The investigation of hydrogen oxidation reaction (HOR) in alkaline conditions has been the subject of a wide interest in the past few years with the rise of alkaline membrane fuel cells (AMFCs). In particular, the quest for the lowest content of platinum group metals (PGMs) in the HOR catalyst is ongoing. In this article, we propose the use of a nanoscale Pd layer partially covering a Ni film to provide the most efficient use of the PGM in the HOR catalyst. The Pd/Ni electrodes were prepared by spontaneous and electrolytic deposition of Pd onto smooth polycrystalline Ni surfaces with different surface compositions. The electrodes were characterized by cyclic voltammetry and atomic force microscopy. Electrocatalytic activity in HOR of the Pd/Ni electrodes was measured in alkaline solution by rotating disc electrode method. In the manuscript, we demonstrate that a Pd coverage as low as 1.5% vs. Ni coverage is sufficient to provide a high current density compared to pure Ni. The current density linearly increases with the Pd coverage up to a Pd coverage of 17%; upon further increase in the Pd coverage, the current density reaches a plateau, i.e. the diffusion limit for the HOR process.The comparison with Pd supported on carbon shows the clear benefit for the bimetallic catalyst.
The adsorption layer of the nonionic surfactant triethoxy monooctylether C8E3 has been investigated at the free water surface by means of both experimental and computer simulation methods. The surface tension of the aqueous solution of C8E3 has been measured by pendant drop shape analysis in the entire concentration range in which C8E3 is soluble in water. The data obtained from these measurements are used to derive the adsorption isotherm. The critical micellar concentration and the surface excess concentration of the saturated adsorption layer are found to be 7.48 mM and 4.03 micromol/m2, respectively, the latter value corresponding to the average area per molecule of 41 A2. In order to analyze the molecular level structure of the unsaturated adsorption layer, Monte Carlo simulations have been performed at four different surface concentration values, i.e., 0.68, 1.36, 2.04, and 2.72 micromol/m2, respectively. It has been found that the water surface is already almost fully covered at the lowest surface density value investigated, and the adsorbed molecules show a strong preference for lying parallel with the interface in elongated conformations. No sign of the penetration of the hydrophilic triethoxy headgroups into the aqueous phase to any extent has been observed. With increasing surface densities the preferential orientation of the apolar octyl tails gradually turns from lying parallel with the interface to pointing toward the vapor phase by their CH3 end, whereas the conformation of the adsorbed molecules becomes gradually less elongated. Both of these changes lead to the increase of the number of C8E3 molecules being in a direct contact (i.e., forming hydrogen bonds) with water. However, the increasing number of the C8E3 molecules hydrogen bonded to water is found to be accompanied by the weakening of this binding, i.e., the decrease of both the number of hydrogen bonds a bound C8E3 molecule forms with water and the magnitude of the average binding energy of the adsorbed C8E3 molecules.
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