Two series of Ni/Ce(Ti/Nb)ZrO2 catalysts were prepared using citrate route and original solvothermal continuous flow synthesis in supercritical isopropanol and studied in dry reforming of methane (DRM). TEM, XPS and FTIRS of adsorbed CO confirm influence of support composition and preparation method on the catalysts’ morphology and surface features. The oxygen mobility was studied by isotope heteroexchange with C18O2. After testing in DRM, carbon deposits after catalysts’ testing in DRM were investigated by temperature-programmed oxidation with thermo-gravimetric analysis. The lowest amounts of carbon deposits were obtained for unmodified Ni-CeZr and Ni-CeNbZr compositions. Ti addition lead to an increased amount of carbon, which was removed at higher temperatures. The use of supercritical supports also resulted in the formation of a higher amount of coke. Catalysts prepared by the supercritical synthesis were tested in DRM for 25 h. The highest activity drop was observed in the first three hours. For all compositions, close values of carbon deposits were revealed.
12 July 2013 in Russian Journal of Electrochemistry
The mechanism of oxygen transfer in layered nickelates having a Ruddlesden-Popper structure and their nanocomposites with Ce0.9Gd0.1O2 − δ (GDC) and Y2(Ti0.8Zr0.2)1.6Mn0.4O7 − δ (YTZM) solid electrolytes having fluorite and pyrochlore structures were studied by the oxygen isotope heteroexchange method in a flow and static reactor, thermoprogrammed desorption, and semiempirical interacting bonds method. The experimental heteroexchange data were adequately described by assuming that all atoms were equivalent in exchange in the bulk of layered nickelates, which was consistent with the cooperative oxygen migration model with fast exchange between the interstitial and regular positions. Strong interaction between the domains of the nickelate phases and solid electrolytes in nanocomposites, accompanied by a redistribution of cations between the phases, hindered the cooperative oxygen migration and led to a decrease in the diffusion coefficient as the exchange rate increased.
1 August 2019 in Russian Journal of Electrochemistry
— Oxygen transport (including oxygen mobility and surface reactivity) is one of the important factors governing electrochemical activity of solid oxide fuel cells electrodes as well as oxygen...
Oxygen and hydrogen mobility are among the important characteristics for the operation of solid oxide fuel cells, permselective membranes and many other electrochemical devices. This, along with other characteristics, enables a high-power density in solid oxide fuel cells due to reducing the electrolyte resistance and enabling the electrode processes to not be limited by the electrode-electrolyte-gas phase triple-phase boundary, as well as providing high oxygen or hydrogen permeation fluxes for membranes due to a high ambipolar conductivity. This work focuses on the oxygen and hydrogen diffusion of mixed ionic (oxide ionic or/and protonic)–electronic conducting materials for these devices, and its role in their performance. The main laws of bulk diffusion and surface exchange are highlighted. Isotope exchange techniques allow us to study these processes in detail. Ionic transport properties of conventional and state-of-the-art materials including perovskites, Ruddlesden–Popper phases, fluorites, pyrochlores, composites, etc., are reviewed.