Kinetic studies on the chlorine evolution reaction (ChlER) on oxide-based materials have been the subject of a number of papers since the seventies, following the introduction of DSAs (Dimensionally Stable Anodes) in chlor-alkali plants. On the basis of experimental data, different pathways have been proposed for the reaction over the years. Actually, specific experimental conditions and different approaches in sample preparation may lead to conflicting explanations. In the present paper, the ChlER kinetics has been studied at four electrode materials based on iridium and titanium oxides (with a 1:2 molar ratio). Electrodes were synthetized at two temperatures (350 and 450 °C) and by two different preparation methods: physical vapor deposition (rf-magnetron sputtering) and a conventional sol-gel technique, using special precursors developed in our laboratory. Both methodologies guarantee a high level of reproducibility. As also observed by other authors, experimental data have shown a lack of linearity in Tafel plots, high b slopes and reaction orders with respect to chloride ≤ 1, which have been justified on the basis of a Volmer-Heyrovsky pathway, by considering a model proposed by Tilak and Conway in 1992. This approach highlighted the role of the adsorbed intermediates, also at low overpotentials, for all electrode materials. To analyze further the kinetics, Langmuir and Frumkin models for intermediates adsorption were considered. Values for the lateral interaction parameter g were estimated, which ranged between 1 and 10, in all cases. Concerning the effect of pH, its influence on the ChlER rate seems to be related only with electrode surface modifications, without any involvement of protons in the rate determining step of the process. A slight inhibiting effect was assessed, by increasing the protons concentration. Eventually, impedance spectroscopy analysis did not appear sensitive to intermediate adsorption, plausibly because of the low variation of the coverage within the Tafel region; a poorly resolved contribution related to porosity was found in the case of samples prepared at 350 °C.
Influence of the nature of the electrode material and process variables on the kinetics of the chlorine evolution reaction. (I) The case of IrO2-based electrocatalysts
ROSESTOLATO, Davide;FREGONI, Jacopo;FERRO, Sergio;DE BATTISTI, Achille
2014
Abstract
Kinetic studies on the chlorine evolution reaction (ChlER) on oxide-based materials have been the subject of a number of papers since the seventies, following the introduction of DSAs (Dimensionally Stable Anodes) in chlor-alkali plants. On the basis of experimental data, different pathways have been proposed for the reaction over the years. Actually, specific experimental conditions and different approaches in sample preparation may lead to conflicting explanations. In the present paper, the ChlER kinetics has been studied at four electrode materials based on iridium and titanium oxides (with a 1:2 molar ratio). Electrodes were synthetized at two temperatures (350 and 450 °C) and by two different preparation methods: physical vapor deposition (rf-magnetron sputtering) and a conventional sol-gel technique, using special precursors developed in our laboratory. Both methodologies guarantee a high level of reproducibility. As also observed by other authors, experimental data have shown a lack of linearity in Tafel plots, high b slopes and reaction orders with respect to chloride ≤ 1, which have been justified on the basis of a Volmer-Heyrovsky pathway, by considering a model proposed by Tilak and Conway in 1992. This approach highlighted the role of the adsorbed intermediates, also at low overpotentials, for all electrode materials. To analyze further the kinetics, Langmuir and Frumkin models for intermediates adsorption were considered. Values for the lateral interaction parameter g were estimated, which ranged between 1 and 10, in all cases. Concerning the effect of pH, its influence on the ChlER rate seems to be related only with electrode surface modifications, without any involvement of protons in the rate determining step of the process. A slight inhibiting effect was assessed, by increasing the protons concentration. Eventually, impedance spectroscopy analysis did not appear sensitive to intermediate adsorption, plausibly because of the low variation of the coverage within the Tafel region; a poorly resolved contribution related to porosity was found in the case of samples prepared at 350 °C.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
