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.

Graphene-supported 2D cobalt oxides for catalytic applications.

2D materials are attracting increasing attention in many strategic applications. In particular, ultra-thin non-layered oxides have been shown to outperform their 3D counter-parts in several health and energy applications, such as the removal of toxic carbon monoxide by low temperature oxidation and the development of high performance supercapacitors. The general reason for that is the increased surface-to-volume ratio, which maximizes exposure of active species and enhances exchange between the (limited) bulk and the surface. The challenge is to synthesize such 2D configurations of 3D oxides, which generally requires quite harsh multi-step, multi-reagent chemical processes. Here we show that natural graphite can be used as a templating matrix to grow non-stoichiometric 2D transition metal oxides. We focus on highly porous, highly reduced cobalt oxides grown from cobalt nitrate and sodium borohydride under sonication. Extensive characterization, including nitrogen physisorption, thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM/TEM), X-ray diffraction (XRD), temperature programmed oxidation and reduction (TPO/TPR), Fourier transformed infrared (FTIR) and Raman spectroscopies, highlights the specific features of the 2D morphologies (nanosheets and nanofilms) obtained. For comparison, 3D morphologies of Co3O4 spinel nanocrystallites are grown from stacked 2D cobalt phthalocyanine-graphene precursors upon controlled thermal oxidation. Finally, low temperature CO oxidation catalysis evidences the superior performance of the graphene-supported CoO-like cobalt oxide 2D nanosheets.

Insights into the Surface Reactivity of Cermet and Perovskite Electrodes in Oxidizing, Reducing, and Humid Environments.

Understanding the surface chemistry of electrode materials under gas environments is important in order to control their performance during electrochemical and catalytic applications. This work compares the surface reactivity of Ni/YSZ and La0.75Sr0.25Cr0.9Fe0.1O3, which are commonly used types of electrodes in solid oxide electrochemical devices. In situ synchrotron-based near-ambient pressure photoemission and absorption spectroscopy experiments, assisted by theoretical spectral simulations and combined with microscopy and electrochemical measurements, are used to monitor the effect of the gas atmosphere on the chemical state, the morphology, and the electrical conductivity of the electrodes. It is shown that the surface of both electrode types readjusts fast to the reactive gas atmosphere and their surface composition is notably modified. In the case of Ni/YSZ, this is followed by evident changes in the oxidation state of nickel, while for La0.75Sr0.25Cr0.9Fe0.1O3, a fine adjustment of the Cr valence and strong Sr segregation is observed. An important difference between the two electrodes is their capacity to maintain adsorbed hydroxyl groups on their surface, which is expected to be critical for the electrocatalytic properties of the materials. The insight gained from the surface analysis may serve as a paradigm for understanding the effect of the gas environment on the electrochemical performance and the electrical conductivity of the electrodes.

Is Steam an Oxidant or a Reductant for Nickel/Doped-Ceria Cermets?

Nickel/doped-ceria composites are promising electrocatalysts for solid-oxide fuel and electrolysis cells. Very often steam is present in the feedstock of the cells, frequently mixed with other gases, such as hydrogen or CO2 . An increase in the steam concentration in the feed mixture is considered accountable for the electrode oxidation and the deactivation of the device. However, direct experimental evidence of the steam interaction with nickel/doped-ceria composites, with adequate surface specificity, are lacking. Herein we explore in situ the surface state of nickel/gadolinium-doped ceria (NiGDC) under O2 , H2 , and H2 O environments by using near-ambient-pressure X-ray photoelectron and absorption spectroscopies. Changes in the surface oxidation state and composition of NiGDC in response to the ambient gas are observed. It is revealed that, in the mbar pressure regime and at intermediate temperature conditions (500-700 °C), steam acts as an oxidant for nickel but has a dual oxidant/reductant function for doped ceria.

Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.

The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles.

Polydopamine-coated open cell polyurethane foams as an inexpensive, flexible yet robust catalyst support: a proof of concept.

Commercially available polyurethane open cell foams are readily coated with mussel-inspired polydopamine. The polydopamine film allows robust immobilisation of TiO2 nanoparticles at the surface of the three-dimensional material. The resulting catalyst is efficient for the photo-degradation of an azo dye, reusable and highly resistant to mechanical stress. A novel type of robust structured catalytic support, easily accessible via an inexpensive and green process, is thus described.

In situ investigation of dissociation and migration phenomena at the Pt/electrolyte interface of an electrochemical cell.

The development of efficient energy conversion systems requires precise engineering of electrochemical interfaces and thus asks for in situ techniques to probe the structure and the composition of the dynamic electrode/electrolyte interfacial region. This work demonstrates the potential of the near ambient pressure X-ray photoelectron spectroscopy (NAPXPS) for in situ studies of processes occurring at the interface between a metal electrode and a liquid electrolyte. By using a model membrane-electrode assembly of a high temperature phosphoric acid-imbibed proton exchange membrane fuel cell, and combining NAPXPS measurements with the density functional theory, it was possible to monitor such fundamental processes as dissociation and migration of the phosphoric acid within a nanostructured Pt electrode under polarization.

Particle-bound PAHs quantification using a 3-stages cascade impactor in French indoor environments.

Cascade Impactor is a powerful sampling method to collect airborne particles as a function of their size. The 3-stages Cascade Impactor used in this study allowed to sample simultaneously particles with aerodynamic diameter Dae>10 µm, 2.5 µm

Nontrivial redox behavior of nanosized cobalt: new insights from ambient pressure X-ray photoelectron and absorption spectroscopies.

The reduction and oxidation of carbon-supported cobalt nanoparticles (3.50±0.22 nm) and a Co (0001) single crystal was investigated by ambient pressure X-ray photoelectron (APPES) and X-ray absorption (XAS) spectroscopies, applied in situ under 0.2 mbar hydrogen or oxygen atmospheres and at temperatures up to 620 K. It was found that cobalt nanoparticles are readily oxidized to a distinct CoO phase, which is significantly more stable to further oxidation or reduction compared to the thick oxide films formed on the Co(0001) crystal. The nontrivial size-dependence of redox behavior is followed by a difference in the electronic structure as suggested by theoretical simulations of the Co L-edge absorption spectra. In particular, contrary to the stable rocksalt and spinel phases that exist in the bulk oxides, cobalt nanoparticles contain a significant portion of metastable wurtzite-type CoO.

When a Metastable Oxide Stabilizes at the Nanoscale: Wurtzite CoO Formation upon Dealloying of PtCo Nanoparticles.

Ambient pressure photoelectron and absorption spectroscopies were applied under 0.2 mbar of O2 and H2 to establish an unequivocal correlation between the surface oxidation state of extended and nanosized PtCo alloys and the gas-phase environment. Fundamental differences in the electronic structure and reactivity of segregated cobalt oxides were associated with surface stabilization of metastable wurtzite-CoO. In addition, the promotion effect of Pt in the reduction of cobalt oxides was pronounced at the nanosized particles but not at the extended foil.

Luminescent ethynyl-pyrene liquid crystals and gels for optoelectronic devices.

Two functional ethynyl-pyrene derivatives have been designed and synthesized by di- and tetra-substitutions of bromo pyrene derivatives with N-(4-ethynylphenyl)-3,4,5-tris(hexadecyloxy)benzamide fragments. The photoluminescence wavelength of the pyrene core can be tuned by the substitution pattern and the state of matter (solid, solution, gel, or liquid crystal). The disubstituted pyrene derivative 1 is not mesomorphic but produces robust and highly fluorescent gels in DMF, toluene, and cyclohexane. The well-defined fibers and ropes of the gel states were characterized by SEM and laser scanning confocal microscopy, and extended over several micrometers. The gels were integrated as active layers in field-effect transistors, which provided good bulk electron and hole charge mobilities as well as light emission generation. The tetra-substituted pyrene derivative is not a gelator but displays a stable liquid crystalline phase with 2D hexagonal symmetry between 20 and 200 degrees C. The pronounced luminescence properties of the mesophase allow one to observe original mesophase textures with flower-like patterns directly by fluorescence microscopy without crossed-polarizers.