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Two-dimensional (2D) materials are used in energy storage and conversion due to their unique electronic structure and large specific area. In this work, 2D vanadium carbide (V2CTx MXene) is fabricated and studied as an efficient and earth-abundant electrocatalyst for electrocatalytic N2 reduction reaction (NRR). When tested in 0.1 M Na2SO4, such electrocatalyst achieves a large NH3 yield rate of 12.6 μg h–1 mg–1cat. and a Faradaic efficiency of 4% at –0.7 V vs. reversible hydrogen electrode. Theoretical calculations show a low reaction barrier of 0.88 eV in the distal route for this catalyst.

Nitrogen can be electrochemically reduced to produce ammonia, which supplies an energy-saving and environmental-benign route at room temperature, but high-efficiency catalysts are sought to reduce the reaction barrier. Here, iron-doped α-MoO3 nanosheets are thus designed and proposed as potential catalysts for fixing N2 to NH3. The α-MoO3 band structure is intentionally modulated by the iron doping, which narrows the band gap of α-MoO3 and turns the semiconductor into a metal-like catalyst. Oxygen vacancies, generated by substituting Mo6+ for Fe3+ anions, are beneficial for nitrogen adsorption at the active sites. In 0.1 M Na2SO4, the Fe-doped MoO3 catalyst reached a high faradaic efficiency of 13.3% and an excellent NH3 yield rate of 28.52 μg h-1 mgcat-1 at -0.7 V versus reversible hydrogen electrode, superior to most of the other metal-based catalysts. Theoretical calculations confirmed that the N2 reduction reaction at the Fe-MoO3 surface followed the distal reaction path.

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO3 nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H+ during the NRR process in neutral electrolyte. In 0.1 M Na2SO4 solution, the electrocatalyst exhibited a remarkable NRR activity with an NH3 yield of 9.66 μg h−1 mg−1cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO3. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.

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.

Apoptotic cells stimulate compensatory proliferation through the caspase-3-cPLA-2-COX-2-PGE-2-STAT3 Phoenix Rising pathway as a healing process in normal tissues. Phoenix Rising is however usurped in cancer, potentially nullifying pro-apoptotic therapies. Cytotoxic therapies also promote cancer cell plasticity through epigenetic reprogramming, leading to epithelial-to-mesenchymal-transition (EMT), chemo-resistance and tumor progression. We explored the relationship between such scenarios, setting-up an innovative, straightforward one-pot in vitro model of therapy-induced prostate cancer repopulation. Cancer (castration-resistant PC3 and androgen-sensitive LNCaP), or normal (RWPE-1) prostate cells, are treated with etoposide and left recovering for 18 days. After a robust apoptotic phase, PC3 setup a coordinate tissue-like response, repopulating and acquiring EMT and chemo-resistance; repopulation occurs via Phoenix Rising, being dependent on high PGE-2 levels achieved through caspase-3-promoted signaling; epigenetic inhibitors interrupt Phoenix Rising after PGE-2, preventing repopulation. Instead, RWPE-1 repopulate via Phoenix Rising without reprogramming, EMT or chemo-resistance, indicating that only cancer cells require reprogramming to complete Phoenix Rising. Intriguingly, LNCaP stop Phoenix-Rising after PGE-2, failing repopulating, suggesting that the propensity to engage/complete Phoenix Rising may influence the outcome of pro-apoptotic therapies. Concluding, we established a reliable system where to study prostate cancer repopulation, showing that epigenetic reprogramming assists Phoenix Rising to promote post-therapy cancer repopulation and acquired cell-resistance (CRAC).

Copyright: © 2021 by the authors. The impact of extra-low dosage (0.01% by weight of cement) Graphene Oxide (GO) on the properties of fresh and hardened nanocomposites was assessed. The use of a minimum amount of 2-D nanofiller would minimize costs and sustainability issues, therefore encouraging the market uptake of nanoengineered cement-based materials. GO was characterized by X-ray Photoelectron Spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), and Raman spectroscopy. GO consisted of stacked sheets up to 600 nm × 800 nm wide and 2 nm thick, oxygen content 31 at%. The impact of GO on the fresh admixtures was evaluated by rheology, flowability, and workability measurements. GO-modified samples were characterized by density measurements, Scanning Electron Microscopy (SEM) analysis, and compression and bending tests. Permeability was investigated using the boiling-water saturation technique, salt ponding test, and Initial Surface Absorption Test (ISAT). At 28 days, GO-nanocomposite exhibited increased density (+14%), improved compressive and flexural strength (+29% and +13%, respectively), and decreased permeability compared to the control sample. The strengthening effect dominated over the adverse effects associated with the worsening of the fresh properties; reduced permeability was mainly attributed to the refining of the pore network induced by the presence of GO.

Immiscible blends of ethylene‐propylene‐diene‐monomer (EPDM) and polyoxymethylene (POM), when EPDM is the major phase were compatibilized on the addition of an ionomer, poly(ethylene‐co‐methacrylic acid). The inclusion of the ionomer reduced the interfacial tension between the two phases, such that the diameter of the POM domains were significantly reduced to between 0.5 and 2 μm, typical of that required to toughen ductile polymers. The mechanical properties of the resultant compatibilized blends were significantly enhanced with increases in Young's modulus (↑54%), tensile strength (σ, ↑139%), elongation at break (e, ↑97%), and tensile toughness (↑500%) with increasing ionomer content, relative to EPDM rubber alone. The ShoreA hardness of the compatibilized blend was 70.1 compared with 56.8 for the immiscible binary blend and, 50.2 for neat EPDM rubber.

Thin films based on aluminum nitride were obtained by fs-laser assisted Pulsed Laser Deposition (fs-PLD) at room temperature on tantalum substrates for studying the electron emission performance in the temperature range 700- 1600 °C, so to investigate the possibility of their exploitation as thermionic cathodes. Results of structural, chemical and morphological analyses show the growth of nanostructured thin films with a significant oxygen contamination, forming a mixture of crystalline aluminum nitride and aluminum oxide as well as metallic aluminum inclusions. Despite the considerable presence of oxygen, the developed cathodes demonstrate to possess promising thermionic emission characteristics, with a work function of 3.15 eV, a valuable Richardson constant of 20.25 A cm−2K−2, and a highly thermo- electronic stability up to operating temperatures of 1600 °C.

Recent improvements in additive layer manufacturing (ALM) have provided new designs of geometrically complex structures with lighter materials and low processing costs. The use of additive manufacturing in spacecraft production is opening up many new possibilities in both design and fabrication, allowing for the reduction of the weight of the structure subsystems. In this aim, polymeric ALM structures can become a choice, in terms of lightweight and demisability, as far as good thermomechanical properties. Moreover, provided that fused-deposition modeling (FDM) is used, nanosats and other structures could be easily produced in space. However, the choice of the material is a crucial step of the process, as the final performance of the printed parts is strongly dependent on three pillars: design, material, and printing process. As a high-performance technopolymer, polyether ether ketone (PEEK) has been adopted to fabricate parts via ALM, however, the space compatibility of 3D-printed parts remains not demonstrated. This work aimed to realize a nanosat polymeric structure via FDM, including all the phases of the development process: thermomechanical design, raw material selection, printing process tuning, and manufacturing of a proof of concept of a technological model. The design phase includes the application of topology optimization to maximize mass saving and take full advantage of the ALM capability. 3D-printed parts were characterized via thermomechanical tests, outgassing tests of 3D-printed parts are reported confirming the outstanding performance of polyether ether ketone and its potential as a material for structural space application.

The electrocatalytic nitrogen reduction reaction (NRR) has been deemed a promising and reliable approach to massively produce ammonia under ambient conditions. A high-efficiency electrocatalyst with an excellent selectivity is highly required to reduce the multiple reaction barriers of N2 + 3H2O → 2NH3 + 1.5O2. Here, we report electrospun zirconia nanofibers as a non-noble NRR electrocatalyst to convert nitrogen to ammonia. Theoretical calculations predict that the Zr sites with oxygen vacancies are favorable for nitrogen adsorption and reduction. Experimentally, the larger concentration of oxygen defects in such an electrocatalyst allowed achieving a NH3 formation rate of 9.63 μg h−1 mgcat.−1 and an optimal faradaic efficiency of 12.1% at −0.7 V vs. the reversible hydrogen electrode in 0.1 M Na2SO4.

Intermittency of renewable energy sources can be profitably faced using efficient energy storage systems. Reversible solid oxide cells (RSOCs) able to operate with carbon-containing species are likely among the most appealing choices. Energy can be obtained by natural gas and/or biogas (SOFC mode), with useful recovery of CO2 in the exhausts. Besides, if the electrode is also active towards CO2 electrolysis (SOEC mode), CO2 is reduced to CO and O2. In this work a composite material with in-situ formed Ni-Fe alloy catalyst consisting of La1.2Sr0.8Fe0.6Mn0.4O4 Ruddlesden-Popper perovskite and Ni-Ce0.85Sm0.15O2-δ fluorite was developed as a multi-functional fuel-electrode for RSOCs. The composite electrode was tested in SOFC mode as anode for hydrogen, dry methane and carbon monoxide oxidation and showed power density outputs of 657, 668 and 527 mW/cm2 at 850 °C, respectively, together with redox stability and coking tolerance for over 120 h. In SOEC mode, it was tested as cathode and delivered 2.66 A/cm2 at 2 V in a 95:5 CO2:CO mixture, retaining a current density of 1 A/cm2 for more than 40 h.

In this work, porous complex and metal-free cathodes based on a (La0.6Sr0.4) (Cr0.5Mn0.5) O3 (LSCM) screen-printed backbone infiltrated with Ce0.9Gd0.1O2 (GDC) were fabricated for solid oxide electrolyzer cells. GDC infiltration has been optimized by structural and microstructural investigation and tested by electrochemical measurements in CO/CO2 mixtures. Infiltrated electrodes with a non-aqueous GDC solution showed the best electro-catalytic activity towards CO2 reduction, exhibiting a much lower polarization resistance, i.e., Rpol = 0.3 Ω&middot, cm2 at 900 &deg, C. The electrochemical performance of LSCM/GDCE in terms of Rpol is comparable to the best-performing Ni-YSZ cathode in the same operating conditions (Rpol = 0.23 Ω&middot, cm2).

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.

In cultural heritage field, significant research efforts have been recently made to improve the efficacy of anti-vegetative treatments and to reduce the environmental impact caused by biocides high concentration. According to the pro-ecological approach, this work reports a novel approach based on the encapsulation/incorporation of environmentally-friendly biocides in different silica nanosystems in order to control the development of biological patinas on outdoor cultural heritage. Two different green biocides have been selected and tested in silica nanosystems: the zosteric acid sodium salt (ZS), a natural antifoulant compound produced by Zostera marina (eelgrass), and the usnic acid (UA), a secondary metabolite produced by some saxicolous lichens. ZS was previously successfully encapsulated but never entrapped in mesoporous silica; instead, UA is, for the first time, encapsulated and in situ entrapped into the silica nanosystems in order to control the release over time. Both silica nanosystems have been characterized as far as their dimensions and superficial properties and loading capability. The antifouling activity was assessed against microorganisms from biopatinas colonising the Aurelian Walls in Rome. Our results have shown that the two nanosystems have complementary properties, thus it is possible to tune the antifouling efficiency by combining the two in different proportions.

Solid oxide photoelectrochemical cells (SOPECs) with inorganic ion-conducting electrolytes provide an alternative solution for light harvesting and conversion. Exploring potential photoelectrodes for SOPECs and understanding their operation mechanisms are crucial for continuously developing this technology. Here, ceria-based thin films were newly explored as photoelectrodes for SOPEC applications. It was found that the photoresponse of ceria-based thin films can be tuned both by Sm-doping-induced defects and by the heating temperature of SOPECs. The whole process was found to depend on the surface electrochemical redox reactions synergistically with the bulk photoelectric effect. Samarium doping level can selectively switch the open-circuit voltages polarity of SOPECs under illumination, thus shifting the potential of photoelectrodes and changing their photoresponse. The role of defect chemistry engineering in determining such a photoelectrochemical process was discussed. Transient absorption and X-ray photoemission spectroscopies, together with the state-of-the-art in operando X-ray absorption spectroscopy, allowed us to provide a compelling explanation of the experimentally observed switching behavior on the basis of the surface reactions and successive charge balance in the bulk.

A thermoresponsive Pluronic/alginate semisynthetic hydrogel is used to bioprint 3D hepatic constructs, with the aim to investigate liver-specific metabolic activity of the 3D constructs compared to traditional 2D adherent cultures. The bioprinting method relies on a bioinert hydrogel and is characterized by high-shape fidelity, mild depositing conditions and easily controllable gelation mechanism. Furthermore, the dissolution of the sacrificial Pluronic templating agent significantly ameliorates the diffusive properties of the printed hydrogel. The present findings demonstrate high viability and liver-specific metabolic activity, as assessed by synthesis of urea, albumin, and expression levels of the detoxifying CYP1A2 enzyme of cells embedded in the 3D hydrogel system. A markedly increased sensitivity to a well-known hepatotoxic drug (acetaminophen) is observed for cells in 3D constructs compared to 2D cultures. Therefore, the 3D model developed herein may represent an in vitro alternative to animal models for investigating drug-induced hepatotoxicity.

Several proton conductive ceramic oxides are evaluated for potential application in ceramic-NiO composite anodes for proton-conducting La0.99Ca0.01NbO4 (LNO) electrolyte-based fuel cells. Chemical compatibility tests show that most of the existing proton-conducting oxides are unfavorable for application in LNO electrolyte-based fuel cells because of undesirable reactions at high temperatures. Further considering the chemical compatibility with NiO and the ability to promote the densification of the deposited LNO electrolyte, LNO-NiO composite anode proves to be the only suitable anode candidate. With humidified hydrogen (∼3%H2O) as the fuel and static air as the oxidant, fuel cells based on LNO electrolyte film deposited on LNO-NiO anodes show a peak power density of 24 mW cm−2 at 750 °C, this value being one of the largest ever reported for LNO-based cells. Further investigation reveals that the polarization resistance of the cell is the major contribution to the total cell resistance, limiting the overall cell performance.

The health monitoring of structures is of great interest in order to check components’ structural life and monitor damages during operation. Self-monitoring materials can provide both the structural and monitoring functionality in one component and exploit their piezoresistive behavior, namely, the variation of electrical resistivity with an applied mechanical strain. In this work, self-monitoring plies were developed to be inserted into glass-fiber reinforced epoxy-based laminates in order to achieve structural monitoring. Nanocomposite epoxy-based resins were developed employing different contents of high surface area carbon black (CB, 6 wt%) and multiwall carbon nanotubes (MWCNT, 0.75 and 1 wt%), and rheologically and thermomechanically characterized. Self-monitoring plies were manufactured by impregnating glass woven fabrics with the resins, and were laminated with non-sensing plies via a vacuum-bag process to produce sensored laminates. The self-monitoring performance of the laminates was assessed during monotonic and cyclic three-point bending tests, as well as ball drop impact tests. A higher sensitivity was found for the CB-based systems (Gauge Factor 6.1), while MWCNTs (0.55 and 1.04) ensure electrical percolation at lower filler contents, as expected. The systems also showed the capability of being used to predict residual life and damage occurred under impact.

An innovative concept of a low-cost pH optode with working volumes of less than 150 µL is presented. The pH monitoring is based on the color changing effect of pH indicators. The optode includes an RGB color sensor patch TCS34725 from Adafruit, a controllable LED and reactor slides and is addressed by a self-written LabVIEW© software. Utilizing the hue value of the HSV color model, it is possible to analyze the color change of the indicator and estimate the pH value of the analyzed samples by exploiting sigmoidal fit models. Measurements carried out with phenol red and DMEM (Dulbecco's Modified Eagle's Medium) reported a standard error of calibration in the physiologic pH range (6.5–7.5) of ±0.04 pH units.

High materials costs and low performance are the persisting bottlenecks that significantly affect the microbial fuel cells (MFCs) applications. The membraneless single-chamber MFC with an air-breathing cathode is a simple configuration where the bacteria play a role in both the anodic and cathodic processes. However, the microbial cathodic semi-reaction is the rate-determining step that can impair the advantage of the natural availability of oxygen in the air. In this work, the microbial catalysis was improved adding cerium oxide nanoparticles (nanoceria) in carbon-based cathodes of air-breathing MFCs, boosting their performance. Two kinds of nanoparticles were tested: CeO2 and Sm-doped CeO2 (Sm-CeO2) on carbon powder, using pristine carbon powder cathodes as a control. The energy generated was 113, 65 and 31 mWh m−2, for Sm-CeO2, CeO2 and control MFCs, respectively, during four subsequent fed cycles of 0.036 mol L−1 Na-acetate in carbonate buffer solution. The better performance of MFCs was correlated to the oxygen preferential and controlled entrapping and release via Ce4+/3+ redox reaction at the carbon particle surface, as well as to the increased cathode active specific surface area. The achieved results suggest that nanoceria can act as oxygen storage for bacteria in the anaerobic biofilm colonizing the cathode.

Copper and gadolinium doped ceria (GDC) anode supported fuel cells were co-sintered at relatively low temperature (900 °C) and successfully tested in the intermediate temperature (IT) range. The GDC electrolyte densification was promoted by a compressive strain induced by increasing the anodic thickness and was evaluated by SEM investigation. Instead of more commonly used La0.8Sr0.2Fe0.6Co0.4O3-δ, strontium and copper-doped lanthanum ferrite La0.8Sr0.2Fe0.8Cu0.2O3-δ (LSFCu) mixed with 30 wt% GDC (LSFCu-GDC) was employed as cathodic material. Preliminary tests on Cu-GDC/GDC/LSFCu-GDC single cells showed promising results at temperature as low as 650 °C using hydrogen as fuel.

We have synthesized two-dimensional carbon nanoparticles by oxidative unfolding of C60 fullerene and demonstrated that the selective sensitivity of this material to the presence of Cu2+ and Pb2+, resulting in variations of the fluorescence intensity and optical absorbance, is related to nanoparticle aggregation processes. This mechanism occurs through coordination of the metal ions and, above a certain ion concentration, leads to precipitation of the carbon material that reduces the metal content in solution. The effect has been characterized by optical measurements while Atomic Absorption Spectroscopy have been carried out for a precise assessment of the real ion concentration in solution.We have synthesized two-dimensional carbon nanoparticles by oxidative unfolding of C60 fullerene and demonstrated that the selective sensitivity of this material to the presence of Cu2+ and Pb2+, resulting in variations of the fluorescence intensity and optical absorbance, is related to nanoparticle aggregation processes. This mechanism occurs through coordination of the metal ions and, above a certain ion concentration, leads to precipitation of the carbon material that reduces the metal content in solution. The effect has been characterized by optical measurements while Atomic Absorption Spectroscopy have been carried out for a precise assessment of the real ion concentration in solution.

© 2019 The Royal Society of Chemistry. A rational design of a high-performance cathode for proton-conducting solid oxide fuel cells (SOFCs) is proposed in this study with the aim of improving the hydration properties of conventional perovskite cathode materials, thus leading to the development of new materials with enhanced proton migration. Herein, potassium is used to dope traditional Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), which is demonstrated to be a beneficial way for improving hydration, both experimentally and theoretically. The theoretical study was needed to overcome practical limits that hindered direct hydrogen mobility measurements. The novel material Ba0.4K0.1Sr0.5Co0.8Fe0.2O3-δ (BKSCF) shows a lower overall proton migration energy compared with that of the sample without K, suggesting that K-doping enhances proton conduction, which shows an improved performance by extending the catalytic sites to the whole cathode area. As a result, a fuel cell built with the novel BKSCF cathode shows an encouraging fuel cell performance of 441 and 1275 mW cm-2 at 600 and 700 °C, respectively, which is significantly higher than that of the cell using the pristine BSCF cathode. This study provides a new and rational way to design a perovskite cathode for proton-conducting SOFCs with high performance.

Solid oxide fuel cells (SOFCs) represent the most efficient devices for producing electrical power from fuels. The limit in their application is due to the high operation temperature of conventional SOFC materials. Progress is made toward lower operating temperatures using alternative oxygen-ion conducting electrolytes, but problems of stability and electronic conductivity still remain. A promising alternative is the use of chemically stable proton-conducting Y-doped BaZrO3 (BZY) electrolytes, but their practical applications are limited by the BZY's relatively low performance. Herein, it is reported that deposition by impregnation of cathode nanoparticles on BZY backbones provides a powerful strategy to improve the BZY-based SOFC performance below 600 °C, allowing an outstanding power output for this chemically stable electrolyte. Moreover, it is demonstrated that keeping the nanostructure is more important than keeping the desired chemical composition. The proposed scalable processing method can make BZY a competitive electrolyte for SOFC applications.

Proton-conducting oxides offer a promising electrolyte solution for intermediate temperature solid oxide fuel cells (SOFCs) due to their high conductivity and low activation energy. However, the lower operation temperature leads to a reduced cathode activity and thus a poorer fuel cell performance. La0.8Sr0.2MnO3−δ (LSM) is the classical cathode material for high-temperature SOFCs, which lack features as a proper SOFC cathode material at intermediate temperatures. Despite this, we here successfully couple nanostructured LSM cathode with proton-conducting electrolytes to operate below 600°C with desirable SOFC performance. Inkjet printing allows depositing nanostructured particles of LSM on Y-doped BaZrO3 (BZY) backbones as cathodes for proton-conducting SOFCs, which provides one of the highest power output for the BZY-based fuel cells below 600°C. This somehow changes the common knowledge that LSM can be applied as a SOFC cathode materials only at high temperatures (above 700°C).

TiO2 coatings on AA6082 aluminium alloy were obtained at low temperature (80 and 100°C) by the sol-gel dip-coating technique starting from titanium tetra-isopropoxide solution in ethyl alcohol. The preparation was carried out in the presence of acetic acid with both functions of catalyst and chelating agent. The curing temperatures used for these coatings are between 80 and 100°C, low enough to make such coatings suitable to incorporate additives such as organic inhibitors or polymeric nanoparticles. The coated samples were characterised by scanning electron microscopy and energy-dispersive spectroscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy (EIS). Compact coatings with a thickness of 500 nm, consisting of amorphous and nearly stoichiometric titanium dioxide, were obtained. EIS results revealed an effective corrosion protection of the substrate for more than 120 h of immersion in 3.5 wt-% NaCl aqueous solution.

High temperature proton conducting oxides, due to their lower activation energy for proton conduction, can achieve high conductivity at relatively low temperatures (500-700 °C). Though BaZr0.8Y0.2O3-δ (BZY) perovskite exhibits good chemical stability and high bulk conductivity, high grain boundary resistance decreases its total conductivity. This work focuses on substitution of Zr4+ with Ni2+ in the perovskite B-site in a targeted fashion in order to promote the sinterability of BZY. Powder X-ray diffraction analysis showed the formation of single phases for Ba0.8-xY0.2NixO3-δ compositions up to x = 0.04. Scanning electron microscopy (SEM) image analysis demonstrated that densification is promoted by the increasing Ni-content, reaching a fully dense microstructure for Ba0.76Y0.2Ni0.04O3-δ (BZYNi04). An anode supported single cell based on BZYNi04 electrolyte showed superior power performance, achieving 240 and 428 mW cm-2 at 600 and 700 °C, respectively.

Full ceramic anodes have been developed over the last decade as an alternative to the state-of-the-art Ni/YSZ cermet. The objective is to overcome the technical limitations of the cermet, especially in high fuel utilization operational mode, when hydrocarbon fuels are used, or in systems where rapid heat up is required. Numerous oxide compositions were proposed and investigated. (La,Sr)Cr0.5Mn0.5O3(LSCM) perovskite has been reported as a very promising anode material because of its high tolerance to carbon and sulfur, and its redox and thermal cycling stability. However, similarly to other oxide anode materials, its overall performance still needed further improvement to match that of Ni/YSZ. The relatively low performance of LSCM compared to Ni/YSZ, used to be attributed to its relatively low electronic conductivity. Recently, we have reported that the pre-coating LSCM with Ni nitrate results in a considerable decrease in the anodic polarization resistance and activation energy. Ni dissolves in the perovskite phase at high temperature under oxidizing atmosphere, and then exsolves in the form of nanoparticles under reducing atmospheres. This type of anode composition with split functionalities (ionic conduction, electronic conduction, and catalytic activity) gives a unique opportunity to investigate the specific influence of each of the above functions on the anodic mechanisms and performance. In this work, electrochemical impedance spectroscopy was used to characterize anode compositions containing LSCM and different levels (15, 40, and 60 wt%) of gadolinia doped ceria (CGO), with and without additional submicron Ni, as well as Ni nanoparticles exsoluted from pre-coated larger LSCM particles. Impedance measurements were performed in a three electrode – half cell configuration from 700 to 900°C under two flow rates of 3% wet H2(50 and 150 ml/min). At 900°C and under 150 mL/min of 3% wet H2, lower values of the polarization resistance (Rp) were measured for the samples containing CGO compared to pure LSCM ones. The Rp showed a slight decrease when the content of CGO was increased (15 to 40 and 60 wt%). This was characterized by a decrease of the high frequency part of the impedance diagrams, likely due to the higher ionic conductivity brought by the addition of CGO. The addition of 5 wt% of submicron Ni to LSCM-CGO led to a remarkable decrease in Rp. This effect was even more spectacular for the samples containing 5 wt% of exsoluted Ni nanoparticles, characterized by a decrease of the whole impedance diagram, and especially the high and the middle frequency parts, which suggests an enhancement of the electrochemical processes related to anode charge transfer. Further analysis of the impedance diagrams, measured for the above anodes at different temperatures and gas flow rates, is in progress in order to define the effect of different anode functionalities on the anodic processes involved, and thus its overall performance.

One of the main problems for the deployment of intermediate-temperature solid oxide fuel cells (IT-SOFCs) is their chemical stability, since most of SOFCs contain alkaline-earth metal elements (Ba, Sr and Ca) that easily react with CO2 forming carbonates. To tackle this problem, we performed a systematic investigation of a series of Ni0.7Co0.3O–Ce0.8Sm0.2O1.9 (NC3O-SDC) composite cathodes, which are CO2-stable and alkaline-earth-free compounds. In this work, NC3O-xSDC (with x = 0-60 wt.%) were synthesized by self-propagating combustion method and investigated as new cathode materials for oxygen-ion conducting SOFCs. The thermal stability and phase structure of NC3O polycrystalline powders were studied using TG-DTA and XRD analysis, which confirmed that NC3O is chemically compatible with SDC. The electrical conductivity and thermal expansion of the NC3O-xSDC samples were measured. The electrochemical properties of NC3O-xSDC/SDC/NC3O-xSDC cells were studied using electrochemical impedance spectroscopy measurements. Among the NC3O-xSDC series, NC3O-30SDC showed a minimum in cathode polarization resistance, being 0.071 Ωcm2 at 800. A maximum power density of 200 mWcm-2 at 600 was obtained using anode-supported SOFCs.

International audience; Bare and Al2O3-coated austenitic steel samples are exposed to lead-fast-reactor relevant corrosive conditions.Selective leaching of Ni, Mn and Cr is observed in bare samples exposed to high temperature stagnant lead(550 DC, 10et8722;8 wt.percent oxygen, 1000 and 4000 h). By contrast, corrosion is not observed in either pristine (4000 h)or irradiated (1000 h) coated samples. Further characterization and testing methods include SEM, TEM, STEM,EDS, cyclic nanoimpact, microindentation, scratch, and thermal cycling. Overall, the results show that thecoatings retain structural integrity under the conditions investigated, which is a crucial prerogative for corrosionprotection with ceramic coatings.

The impregnation method has been considered as one of the most successful techniques for the fabrication of highly efficient electrodes for solid oxide fuel and electrolysis cells (SOCs) at the lab scale. However, because the impregnation is usually performed manually, its irreproducibility remains a major problem that can be solved by using controllable techniques, such as inkjet printing. In this paper, lanthanum strontium manganite (LSM)/yttria stabilized zirconia (YSZ) air electrodes were prepared by infiltrating YSZ porous bodies with LSM precursor solution using inkjet printing, followed by annealing at 800°C for 2 hours. XRD analysis confirmed the formation of the LSM phase, which was in the form of nanoparticles with size in the 50-70 nm range on the YSZ walls, as revealed by FEG-SEM observations. The effect of printing parameters on the distribution of the impregnated phase was investigated and discussed.

La0.8Sr0.2Ga0.8Mg0.2O3-delta (LSGM) perovskite oxide was selected as electrolyte to fabricate reduced-temperature solid oxide fuel cells (SOFCs). Porous/dense ceramic bilayers were optimized by using different pore forming agents. Reduced temperature (700 degrees C) infiltration method was employed to obtain anodes with nano-sized metal oxidation catalysts. The type and amount of porogen necessary to get a proper anodic porosity were evaluated together with the amount of infiltrated Ni catalyst to obtain promising electrochemical results. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

We present an ab initio investigation of the interaction between methane, its dehydrogenated forms and the cerium oxide surface. In particular, the stoichiometric CeO2(111) surface and the one with oxygen vacancies are considered. We study the geometries, energetics and electronic structures of various configurations of these molecules adsorbed on the surface in vacuum, and we extend the analysis to realistic environmental conditions. A phase diagram of the adsorbate–surface system is constructed and relevant transition phases are analyzed in detail, showing the conditions where partial oxidation of methane can occur.

Solid oxide electrolysis cells (SOECs) are expedient to solve the site-specific and intermittent problems for current renewable energies, such as solar, wind and tidal power, as SOECs can convert these renewable energies into chemical energy in the form of H2 that is clean and easily to be transported. Most of the studies on SOECs are focused on oxygen-ion conducting SOECs, using mainly yttria-stabilized zirconia (YSZ) as electrolyte. However, problems such as the dilution of produced H2, high temperature operation, and oxidation of Ni-based fuel electrode occur, which the use of proton-conducting SOECs can circumvent. In addition, the high conductivity of proton-conducting oxides with respect to YSZ enables proton-conducting SOECs operating at intermediate temperatures [1]. The few works reporting on proton-conducting SOECs show the use of BaCeO3-based electrolytes, which has been demonstrated to be chemically unstable in H2O. Although proton-conducting BaZrO3-based materials are the most promising electrolyte candidates for proton-conducting SOECs due to the excellent chemical stability and high bulk conductivity [2], their processing difficulties due to poor sinterability and high-resistive grain boundaries prevented the deployment in SOEC devices. In this report, we pioneeringly used BaZrO3-based electrolytes for SOECs, demonstrating that tailoring the electrolyte and electrode materials results in further improving the electrolysis cell performance. Anode supported BaZr0.9Y0.1O3-δ (BZY) electrolyte films were fabricated using an ionic diffusion method [3]. Both thermodynamic calculation and experimental results suggest that BZY has an excellent chemical stability in H2O, which is critical for practical applications. A current density of 119 mA cm-2 was obtained at 600°C, with an applied voltage of 1.65 V for the electrolysis cell, which is comparable or even higher than that for proton-conducting SOECs with BaCeO3-based electrolyte at similar conditions, while BZY electrolyte offers much better chemical stability. This cell also operated at 600 oC for more than 80 h without any obvious degradation, while the BaCeO3-cells are reported to only last tenths of minutes or a few hours [4]. To improve the cell performance, BaZr0. 7Y0. 2Pr0.1O3-δ (BZPY10), which is a more conductive proton-conducting electrolyte material, wass used for the SOEC. With La0.8Sr0.2MnO3-δ (LSM)-BZPY10 composite air electrode, the SOEC with BZPY10 electrolyte reached a current density of 576 mA cm-2 with an applied voltage of 1.6 V at 600 oC. This cell performance is much improved compared with the above discussed BZY cell. Further cell performance improvement was achieved by tailoring the air electrode material with BaZr0. 5Y0. 2Pr0. 3O3-δ (BZPY30), which is a mixed protonic-electronic conductor rather than a pure protonic conductor [5]. By coupling BZPY30 with LSM, the triple phase boundary (TPB) is much improved due to the mixed conducting behavior of BZPY30, which is beneficial to the reaction. As a result, the cell with BZPY30-LSM air electrode produced a current density of 1007 mA cm-2 with an applied voltage of 1.6 V at 600 oC. An obvious cell performance improvement is obtained with the tailored electrode. Reference s L. Bi, S. Boulfrad and E. Traversa, Chem. Soc. Rev., 2014, 43, 8195-8300. D. Pergolesi, E. Fabbri, A. D'Epifanio, E. Di Bartolomeo, A. Tebano, S. Sanna, S. Licoccia, G. Balestrino and E. Traversa, Nature Mater., 2010, 9, 846-852. L. Bi, E. Fabbri, Z. Q. Sun and E. Traversa, Energy Environ. Sci., 2011, 4, 409-412. L. Bi, S.P. Shafi and E. Traversa, J. Mater. Chem. A, 2015, DOI: 10.1039/c4ta07202b. E. Fabbri, L. Bi, D. Pergolesi and E. Traversa, Energy Environ. Sci., 2011, 4, 4984-4993.