A DEMS study of methanol and formic acid oxidation on boron-doped diamond electrode

The electrochemical oxidation of methanol and formic acid in 1 M HClO4 is studied on boron-doped diamond electrode using differential electrochemical mass spectrometry (DEMS). DEMS is used to identify products and intermediates of the reaction monitored online during the potential sweep. The measurements show that the oxidation of both methanol and formic acid proceeds close to the potential of the oxygen evolution reaction, resulting in the appearance of an oxidation wave. During the oxidation, the oxygen evolution reaction shifts toward a higher potential, i.e., becomes a secondary reaction. Depending on the potential, either the formation of intermediates (partial oxidation) or the complete mineralization of organics, simultaneous with oxygen evolution, is observed. Diffusion limitation of the oxidation is clearly observed in parallel to the increase in O-2 formation. Methylformate is formed from methanol at potentials at which the local concentration of OH radicals is not sufficient for a complete mineralization. Formic acid oxidation proceeds in two waves; before the onset of oxygen evolution, an intermediate (probably oxalic acid) is produced in parallel to CO2 formation. Only in parallel to oxygen evolution is mineralization to CO2 is complete. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3207009] All rights reserved.

Reactivity of electrogenerated free hydroxyl radicals and activation of dioxygen on boron-doped diamond electrodes

Agnieszka Kapalka

Synthetic boron-doped diamond (BDD) thin film is an electrode material with high chemical and dimensional stability, low background current and a very wide potential window of water stability. Upon anodic polarization, BDD generates hydroxyl radicals that mediate the oxidation processes in the vicinity of the electrode surface. These hydroxyl radials are assumed to be free, i.e., not adsorbed on the electrode surface. Hydroxyl radicals are formed on BDD during water discharge, which is the rate determining step of oxygen evolution reaction. Oxygen evolution on BDD occurs at a high overpotential (over 1 V) with respect to the thermodynamic potential for O2 formation (E0OER = 1.23 V vs. SHE), but very close to the thermodynamic potential of HO• formation (E0HO• = 2.38 V vs. SHE). In the presence of organics, the onset potential of HO• formation changes, which affects the current–potential curves. As a consequence, oxidation of most of organic compounds on BDD results in a shift of the current–potential curves toward lower potentials. An exception is acetic acid, which adsorbs on the electrode surface causing auto-inhibition of its oxidation (oxidation is shifted toward higher potentials). In general, however, oxidation of organics on BDD is a fast reaction, controlled by the mass transport of organics to the anode surface. In the presence of an organic compound, hydroxyl radicals initiate chain reactions resulting in involvement (activation) of molecular oxygen dissolved in aerated aqueous solution. Direct evidence for this process was found during oxidation of acetic acid solution saturated with isotopically labelled 18O2. As a result, C18O2 and C16O18O were evolved proving that molecular oxygen participates in the mineralization of acetic acid. This electrochemically induced activation process is probably initiated by organic free radicals (R•) formed during reaction between organic compounds and hydroxyl radicals. Organic free radicals react further with molecular oxygen to form peroxy radical (RO2•). Organic peroxy radicals are very reactive and can initiate subsequent chain reactions leading, via several possible intermediates, to complete oxidation of organic compound. In fact, similar mechanism has been reported in radiolysis (upon X-ray or γ-ray) of aqueous solutions of acetic acid. This non-faradaic enhancement of the electrooxidation processes opens the possibilities for designing a less energy consuming degradation of organic pollutants on BDD anodes.

EPFL2008

Promotion électrochimique des catalyseurs à base de rhodium et d'iridium

Justyna Eaves

In this thesis, the electrochemical promotion of lr and Rh based catalysts was studied for the complete combustion of ethylene and propylene. The study was performed by using two types of electrocatalytical cells: a classical, pellet type cell and a tubular cell. This work has two major goals. The first one is the optimization of the employed electrocatalytical systems from electrochemical point of view. The second one concerns the study of the mechanism of the electrochemical promotion. The major part of this work concerns the electrochemical characterization of two cell types: a pellet type cell and a tubular cell. On the basis of the obtained results the modélisation of the potential and current distribution was performed, providing key parameters for the development of more efficient cell configurations. On one hand, these configurations ensure an uniform current distribution on the working electrode and enable correct catalyst potential measurement. On the other hand, it minimizes the current bypass in the bipolar tubular cell. The aim of the investigation in a two-compartment reactor was to evaluate and to compare the Au and Ir electrodes used in this work. Under 400°C, gold was found to be much worse material than lrÛ2 both as reference and counter electrode. Its potential was affected by oxygen and propylene adsorption and no equilibrium of electrochemical reaction was obtained at such low temperature. On the base of this knowledge, several materials better adapted to electrochemical promotion conditions have been proposed. Using the two-compartment reactor potential measurements under steady state conditions allowed to verify the mechanism of the propylene combustion on Rh and that of ethylene combustion on lr based catalysts proposed in the literature. Ameliorations of the existent kinetic models were proposed. The kinetic measurements were then analyzed with the additional help of ex situ XPS analysis. This study allowed to link the oxidation state of the catalyst surface with the extent of electrochemical promotion of the catalysts. It also allowed the ex situ observation of the appearance of new oxygen (oxide) species on the gas exposed surface of Ir catalyst. This new type of oxygen was different from the oxygen of Ir02 oxide, and it can represent the promoting species, according to backspiïïover theory. The same oxygen species was observed on well oxidized Ir02 catalyst surface, even before the polarization of this catalyst. Its presence was associated to the catalyst-support effect. It explains the high activity of Ir02 catalyst by comparison with the catalytic activity of lr metal. XPS analysis of Rh based catalysts indicated the possibly formation of an inferior Rh oxide (close to RhO) due to polarization. This may be a possible explanation of the observed permanent electrochemical promotion. Voltammetric charge measurements in very narrow potential window were performed while changing the catalyst thickness. The charge was demonstrated to be proportional to the catalyst thickness, suggesting the presence of the charged species on the gas exposed catalyst surface. The analogy between this situation and that of the emerged electrodes in liquid state electrochemistry was emphasized. The voltammograms obtained in this study were interpreted in the quite new, original way, which allowed to calculate the capacity of the different catalyst interfaces, the gas/catalyst interface, and the triple phase boundary, in good agreement with reference values from impedance spectroscopy measurements. Finally, the reaction rate transients during galvanostatic polarization of lr based catalyst have been moralized. The model fits well the experimental results.

EPFL2004

Electrochemical behavior of synthetic diamond thin film electrodes

Christos Comninellis, György Foti

The inertness and unique electrochem. properties of diamond present great potential for a variety of applications in aggressive environments. Preliminary results showed the widest known electrochem. window before water decompn., allowing new possibilities for both anodic and cathodic reactions. Studies of the oxidn. of org. compds. was performed with alcs. such as isopropanol, phenol and org. acids. Cyclic voltammetry demonstrates no activity in the potential range where water is stable. In the potential region of oxygen evolution, the org. compds. are mainly oxidized to CO2. No deactivation or redn. in the thickness of the electrode was obsd. No fouling of the diamond surface was detected. Also, no hydrodynamic effects were obsd. Concd. (1 M) and dild. (3 * 10-4 M) cyanide solns. were oxidized on diamond electrodes both in the presence and in the absence of chloride ions. The results show a direct oxidn. with a current efficiency of .apprx.40% for concd. solns. At low cyanide concns., the current efficiency is strongly increased by the presence of Cl-. Electrochem. redn. of cadmium and copper was carried out on diamond electrodes. Nonadherent deposits were obtained on diamond cathodes. [on SciFinder (R)]