M. Łukaszewski

Electrochemical behavior of palladium–gold alloys

Abstract The behavior of Pd–Au alloys, prepared by electrochemical codeposition, has been studied in acidic solutions (1 M H 2 SO 4 ) using mainly the cyclic voltammetry technique. Morphology of the alloy surface and bulk compositions were examined by SEM/EDAX method. Various types of voltametric behavior during potential cycling in the oxygen region are presented. The influence of hydrogen absorption on electrochemical properties of surface oxides is demonstrated. The problem of the nature of oxygen electrochemisorbed on Pd–Au alloys is discussed.

Hydrogen Electrosorption in Pd‐Pt‐Rh Alloys in the Presence of Adsorbed CO

Abstract Electrosorption of hydrogen in Pd‐Pt‐Rh alloys in the presence of adsorbed carbon monoxide has been examined using cyclic voltammetry (CV). CO adsorption has a remarkable influence on both hydrogen adsorption and absorption. Hydrogen adsorption is strongly inhibited by CO adsorption products. The processes of hydrogen absorption and desorption are not totally blocked but proceed much slower than in the absence of CO adsorbates. On electrodes covered with adsorbed CO oxidation of absorbed hydrogen is shifted to higher potentials. †Dedicated to the memory of Professor Harry B. Mark Jr.

On the Nature of Voltammetric Signals Originating from Hydrogen Electrosorption into Palladium-Noble Metal Alloys

Hydrogen sorption/desorption signals observed on cyclic voltammograms in experiments on hydrogen electrosorption into Pd-noble metal alloys (Pd-Au, Pd-Pt, Pd-Rh, Pd-Ru, Pd-Pt-Rh, Pd-Pt-Au) were characterized. The influence of electrosorption potential, scan rate and alloy bulk composition on the features of the hydrogen peaks was investigated. The experimental results were compared with those obtained on the basis of a model taken from the literature. It was confirmed that the rate of the α-β phase transition controls the overall rate of the process of hydrogen absorption/desorption into/from thin Pd-based electrodes. It was demonstrated that from the analysis of the changes of the hydrogen oxidation peak potential with the hydrogen electrosorption potential in cyclic voltammetric experiments it is possible to determine the limiting Pd bulk content, below which the β-phase in the alloy-hydrogen system is not formed.

Comparative Physicochemical and Electrochemical Characterization of the Structure and Composition of Thin Pd Binary and Ternary Codeposits with Pt, Ru, and Rh

Pd-Ru, Pd-Rh, Pd-Pt-Ru, and Pd-Rh-Ru electrodes were prepared as thin layers by potentiostatic codeposition or chemical co-precipitation of metals from baths containing mixtures of chloride salts. The formation of substitutional solid solutions, with lattice parameters smaller than that of pure Pd, was confirmed by X-ray diffraction (XRD). The compositions at various levels of sample volume and thickness were analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-AES), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and also electrochemically by cyclic voltammetry (CV) in 0.5 M H2SO4. The differences between surface, subsurface, and bulk compositions were compared for various systems in a wide composition spectrum.