Impedance spectroscopic investigation of a Rh/YSZ catalyst under polarization

Electrochemical impedance spectra at 450-600 °C and $${P_{{\rm{O}}_{\rm{2}} } = 0.5}$$ kPa of a rhodium catalyst interfaced with yttria-stabilized-zirconia (Rh/YSZ) were compared with a model based on the mechanism of electrochemical promotion. In the proposed equivalent electric circuit, existence of an "effective” double layer at the gas-exposed catalyst surface and its potential-controlled modification via diffusion of oxygen ions between the O2− conducting solid electrolyte support (YSZ) and the catalyst are represented by two additional elements: adsorption capacitance and Warburg impedance. Under positive polarization, the adsorption capacitance increases dramatically indicating reinforcement of the "effective” double layer at the catalyst/gas interface, in agreement with the observation known from electrochemical promotion practice that positive polarization of a rhodium electrode leads to rhodium oxide reduction, hence, to dramatic increase in catalytic reaction rat

Relation between potential and catalytic activity of rhodium in propylene combustion

The relation between the catalyst potential and the catalytic performance has been investigated in the gas-phase combustion of propylene with oxygen over rhodium catalysts at 375 °C. The rhodium catalyst, deposited on yttria-stabilized zirconia (YSZ) solid electrolyte, also served as working electrode in the electrochemical cell. Under open-circuit conditions, the measured catalyst potential was found to be a sensitive indicator of the oxidation state of the rhodium catalyst, which influences the catalytic reaction rate dramatically and depends strongly both on the method of catalyst film preparation and on the composition of the reacting gas mixture. In turn, under closed-circuit conditions, the applied catalyst potential is a convenient tool to maintain the catalyst in its more active, reduced form and to control its catalytic performance. The activity of atomic oxygen at the three-phase boundary (tpb) during open-circuit catalytic reaction was estimated from solid electrolyte potentiometric (SEP) measurements, in good agreement with the average surface oxidation state obtained from XRD and XPS analyses. O/Rh atomic ratios higher than stoichiometric were found by XPS at the outer surface of the catalysts suggesting a strong open circuit O2− spillover due to strong metal support interactions (SMSI) and a concomitant extension of the electric double layer to the gas-exposed catalyst surface, similarly to emersed electrodes in aqueous electrochemistry. Applying potentials up to several hundreds of mV, highly nonfaradaic promotion of propylene combustion was achieved. Electrochemical promotion of catalysis (EPOC) was most efficient at stoichiometric gas composition, that is, close to the limit of surface reduction, and with the catalyst exhibiting the smallest O2− spillover population at open-circuit condition

Electrochemical modification of the catalytic activity of TiO2/YSZ supported rhodium films

The electrochemical activation of ethylene oxidation was studied over rhodium catalysts of different thickness (40, 100 and 160 nm) sputtered on top of a thin layer of TiO2 deposited on YSZ. The strong relationship between catalytic activity and oxidation state of rhodium was confirmed. Under open-circuit operation the catalyst potential appears as a suitable indicator of the surface oxidation state of rhodium allowing a prediction of the catalytic behavior from solid electrolyte potentiometric measurements. Under closed-circuit conditions the catalyst potential was used as a tool to tune the catalytic activity of rhodium which showed increasing promotional efficiency with decreasing catalyst film thicknes

A novel method for the preparation of bi-metallic (Pt-Au) nanoparticles on boron doped diamond (BDD) substrate: application to the oxygen reduction reaction

A novel method was developed to synthesize bi-metallic nanoparticles (Au-Pt) on boron-doped diamond (BDD) substrate. This method consisted of (a) deposition of a small amount of gold (equivalent to a few monolayers) by sputtering on the BDD surface, (b) heat treatment of the obtained sample at 600°C in air, resulting in the formation of stable nanoparticles on BDD (Au/BDD electrode), (c) electrodeposition of Pt on the Au/BDD surface occurring preferentially on the Au nanoparticles, and finally (d) heat treatment at 400°C to enhance the interaction between Au and Pt. The ratio between Au and Pt nanoparticles can be modified by modifying the amount of electrodeposited Pt and was estimated using cyclic voltammetry. These Pt-Au/BDD composite electrodes were used to study oxygen reduction using both potential sweep (cyclic voltammetry) and hydrodynamic (turbine electrochemical cell) method

Effect of microstructure on the electrochemical behavior of Pt/YSZ electrodes

Two types of O2,Pt/YSZ electrode preparation (Pt/YSZ cermet and sputtered platinum film) have been characterized by SEM and by cyclic voltammetry and chronoamperometry at 450 °C in 20 kPa oxygen. Cyclic voltammetry on the cermet and on the as-sputtered non-porous film electrode evidenced the characteristics of the PtO x /Pt couple. The corresponding redox reaction occurs at the metal/electrolyte interface and it manifests itself by an anodic wave and one of more cathodic peaks in the voltammogram. Heat treatment of the sputtered electrode at 700 °C in oxygen atmosphere resulted in a porous structure by coalescence of the film. Cyclic voltammetry of the porous film electrode featured the characteristics of the O2/O2− couple, i.e. the redox reaction of gaseous oxygen occurring at the tpb. Chronoamperometry at anodic potentials showed similar features for both electrode preparations: an initial inhibition, a current peak and a slow activation, the latter being related to the phenomenon of electrochemical promotion of catalysi

Deposition of clusters and nanoparticles onto boron-doped diamond electrodes for electrocatalysis

Metal and metal oxide particles and nanoparticles, differing from each other by their nature and synthesis technique, were deposited onto boron-doped diamond (BDD) thin film electrodes. The applicability in electrocatalysis of thermally decomposed IrO2 and Au nanoparticles, electrodeposited Pt particles, dendrimer-encapsulated Pt nanoparticles (Pt DENs) and microemulsion-synthesized Pt/Ru nanoparticles was studied, once deposited on BDD substrate. In all cases, the electrochemical response of the composite electrodes could be solely attributed to the supported particles. All the particles, with the exception of Pt DENs, exhibited electrocatalytic activity. Pt DENs inactivity has been attributed to insufficient removal of the dendrimer polymer matrix. It was concluded that the BDD electrode is a suitable substrate for the electrochemical investigation of supported catalytic nanoparticle

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO2 anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm−3 were carried out on a Ta/PbO2 anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm−3). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%

Electrochemical oxidation of water on synthetic boron-doped diamond thin film anodes

Electrolysis in aqueous 1 M HClO4 and 1 M H2SO4 solutions has been carried out under galvanostatic conditions using boron-doped diamond electrodes (BDD). Analyses of the oxidation products have shown that in 1 M HClO4 the main reaction is oxygen evolution, while in H2SO4 the main reaction is the formation of H2S2O8. In both electrolytes small amounts of O3 and H2O2 are formed. Finally, a simplified mechanism involving hydroxyl radicals formed by water discharge has been proposed for water oxidation on boron-doped diamond anode

Deposition of tin oxide, iridium and iridium oxide films by metal-organic chemical vapor deposition for electrochemical wastewater treatment

In this research, the specific electrodes were prepared by metal-organic chemical vapor deposition (MOCVD) in a hot-wall CVD reactor with the presence of O2 under reduced pressure. The Ir protective layer was deposited by using (Methylcyclopentadienyl) (1,5-cyclooctadiene) iridium (I), (MeCp)Ir(COD), as precursor. Tetraethyltin (TET) was used as precursor for the deposition of SnO2 active layer. The optimum condition for Ir film deposition was at 300 °C, 125 of O2/(MeCp)Ir(COD) molar ratio and 12 Torr of total pressure. While that of SnO2 active layer was at 380 °C, 1200 of O2/TET molar ratio and 15 Torr of total pressure. The prepared SnO2/Ir/Ti electrodes were tested for anodic oxidation of organic pollutant in a simple three-electrode electrochemical reactor using oxalic acid as model solution. The electrochemical experiments indicate that more than 80% of organic pollutant was removed after 2.1 Ah/L of charge has been applied. The kinetic investigation gives a two-step process for organic pollutant degradation, the kinetic was zero-order and first-order with respect to TOC of model solution for high and low TOC concentrations, respectively

Electrochemical comparison between IrO2 prepared by anodic oxidation of pure iridium and IrO2 prepared by thermal decomposition of H2IrC16 precursor solution

Surface redox activities, oxygen evolution reaction (OER), oxidation of formic acid (FA), and anodic stability were investigated and compared for IrO2 electrodes prepared by two techniques: the thermal decomposition of H2IrCl6 precursor (TDIROF) and the anodic oxidation of metallic iridium (AIROF). Surface redox activities involved on the AIROF were found to be much faster than those involved on the TDIROF. Concerning the oxygen evolution reaction, both films show a similar mechanism and specific electrocatalytic activities. The situation seems to be different for FA oxidation. In fact, on TDIROF, the oxidation of FA and the OER compete involving the same surface redox couple Ir(VI)/Ir(IV) contrary to FA oxidation on AIROF, where the Ir(V)/Ir(IV) surface redox couple is involved. Finally, electrode stability measurements have shown that contrary to TDIROF, which are very stable under anodic polarization, the AIROF are rapidly corroded under anodic treatment. This corrosion is enhanced even further in the presence of formic acid