PHOIBOS 150 1D-DLD

The hydrogenation of CO₂ to methanol is a viable alternative for reducing greenhouse gases net emissions as well as a route for hydrogen storage and transportation. In this context, the synthesis of active and selective catalysts is a relevant objective. In this work, we study the promotion of Pd with Ga and Zn in the hydrogenation of CO₂ to methanol at 800 kPa and 220–280 °C. Mono and intermetallic catalysts (Pd/SiO₂, PdGa/SiO₂ and Pd-Zn/SiO₂) were synthesized by incipient wetness impregnation with the aid of triethanolamine as an organic additive, obtaining similar average metal particle sizes (between 9 and 12 nm). Kinetic analysis reveals that the addition of Ga and Zn increases the turnover frequency for methanol formation by an order of magnitude without significant changes in the reaction rate of the reverse water-gas shift (r-WGS) which is a parallel undesired reaction. The selectivity to methanol (at 220 °C) thus increases from 3% for Pd/SiO₂ to 12% for Pd-Ga/SiO₂ and 30% for Pd-Zn/SiO2. XPS studies, Infrared analysis of CO adsorption, and XRD analyses show the presence of intermetallic phases Pd₂Ga and PdZn on the surface. The results suggest that Ga and Zn promote Pd, increasing its activity towards the synthesis of methanol, by creating more active sites for this reaction. These sites are likely formed by intermetallic compounds such as Pd₂Ga and PdZn.

Furfuryl alcohol, a vital intermediate for the production of foundry resins, fragrances, pharmaceuticals and
pesticide, is produced by hydrogenation of furfural in gas phase or liquid phase. The furfuryl alcohol production
in gas phase over silica supported copper catalyst is favored thanks to the environmental and technical advantages.
The effect of preparation methods of silica supported copper catalysts on the structure and performance
was investigated by means of ICP, N₂ physisorption, ex-situ/in-situ XRD, in-situ XPS, FT-IR, H₂-TPR, TEM,
N₂O titration, TG as well as furfural hydrogenation. The results indicated that the different catalyst synthesis
strategies led to the diverse copper species in the calcined samples and disparate Cu⁰ surface area as well as
different molar ratio of Cu⁺/(Cu⁺+Cu⁰) in the fresh samples. The performance of impregnation derived
sample was poorer than that of commercial CuCr-Strem catalyst. The catalysts prepared by deposition precipitation
and ion exchange exhibited similar performance to the CuCr-Strem. The ammonia evaporation derived
catalyst (Cu/SiO₂-EA) showed superior performance in the activity, selectivity and stability among all the studied
catalysts. The excellent performance was related to the highest surface area of Cu⁰, smallest copper particle
size, large surface area and pore volume as well as appropriate higher Cu⁺/(Cu⁺+Cu⁰) ratio. Furthermore, all
the copper catalysts went through deactivation, which was caused by carbon deposition, during the reaction.
Owing to the largest amount of Cu⁰ sites and large SBET, the Cu/SiO₂-EA exhibited the slowest deactivation rate.

Surface islands formed by grain-boundary diffusion has been studied in Ni/Cu nanolayers by in-situ low energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, scanning probe microscopy and ex-situ depth profiling based on ion sputtering. In this paper a new experimental approach of measurement of grain-boundary diffusion coefficients is presented. Appearing time of copper atoms diffused through a few nanometer thick nickel layer has been detected by low energy ion scattering spectroscopy with high sensitivity. The grain-boundary diffusion coefficient can be directly calculated from this appearing time without using segregation factors in calculations. The temperature range of 423–463 K insures the pure C-type diffusion kinetic regime. The most important result is that surface coverage of Ni layer by Cu atoms reaches a maximum during annealing and stays constant if the annealing procedure is continued. Scanning probe microscopy measurements show a Volmer-Weber type layer growth of Cu layer on the Ni surface in the form of Cu atomic islands. Depth distribution of Cu in Ni layer has been determined by depth profile analysis.

The promotion of Ga on SiO₂ supported Cu in the hydrogenation of CO₂ to methanol at 800 kPa and 200–280 °C was investigated. Cu/SiO₂ and CuGa/SiO₂ catalysts were prepared by a water-in-oil microemulsion technique resulting in Cu clusters of 4–6.5 nm. It was found that Ga addition increased the methanol formation rate by an order of magnitude without significantly changing that for reverse water gas shift (RWGS). This trend is also evidenced by the decrease in the apparent activation barrier for methanol formation from 78 (for Cu/SiO₂) to 26–39 kJ mol⁻¹ when Ga was added, but not for RWGS (107–132 kJ mol⁻¹). Kinetic and in situ DRIFTS analyses revealed that formate intermediates are adsorbed on both Cu and Ga₂O₃ and that methoxy hydrogenation could be the rate determining step of methanol synthesis. In the case of RWGS, a zero order of CO formation with respect to H₂ concentration was consistent with a redox mechanism and with the reaction occurring predominantly on Cu sites. The results suggest that Ga promotes Cu increasing methanol selectivity, likely by creating new active sites for methanol formation without modifying its oxidation state, which under reaction conditions remains mostly metallic.

Hydrogen energy is considered to be a promising alternative for the sustainable and environmentally friendly solution of the global energy problem. One of the major obstacles of hydrogen energy applications is to maintain safe and efficient storage of hydrogen which can also be achieved chemically using suitable carrier materials. Formic acid (HCOOH, FA) can be utilized as a hydrogen carrier due to its low molecular weight (46 g/mol) and high hydrogen density (%4.4 weight). FA is a stable, non-flammable, and non-toxic biomass side-product rendering it a perfect candidate for an alternative hydrogen vector. Design of novel heterogeneous catalysts which can substitute the existing homogeneous catalytic systems may allow overcoming catalyst isolation and recovery costs and associated logistical problems hindering their applications in on-board operations.

FA can be catalytically decomposed via dehydrogenation and dehydration reactions. Selective dehydrogenation of FA is crucial because, the production of CO from dehydration mechanism can suppress the activity of the catalyst by blocking/poisoning the precious metal sites. Consequently, development of CO-resistant, selective, catalytically active, and reusable heterogeneous catalysts has a great significance. In the current work, a new material that can produce H₂(g) from FA under ambient conditions in the absence of additives with high CO-poisoning tolerance will be introduced, which is comprised of Pd-based trimetallic active centers functionalized with Ag and Cr in addition to amine-functionalized MnO_x promoters dispersed on a SiO₂ support surface.

An impressive gravimetric capacitance of 1300 F g−1 (surface capacitance ∼3.3 mF cm−2) reported by Choi et al., 2006 for nanosized vanadium nitride has stimulated considerable interest in vanadium nitride as a potential electrode material for energy storing systems – supercapacitors. The postulated mechanism of charge storage in vanadium nitride materials involves redox reactions in the thin surface layer of vanadium oxide while the core vanadium nitride serves exclusively as a conducting platform. In this study we have synthesized pure oxygen-free vanadium nitride films and have found that they are capable of delivering a surface capacitance of up to ∼3 mF cm−2 at a potential scan rate of 3 mV s−1 and ∼2 mF cm−2 at a potential scan rate of 1 V s−1 in aqueous electrolytes. Combining electrochemical testing with X-ray photoelectron spectroscopy characterization has revealed that redox reactions play no or little role in the electrochemical response of pure VN, in contrast to the common wisdom stemming from the electrochemical response of oxygen-containing films. An alternative charge storage mechanism – space charge accumulation in a subsurface layer of ∼100 nm – was put forward to explain the experimentally observed capacitance of VN films in aqueous electrolytes.

Thin silicon layers containing about 20% carbon and 20% oxygen were deposited on copper substrates by potentiostatic electroreduction from a 1 M SiCl4 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethyl) sulfonylimide [BMP][TFSI] electrolyte. The electrodeposition process was investigated by means of voltammetric techniques, coupled with in-situ microgravimetry (quartz crystal microbalance, QCM). The electrochemical and QCM data suggest a possible contribution of a partial Si4+ to Si2+ reduction and/or a restructuring of the metallic substrate. Considerable impact of side reactions parallel to the deposition process was indicated by QCM measurements performed under potentiostatic and potentiodynamic conditions. The deposition of silicon-based films was confirmed by energy dispersive X-ray analysis (EDX). Analysis of the chemical composition of the deposit and its elemental distribution were achieved by depth profiling X-ray photoelectron spectroscopy (XPS). The electrodeposited silicon containing layers showed stable lithiation and delithiation with capacity values of about 1200 mAhg−1 and 80% capacity retention after 300 cycles in standard EC/DMC electrolytes. In ionic liquid (IL) the material displayed lower capacity of ca. 500 mAhg−1, which can be attributed to the higher viscosity of this electrolyte and deposition of IL decomposition products during lithiation.

We show that it is possible to use a multichannel electron detector in a zone plate based photoemission spectromicroscopy in a snap shot mode to reduce the total acquisition time for a given counting time by 50% relative to the standard scanning mode while preserving the feature of the spectra. We describe the result of tests performed at Elettra using its microbeam (150 nm) together with a 48-channel detector designed for the PHOIBOS 100 analyzer optimized for extremely small x-ray sources. We also give a short summary of the technical features of the detector and describe one possible calibration procedure for its use in the snap shot mode. We show initial results from using this device to perform chemical maps of surfaces at a resolution of 150 nm.