Search Results (106)

For the first time, a new composite voltammetric sensor based on yttria-stabilized zirconia doped with neodymium-carbon black-Nafion glassy carbon electrode (YSZNd-CB-Nafion/GCE) for the determination of metoprolol (MET) has been developed. The instrumental parameters and supporting electrolyte were optimized. For 105 s accumulation time, linearity was achieved in the range of 0.01 to 0.2 µM. The limit of detection (for 105 s accumulation time) was equal to 2.9 nM (2 µg/L), and was the best result in comparison to other voltametric sensors. The reproducibility of the metoprolol signal presented as relative standard deviation (RSD) was equal to 1.9% (n = 7). Additionally, our electrode is characterized by high stability, is easy to use, and has a short preparation time. The proposed sensor was found useful for MET determination in plasma and urine, as well as for pharmaceutical samples, with a good recovery parameter (96–108%). Flow injection analysis (FIA) with amperometric detection was also performed for MET determination. The recovery was calculated and was in the range 101–103%, suggesting that the proposed material may be applied in flow injection analysis. Full article

Recently, there has been rapid development of electrochemical sensors, and there have been numerous reports in the literature that describe new constructions with improved performance parameters. Undoubtedly, this is due to the fact that those sensors are characterized by very good analytical parameters, and at the same time, they are cheap and easy to use, which distinguishes them from other analytical tools. One of the trends observed in their development is the search for new functional materials. This review focuses on potentiometric sensors designed with the use of various metal oxides. Metal oxides, because of their remarkable properties including high electrical capacity and mixed ion-electron conductivity, have found applications as both sensing layers (e.g., of screen-printing pH sensors) or solid-contact layers and paste components in solid-contact and paste-ion-selective electrodes. All the mentioned applications of metal oxides are described in the scope of the paper. This paper presents a survey on the use of metal oxides in the field of the potentiometry method as both single-component layers and as a component of hybrid materials. Metal oxides are allowed to obtain potentiometric sensors of all-solid-state construction characterized by remarkable analytical parameters. These new types of sensors exhibit properties that are competitive with those of the commonly used conventional electrodes. Different construction solutions and various metal oxides were compared in the scope of this review based on their analytical parameters. Full article

The concentration dependence of the conductivity of ion exchange membranes (IEMs), as well as other transport properties, has been well explained by the contemporary two-phase model (Zabolotsky et al., 1993) considering a gel phase and an inter-gel phase filled with electroneutral solution. Here, this two-phase model has been adopted and first applied in electrolytes containing mixed counter-ions to investigate the correlation between the membrane ionic conductivity and its microstructure. For three representative commercial cation exchange membranes (CEMs), the total membrane conductivity (${\kappa }^T$) when in equilibrium with mixed MgSO₄ + Na₂SO₄ and H₂SO₄ + Na₂SO₄ electrolytes could be well predicted with the experimental composition of counter-ions in the gel and inter-gel phase, as well as the counter-ion mobility in the gel phase when the membrane is in a single electrolyte. It is found that the volume fraction of the inter-gel phase ($f_2$) has little impact on the predicted results. The accuracy of the model can be largely improved by calculating the inter-gel phase conductivity (${\kappa }^{in}$) with the ionic mobility being the same as that in the external solution (obtained via simulation in the OLI Studio), rather than simply as equivalent to the conductivity of the external solution (${\kappa }^s$). Moreover, a nonlinear correlation between the CEMs’ conductivities and the counter-ion composition in the gel phase is observed in the mixed MgSO₄ + Na₂SO₄ solution, as well as for the Nafion117 membrane in the presence of sulfuric acid. For CEMs in mixed MgSO₄ + Na₂SO₄ electrolytes, the calculated conductivity values considering the interaction parameter $\sigma$, similar to the Kohlrausch’s law, are closer to the experimental ones. Overall, this work provides new insights into membrane conductivity with mixed counter-ions and testifies to the applicability of the contemporary two-phase model. Full article

The superhydrophobic feature is highly desirable for oil/water separation (OWS) operation to achieve excellent separation efficiency. However, using hazardous materials in fabricating superhydrophobic surfaces is always the main concern. Herein, superhydrophobic filters were prepared via an eco-friendly approach by anchoring silica particles (SiO₂) onto the cotton fabric surface, followed by surface coating using natural material—myristic acid via a dip coating method. Tetraethyl orthosilicate (TEOS) was used in the synthesis of SiO₂ particles from the silica sol. In addition, the impact of the drying temperature on the wettability of the superhydrophobic filter was investigated. Moreover, the pristine cotton fabric and as-prepared superhydrophobic cotton filters were characterised based on Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) and contact angle (CA) measurement. The superhydrophobic cotton filter was used to perform OWS using an oil-water mixture containing either chloroform, hexane, toluene, xylene or dichloroethane. The separation efficiency of the OWS using the superhydrophobic filter was as high as 99.9%. Moreover, the superhydrophobic fabric filter also demonstrated excellent durability, chemical stability, self-healing ability and reusability. Full article

A new voltammetry method for the highly sensitive antibacterial drug ciprofloxacin (CIP) is presented using glassy carbon electrodes modified with hierarchical electrospun carbon nanofibers with NiCo nanoparticles (eCNF/CNT/NiCo-GCE). The use of a modified glassy carbon electrode in the form of hierarchical electrospun carbon nanofibers with NiCo nanoparticles (eCNF/CNT/NiCo) led to an LOD value as low as 6.0 µmol L⁻¹ with a measurement sensitivity of 3.33 µA µmol L⁻¹. The described procedure was successfully applied for CIP determination in samples with complex matrices, such as urine or plasma, and also in pharmaceutical products and antibiotic discs with satisfactory recovery values ranging between 94–104%. The proposed electrode was characterised by great stability, with the possibility of use for about 4 weeks without any significant change in the CIP peak current. The repeatability of the CIP response on the eCNF/CNT/NiCo/GC is also very good; its value measured and expressed as RSD is equal to 2.4% for a CIP concentration of 0.025 µmol L⁻¹ (for 7 consecutive CIP voltammogram registrations). The procedure for electrode preparation is quick and simple and does not involve the use of expensive apparatus. Full article

Electrically conductive membranes are a class of stimuli-responsive materials, which allow the adjustment of selectivity for and the rejection of charged species by varying the surface potential. The electrical assistance provides a powerful tool for overcoming the selectivity–permeability trade-off due to its interaction with charged solutes, allowing the passage of neutral solvent molecules. In this work, a mathematical model for the nanofiltration of binary aqueous electrolytes by an electrically conductive membrane is proposed. The model takes into account the steric as well as Donnan exclusion of charged species due to the simultaneous presence of chemical and electronic surface charges. It is shown that the rejection reaches its minimum at the potential of zero charge (PZC), where the electronic and chemical charges compensate for each other. The rejection increases when the surface potential varies in positive and negative directions with respect to the PZC. The proposed model is successfully applied to a description of experimental data on the rejection of salts and anionic dyes by PANi–PSS/CNT and MXene/CNT nanofiltration membranes. The results provide new insights into the selectivity mechanisms of conductive membranes and can be employed to describe electrically enhanced nanofiltration processes. Full article

Samarium-doped ceria (SDC) is considered as an alternative electrolyte material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) because its conductivity is higher than that of commonly used yttria-stabilized zirconia (YSZ). The paper compares the properties of anode-supported SOFCs with magnetron sputtered single-layer SDC and multilayer SDC/YSZ/SDC thin-film electrolyte, with the YSZ blocking layer 0.5, 1, and 1.5 μm thick. The thickness of the upper and lower SDC layers of the multilayer electrolyte are constant and amount to 3 and 1 μm, respectively. The thickness of single-layer SDC electrolyte is 5.5 μm. The SOFC performance is studied by measuring current–voltage characteristics and impedance spectra in the range of 500–800 °C. X-ray diffraction and scanning electron microscopy are used to investigate the structure of the deposited electrolyte and other fuel cell layers. SOFCs with the single-layer SDC electrolyte show the best performance at 650 °C. At this temperature, open circuit voltage and maximum power density are 0.8 V and 651 mW/cm², respectively. The formation of the SDC electrolyte with the YSZ blocking layer improves the open circuit voltage up to 1.1 V and increases the maximum power density at the temperatures over 600 °C. It is shown that the optimal thickness of the YSZ blocking layer is 1 µm. The fuel cell with the multilayer SDC/YSZ/SDC electrolyte, with the layer thicknesses of 3/1/1 µm, has the maximum power density of 2263 and 1132 mW/cm² at 800 and 650 °C, respectively. Full article

Aniline is a highly toxic organic pollutant with “carcinogenic, teratogenic and mutagenesis” characteristics. In the present paper, a membrane distillation and crystallization (MDCr) process was proposed to achieve zero liquid discharge (ZLD) of aniline wastewater. Hydrophobic polyvinylidene fluoride (PVDF) membranes were used in the membrane distillation (MD) process. The effects of the feed solution temperature and flow rate on the MD performance were investigated. The results showed that the flux of the MD process was up to 20 L·m⁻²·h⁻¹ and the salt rejection was above 99% under the feeding condition of 60 °C and 500 mL/min. The effect of Fenton oxidation pretreatment on the removal rate of aniline in aniline wastewater was also investigated, and the possibility of realizing the ZLD of aniline wastewater in the MDCr process was verified. Full article

A unique facilitation on the transport flux of Cu(II) was investigated by using modified polymer inclusion membranes (PIMs). LIX^®84I-based polymer inclusion membranes (LIX^®-based PIMs) using poly(vinyl chloride) (PVC) as support, 2-nitrophenyl octyl ether (NPOE) as plasticizer and Lix84I as carrier were modified by reagents with different polar groups. The modified LIX^®-based PIMs showed an increasing transport flux of Cu(II) with the help of ethanol or Versatic acid 10 modifiers. The metal fluxes with the modified LIX^®-based PIMs were observed varying with the amount of modifiers, and the transmission time was cut by half for the modified LIX^®-based PIM cast with Versatic acid 10. The physical–chemical characteristics of the prepared blank PIMs with different Versatic acid 10 were further characterized by using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), contract angle measurements and electro-chemical impedance spectroscopy (EIS). The characterization results indicated that the modified LIX^®-based PIMs cast with Versatic acid 10 appeared to be more hydrophilic with increasing membrane dielectric constant and electrical conductivity that allowed better accessibility of Cu(II) across PIMs. Hence, it was deduced that hydrophilic modification might be a potential method to improve the transport flux of the PIM system. Full article

The strategy to increase the performance of the single solid oxide fuel cell (SOFC) with a supporting membrane of Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte has been implemented in this study by introducing a thin anode barrier layer of the BaCe_0.8Sm_0.2O₃ + 1 wt% CuO (BCS-CuO) electrolyte and, additionally, a modifying layer of a Ce_0.8Sm_0.1Pr_0.1O_1.9 (PSDC) electrolyte. The method of electrophoretic deposition (EPD) is used to form thin electrolyte layers on a dense supporting membrane. The electrical conductivity of the SDC substrate surface is achieved by the synthesis of a conductive polypyrrole sublayer. The kinetic parameters of the EPD process from the PSDC suspension are studied. The volt-ampere characteristics and power output of the obtained SOFC cells with the PSDC modifying layer on the cathode side and the BCS-CuO blocking layer on the anode side (BCS-CuO/SDC/PSDC) and with a BCS-CuO blocking layer on the anode side (BCS-CuO/SDC) and oxide electrodes have been studied. The effect of increasing the power output of the cell with the BCS-CuO/SDC/PSDC electrolyte membrane due to a decrease in the ohmic and polarization resistances of the cell is demonstrated. The approaches developed in this work can be applied to the development of SOFCs with both supporting and thin-film MIEC electrolyte membranes. Full article

In the presented study, films from tetragonal Li₇La₃Zr₂O₁₂ were obtained by electrophoretic deposition (EPD) for the first time. To obtain a continuous and homogeneous coating on Ni and Ti substrates, iodine was added to the Li₇La₃Zr₂O₁₂ suspension. The EPD regime was developed to carry out the stable process of deposition. The influence of annealing temperature on phase composition, microstructure, and conductivity of membranes obtained was studied. It was established that the phase transition from tetragonal to low-temperature cubic modification of solid electrolyte was observed after its heat treatment at 400 °C. This phase transition was also confirmed by high-temperature X-ray diffraction analysis of Li₇La₃Zr₂O₁₂ powder. Increasing the annealing temperature leads to the formation of additional phases in the form of fibers and their growth from 32 (dried film) to 104 μm (annealed at 500 °C). The formation of this phase occurred due to the chemical reaction of Li₇La₃Zr₂O₁₂ films obtained by electrophoretic deposition with air components during heat treatment. The total conductivity of Li₇La₃Zr₂O₁₂ films obtained has values of ~10⁻¹⁰ and ~10⁻⁷ S cm⁻¹ at 100 and 200 °C, respectively. The method of EPD can be used to obtain solid electrolyte membranes based on Li₇La₃Zr₂O₁₂ for all-solid-state batteries. Full article

In electromembrane systems, the transfer of ions near ion-exchange membranes causes concentration polarization, which significantly complicates mass transfer. Spacers are used to reduce the effect of concentration polarization and increase mass transfer. In this article, for the first time, a theoretical study is carried out, using a two-dimensional mathematical model, of the effect of spacers on the mass transfer process in the desalination channel formed by anion-exchange and cation-exchange membranes under conditions when they cause a developed Karman vortex street. The main idea is that, when the separation of vortices occurs on both sides in turn from the spacer located in the core of the flow where the concentration is maximum, the developed non-stationary Karman vortex street ensures the flow of the solution from the core of the flow alternately into the depleted diffusion layers near the ion-exchange membranes. This reduces the concentration polarization and, accordingly, increases the transport of salt ions. The mathematical model is a boundary value problem for the coupled system of Nernst–Planck–Poisson and Navier–Stokes equations for the potentiodynamic regime. The comparison of the current–voltage characteristics calculated for the desalination channel with and without a spacer showed a significant increase in the intensity of mass transfer due to the development of the Karman vortex street behind the spacer. Full article

Dense homogeneous nanocomposite TiSiCN coatings with a thickness of up to 15 microns and a hardness of up to 42 GPa were obtained by the method of reactive titanium evaporation in a hollow cathode arc discharge in an Ar + C₂H₂ + N₂-gas mixture with the addition of hexamethyldisilazane (HMDS). An analysis of the plasma composition showed that this method allowed for a wide range of changes in the activation degree of all components of the gas mixture, providing a high (up to 20 mA/cm²) ion current density. It is possible to widely change the chemical composition, microstructure, deposition rate, and properties of coatings obtained by this method, by changing the pressure, composition, and activation degree of the vapor–gas mixture. An increase in the fluxes of C₂H₂, N₂, HMDS, and discharge current leads to an increase in the rate of coating formation. However, the optimal coatings from the point of view of microhardness were obtained at a low discharge current of 10 A and relatively low contents of C₂H₂ (1 sccm) and HMDS (0.3 g/h), exceeding which leads to a decrease in the hardness of the films and the deterioration of their quality, which can be explained by the excessive ionic exposure and the non-optimal chemical composition of the coatings. Full article

For the production of polyhydroxyalkanoates (PHA) using nitrogen-rich feedstocks (e.g., protein-rich resources), the typical strategy of restricting cell growth as a means to enhance overall PHA productivity by nitrogen limitation is not applicable. In this case, a possible alternative to remove the nitrogen excess (NH₄⁺/NH₃) is by applying membrane separation processes. In the present study, the use of Donnan dialysis to separate ammonium ions from volatile fatty acids present in the media for the production of PHA was evaluated. Synthetic and real feed solutions were used, applying NaCl and HCl receiver solutions separated by commercial cation-exchange membranes. For this specific purpose, Fumasep and Ralex membranes showed better performance than Ionsep. Sorption of ammonium ions occurred in the Ralex membrane, thus intensifying the ammonium extraction. The separation performances with NaCl and HCl as receiver solutions were similar, despite sorption occurring in the Ralex membrane more intensely in the presence of NaCl. Higher volumetric flow rates, NaCl receiver concentrations, and volume ratios of feed:receiver solutions enhanced the degree of ammonium recovery. The application of an external electric potential difference to the two-compartment system did not significantly enhance the rate of ammonium appearance in the receiver solution. The results obtained using a real ammonium-containing solution after fermentation of cheese whey showed that Donnan dialysis can be successfully applied for ammonium recovery from such solutions. Full article