Electrochemically deposited iridium-oxide: Estimation of intrinsic activity and stability in oxygen evolution in acid solution

Hydrated iridiumoxyhydroxide (IrOx) films were electrochemically deposited from an alkaline oxalic solution at constant anodic potentials and by applying a potential cycling protocol, in both cases with variation of the electrodeposition time. FromUV-vis spetroscopy of the solution for the deposition and their characterization it was concluded that a mixture of Ir(III)/Ir(IV) monomers participates in the deposition of IrOx film. X-ray photoelectron spectroscopy (XPS) of IrOx films indicated that both types of films contained hydrated Ir(IV) hydroxide as the dominant species, but in the film deposited by potential cycling the presence of the additional Ir(III) species was evident. The scanning electon microscopy (SEM) analysis of the surface morphology revealed that films deposited by potential cycling were more uniform than the films deposited at a constant potential. The amount of electrochemically active Ir-species on the surface of deposited IrOx films was estimated from the voltammetric charge of the Ir(III)/Ir(IV) transition. Depending on the film electrodeposition parameters, the values between 15 and 1080 nmol cm-2 were obtained. The electrochemically active surface area (ECSA) of IrOx films was calculated from cyclic voltammetry and electrochemical impedance spectroscopy (EIS) measurements and ranged from 3 to 131 cm(2) per 1 cm(2) of geometric surface area for various films. The activity and stability of IrOx films toward oxygen evolution reaction (OER) was investigated in 0.5 M H2SO4 solution under potentiostatic conditions. The intrinsic activity, stated as turnover frequency and specific current density normalized per ECSA, showed that the OER activity of IrOx films deposited by potential cycling are up to two and a half times higher than the activity of films deposited at a constant anodic potential. Potentiostatic stability test showed a decrease in OER current over time for both type of the films. Determination of ECSA, the amount of electroactive Ir species, XPS spectrum and SEM imaging after the test indicated that the decrease in OER activity was caused by partial dissolution and delamination of the film as well as by oxidation of highly active hydroxide Ir(III) species

Carbon Supported PtSn versus PtSnO2 Catalysts in Methanol Oxidation

Pt, PtSn and PtSnO2 catalysts supported on high surface area carbon synthesized by microwave assisted polyol procedure were tested for methanol oxidation. Based on TGA, EDX and XRD analysis, PtSn/C is composed of Pt and Pt3Sn phase while the rest of Sn is present in a form of very small tin oxide particles. This paper focuses on structure-activity relationships for CO tolerance and methanol oxidation reactions after addition of Sn to Pt catalysts. Alloying of Sn with Pt improves the rate of CO oxidation despite the fact that the pure Sn does not react with CO and therefore activity for methanol oxidation increases similar to 2 times in comparison to Pt/C catalyst. PtSn/C catalyst shows small advantage in comparison with PtSnO2/C catalyst due to the alloyed Sn and its electronic effect. Long term stability tests also confirmed that PtSn/C catalyst is somewhat better in comparison to PtSnO2/C

Ni-Sn coatings as cathodes for hydrogen evolution in alkaline solution. Chemical composition, phase composition and morphology effects

In this work the hydrogen evolution reaction (HER) onto Ni-Sn alloy coatings deposited at different current densities from the bath containing 0.1 M Sn2+ and 0.1 M Ni2+ ions in the pyrophosphate-glycine solution, was investigated by polarization curves and electrochemical impedance spectroscopy (EIS) measurements. Their morphology and chemical composition were investigated by scanning electron microscopy equipped with an energy-dispersive X-ray spectroscopy (SEM-EDS), while the phase composition was investigated by X-ray powder diffraction (XRPD). It was shown that their chemical composition, phase composition and morphology depend on the deposition current density. In deposited samples all detected phases, face centered cubic (fcc) Ni, close packed (hcp) hexagonal Ni3Sn, hexagonal Ni(1-i-x)Sn (0 lt x lt 0.5) which adopts NiAs structure type and monoclinic Ni3Sn4 (CoSn structure type), were of low crystallinity. The increase of the Ni-Sn alloy coatings catalytic activity for HER in 6 M KOH with increasing the deposition current density was shown to be the consequence of the change of all three parameters: chemical composition, phase composition and morphology, with the effect of morphology being the most pronounced

Tetragonal CoMn2O4 nanocrystals on electrospun carbon fibers as high-performance battery-type supercapacitor electrode materials

We herein report a simple two-step procedure for fabricating tetragonal CoMn2O4 spinel nanocrystals on carbon fibers. The battery-type behavior of these composite fibers arises from the redox activity of CoMn2O4 in an alkaline aqueous solution, which, in combination with the carbon fibers, endows good electrochemical performance and long-term stability. The C"CoMn2O4 electrode exhibited high specific capacity, up to 62 mA h g(-1) at 1 A g(-1) with a capacity retention of around 90% after 4000 cycles. A symmetrical coin-cell device assembled with the composite electrodes delivered a high energy density of 7.3 W h kg(-1) at a power density of 0.1 kW kg(-1), which is around 13 times higher than that of bare carbon electrodes. The coin cell was cycled for 5000 cycles with 96.3% capacitance retention, at a voltage of up to 0.8 V, demonstrating excellent cycling stability

Electrochemical and Crystallographic Aspects of Lead Granular Growth

Lead granules synthesized by the potentiostatic regime of electrolysis were characterized by the scanning electron microscopy technique. Effect of the different parameters of electrolysis, such as solution composition, overpotential of electrodeposition, and quantity of the electricity, on lead granular growth has been systematically investigated. Aside from the electrochemical aspects of lead granular growth, crystallographic aspects of the obtained granules were also analyzed. In the dependence of the electrodeposition conditions, granules of various shapes were obtained. The granules, such as octahedrons and hexagons, as well as many various types of twinned particles: single-twinned, multiply-twinned, lamellar-twinned, and many other complicated shapes denoted as polyparticles, were synthesized through regulation of the parameters of electrolysis. Increasing both the concentration of Pb2+ ions and overpotential of the electrodeposition favored the formation of more complicated forms. Formation of granules of specified crystallographic characteristics was also correlated with the basic principle of metal electrocrystallization