Unveiling Key Interface Characteristics of Ni/Yttria-Stabilized Zirconia Solid Oxide Cell Electrodes in H2O Electroreduction Using Operando X-ray Photoelectron Spectroscopy.

Nickel/yttria-stabilized zirconia (YSZ) composites are the most commonly used fuel electrodes for solid oxide cells. While microstructural changes of Ni/YSZ during operational conditions have been thoroughly investigated, there is limited knowledge regarding Ni/YSZ surface chemistry under working conditions. In this study, we examine the interaction between Ni/YSZ electrodes and water vapor under open circuit and polarization conditions, utilizing near ambient pressure soft and hard X-ray photoelectron spectroscopies. Miniature cells with conventional porous Ni/YSZ composite cermet cathodes were modified to facilitate the direct spectroscopic observation of the functional electrode's areas close to the interface with the YSZ electrolyte. The results highlight dynamic changes in the oxidation state and composition of Ni/YSZ under H2 and H2O atmospheres. We also quantify the accumulation of impurities on the electrode surface. Through adjustments in the pretreatment of the cell, the correlation between the nickel surface oxidation state and the cell's electrochemical performance during H2O electroreduction is established. It is unequivocally shown that nickel surface oxidation in H2O electrolysis favors NiO over Ni(OH)x, providing critical insights into the mechanism of Ni-phase redistribution within the electrode during long-term operation. Depth-dependent photoemission measurements, combined with theoretical quantitative simulations, reveal that NiO and Ni phases are uniformly mixed on the surface during H2O electrolysis. This differs from the conventional expectation of a NiO-shell/Ni-core configuration in gas phase oxidation. These findings provide crucial insights into the surface chemistry of Ni/YSZ electrodes under conditions relevant to H2O electrolysis, elucidating their impact on the electrochemical performance of the cell.

Interfacial Chemistry in the Electrocatalytic Hydrogenation of CO2 over C-Supported Cu-Based Systems.

Operando soft and hard X-ray spectroscopic techniques were used in combination with plane-wave density functional theory (DFT) simulations to rationalize the enhanced activities of Zn-containing Cu nanostructured electrocatalysts in the electrocatalytic CO2 hydrogenation reaction. We show that at a potential for CO2 hydrogenation, Zn is alloyed with Cu in the bulk of the nanoparticles with no metallic Zn segregated; at the interface, low reducible Cu(I)-O species are consumed. Additional spectroscopic features are observed, which are identified as various surface Cu(I) ligated species; these respond to the potential, revealing characteristic interfacial dynamics. Similar behavior was observed for the Fe-Cu system in its active state, confirming the general validity of this mechanism; however, the performance of this system deteriorates after successive applied cathodic potentials, as the hydrogen evolution reaction then becomes the main reaction pathway. In contrast to an active system, Cu(I)-O is now consumed at cathodic potentials and not reversibly reformed when the voltage is allowed to equilibrate at the open-circuit voltage; rather, only the oxidation to Cu(II) is observed. We show that the Cu-Zn system represents the optimal active ensembles with stabilized Cu(I)-O; DFT simulations rationalize this observation by indicating that Cu-Zn-O neighboring atoms are able to activate CO2, whereas Cu-Cu sites provide the supply of H atoms for the hydrogenation reaction. Our results demonstrate an electronic effect exerted by the heterometal, which depends on its intimate distribution within the Cu phase and confirms the general validity of these mechanistic insights for future electrocatalyst design strategies.

CO(2)-selective methanol steam reforming on In-doped Pd studied by in situ X-ray photoelectron spectroscopy.

In situ X-ray photoelectron spectroscopy (in situ XPS) was used to study the structural and catalytic properties of Pd-In near-surface intermetallic phases in correlation with previously studied PdZn and PdGa.Room temperature deposition of ∼4 monolayer equivalents (MLEs) of In metal on Pd foil and subsequent annealing to 453 K in vacuum yields a ∼1:1 Pd/In near-surface multilayer intermetallic phase. This Pd(1)In(1) phase exhibits a similar "Cu-like" electronic structure and indium depth distribution as its methanol steam reforming (MSR)-selective multilayer Pd(1)Zn(1) counterpart.Catalytic characterization of the multilayer Pd(1)In(1) phase in MSR yielded a CO(2)-selectivity of almost 100% between 493 and 550 K. In contrast to previously studied In(2)O(3)-supported PdIn nanoparticles and pure In(2)O(3), intermediate formaldehyde is only partially converted to CO(2) using this Pd(1)In(1) phase. Strongly correlated with PdZn, on an In-diluted PdIn intermetallic phase with "Pd-like" electronic structure, prepared by thermal annealing at 623 K, methanol steam reforming is suppressed and enhanced CO formation via full methanol dehydrogenation is observed.To achieve CO(2)-TOF values on the isolated Pd(1)In(1) intermetallic phase as high as on supported PdIn/In(2)O(3), at least 593 K reaction temperature is required. A bimetal-oxide synergism, with both bimetallic and oxide synergistically contributing to the observed catalytic activity and selectivity, manifests itself by accelerated formaldehyde-to-CO(2) conversion at markedly lowered temperatures as compared to separate oxide and bimetal. Combination of suppression of full methanol dehydrogenation to CO on Pd(1)In(1) inhibited inverse water-gas-shift reaction on In(2)O(3) and fast water activation/conversion of formaldehyde is the key to the low-temperature activity and high CO(2)-selectivity of the supported catalyst.