Ανάπτυξη λεπτών υμενίων για χρήση στην ηλεκτροχημική ενίσχυση της κατάλυσης

Abstract

In the present work the electrochemical promotion of Pt/YSZ and Pt/TiO2/YSZ catalyst-electrodes has been investigated, for the model reaction of C2H4 oxidation in an atmospheric pressure single chamber reactor, under oxygen excess between 280 and 375oC. It has been found that the presence of a dispersed TiO2 thin layer between the catalyst electrode and the solid electrolyte (YSZ), results in a significant increase of the magnitude of the electrochemical promotion of catalysis (EPOC) effect. The rate enhancement ratio upon current application and the faradaic efficiency values, were found to be a factor of 2.5 and 4 respectively, higher than those in absence of TiO2. This significantly enhanced EPOC effect via the addition of TiO2 suggests that the presence of the porous TiO2 layer enhances the transport of promoting O2- species onto the Pt catalyst surface. This enhancement may be partly due to morphological factors, such as increased Pt dispersion and three-phase-boundary length in presence of the TiO2 porous layer, but appears to be mainly caused by the mixed ionic-electronic conductivity of the TiO2 layer which results to enhanced O2- transport to the Pt surface via a self-driven electrochemical promotion O2- transport mechanism. Also, the use of thin catalytic Pt sputtered electrodes (Pt/YSZ/Au) was examined in the MEPR for the model reaction of C2H4 oxidation. It was found that such thin electrodes are catalytically active and can be electropromoted even under high gas flow rates (25 l/min) or high space velocity (HSV~12000 s-1), close to those that the industrial reactors operate. A single chamber reactor equipped with a Cu/TiO2/YSZ electrode and a monolithic electropromoted reactor (MEPR) with up to 20 thin Cu/TiO2/YSZ plate cells were also used to investigate the hydrogenation of CO2 at atmospheric pressure. Utilizing the single chamber reactor CO and CH4 was produced with selectivity to CH4 up to 17%. Both positive and negative applied potential significantly enhance the hydrogenation rate and selectivity to CH4. It was found that the addition of small (~0.5kPa) amounts of CH3OH in the feed has a pronounced promotional effect on the reaction rate and selectivity of the Cu/TiO2/YSZ cells. The selective reduction of CO2 to CH4 starts at 280oC (vs 350oC in absence of CH3OH) with near 100% CH4 selectivity at open-circuit and under polarization conditions at temperatures 280–380oC. Utilizing a MEPR equipped with 20 Cu/TiO2/YSZ cells CO, CH4 and C2H4 were produced with selectivities to CH4 and C2H4 up to 80% and 2%. The maximum CO2 conversion reached 40% at 380oC. The addition of small (~0.5 kPa) amounts of CH3OH in the feed has also a pronounced promotional effect on the reaction rate and selectivity to CH4 (near 100%) at open-circuit and under polarization conditions at temperatures 220–380oC. The results show the possibility of direct CO2 conversion to useful products in a MEPR via electrochemical promotion at atmospheric pressure.