Valérie Briois

Preparation of ZnO nanoparticles: Structural study of the molecular precursor

The structure of zinc acetate derived precursor currently used in the sol-gel synthesis of ZnO nanoparticles is described. The reaction products obtained before and after reflux of ethanolic zinc acetate solution have been studied by UV-Vis, photoluminescence, FTIR and EXAFS at the Zn K edge. EXAFS results evidence for both precursor solutions a change from the octahedral coordination sphere of oxygen atoms characteristic of the solid zinc acetate dihydrate compound into a four-fold environment. The EXAFS spectra of precursor solutions can be satisfactorily reproduced using the molecular structure reported for Zn4O(Ac)6 (Ac = COOCH3). UV-Vis and FTIR measurements are also in agreement with the formation of this oligomeric precursor. The structural modification is more pronounced after reflux at 80°C, because the increase of the Zn4O(Ac)6 amount and the formation of nearly 3.0 nm sized ZnO nanoparticle.

Multi-scale structural description of siloxane–PPO hybrid ionic conductors doped by sodium salts

Alkaline metal doped organic–inorganic hybrids have potential applications in the field of portable energy sources. Attractive sol–gel derived urea cross-linked polyether, siloxane–PPO (poly(propylene oxide)) hybrids doped with sodium salts (NaClO4 and NaBF4) were examined by multi-spectroscopic approach that includes complex impedance, X-ray powder diffraction (XRPD), small angle X-ray scattering (SAXS), 29Si and 23Na magic-angle spinning nuclear magnetic resonance (NMR/MAS), Na K-edge X-ray absorption near edge structure (XANES) and Raman spectroscopies. The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the thermal and electrical properties. The main conclusion derived from this study is that the NaBF4 salt has a much lower solubility in the hybrid matrix than the NaClO4 salt. Furthermore, the addition of a large amount of salt plays a major role in the hybrid nanostructure and electrical properties, modifying the PPO chain conformation, weakening or breaking the hydrogen bond of the polyether–urea associations and changing the polycondensation and aggregation processes involving the siloxane species.

Short Range Order Evolution in the Preparation of SnO2 Based Materials

The evolution of Eu3+ doped SnO2 xerogels to the cassiterite structure observed during sintering was studied by means of Eu3+ spectroscopy, XRD and EXAFS at the Sn K-edge. Eu3+ ions adsorbed at the surface of colloidal particles present a broad distribution of sites, typical of oxide glasses. With sintering at 300°C, this distribution is still broadened. Crystallization is clearly observed by the three techniques with increasing sintering temperature. It is found that the addition of Eu3+ limits the crystallite growth.

Effect of in concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450°C

Abstract Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450°C on glass substrates from solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c -axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn=10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In=5 at.%) shows that In substitutes Zn in the wurtzite structure.

X-ray Absorption and Emission Spectroscopies of X-Bridged Diiron Phthalocyanine Complexes (FePc)2X (X = C, N, O) Combined with DFT Study of (FePc)2X and Their High-Valent Diiron Oxo Complexes

μ-Nitrido diiron phthalocyanine [PcFe(+3.5)NFe(+3.5)Pc](0) is an efficient catalyst, able to catalyze the oxidation of methane under near-ambient conditions. In this work, we compared the properties of structurally similar μ-carbido (1), μ-nitrido (2), and μ-oxo (3) dimers of iron phthalocyanine. The goal was to discern the structural and electronic differences between these complexes and to propose a rationale for the exceptional activity of 2. Extended X-ray fine-structure spectroscopy, high-resolution X-ray emission spectroscopy, and resonant inelastic X-ray scattering were applied to study the geometry and electronic structure of iron species in the series 1-3. The data provided by core hole spectroscopies were compared to the results of DFT calculations and found to coherently describe the structural and electronic properties of 1-3 as having equivalent iron centers with formal iron oxidation degrees of 3, 3.5, and 4 for the μ-oxo, μ-nitrido, and μ-carbido dimers, respectively. However, the bond length to the bringing atom changed in an unexpected sequence Fe-O > Fe-N < Fe-C, indicating redox non-innocence of the brigding μ-carbido ligand in 1. According to the X-ray emission spectroscopy, the μ-nitrido dimer 2 is a low-spin compound, with the highest covalency in the series 1-3. The DFT-calculated geometry and electronic structures as well as core hole spectra of hypothetical high-valent oxo complexes of 1-3 were compared, in order to explain the particular catalytic activity of 2 and to estimate the prospects of spectroscopic observation of such species. It appears that the terminal Fe═O bond is the longest in the oxo complex of 2, due to the strong trans-effect of the nitrido ligand. The corresponding LUMO of the μ-nitrido diiron oxo complex has the lowest energy among the three oxo complexes. Therefore, the oxo complex of 2 is expected to have the highest oxidative power.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

ROCK: the new Quick-EXAFS beamline at SOLEIL

ROCK is a new beamline at SOLEIL dedicated to Quick-EXAFS measurements. The optical layout has been optimized to get full advantage of the monochromators, which were designed at SOLEIL and successfully used at SAMBA from 2009 to 2014. ROCK has started user operations since March 2015. It is mainly employed to monitor fast kinetic processes in materials used in catalysis and energy sciences. A review of the ROCK performances and capabilities is presented. The high automation achieved for fast change of monochromators, optimization of mirrors for harmonic rejection and detectors allows the simultaneous operando characterization of different chemical elements present in a material during the same reaction.

Correlation between Structural and Catalytic Properties of Copper Supported on Porous Alumina for the Ethanol Dehydrogenation Reaction

Structural and surface features of highly dispersed copper catalysts supported on hierarchical porous alumina were evaluated for the ethanol dehydrogenation reaction. The catalysts were prepared by incipient wetness impregnation of alumina obtained by a dual template sol–gel procedure. Structural characterizations provided evidence that the copper was highly dispersed on the alumina in the form of monomeric octahedral Cu2+ species adsorbed into an incomplete layer. A two‐step reduction was observed for the catalysts in a temperature range of 50–250u2009°C under H2/He flow. The temperature for onset of reduction and the percentage of Cu+ species formed upon activation were dependent on the Cu loading. At lower Cu loadings, the amount of Cu+ increased, leading to a slower and less complete reduction. Based on the apparent activation energy and turnover frequency, it could be concluded that Cu+ containing a mixture of Cu+/Cu0 results in a more efficient catalyst than Cu0 for the ethanol dehydrogenation reaction.

Stimuli-Responsive Controlled Growth of Mono- and Bidimensional Particles from Basic Zirconium Sulfate Hydrosols

A thermostimulated sol-gel transition in a system prepared by mixing a ZrOCl(2) acidified solution to a hot H(2)SO(4) aqueous solution was studied by dynamic rheological measurements and quasi-elastic light scattering. The effect of temperature and of molar ratio R(S) = [Zr]/[SO(4)] on the gelation kinetics was analyzed using the mass fractal aggregate growth model. This study shows that the linear growth of aggregates occurs at the early period of transformation, while bidimensional growth occurs at the advanced stage. The bidimensional growth can be shifted toward monodimensional growth by decreasing the aggregation rate by controlling the temperature and/or molar ratio R(S). EXAFS and Raman results gave evidence that the linear chain growth is supported by covalent sulfate bonding between primary building blocks. At the advanced stage of aggregation, the assembly of linear chains through hydrogen bonding gave rise to the growth of bidimensional particles.

Siloxane–polypropyleneoxide hybrid ormolytes: structure–ionic conductivity relationships

Siloxane-polypropyleneoxide (PPO) hybrids doped with sodium perchlorate (NaClO 4 ) obtained by the sol gel process were prepared with two PPO molecular weights (2000 and 4000 g/mol) and two sodium concentrations such as [O]/[Na] = 4 and 15 (O being the ether-type oxygen of PPO chains). The structure of these hybrids was investigated by 23 Na nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy at the sodium K-edge (1071.8 eV) whereas complex impedance spectroscopy was used to determine their ionic conductivity. Three sodium sites were determined by NMR. The conjunction of NMR and X-ray absorption results allows us to identify one site in which Na is in a NaCI structure, a second one in which Na is in contact with perchlorate anions. The third site is attributed to mobile sodium species in interaction with the polymeric chain. The relative proportion of the different sites in the materials determines the ionic conductivity of the materials at room temperature: the largest ionic conductivity is 8.9 × 10 -6 Ω -1 cm -1 and is observed on the material with the larger amount (at least 85%) of sites in which sodium interacts with the polymer.