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Highly performing perovskite-based anodes for methane mixtures-fueled solid oxide fuel cells (SOFC) are proposed. Catalytic activities of La0.6Sr0.4Fe1-xPdxO3-δ (LSFPd) with x = 0.05, 0.1 toward dry reforming of methane (DMR) and partial oxidation of methane (POM) reactions are investigated. The addition of (30wt%) Ce0.85Gd0.15O2-δ (GDC) and of (30wt%) Ni(5wt%)-GDC to the perovskite compounds was evaluated to enhance both electrocatalytic and electrochemical properties. Electrolyte-supported cells based on La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) pellets and LSFPd perovskite oxides at both electrodes are fabricated and tested using CH4, CH4/Ar and CH4/CO2 mixtures in the 750–850°C temperature range. Fuel cell tests using anodic mixtures such as LSFPd/GDC and LSFPd/Ni-GDC are also performed. A discussion based on the comparison between catalytic and electrochemical results and on the possible reforming and/or oxidation reactions taking place at the anode is detailed.

Perovskite oxides such as ferrites have been widely investigated for their remarkable electrochemical activity as SOFC electrodes. However, their phase instability in reducing conditions remains an issue for anode application. The role of Mn substitution into B-site of La0.6Sr0.4FeO3-δ (LSF) perovskite oxide was investigated. New insights on the structural evolution of La0.6Sr0.4Fe0.8Mn0.2O3-δ (LSFMn) upon high temperature reduction were revealed. In oxidizing atmosphere, Mn substitution reduces the oxygen vacancy concentration while, switching to reducing conditions, it drives the transition from rhombohedral perovskite to single Ruddlesden-Popper phase, affecting the Fe0 exsolution. Redox-cycles of LSFMn were investigated and the properties of re-oxidized compounds were highlighted. The effect of Mn substitution on perovskite conductivity was also evaluated both in oxidizing and reducing conditions.

A structured catalyst for the dry reforming of methane (DRM) was investigated as a biogas pre-reformer for indirect internal reforming solid oxide fuel cell (IIR-SOFC). For this purpose, a NiCrAl open-cell foam was chosen as support and Ni-based samarium doped ceria (Ni-SmDC) as catalyst. Ni-SmDC powder is a highly performing catalyst showing a remarkable carbon resistance due to the presence of oxygen vacancies that promote coke gasification by CO2 activation. Ni-SmDC powder was deposited on the metallic support by wash-coating method. The metallic foam, the powder, and the structured catalyst were characterized by several techniques such as: N2 adsorption-desorption technique, X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), focused ion beam (FIB), temperature programmed reduction (H2-TPR), and Raman spectroscopy. Catalytic tests were performed on structured catalysts to evaluate activity, selectivity, and stability at SOFC operating conditions.

Carbon dioxide collected from outdoor atmosphere or produced in aerospace cabin, may be recycled to produce methane and water by methanation reaction (Sabatier reaction). This reaction needs a heterogeneous catalyst to decrease the reaction temperature and increase the selectivity. A proper catalyst for in-situ CO 2 recycling into methane requires: i) high CO 2 conversion with high CH 4 selectivity at low operating temperature, ii) high stability towards degradation, being required that catalyst remains highly active during the entire production process. This paper presents a preliminary study of a catalyst based on Ni supported on cerium oxide, prepared by one-pot hydrothermal method, leading to a nanorod morphology with high and uniform nickel dispersion. Morphology and chemical properties of the material were characterized by BET, H 2 -TPR, XRD and FE-SEM/EDS. The catalyst was tested in a flow system at atmospheric pressure, using reagents with stoichiometric ratio (CO 2 :H 2 =1:4) or enriched in hydrogen. The Ni/r-CeO 2 catalyst showed high stability over time on stream, in oxidizing condition and after switch off-switch on test.

Chlorinated solvents are extensively used in many activities and hence in the past decades impacted a large number of sites. The presence of these contaminants in groundwater is challenging particularly for the management of the vapor intrusion pathway. In this work we examine the potential feasibility of using horizontal permeable reactive barriers (HPRBs) placed in the unsaturated zone to treat chlorinated solvent vapors emitted from groundwater. Zero-valent iron (ZVI) powders, partially saturated with water and characterized by different specific surface areas (SSA), were tested, alone or mixed with sand, in lab-scale batch reactors using TCE as model compound. Depending on the type of iron powder used, a reduction of TCE concentration in the vapor phase from approximately 35% up to 99% was observed after 3 weeks of treatment. The best performance in terms of TCE reduction was obtained using the ZVI characterized by the intermediated values of the specific surface area (SSA). This finding, which is in contrast with the results generally observed in in aqueous solutions, was tentatively attributed to a non-selective higher reactivity of the fine-grained iron samples with water and dissolved oxygen (with a consequent iron passivation) or to the occurrence of a diffusion-limited reaction kinetics. Based on the first-order kinetic degradation rate constants estimated from the experimental data, a horizontal barrier of 1 m containing ZVI or a mixture of ZVI and sand can potentially lead to an attenuation of TCE vapors over 99%.

In the attempt of satisfying the quest for new antifouling products tailored for applications on Cultural Heritage, we have synthesized and characterized two different silica nanosystems. The first consists of core-shell nanocapsules and the second one of mesostructured nanoparticles. Both systems have been successfully loaded in situ with the commercial biocide 2-mercaptobenzothizole (MBT). The synthesis procedure and particles characterization measurements, as far as their dimensions and superficial properties, loading capability, and release rate in aqueous solution, are reported. We stress that both particles have the dimensions required to avoid undesired light scattering once dispersed on the artefact surface. Interestingly, the two nanoparticles have complementary properties, suggesting that combining them in a coating may have a higher potential for production of new generation active products.

Ni-based oxides are widely investigated as catalysts for CO2 methanation due to their high activity, high selectivity and low cost. The catalytic performances of Ni-based catalysts depend on support properties that strongly influence the dispersion of the catalytic active phase and the Ni&ndash, support interaction. Although the CO2 methanation is widely studied, the structure sensitivity of methanation on nickel is not completely assessed. Ni/CeO2 nanorods with different nickel/ceria molar ratios (0.05, 0.10, 0.20, 0.30) were prepared by one-pot hydrothermal synthesis. The effect of nickel content and metal particle size on catalytic activity and selectivity for CO2 methanation were studied using CO2:H2 = 1:4 stoichiometric ratio at high space velocity (300 L g&minus, 1 h&minus, 1). Sample structure and morphology were studied by X-ray diffraction (XRD), Brunauer&ndash, Emmet&ndash, Teller (BET) analysis, field-emission scanning electron microscopy/energy-dispersive spectroscopy (FE-SEM/EDS), H2-temperature programmed reduction (TPR), H2-temperature-programmed desorption (TPD). Both the CO production and the turnover frequency appear depending on nickel particle size, suggesting a structure sensitivity of the CO2 methanation on nickel supported on ceria.

Cycling high temperature CO2 capture using CaO&ndash, based solid sorbents, known as the calcium looping (CaL) process, is gaining considerable scientific and industrial interest due to the high theoretical sorbent capacity (0.78 gCO2/gCaO), the low specific cost, and the negligible environmental impact of the employed materials. In this work, we investigated the self&ndash, combustion synthesis of CaO&ndash, CaZrO3 sorbents with different CaO contents (40, 60, and 80 wt%) for use in the CaL process. CaZrO3 was used as a spacer to avoid CaO grains sintering at high temperature and to reduce the diffusional resistances of CO2 migrating towards the inner grains of the synthetic sorbent. Samples were characterized by X&ndash, ray diffraction (XRD), Brunauer&ndash, Emmett&ndash, Teller (BET), and scanning electron microscopy (SEM) analyses. The reaction between CO2 and CaO (i.e., carbonation) was carried out in 20 vol% CO2 at 650 &deg, C and calcination (i.e., decomposition of CaCO3 to CaO and CO2) at 900 &deg, C in pure Ar or with 85 vol% CO2 using a thermogravimetric analyzer (thermogravimetric/differential thermal analysis (TG&ndash, DTA)). The most stable sorbent was with 40 wt% of CaO showing a CO2 uptake of up to 0.31 g CO2/gsorbent and 0.26 g CO2/gsorbent operating under mild and severe conditions, respectively. The experimental data corroborated the prediction of the shrinking core spherical model in the first phase of the carbonation. A maximum reaction rate of 0.12&ndash, 0.13 min-1 was evaluated in the first cycle under mild and severe conditions of regeneration.

This paper describes an E-Nose aimed to Pesticide Detection which uses an array of different commercial gas sensors. In order to optimize the array reducing the redundancies due to similar sensors answers, Wilks' A-statistic has been used.

In the present study, the catalytic activity of palladium oxide (PdOx) supported on ceria nanorods (CeO2-NR) for aerobic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) was evaluated. The CeO2-NR was synthesized hydrothermally and the Pd(NO3)2 was deposited by a wet impregnation method, followed by calcination to acquire PdOx/CeO2-NR. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electron microscopy (TEM), Brunauer&ndash, Emmet&ndash, Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). In addition, the TPR-reduced PdOx/CeO2-NR (PdOx/CeO2-NR-Red) was studied by XRD, BET, and XPS. Characterizations showed the formation of CeO2-NR with (111) exposed plane and relatively high BET surface area. PdOx (x &gt, 1) was detected to be the major oxide species on the PdOx/CeO2-NR. The activities of the catalysts in BnOH oxidation were evaluated using air, as an environmentally friendly oxidant, and various solvents. Effects of temperature and palladium oxidation state were investigated. The PdOx/CeO2-NR showed remarkable activity when protic solvents were utilized. The best result was achieved using PdOx/CeO2-NR and boiling ethanol as solvent, leading to 93% BnOH conversion and 96% selectivity toward PhCHO. A mechanistic hypothesis for BnOH oxidation with PdOx/CeO2-NR in ethanol is presented.