Ambient Pressure XPS Study of Mixed Conducting Perovskite-type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization

The oxygen exchange activity of mixed conducting oxide surfaces has been widely investigated, but a detailed understanding of the corresponding reaction mechanisms and the rate-limiting steps is largely still missing. Combined in situ investigation of electrochemically polarized model electrode surfaces under realistic temperature and pressure conditions by near-ambient pressure (NAP) XPS and impedance spectroscopy enables very surface-sensitive chemical analysis and may detect species that are involved in the rate-limiting step. In the present study, acceptor-doped perovskite-type La0.6Sr0.4CoO3-δ (LSC), La0.6Sr0.4FeO3-δ (LSF), and SrTi0.7Fe0.3O3-δ (STF) thin film model electrodes were investigated under well-defined electrochemical polarization as cathodes in oxidizing (O2) and as anodes in reducing (H2/H2O) atmospheres. In oxidizing atmosphere all materials exhibit additional surface species of strontium and oxygen. The polaron-type electronic conduction mechanism of LSF and STF and the metal-like mechanism of LSC are reflected by distinct differences in the valence band spectra. Switching between oxidizing and reducing atmosphere as well as electrochemical polarization cause reversible shifts in the measured binding energy. This can be correlated to a Fermi level shift due to variations in the chemical potential of oxygen. Changes of oxidation states were detected on Fe, which appears as FeIII in oxidizing atmosphere and as mixed FeII/III in H2/H2O. Cathodic polarization in reducing atmosphere leads to the reversible formation of a catalytically active Fe0 phase

Origin of different deactivation of Pd/SnO₂ and Pd/GeO₂ catalysts in methanol dehydrogenation and reforming: A comparative study

Pd particles supported on SnO2 and GeO2 have been structurally investigated by X-ray diffraction, (High-Resolution) transmission and scanning electron microscopy after different reductive treatments to monitor the eventual formation of bimetallic phases and catalytically tested in methanol dehydrogenation/reforming. For both oxides this included a thin film sample with well-defined Pd particles and a powder catalyst prepared by incipient wetness impregnation. The hexagonal and the tetragonal polymorph were studied for powder GeO2. Pd2Ge formation was observed on all GeO2-supported catalysts, strongly depending on the specific sample used. Reduction of the thin film at 573 K resulted in full transformation into the bimetallic state. The partial solubility of hexagonal GeO2 in water and its thermal structural instability yielded Pd2Ge formation at 473 K, at the cost of a structurally inhomogeneous support and Ge metal formation at higher reduction temperatures. Pd on tetragonal GeO2 entered a state of strong metal–support interaction after reduction at 573–673 K, resulting in coalescing Pd2Ge particles on a sintered and re-crystallized support, apparently partially covering the bimetallic particles and decreasing the catalytic activity. Pd2Ge on amorphous thin film and hexagonal GeO2 converted methanol primarily via dehydrogenation to CO and H2. At 573 K, formation of Pd2Sn and also PdSn occurred on the Pd/SnO2 thin film. Pd3Sn2 (and to some extent Pd2Sn) were predominantly obtained on the respective powder catalyst. Strong deactivation with increasing reduction temperature was observed, likely not based on the classical strong metal–support interaction effect, but rather on a combination of missing active structural ensembles on Sn-enriched bimetallic phases and the formation of metallic β-Sn. Correlations to Pd and its bimetallics supported on ZnO, Ga2O3 and In2O3 were also discussed

Methane Decomposition and Carbon Growth on Y₂O₃, Yttria-Stabilized Zirconia, and ZrO₂

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3 and ZrO2 by a range of different chemical, structural and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results therefore indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. By comparison of the three oxides we could moreover elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents

Structural and Electrochemical Properties of Physisorbed and Chemisorbed Water Layers on the Ceramic Oxides Y2O3, YSZ, and ZrO2

A combination of operando Fourier transform infrared spectroscopy, operando electrochemical-impedance spectroscopy, and moisture-sorption measurements has been exploited to study the adsorption and conduction behavior of H2O and D2O on the technologically important ceramic oxides YSZ (8 mol % Y2O3), ZrO2, and Y2O3. Because the characterization of the chemisorbed and physisorbed water layers is imperative to a full understanding of (electro-)catalytically active doped oxide surfaces and their application in technology, the presented data provide the specific reactivity of these oxides toward water over a pressure-and-temperature parameter range extending up to, e.g., solid-oxide fuel cell (SOFC)-relevant conditions. The characteristic changes of the related infrared bands could directly be linked to the associated conductivity and moisture-sorption data. For YSZ, a sequential dissociative water (“ice-like” layer) and polymeric chained water (“liquid-like”) water-adsorption model for isothermal and isobaric conditions over a pressure range of 10-5 to 24 mbar and a temperature range from room temperature up to 1173 K could be experimentally verified. On pure monoclinic ZrO2, in contrast to highly hydroxylated YSZ and Y2O3, a high surface concentration of OH groups from water chemisorption is absent at any temperature and pressure. Thus, the ice-like and following molecular water layers exhibit no measurable protonic conduction. We show that the water layers, even under these rather extreme experimental conditions, play a key role in understanding the function of these materials. Furthermore, the reported data are supposed to provide an extended basis for the further investigation of close-to-real gas adsorption or catalyzed heterogeneous reactions.(VLID)1371561Accepted versio

Tuning of the Copper-Zirconia Phase Boundary for Selectivity Control of Methanol Conversion

Chemical-vapor deposition (CVD) of a Zr(O-tBu)4 precursor on different Cu substrates was used to prepare model systems for ZrOxHy-Cu catalysts and to test their reactivity and selectivity in methanol steam reforming (MSR). A partially hydroxylated and initially fully oxidized submonolayer ZrOxHy surface species results, exhibiting a pronounced catalytic synergism between the ZrOxHy overlayer and Cu only with respect to partial methanol dehydrogenation to formaldehyde. Thus, it differs strongly from in situ grown ZrOxHy layers on Cu formed from an initially bimetallic mixed Zr/ZrOx state under MSR conditions. CVD-grown Zr-OH groups are not stable under MSR conditions; thus reversible in situ hydroxylation and water-activating reaction channels are suppressed. Comparison of the two model systems indicates that only a dedicated Cu-ZrOxHy interface with in situ formed and reversibly hydroxylated sites (accessible only from initially (inter)metallic Cu/Zr species at the surface) leads to water activation, total oxidation of intermediate formaldehyde, and enhanced CO2 selectivity.(VLID)1371551Accepted versio

Electrocatalytic Enhancement of CO Methanation at the Metal Electrolyte Interface Studied Using In Situ X ray Photoelectron Spectroscopy

For the direct reduction of CO2 and H2O in solid oxide electrolysis cells SOECs with cermet electrodes toward methane, a fundamental understanding of the role of elemental carbon as a key intermediate within the reaction pathway is of eminent interest. The present synchrotron based in situ near ambient pressure X ray photoelectron spectroscopy NAP XPS study shows that alloying of Ni yttria stabilized zirconia YSZ cermet electrodes with Cu can be used to control the electrochemical accumulation of interfacial carbon and to optimize its reactivity toward CO2. In the presence of syngas, sufficiently high cathodic potentials induce excess methane on the studied Ni yttria stabilized zirconia YSZ , NiCu YSZ and Pt gadolinium doped ceria GDC cermet systems. The hydrogenation of carbon, resulting from CO activation at the triple phase boundary of Pt GDC, is most efficien

The Chemical Evolution of the La0.6Sr0.4CoO3−δ Surface Under SOFC Operating Conditions and Its Implications for Electrochemical Oxygen Exchange Activity

© The Author(s) 2018Owing to its extraordinary high activity for catalysing the oxygen exchange reaction, strontium doped LaCoO3 (LSC) is one of the most promising materials for solid oxide fuel cell (SOFC) cathodes. However, under SOFC operating conditions this material suffers from performance degradation. This loss of electrochemical activity has been extensively studied in the past and an accumulation of strontium at the LSC surface has been shown to be responsible for most of the degradation effects. The present study sheds further light onto LSC surface changes also occurring under SOFC operating conditions. In-situ near ambient pressure X-ray photoelectron spectroscopy measurements were conducted at temperatures between 400 and 790 °C. Simultaneously, electrochemical impedance measurements were performed to characterise the catalytic activity of the LSC electrode surface for O2 reduction. This combination allowed a correlation of the loss in electro-catalytic activity with the appearance of an additional La-containing Sr-oxide species at the LSC surface. This additional Sr-oxide species preferentially covers electrochemically active Co sites at the surface, and thus very effectively decreases the oxygen exchange performance of LSC. Formation of precipitates, in contrast, was found to play a less important role for the electrochemical degradation of LSC.Fonds zur Förderung der wissenschaftlichen Forschung (FWF)212921411