Photoelectrochemical activity of oxide films on silver-palladium alloys in an alkaline solution
Abstract
The continuously increasing energy needs of humanity are causing a number of serious environmental problems. One of the methods for the solution of such problems is the photocatalytic or photoelectrochemical production of a fairly environmentally friendly fuel - hydrogen gas. The studies in this field are mainly associated with the search for semiconductor material that is most suitable for photocatalysis. Oxides of some metals, including silver, can be used as such a material. The photocatalytic or
photoelectrochemical activity of the oxide is determined by the features of its electronic structure and can increase significantly when combined with another oxide. Therefore, anodic oxidation of binary alloys is considered as an accessible and, most importantly, controlled method for combining oxides of various metals. The aim of this study was to reveal the role of alloying of silver with palladium in the photoelectrochemical activity of oxide films anodicly formed in deaerated 0.1 M KOH.
The anodic formation of oxide films was carried out by the potentiodynamic method in an alkaline medium on silver and its alloys with palladium, the concentration of which ranged from 5 to 30 at. %. Photoelectrochemical activity was assessed by the magnitude of the photocurrent generated in the oxide film directly during its formation and subsequent reduction. The photocurrent was measured in a pulsed lighting mode of the electrode surface with a quasimonochromatic LED with a wavelength of 470 nm.
A positive photocurrent was recorded on all studied samples, which indicates the predominance of donor structural defects in the forming oxide film. With an increase in the concentration of palladium in the alloy, the range of potentials of photoelectrochemical activity of formed anodicly oxide films expanded. The maximum photocurrent achieved during the anodic potentiodynamic formation of the oxide film was higher, the lower the palladium concentration was. During the cathodic potentiodynamic reduction of the formed oxide films, it was possible to record even higher values of photocurrents than during their anodic formation. The highest photoelectrochemical activity, characterized by a photocurrent density of 2.89 μA/cm2 and incidental proton-to-electron conversion efficiency of 7.6%, was observed in the oxide film anodically
formed on silver by the time the potential reached 0.6 V. Comparable values of the photocurrent and quantum efficiency (2.12 μA/cm2 and 5.6%) were recorded in the oxide film on the alloy with a palladium concentration of 10 at. % during its potentiodynamic reduction
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