Functionalisation of surfaces and interfaces : molecules, particles and crystals

Abstract

This thesis is concerned with understanding and directing the functionalisation of solid surfaces with materials: molecules, nanoparticles and crystals. Both conducting (electrode) and insulating surfaces are of interest. For molecular functionalisation, a sweep potential procedure has been developed to assist the formation of self assembled monolayers (SAMs) of a ruthenium thiolated complex. Electrochemical investigations were employed to characterised the SAM formed on a platinum electrode. Nanoparticles formation explored two distinct routes. First Pd nanoparticles were successfully formed within ultra-thin Nafion films via impregnation and a chemical reduction method. Morphological investigations utilised atomic force microscopy. The electrocatalytic properties of the nanocomposite material were elucidated for the hydrogen oxidation reaction. The methodology used for the preparation of this nanocomposite material shows promise for applications in sensors and fuel cells. Second, the potential-assisted deposition of pre–formed perthiolated-ß-cyclodextrin-capped Pt nanoparticles method is described. Pt nanoparticles (5 nm diameter) were deposited in a controlled fashion on indium tin oxide and highly oriented pyrolytic graphite electrodes. The Pt anoparticles formed in this way were electrocatalytically active towards hydrogen generation and oxidation. This new approach for the deposition of metal nanoparticles with controlled surface density provides a new tool for the investigation of electrocatalytic processes. A major focus of the second part of the thesis has been the development of methods to study crystal deposition at extreme supersaturation. For this purpose a delivery system for calcium carbonate at high-supersaturation ion has been coupled with a quartz crystal microbalance and in–situ optical microscopy. The dynamics and quantitative evaluation of calcium carbonate deposition onto foreign solid substrates, and the effect of various additives, are described. Ex– situ studies, scanning electron microscopy and microRaman spectroscopy, allowed the morphological characterisation of the phases deposited. The transformation of ACC to calcite has been explored in details. In the study of additives, a significant finding was that citrate concentration shows a nonmonotonic behaviour on the amount of scale deposited. Fast screening of different additives (polymeric and molecular) and a quantitative ranking of their inhibitory properties on calcium carbonate deposition on a gold surface is described. Molecular and polymeric additives showed different inhibitory mechanisms on the scaling process and the technique employed gave a better insight into their mode of action