This project has dealt with the mechanistic study of the electrocatalytic nitrite reduction, the selectivity-determining step of nitrate reduction. Nitrate is a polluting ion targeted by wastewater... Show moreThis project has dealt with the mechanistic study of the electrocatalytic nitrite reduction, the selectivity-determining step of nitrate reduction. Nitrate is a polluting ion targeted by wastewater remediation; electrochemistry strives to achieve selectivity to harmless products (N2). A multi-pronged approach has been followed, aimed at establishing the influence of several variables (electrocatalyst material, surface structure, pH and electrode potential) on the catalytic activity and the product distribution, which has been determined with in situ analytical techniques (mass spectrometry and infrared spectroscopy). The molecular underpinnings of nitrite reduction have thereby been unravelled for transition metals, showing that an optimal catalytic performance is achieved when metals intermediate affinities to reaction intermediates (Sabatier Principle). The all-important concept of structure sensitivity also applies to nitrite reduction at Pt electrodes, although only in alkaline media: a Pt(100) single-crystal is the sole Pt surface able to achieve the desired direct conversion of nitrite into 100% N2. Such selectivity is unparalleled for a simple monometallic surface and is an outstanding finding. Additionally, the nitrite-reducing performance of bio-inspired catalysts, (electroactive metalloporphyrins) was investigated. A further side-project of this PhD thesis has also been the electrochemical characterization of preferentially-oriented cuboid Pt nanoparticles synthesized with the innovative __cathodic corrosion__. Show less
This thesis describes the results of the fundamental research on the electro-oxidation of ethanol. In addition, the oxidation of intermediates in the ethanol electro-oxidation reaction, such as... Show moreThis thesis describes the results of the fundamental research on the electro-oxidation of ethanol. In addition, the oxidation of intermediates in the ethanol electro-oxidation reaction, such as acetaldehyde and adsorbed CO, has also been studied. The goal of this research is to provide deeper insight into the molecular level understanding of the mechanism, and how various operational parameters affect this mechanism. With these insights, the development of low temperature direct ethanol fuel cells (DEFC) can be advanced, since, ultimately, the goal of fundamental catalysis research is the rational design of new catalysts, for which the understanding of molecular mechanisms is of essential importance. The mechanism of the electro-oxidation reaction is investigated using electrochemical techniques, such as cyclic voltammetry and chronoamperometry, as well as in situ characterization techniques, such as surface enhanced Raman spectroscopy (SERS), Fourier transform infrared spectroscopy (FTIR) and online electrochemical mass spectrometry (OLEMS). Show less
