.
Publication IV demonstrates how the liquid|liquid interface can be used to study the formation of nanoparticles in a homogeneous phase. In the study, silver ions were transferred by facilitated ion transfer from the aque- ous to the organic phase where their reduction and agglomeration to form particles occurs. 1-Phenylpyrrole functions both as the complexation agent in the facilitated ion transfer reaction and as the reductant in the electron transfer reaction. The oxidation of 1-phenylpyrrole was believed to result in poly(phenylpyrrole). The reaction rate was noted to be too slow for practical
purposes.
In chapter V, the reaction between palladate and thiophene-3-acetic acid resulting in 1-4 nm sized nanoparticles was discussed. The nanoparticles were characterized by TEM, XPS, WAXS, SAXS and UV-Vis. These particles were soluble in aqueous solutions, with pH-tunable solubility properties. Al- though no direct evidence was obtained, the oxidation of thiophene-3-acetic is believed to result in oligomerization.
Publication V demonstrates the use of a colloidal aqueous phase for the two-phase electrocatalytic dehalogenation of 2-bromoacetophenone. Addi- tionally, it was shown by cyclic voltammetry and electrophoretic light scat- tering measurements that the aqueous colloids can be charged with electrons by a two-phase process involving decamethylferrocene as the electron donor.
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