Search results for: solid-state electrolyte

Authors: Mitali Saha, Soma Das

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The fabrication of nanoscale materials for use in chemical sensing, biosensing and biological analyses has proven a promising avenue in the last few years. Cholesterol has aroused considerable interest in recent years on account of its being an important parameter in clinical diagnosis. There is a strong positive correlation between high serum cholesterol level and arteriosclerosis, hypertension, and myocardial infarction. Enzyme-based electrochemical biosensors have shown high selectivity and excellent sensitivity, but the enzyme is easily denatured during its immobilization procedure and its activity is also affected by temperature, pH, and toxic chemicals. Besides, the reproducibility of enzyme-based sensors is not very good which further restrict the application of cholesterol biosensor. It has been demonstrated that carbon nanotubes could promote electron transfer with various redox active proteins, ranging from cytochrome c to glucose oxidase with a deeply embedded redox center. In continuation of our earlier work on the synthesis and applications of carbon and metal based nanoparticles, we have reported here the synthesis of carbon nanotubes (CCNT) by burning coconut oil under insufficient flow of air using an oil lamp. The soot was collected from the top portion of the flame, where the temperature was around 6500C which was purified, functionalized and then characterized by SEM, p-XRD and Raman spectroscopy. The SEM micrographs showed the formation of tubular structure of CCNT having diameter below 100 nm. The XRD pattern indicated the presence of two predominant peaks at 25.20 and 43.80, which corresponded to (002) and (100) planes of CCNT respectively. The Raman spectrum (514 nm excitation) showed the presence of 1600 cm-1 (G-band) related to the vibration of sp2-bonded carbon and at 1350 cm-1 (D-band) responsible for the vibrations of sp3-bonded carbon. A nonenzymatic cholesterol biosensor was then fabricated on an insulating Teflon material containing three silver wires at the surface, covered by CCNT, obtained from coconut oil. Here, CCNTs worked as working as well as counter electrodes whereas reference electrode and electric contacts were made of silver. The dimensions of the electrode was 3.5 cm×1.0 cm×0.5 cm (length× width × height) and it is ideal for working with 50 µL volume like the standard screen printed electrodes. The voltammetric behavior of cholesterol at CCNT electrode was investigated by cyclic voltammeter and differential pulse voltammeter using 0.001 M H2SO4 as electrolyte. The influence of the experimental parameters on the peak currents of cholesterol like pH, accumulation time, and scan rates were optimized. Under optimum conditions, the peak current was found to be linear in the cholesterol concentration range from 1 µM to 50 µM with a sensitivity of ~15.31 μAμM−1cm−2 with lower detection limit of 0.017 µM and response time of about 6s. The long-term storage stability of the sensor was tested for 30 days and the current response was found to be ~85% of its initial response after 30 days.

Keywords: coconut oil, CCNT, cholesterol, biosensor

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Authors: Sundaram Chandrasekaran, Seung Hyun Hur

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Exploring strategies for oxygen vacancy engineering under mild conditions and understanding the relationship between dislocations and photoelectrochemical (PEC) cell performance are challenging issues for designing high performance PEC devices. Therefore, it is very important to understand that how the oxygen vacancies (VO) or other defect states affect the performance of the photocatalyst in photoelectric transfer. So far, it has been found that defects in nano or micro crystals can have two possible significances on the PEC performance. Firstly, an electron-hole pair produced at the interface of photoelectrode and electrolyte can recombine at the defect centers under illumination of light, thereby reducing the PEC performances. On the other hand, the defects could lead to a higher light absorption in the longer wavelength region and may act as energy centers for the water splitting reaction that can improve the PEC performances. Even if the dislocation growth of ZnO has been verified by the full density functional theory (DFT) calculations and local density approximation calculations (LDA), it requires further studies to correlate the structures of ZnO and PEC performances. Exploring the hybrid structures composed of graphene oxide (GO) and ZnO nanostructures offer not only the vision of how the complex structure form from a simple starting materials but also the tools to improve PEC performances by understanding the underlying mechanisms of mutual interactions. As there are few studies for the ZnO growth with other materials and the growth mechanism in those cases has not been clearly explored yet, it is very important to understand the fundamental growth process of nanomaterials with the specific materials, so that rational and controllable syntheses of efficient ZnO-based hybrid materials can be designed to prepare nanostructures that can exhibit significant PEC performances. Herein, we fabricated various ZnO nanostructures such as hollow sphere, bucky bowl, nanorod and triangle, investigated their pH dependent growth mechanism, and correlated the PEC performances with them. Especially, the origin of well-controlled dislocation-driven growth and its transformation mechanism of ZnO nanorods to triangles on the GO surface were discussed in detail. Surprisingly, the addition of GO during the synthesis process not only tunes the morphology of ZnO nanocrystals and also creates more oxygen vacancies (oxygen defects) in the lattice of ZnO, which obviously suggest that the oxygen vacancies be created by the redox reaction between GO and ZnO in which the surface oxygen is extracted from the surface of ZnO by the functional groups of GO. On the basis of our experimental and theoretical analysis, the detailed mechanism for the formation of specific structural shapes and oxygen vacancies via dislocation, and its impact in PEC performances are explored. In water splitting performance, the maximum photocurrent density of GO-ZnO triangles was 1.517mA/cm-2 (under UV light ~ 360 nm) vs. RHE with high incident photon to current conversion Efficiency (IPCE) of 10.41%, which is the highest among all samples fabricated in this study and also one of the highest IPCE reported so far obtained from GO-ZnO triangular shaped photocatalyst.

Keywords: dislocation driven growth, zinc oxide, graphene oxide, water splitting

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Authors: Boukary Lam, Sebastien Deon, Patrick Fievet, Nadia Crini, Gregorio Crini

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Treatment of heavy metal-contaminated industrial wastewater has become a major challenge over the last decades. Conventional processes for the treatment of metal-containing effluents do not always simultaneously satisfy both legislative and economic criteria. In this context, coupling of processes can then be a promising alternative to the conventional approaches used by industry. The polymer-assisted ultrafiltration (PAUF) process is one of these coupling processes. Its principle is based on a sequence of steps with reaction (e.g., complexation) between metal ions and a polymer and a step involving the rejection of the formed species by means of a UF membrane. Unlike free ions, which can cross the UF membrane due to their small size, the polymer/ion species, the size of which is larger than pore size, are rejected. The PAUF process was deeply investigated herein in the case of removal of nickel ions by adding chitosan and carboxymethyl cellulose (CMC). Experiments were conducted with synthetic solutions containing 1 to 100 ppm of nickel ions with or without the presence of NaCl (0.05 to 0.2 M), and an industrial discharge water (containing several metal ions) with and without polymer. Chitosan with a molecular weight of 1.8×105 g mol⁻¹ and a degree of acetylation close to 15% was used. CMC with a degree of substitution of 0.7 and a molecular weight of 9×105 g mol⁻¹ was employed. Filtration experiments were performed under cross-flow conditions with a filtration cell equipped with a polyamide thin film composite flat-sheet membrane (3.5 kDa). Without the step of polymer addition, it was found that nickel rejection decreases from 80 to 0% with increasing metal ion concentration and salt concentration. This behavior agrees qualitatively with the Donnan exclusion principle: the increase in the electrolyte concentration screens the electrostatic interaction between ions and the membrane fixed the charge, which decreases their rejection. It was shown that addition of a sufficient amount of polymer (greater than 10⁻² M of monomer unit) can offset this decrease and allow good metal removal. However, the permeation flux was found to be somewhat reduced due to the increase in osmotic pressure and viscosity. It was also highlighted that the increase in pH (from 3 to 9) has a strong influence on removal performances: the higher pH value, the better removal performance. The two polymers have shown similar performance enhancement at natural pH. However, chitosan has proved more efficient in slightly basic conditions (above its pKa) whereas CMC has demonstrated very weak rejection performances when pH is below its pKa. In terms of metal rejection, chitosan is thus probably the better option for basic or strongly acid (pH < 4) conditions. Nevertheless, CMC should probably be preferred to chitosan in natural conditions (5 < pH < 8) since its impact on the permeation flux is less significant. Finally, ultrafiltration of an industrial discharge water has shown that the increase in metal ion rejection induced by the polymer addition is very low due to the competing phenomenon between the various ions present in the complex mixture.

Keywords: carboxymethyl cellulose, chitosan, heavy metals, nickel ion, polymer-assisted ultrafiltration

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Authors: Hamadi Cherif, Christophe Coquelet, Paolo Stringari, Denis Clodic, Laura Pellegrini, Stefania Moioli, Stefano Langè

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Biogas is a promising technology which can be used as a vehicle fuel, for heat and electricity production, or injected in the national gas grid. It is storable, transportable, not intermittent and substitutable for fossil fuels. This gas produced from the wastewater treatment by degradation of organic matter under anaerobic conditions is mainly composed of methane and carbon dioxide. To be used as a renewable fuel, biogas, whose energy comes only from methane, must be purified from carbon dioxide and other impurities such as water vapor, siloxanes and hydrogen sulfide. Purification of biogas for this application particularly requires the removal of hydrogen sulfide, which negatively affects the operation and viability of equipment especially pumps, heat exchangers and pipes, causing their corrosion. Several methods are available to eliminate hydrogen sulfide from biogas. Herein, reactive absorption in structured packed column by means of chemical absorption in aqueous sodium hydroxide solutions is considered. This study is based on simulations using Aspen Plus™ V8.0, and comparisons are done with data from an industrial pilot plant treating 85 Nm3/h of biogas which contains about 30 ppm of hydrogen sulfide. The rate-based model approach has been used for simulations in order to determine the efficiencies of separation for different operating conditions. To describe vapor-liquid equilibrium, a γ/ϕ approach has been considered: the Electrolyte NRTL model has been adopted to represent non-idealities in the liquid phase, while the Redlich-Kwong equation of state has been used for the vapor phase. In order to validate the thermodynamic model, Henry’s law constants of each compound in water have been verified against experimental data. Default values available in Aspen Plus™ V8.0 for the properties of pure components properties as heat capacity, density, viscosity and surface tension have also been verified. The obtained results for physical and chemical properties are in a good agreement with experimental data. Reactions involved in the process have been studied rigorously. Equilibrium constants for equilibrium reactions and the reaction rate constant for the kinetically controlled reaction between carbon dioxide and the hydroxide ion have been checked. Results of simulations of the pilot plant purification section show the influence of low temperatures, concentration of sodium hydroxide and hydrodynamic parameters on the selective absorption of hydrogen sulfide. These results show an acceptable degree of accuracy when compared with the experimental data obtained from the pilot plant. Results show also the great efficiency of sodium hydroxide for the removal of hydrogen sulfide. The content of this compound in the gas leaving the column is under 1 ppm.

Keywords: biogas, hydrogen sulfide, reactive absorption, sodium hydroxide, structured packed column

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Authors: Pinar Erturk, Sevde Altuntas, Fatih Buyukserin

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In order to obtain an effective integration between an implant and a bone, implant surfaces should have similar properties to bone tissue surfaces. Especially mimicry of the chemical, mechanical and topographic properties of the implant to the bone is crucial for fast and effective osseointegration. Titanium-based biomaterials are more preferred in clinical use, and there are studies of coating these implants with oxide layers that have chemical/nanotopographic properties stimulating cell interactions for enhanced osseointegration. There are low success rates of current implantations, especially in craniofacial implant applications, which are large and vital zones, and the oxide layer coating increases bone-implant integration providing long-lasting implants without requiring revision surgery. Our aim in this study is to examine bone-cell behavior on titanium implants with an aluminum oxide layer (AAO) on effective osseointegration potential in the deformation of large zones with difficult spontaneous healing. In our study, aluminum layer coated titanium surfaces were anodized in sulfuric, phosphoric, and oxalic acid, which are the most common used AAO anodization electrolytes. After morphologic, chemical, and mechanical tests on AAO coated Ti substrates, viability, adhesion, and mineralization of adult bone cells on these substrates were analyzed. Besides with atomic layer deposition (ALD) as a sensitive and conformal technique, these surfaces were coated with pure alumina (5 nm); thus, cell studies were performed on ALD-coated nanoporous oxide layers with suppressed ionic content too. Lastly, in order to investigate the effect of the topography on the cell behavior, flat non-porous alumina layers on silicon wafers formed by ALD were compared with the porous ones. Cell viability ratio was similar between anodized surfaces, but pure alumina coated titanium and anodized surfaces showed a higher viability ratio compared to bare titanium and bare anodized ones. Alumina coated titanium surfaces, which anodized in phosphoric acid, showed significantly different mineralization ratios after 21 days over other bare titanium and titanium surfaces which anodized in other electrolytes. Bare titanium was the second surface that had the highest mineralization ratio. Otherwise, titanium, which is anodized in oxalic acid electrolyte, demonstrated the lowest mineralization. No significant difference was shown between bare titanium and anodized surfaces except AAO titanium surface anodized in phosphoric acid. Currently, osteogenic activities of these cells on the genetic level are investigated by quantitative real-time polymerase chain reaction (qRT-PCR) analysis results of RUNX-2, VEGF, OPG, and osteopontin genes. Also, as a result of the activities of the genes mentioned before, Western Blot will be used for protein detection. Acknowledgment: The project is supported by The Scientific and Technological Research Council of Turkey.

Keywords: alumina, craniofacial implant, MG-63 cell line, osseointegration, oxalic acid, phosphoric acid, sulphuric acid, titanium

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Authors: Marisa Rio, Sharanya Bola, Richard H. W. Funk, Gerald Gerlach

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Cell migration, wound healing and regeneration are some of the physiological phenomena in which electric fields (EFs) have proven to have an important function. Physiologically, cells experience electrical signals in the form of transmembrane potentials, ion fluxes through protein channels as well as electric fields at their surface. As soon as a wound is created, the disruption of the epithelial layers generates an electric field of ca. 40-200 mV/mm, directing cell migration towards the wound site, starting the healing process. In vitro electrotaxis, experiments have shown cells respond to DC EFs polarizing and migrating towards one of the poles (cathode or anode). A standard electrotaxis experiment consists of an electrotaxis chamber where cells are cultured, a DC power source and agar salt bridges that help delaying toxic products from the electrodes to attain the cell surface. The electric field strengths used in such an experiment are uniform and homogeneous. In contrast, the endogenous electric field strength around a wound tend to be multi-field and non-homogeneous. In this study, we present a custom device that enables electrotaxis experiments in non-homogeneous DC electric fields. Its main feature involves the replacement of conventional metallic electrodes, separated from the electrotaxis channel by agarose gel bridges, through electrolyte-filled microchannels. The connection to the DC source is made by Ag/AgCl electrodes, incased in agarose gel and placed at the end of each microfluidic channel. An SU-8 membrane closes the fluidic channels and simultaneously serves as the single connection from each of them to the central electrotaxis chamber. The electric field distribution and current density were numerically simulated with the steady-state electric conduction module from ANSYS 16.0. Simulation data confirms the application of nonhomogeneous EF of physiological strength. To validate the biocompatibility of the device cellular viability of the photoreceptor-derived 661W cell line was accessed. The cells have not shown any signs of apoptosis, damage or detachment during stimulation. Furthermore, immunofluorescence staining, namely by vinculin and actin labelling, allowed the assessment of adhesion efficiency and orientation of the cytoskeleton, respectively. Cellular motility in the presence and absence of applied DC EFs was verified. The movement of individual cells was tracked for the duration of the experiments, confirming the EF-induced, cathodal-directed motility of the studied cell line. The in vitro monolayer wound assay, or “scratch assay” is a standard protocol to quantitatively access cell migration in vitro. It encompasses the growth of a confluent cell monolayer followed by the mechanic creation of a scratch, representing a wound. Hence, wound dynamics was monitored over time and compared for control and applied the electric field to quantify cellular population motility.

Keywords: DC non-homogeneous electric fields, electrotaxis, microfluidic biochip, wound healing

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Authors: A. Volperts, G. Dobele, A. Zhurinsh, I. Kruusenberg, A. Plavniece, J. Locs

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Nowadays energy consumption constantly increases and development of effective and cheap electrochemical sources of power, such as fuel cells and electrochemical capacitors, is topical. Due to their high specific power, charge and discharge rates, working lifetime supercapacitor based energy accumulation systems are more and more extensively being used in mobile and stationary devices. Lignocellulosic materials are widely used as precursors and account for around 45% of the total raw materials used for the manufacture of activated carbon which is the most suitable material for supercapacitors. First part of our research is devoted to study of influence of main stages of wood thermochemical activation parameters on activated carbons porous structure formation. It was found that the main factors governing the properties of carbon materials are specific surface area, volume and pore size distribution, particles dispersity, ash content and oxygen containing groups content. Influence of activated carbons attributes on capacitance and working properties of supercapacitor are demonstrated. The correlation between activated carbons porous structure indices and electrochemical specifications of supercapacitors with electrodes made from these materials has been determined. It is shown that if synthesized activated carbons are used in supercapacitors then high specific capacitances can be reached – more than 380 F/g in 4.9M sulfuric acid based electrolytes and more than 170 F/g in 1 M tetraethylammonium tetrafluoroborate in acetonitrile electrolyte. Power specifications and minimal price of H₂-O₂ fuel cells are limited by the expensive platinum-based catalysts. The main direction in development of non-platinum catalysts for the oxygen reduction is the study of cheap porous carbonaceous materials which can be obtained by the pyrolysis of polymers including renewable biomass. It is known that nitrogen atoms in carbon materials to a high degree determine properties of the doped activated carbons, such as high electrochemical stability, hardness, electric resistance, etc. The lack of sufficient knowledge on the doping of the carbon materials calls for the ongoing researches of properties and structure of modified carbon matrix. In the second part of this study, highly porous activated carbons were synthesized using alkali thermochemical activation from wood, cellulose and cellulose production residues – craft lignin and sewage sludge. Activated carbon samples were doped with dicyandiamide and melamine for the application as fuel cell cathodes. Conditions of nitrogen introduction (solvent, treatment temperature) and its content in the carbonaceous material, as well as porous structure characteristics, such as specific surface and pore size distribution, were studied. It was found that efficiency of doping reaction depends on the elemental oxygen content in the activated carbon. Relationships between nitrogen content, porous structure characteristics and electrodes electrochemical properties are demonstrated.

Keywords: activated carbons, low-temperature fuel cells, nitrogen doping, porous structure, supercapacitors

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Authors: Cyril O. Ehi-Eromosele, Ajayi Kayode

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The Li-rich layered metal oxides (LLO) are the most promising candidates for promising electrodes of high energy Li-ion battery (LIB). In literature, these electrode system has either been designed as a hetero-structure of the primary components (composite) or as a core-shell structure with improved electrochemistry reported for both configurations when compared with its primary components. With the on-going efforts to improve on the electrochemical performance of the LIB, it is important to investigate comparatively the structural and electrochemical characteristics of the core-shell like and ‘composite’ forms of these materials with the same compositions and synthesis conditions which could influence future engineering of these materials. Therefore, this study concerns the structural and electrochemical properties of the ‘composite’ and core-shell like LLO cathode materials with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₂O₂ (LiNi₀.₅Mn₀.₃Co₀.₂O₂ as core and Li₂MnO₃ as the shell). The results show that the core-shell sample (–CS) gave better electrochemical performance than the ‘composite’ sample (–C). Both samples gave the same initial charge capacity of ~300 mAh/g when cycled at 10 mA/g and comparable charge capacity (246 mAh/g for the –CS sample and 240 mAh/g for the –C sample) when cycled at 200 mA/g. However, the –CS sample gave a higher initial discharge capacity at both current densities. The discharge capacity of the –CS sample was 232 mAh/g and 164 mAh/g while the –C sample is 208 mAh/g and 143 mAh/g at the current densities of 10 mA/g and 200 mA/g, respectively. Electrochemical impedance spectroscopy (EIS) results show that the –CS sample generally exhibited a smaller resistance than the –C sample both for the uncycled and after 50th cycle. Detailed structural analysis is on-going, but preliminary results show that the –CS sample had bigger unit cell volume and a higher degree of cation mixing. The thermal stability of the –CS sample was higher than the –C sample. XPS investigation also showed that the pristine –C sample gave a more reactive surface (showing formation of carbonate species to a greater degree) which could result in the greater resistance seen in the EIS result. To reinforce the results obtained for the 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₃O₂ composition, the same investigations were extended to another ‘composite’ and core-shell like LLO cathode materials also with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂. In this case, the aim was to determine the electrochemical performance of the material using a low Ni content (LiNi₀.₃Mn₀.₃Co₀.₃O₂) as the core to clarify the contributions of the core-shell configuration to the electrochemical performance of these materials. Ni-rich layered oxides show active catalytic surface leading to electrolyte oxidation resulting in poor thermal stability and cycle life. Here, the core-shell sample also gave better electrochemical performance than the ‘composite’ sample with 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂ composition. Furthermore, superior electrochemical performance was also recorded for the core-shell like spinel modified LLO (0.5Li₂MnO₃-0.45LiNi₀.₅Mn₀.₃Co₀.₂O₂-0.05LiNi₀.₅Mn₁.₅O₄) when compared to the composite system. These results show that the core-shell configuration can generally be used to improve the structural and electrochemical properties of the LLO and spinel modified LLO materials.

Keywords: lithium-ion battery, lithium rich oxide cathode, core-shell structure, composite structure

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Authors: J. Martin, A. Nominé, T. Czerwiec, G. Henrion, T. Belmonte

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The plasma electrolytic oxidation (PEO) is a particular electrochemical process to produce protective oxide ceramic coatings on light-weight metals (Al, Mg, Ti). When applied to aluminum alloys, the resulting PEO coating exhibit improved wear and corrosion resistance because thick, hard, compact and adherent crystalline alumina layers can be achieved. Several investigations have been carried out to improve the efficiency of the PEO process and one particular way consists in tuning the suitable electrical regime. Despite the considerable interest in this process, there is still no clear understanding of the underlying discharge mechanisms that make possible metal oxidation up to hundreds of µm through the ceramic layer. A key parameter that governs the PEO process is the numerous short-lived micro-discharges (micro-plasma in liquid) that occur continuously over the processed surface when the high applied voltage exceeds the critical dielectric breakdown value of the growing ceramic layer. By using a bipolar pulsed current to supply the electrodes, we previously observed that micro-discharges are delayed with respect to the rising edge of the anodic current. Nevertheless, explanation of the origin of such phenomena is still not clear and needs more systematic investigations. The aim of the present communication is to identify the relationship that exists between this delay and the mechanisms responsible of the oxide growth. For this purpose, the delay of micro-discharges ignition is investigated as the function of various electrical parameters such as the current density (J), the current pulse frequency (F) and the anodic to cathodic charge quantity ratio (R = Qp/Qn) delivered to the electrodes. The PEO process was conducted on Al2214 aluminum alloy substrates in a solution containing potassium hydroxide [KOH] and sodium silicate diluted in deionized water. The light emitted from micro-discharges was detected by a photomultiplier and the micro-discharge parameters (number, size, life-time) were measured during the process by means of ultra-fast video imaging (125 kfr./s). SEM observations and roughness measurements were performed to characterize the morphology of the elaborated oxide coatings while XRD was carried out to evaluate the amount of corundum -Al203 phase. Results show that whatever the applied current waveform, the delay of micro-discharge appearance increases as the process goes on. Moreover, the delay is shorter when the current density J (A/dm2), the current pulse frequency F (Hz) and the ratio of charge quantity R are high. It also appears that shorter delays are associated to stronger micro-discharges (localized, long and large micro-discharges) which have a detrimental effect on the elaborated oxide layers (thin and porous). On the basis of the results, a model for the growth of the PEO oxide layers will be presented and discussed. Experimental results support that a mechanism of electrical charge accumulation at the oxide surface / electrolyte interface takes place until the dielectric breakdown occurs and thus until micro-discharges appear.

Keywords: aluminium, micro-discharges, oxidation mechanisms, plasma electrolytic oxidation

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Authors: Davide Gotti, Milan Prodanovic, Sergio Pinilla, David Muñoz-Torrero

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Since its proposal, the Doyle-Fuller-Newman (DFN) lithium-ion battery model has gained popularity in the electrochemical field. In fact, this model provides the user with theoretical support for designing the lithium-ion battery parameters, such as the material particle or the diffusion coefficient adjustment direction. However, the model is mathematically complex as it is composed of several partial differential equations (PDEs) such as Fick’s law of diffusion, the MacInnes and Ohm’s equations, among other phenomena. Thus, to efficiently use the model in a time-domain simulation environment, the selection of the discretization technique is of a pivotal importance. There are several numerical methods available in the literature that can be used to carry out this task. In this study, a comparison between the explicit Euler, Crank-Nicolson, and Chebyshev discretization methods is proposed. These three methods are compared in terms of accuracy, stability, and computational times. Firstly, the explicit Euler discretization technique is analyzed. This method is straightforward to implement and is computationally fast. In this work, the accuracy of the method and its stability properties are shown for the electrolyte diffusion partial differential equation. Subsequently, the Crank-Nicolson method is considered. It represents a combination of the implicit and explicit Euler methods that has the advantage of being of the second order in time and is intrinsically stable, thus overcoming the disadvantages of the simpler Euler explicit method. As shown in the full paper, the Crank-Nicolson method provides accurate results when applied to the DFN model. Its stability does not depend on the integration time step, thus it is feasible for both short- and long-term tests. This last remark is particularly important as this discretization technique would allow the user to implement parameter estimation and optimization techniques such as system or genetic parameter identification methods using this model. Finally, the Chebyshev discretization technique is implemented in the DFN model. This discretization method features swift convergence properties and, as other spectral methods used to solve differential equations, achieves the same accuracy with a smaller number of discretization nodes. However, as shown in the literature, these methods are not suitable for handling sharp gradients, which are common during the first instants of the charge and discharge phases of the battery. The numerical results obtained and presented in this study aim to provide the guidelines on how to select the adequate discretization technique for the DFN model according to the type of application to be performed, highlighting the pros and cons of the three methods. Specifically, the non-eligibility of the simple Euler method for longterm tests will be presented. Afterwards, the Crank-Nicolson and the Chebyshev discretization methods will be compared in terms of accuracy and computational times under a wide range of battery operating scenarios. These include both long-term simulations for aging tests, and short- and mid-term battery charge/discharge cycles, typically relevant in battery applications like grid primary frequency and inertia control and electrical vehicle breaking and acceleration.

Keywords: Doyle-Fuller-Newman battery model, partial differential equations, discretization, numerical methods

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Authors: Mihaela Beregoi, Horia Iovu, Cristina Busuioc, Alexandru Evanghelidis, Elena Matei, Monica Enculescu, Ionut Enculescu

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Nanomaterials field is very attractive for all researchers who are attempting to develop new devices with the same or improved properties than the micro-sized ones, while reducing the reagents and power consumptions. In this way, a wide range of nanomaterials were fabricated and integrated in applications for electronics, optoelectronics, solar cells, tissue reconstruction and drug delivery. Obviously, the most appealing ones are those dedicated to the medical domain. Different types of nano-sized materials, such as particles, fibers, films etc., can be synthesized by using physical, chemical or electrochemical methods. One of these techniques is electrospinning, which enable the production of fibers with nanometric dimensions by pumping a polymeric solution in a high electric field; due to the electrostatic charging and solvent evaporation, the precursor mixture is converted into nonwoven meshes with different fiber densities and mechanical properties. Moreover, polyaniline is a conducting polymer with interesting optical properties, suitable for displays and electrochromic windows. Otherwise, polyaniline is an electroactive polymer that can contract/expand by applying electric stimuli, due to the oxidation/reduction reactions which take place in the polymer chains. These two main properties can be exploited in order to synthesize smart materials that change their dimensions, exhibiting in the same time good electrochromic properties. In the context aforesaid, a poly(methyl metacrylate) solution was spun to get webs composed of fibers with diameter values between 500 nm and 1 µm. Further, the polymer meshes were covered with a gold layer in order to make them conductive and also appropriate as working electrode in an electrochemical cell. The gold shell was deposited by DC sputtering. Such metalized fibers can be transformed into smart materials by covering them with a thin layer of conductive polymer. Thus, the webs were coated with a polyaniline film by the electrochemical route, starting from and aqueous solution of aniline and sulfuric acid, where sulfuric acid acts as oxidant agent. For the polymerization of aniline, a saturated calomel electrode was employed as reference, a platinum plate as counter electrode and the gold covered webs as working electrode. Chronoamperometry was selected as deposition method for polyaniline, by modifying the deposition time. Metalized meshes with different fiber densities were used, the transmission ranging between 70 and 80 %. The morphological investigation showed that polyaniline layer has a granular structure for all deposition experiments. As well, some preliminary optical tests were done by using sulfuric acid as electrolyte, which revealed the modification of polyaniline colour from green to dark blue when applying a voltage. In conclusion, new multilayered materials were obtained by a simple approach: the merge of the electrospinning method benefits with polyaniline chemistry. This synthesis method allows the fabrication of structures with reproducible characteristics, suitable for display or tissue substituents.

Keywords: electrospinning, fibers, smart materials, polyaniline

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Authors: Somnath Bhattacharyya

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The mobile adsorbed surface charge on hydrophobic surfaces can modify the velocity slip condition as well as create a Marangoni stress at the interface. The functionalized hydrophobic walls of micro/nanopores, e.g., graphene nanochannels, may possess physio-sorbed ions. The lateral mobility of the physisorbed absorbed ions creates a friction force as well as an electric force, leading to a modification in the velocity slip condition at the hydrophobic surface. In addition, the non-uniform distribution of these surface ions creates a surface tension gradient, leading to a Marangoni stress. The impact of the mobile surface charge on streaming potential and electrochemical energy conversion efficiency in a pressure-driven flow of ionized liquid through the nanopore is addressed. Also, enhanced electro-osmotic flow through the hydrophobic nanochannel is also analyzed. The mean-filed electrokinetic model is modified to take into account the short-range non-electrostatic steric interactions and the long-range Coulomb correlations. The steric interaction is modeled by considering the ions as charged hard spheres of finite radius suspended in the electrolyte medium. The electrochemical potential is modified by including the volume exclusion effect, which is modeled based on the BMCSL equation of state. The electrostatic correlation is accounted for in the ionic self-energy. The extremal of the self-energy leads to a fourth-order Poisson equation for the electric field. The ion transport is governed by the modified Nernst-Planck equation, which includes the ion steric interactions; born force arises due to the spatial variation of the dielectric permittivity and the dielectrophoretic force on the hydrated ions. This ion transport equation is coupled with the Navier-Stokes equation describing the flow of the ionized fluid and the 3fourth-order Poisson equation for the electric field. We numerically solve the coupled set of nonlinear governing equations along with the prescribed boundary conditions by adopting a control volume approach over a staggered grid arrangement. In the staggered grid arrangements, velocity components are stored on the midpoint of the cell faces to which they are normal, whereas the remaining scalar variables are stored at the center of each cell. The convection and electromigration terms are discretized at each interface of the control volumes using the total variation diminishing (TVD) approach to capture the strong convection resulting from the highly enhanced fluid flow due to the modified model. In order to link pressure to the continuity equation, we adopt a pressure correction-based iterative SIMPLE (Semi-Implicit Method for Pressure-Linked Equations) algorithm, in which the discretized continuity equation is converted to a Poisson equation involving pressure correction terms. Our results show that the physisorbed ions on a hydrophobic surface create an enhanced slip velocity when streaming potential, which enhances the convection current. However, the electroosmotic flow attenuates due to the mobile surface ions.

Keywords: microfluidics, electroosmosis, streaming potential, electrostatic correlation, finite sized ions

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Authors: Sudeshna Chandra, Christian Gäbler, Christian Schliebe, Heinrich Lang

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Highly branched dendrimers provide structural homogeneity, controlled composition, comparable size to biomolecules, internal porosity and multiple functional groups for conjugating reactions. Electro-active dendrimers containing multiple redox units have generated great interest in their use as electrode modifiers for development of biosensors. The electron transfer between the redox-active dendrimers and the biomolecules play a key role in developing a biosensor. Ferrocenes have multiple and electrochemically equivalent redox units that can act as electron “pool” in a system. The ferrocenyl-terminated polyamidoamine dendrimer is capable of transferring multiple numbers of electrons under the same applied potential. Therefore, they can be used for dual purposes: one in building a film over the electrode for immunosensors and the other for immobilizing biomolecules for sensing. Electrochemical immunosensor, thus developed, exhibit fast and sensitive analysis, inexpensive and involve no prior sample pre-treatment. Electrochemical amperometric immunosensors are even more promising because they can achieve a very low detection limit with high sensitivity. Detection of the cancer biomarkers at an early stage can provide crucial information for foundational research of life science, clinical diagnosis and prevention of disease. Elevated concentration of biomarkers in body fluid is an early indication of some type of cancerous disease and among all the biomarkers, IgG is the most common and extensively used clinical cancer biomarkers. We present an IgG (=immunoglobulin) electrochemical immunosensor using a newly synthesized redox-active ferrocenyl dendrimer of generation 2 (G2Fc) as glassy carbon electrode material for immobilizing the antibody. The electrochemical performance of the modified electrodes was assessed in both aqueous and non-aqueous media using varying scan rates to elucidate the reaction mechanism. The potential shift was found to be higher in an aqueous electrolyte due to presence of more H-bond which reduced the electrostatic attraction within the amido groups of the dendrimers. The cyclic voltammetric studies of the G2Fc-modified GCE in 0.1 M PBS solution of pH 7.2 showed a pair of well-defined redox peaks. The peak current decreased significantly with the immobilization of the anti-goat IgG. After the immunosensor is blocked with BSA, a further decrease in the peak current was observed due to the attachment of the protein BSA to the immunosensor. A significant decrease in the current signal of the BSA/anti-IgG/G2Fc/GCE was observed upon immobilizing IgG which may be due to the formation of immune-conjugates that blocks the tunneling of mass and electron transfer. The current signal was found to be directly related to the amount of IgG captured on the electrode surface. With increase in the concentration of IgG, there is a formation of an increasing amount of immune-conjugates that decreased the peak current. The incubation time and concentration of the antibody was optimized for better analytical performance of the immunosensor. The developed amperometric immunosensor is sensitive to IgG concentration as low as 2 ng/mL. Tailoring of redox-active dendrimers provides enhanced electroactivity to the system and enlarges the sensor surface for binding the antibodies. It may be assumed that both electron transfer and diffusion contribute to the signal transformation between the dendrimers and the antibody.

Keywords: ferrocenyl dendrimers, electrochemical immunosensors, immunoglobulin, amperometry

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Authors: Sabina Żołędowska, Tadeusz Ossowski, Robert Bogdanowicz, Jacek Ryl, Paweł Rostkowski, Michał Kruczkowski, Michał Sobaszek, Zofia Cebula, Grzegorz Skowierzak, Paweł Jakóbczyk, Lilit Hovhannisyan, Paweł Ślepski, Iwona Kaczmarczyk, Mattia Pierpaoli, Bartłomiej Dec, Dawid Nidzworski

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The circular economy of water presents a pressing environmental challenge in our society. Water contains various harmful substances, such as drugs, antibiotics, hormones, and dioxides, which can pose silent threats. Water pollution has severe consequences for aquatic ecosystems. It disrupts the balance of ecosystems by harming aquatic plants, animals, and microorganisms. Water pollution poses significant risks to human health. Exposure to toxic chemicals through contaminated water can have long-term health effects, such as cancer, developmental disorders, and hormonal imbalances. However, effective remediation systems can be implemented to remove these contaminants using electrocatalytic processes, which offer an environmentally friendly alternative to other treatment methods, and one of them is the innovative iCLARE system. The project's primary focus revolves around a few main topics: Reactor design and construction, selection of a specific type of reticulated vitreous carbon foams (RVC), analytical studies of harmful contaminants parameters and AI implementation. This high-performance electrochemical reactor will be build based on a novel type of electrode material. The proposed approach utilizes the application of reticulated vitreous carbon foams (RVC) with deposited modified metal oxides (MMO) and diamond thin films. The following setup is characterized by high surface area development and satisfactory mechanical and electrochemical properties, designed for high electrocatalytic process efficiency. The consortium validated electrode modification methods that are the base of the iCLARE product and established the procedures for the detection of chemicals detection: - deposition of metal oxides WO3 and V2O5-deposition of boron-doped diamond/nanowalls structures by CVD process. The chosen electrodes (porous Ferroterm electrodes) were stress tested for various parameters that might occur inside the iCLARE machine–corosis, the long-term structure of the electrode surface during electrochemical processes, and energetic efficacy using cyclic polarization and electrochemical impedance spectroscopy (before and after electrolysis) and dynamic electrochemical impedance spectroscopy (DEIS). This tool allows real-time monitoring of the changes at the electrode/electrolyte interphase. On the other hand, the toxicity of iCLARE chemicals and products of electrolysis are evaluated before and after the treatment using MARA examination (IBMM) and HPLC-MS-MS (NILU), giving us information about the harmfulness of using electrode material and the efficiency of iClare system in the disposal of pollutants. Implementation of data into the system that uses artificial intelligence and the possibility of practical application is in progress (SensDx).

Keywords: waste water treatement, RVC, electrocatalysis, paracetamol

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Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

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Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

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Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

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Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

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Authors: Merrick Lopez, Aashish Abraham, Melissa Egge, Marissa Hood, Jui Shah

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A 3 year old male with unknown medical history presented initially with encephalopathy, intubated for respiratory failure, and admitted to the pediatric intensive care unit (PICU) with refractory shock. During resuscitation in the emergency department, he was found to be in severe metabolic acidosis with a pH of 7.03 and escalated on vasopressor drips for hypotension. His initial sodium was 174. He was noted to have burn injuries to his scalp, forehead, right axilla, bilateral arm creases and lower legs. He had rhabdomyolysis (initial creatinine kinase 5,430 U/L with peak levels of 62,340 normal <335 U/L), cardiac injury (initial troponin 88 ng/L with peak at 145 ng/L, normal <15ng/L), hypernatremia (peak 174, normal 140), hypocalcemia, liver injury, acute kidney injury, and neuronal loss on magnetic resonance imaging (MRI). Soft restraints and a shock collar were found in the home. He was critically ill for 8 days, but was gradually weaned off drips, extubated, and started on feeds. Discussion Electrical injury, specifically lightning injury is an uncommon but devastating cause of injury in pediatric patients. This patient with suspected abusive use of a dog shock collar presented similar to a lightning strike. Common entrance points include the hands and head, similar to our patient with linear wounds on his forehead. When current enters, it passes through tissues with the least resistance. Nerves, blood vessels, and muscles, have high fluid and electrolyte content and are commonly affected. Exit points are extremities: our child who had circumferential burns around his arm creases and ankles. Linear burns preferentially follow areas of high sweat concentration, and are thought to be due to vaporization of water on the skin’s surface. The most common cause of death from a lightning strike is due to cardiopulmonary arrest. The massive depolarization of the myocardium can result in arrhythmias and myocardial necrosis. The patient presented in cardiogenic shock with evident cardiac damage. Electricity going through vessels can lead to vaporization of intravascular water. This can explain his severe hypernatremia. He also sustained other internal organ injuries (adrenal glands, pancreas, liver, and kidney). Electrical discharge also leads to direct skeletal muscle injury in addition to prolonged muscular spasm. Rhabdomyolysis, the acute damage of muscle, leads to release of potentially toxic components into the circulation which could lead to acute renal failure. The patient had severe rhabdomyolysis and renal injury. Early hypocalcemia has been consistently demonstrated in patients with rhabdomyolysis. This was present in the patient and led to increased vasopressor needs. Central nervous system injuries are also common which can include encephalopathy, hypoxic injury, and cerebral infarction. The patient had evidence of brain injury as seen on MRI. Conclusion Electrical injuries due to lightning strikes and abusive use of a dog shock collar are rare, but can both present in similar ways with respiratory failure, shock, hypernatremia, rhabdomyolysis, brain injury, and multiorgan damage. Although rare, it is essential for early identification and prompt management for acute and chronic complications in these children.

Keywords: cardiogenic shock, dog shock collar, lightning strike, rhabdomyolysis

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Authors: Łukasz Mazur, Kamil Domaradzki, Bartosz Kamecki, Justyna Ignaczak, Sebastian Molin, Aleksander Gil, Tomasz Brylewski

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The rising global power consumption necessitates the development of new energy storage solutions. Prospective technologies include solid oxide electrolyzer cells (SOECs), which convert surplus electrical energy into hydrogen. An electrolyzer cell consists of a porous anode, and cathode, and a dense electrolyte. Power output is increased by connecting cells into stacks using interconnects. Interconnects are currently made from high-chromium ferritic steels – for example, Crofer 22 APU – which exhibit high oxidation resistance and a thermal expansion coefficient that is similar to that of electrode materials. These materials have one disadvantage – their area-specific resistance (ASR) gradually increases due to the formation of a Cr₂O₃ scale on their surface as a result of oxidation. The chromia in the scale also reacts with the water vapor present in the reaction media, forming volatile chromium oxyhydroxides, which in turn react with electrode materials and cause their deterioration. The electrochemical efficiency of SOECs thus decreases. To mitigate this, the interconnect surface can be modified with protective-conducting coatings of spinel or other materials. The high prices of SOEC components -especially the Crofer 22 APU- have prevented their widespread adoption. More inexpensive counterparts, therefore, need to be found, and their properties need to be enhanced to make them viable. Candidates include the Nirosta 4016/1,4016 low-chromium ferritic steel with a chromium content of just 16.3 wt%. This steel's resistance to high-temperature oxidation was improved by depositing Gd₂O₃ nanoparticles on its surface via either dip coating or electrolysis. Modification with CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles deposited by means of spray pyrolysis was also tested. These methods were selected because of their low cost and simplicity of application. The aim of this study was to investigate the oxidation kinetics of Nirosta 4016/1,4016 modified using the afore-mentioned methods and to subsequently measure the obtained samples' ASR. The samples were oxidized for 100 h in the air as well as air/H₂O and Ar/H₂/H₂O mixtures at 1073 K. Such conditions reflect those found in the anode and cathode operating space during real-life use of SOECs. Phase and chemical composition and the microstructure of oxidation products were determined using XRD and SEM-EDS. ASR was measured over the range of 623-1073 K using a four-point, two-probe DC technique. The results indicate that the applied nanoparticles improve the oxidation resistance and electrical properties of the studied layered systems. The properties of individual systems varied significantly depending on the applied reaction medium. Gd₂O₃ nanoparticles improved oxidation resistance to a greater degree than either CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles. On the other hand, the cerium-containing nanoparticles improved electrical properties regardless of the reaction medium. The ASR values of all surface-modified steel samples were below the 0.1 Ω.cm² threshold set for interconnect materials, which was exceeded in the case of the unmodified reference sample. It can be concluded that the applied modifications increased the oxidation resistance of Nirosta 4016/1.4016 to a level that allows its use as SOEC interconnect material. Acknowledgments: Funding of Research project supported by program "Excellence initiative – research university" for the AGH University of Krakow" is gratefully acknowledged (TB).

Keywords: cerium oxide, ferritic stainless steel, gadolinium oxide, interconnect, SOEC

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Authors: Tahani Mashikhi

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Countries worldwide rely on electric power as a critical economic growth and progress factor. Renewable energy sources, often referred to as alternative energy sources, such as wind, solar energy, geothermal energy, biomass, and hydropower, have garnered significant interest in response to the rising consumption of fossil fuels. Dye-sensitized solar cells (DSSCs) are a highly promising alternative for energy production as they possess numerous advantages compared to traditional silicon solar cells and thin-film solar cells. These include their low cost, high flexibility, straightforward preparation methodology, ease of production, low toxicity, different colors, semi-transparent quality, and high power conversion efficiency. A solar cell, also known as a photovoltaic cell, is a device that converts the energy of light from the sun into electrical energy through the photovoltaic effect. The Gratzel cell is the initial dye-sensitized solar cell made from colloidal titanium dioxide. The operational mechanism of DSSCs relies on various key elements, such as a layer composed of wide band gap semiconducting oxide materials (e.g. titanium dioxide [TiO₂]), as well as a photosensitizer or dye that absorbs sunlight to inject electrons into the conduction band, the electrolyte utilizes the triiodide/iodide redox pair (I− /I₃−) to regenerate dye molecules and a counter electrode made of carbon or platinum facilitates the movement of electrons across the circuit. Electrospray deposition permits the deposition of fragile, non-volatile molecules in a vacuum environment, including dye sensitizers, complex molecules, nanoparticles, and biomolecules. Surface science techniques, particularly X-ray photoelectron spectroscopy, are employed to examine dye-sensitized solar cells. This study investigates the possible application of electrospray deposition to build high-quality layers in situ in a vacuum. Two distinct categories of dyes can be employed as sensitizers in DSSCs: organometallic semiconductor sensitizers and purely organic dyes. Most organometallic dyes, including Ru533, RuC, and RuP, contain a ruthenium atom, which is a rare element. This ruthenium atom enhances the efficiency of dye-sensitized solar cells (DSSCs). These dyes are characterized by their high cost and typically appear as dark purple powders. On the other hand, organic dyes, such as SQ2, RK1, D5, SC4, and R6, exhibit reduced efficacy due to the lack of a ruthenium atom. These dyes appear in green, red, orange, and blue powder-colored. This study will specifically concentrate on metal-organic dyes. The adsorption of dye molecules onto the rutile TiO₂ (110) surface has been deposited in situ under ultra-high vacuum conditions by combining an electrospray deposition method with X-ray photoelectron spectroscopy. The X-ray photoelectron spectroscopy (XPS) technique examines chemical bonds and interactions between molecules and TiO₂ surfaces. The dyes were deposited at varying times, from 5 minutes to 40 minutes, to achieve distinct layers of coverage categorized as sub-monolayer, monolayer, few layers, or multilayer. Based on the O 1s photoelectron spectra data, it can be observed that the monolayer establishes a strong chemical bond with the Ti atoms of the oxide substrate by deprotonating the carboxylic acid groups through 2M-bidentate bridging anchors. The C 1s and N 1s photoelectron spectra indicate that the molecule remains intact at the surface. This can be due to the existence of all functional groups and a ruthenium atom, where the binding energy of Ru 3d is consistent with Ru2+.

Keywords: deposit, dye, electrospray, TiO₂, XPS

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Authors: Shreya Saxena, Felix Miller-Molloy, Phillipa Bowen, Greg Fellows, Elizabeth Bowen

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Background: Complex fluid balance abnormalities are well-established post-neurosurgery and traumatic brain injury (TBI). The triple-phase response requires fluid management strategies reactive to urine output and sodium homeostasis as patients shift between Diabetes Insipidus (DI) and Syndrome of Inappropriate ADH (SIADH). It was observed, at a tertiary paediatric center, a relatively high prevalence of the above complications within a cohort of paediatric post-neurosurgical and TBI patients. An audit of the clinical practice against set institutional guidelines was undertaken and analyzed to understand why this was occurring. Based on those results, new guidelines were developed with structured educational packages for the specialist teams involved. This was then reaudited, and the findings were compared. Methods: Two independent audits were conducted across two time periods, pre and post guideline change. Primary data was collected retrospectively, including both qualitative and quantitative data sets from the CQUIN neurosurgical database and electronic medical records. All paediatric patients post posterior fossa (PFT) or supratentorial surgery or with a TBI were included. A literature review of evidence-based practice, initial audit data, and stakeholder feedback was used to develop new clinical guidelines and nursing standard operation procedures. Compliance against these newly developed guidelines was re-assessed and a thematic, trend-based analysis of the two sets of results was conducted. Results: Audit-1 January2017-June2018, n=80; Audit-2 January2020-June2021, n=30 (reduced operative capacity due to COVID-19 pandemic). Overall, improvements in the monitoring of both fluid balance and electrolyte trends were demonstrated; 51% vs. 77% and 78% vs. 94%, respectively. The number of clear fluid management plans documented postoperatively also increased (odds ratio of 4), leading to earlier recognition and management of evolving fluid-balance abnormalities. The local paediatric endocrine team was involved in the care of all complex cases and notified sooner for those considered to be developing DI or SIADH (14% to 35%). However, significant Na fluctuations (>12mmol in 24 hours) remained similar – 5 vs six patients – found to be due to complex pituitary hypothalamic pathology – and the recommended adaptive fluid management strategy was still not always used. Qualitative data regarding useability and understanding of fluid-balance abnormalities and the revised guidelines were obtained from health professionals via surveys and discussion in the specialist teams providing care. The feedback highlighted the new guidelines provided a more consistent approach to the post-operative care of these patients and was a better platform for communication amongst the different specialist teams involved. The potential limitation to our study would be the small sample size on which to conduct formal analyses; however, this reflects the population that we were investigating, which we cannot control. Conclusion: The revised clinical guidelines, based on audited data, evidence-based literature review and stakeholder consultations, have demonstrated an improvement in understanding of the neuro-endocrine complications that are possible, as well as increased compliance to post-operative monitoring of fluid balance and electrolytes in this cohort of patients. Emphasis has been placed on preventative rather than treatment of DI and SIADH. Consequently, this has positively impacted patient safety for the center and highlighted the importance of educational awareness and multi-disciplinary team working.

Keywords: post-operative, fluid-balance management, neuro-endocrine complications, paediatric

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Authors: Anisa Suraya Ab Razak, Izza Hayat

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Introduction: The diagnosis and management of severe hyponatremia in neuropsychiatric patients present a significant challenge to physicians. Several factors contribute, including diagnostic shadowing and attributing abnormal behavior to intellectual disability or psychiatric conditions. Hyponatraemia is the commonest electrolyte abnormality in the inpatient population, ranging from mild/asymptomatic, moderate to severe levels with life-threatening symptoms such as seizures, coma and death. There are several documented fatal case reports in the literature of severe hyponatremia secondary to psychogenic polydipsia, often diagnosed only in autopsy. This paper presents a case study of acute severe hyponatremia in a neuropsychiatric patient with early diagnosis and admission to intensive care. Case study: A 21-year old Caucasian male with known epilepsy and learning disability was admitted from residential living with generalized tonic-clonic self-terminating seizures after refusing medications for several weeks. Evidence of superficial head injury was detected on physical examination. His laboratory data demonstrated mild hyponatremia (125 mmol/L). Computed tomography imaging of his brain demonstrated no acute bleed or space-occupying lesion. He exhibited abnormal behavior - restlessness, drinking water from bathroom taps, inability to engage, paranoia, and hypersexuality. No collateral history was available to establish his baseline behavior. He was loaded with intravenous sodium valproate and leveritircaetam. Three hours later, he developed vomiting and a generalized tonic-clonic seizure lasting forty seconds. He remained drowsy for several hours and regained minimal recovery of consciousness. A repeat set of blood tests demonstrated profound hyponatremia (117 mmol/L). Outcomes: He was referred to intensive care for peripheral intravenous infusion of 2.7% sodium chloride solution with two-hourly laboratory monitoring of sodium concentration. Laboratory monitoring identified dangerously rapid correction of serum sodium concentration, and hypertonic saline was switched to a 5% dextrose solution to reduce the risk of acute large-volume fluid shifts from the cerebral intracellular compartment to the extracellular compartment. He underwent urethral catheterization and produced 8 liters of urine over 24 hours. Serum sodium concentration remained stable after 24 hours of correction fluids. His GCS recovered to baseline after 48 hours with improvement in behavior -he engaged with healthcare professionals, understood the importance of taking medications, admitted to illicit drug use and drinking massive amounts of water. He was transferred from high-dependency care to ward level and was initiated on multiple trials of anti-epileptics before achieving seizure-free days two weeks after resolution of acute hyponatremia. Conclusion: Psychogenic polydipsia is often found in young patients with intellectual disability or psychiatric disorders. Patients drink large volumes of water daily ranging from ten to forty liters, resulting in acute severe hyponatremia with mortality rates as high as 20%. Poor outcomes are due to challenges faced by physicians in making an early diagnosis and treating acute hyponatremia safely. A low index of suspicion of water intoxication is required in this population, including patients with known epilepsy. Monitoring urine output proved to be clinically effective in aiding diagnosis. Early referral and admission to intensive care should be considered for safe correction of sodium concentration while minimizing risk of fatal complications e.g. central pontine myelinolysis.

Keywords: epilepsy, psychogenic polydipsia, seizure, severe hyponatremia

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