Search Results (18)

This work presents a novel one-step plasma–solution synthesis of Prussian Blue (PB) and copper hexacyanoferrate (Cu-PBA) nanoparticles via underwater pulsed DC discharge. For the first time, the direct plasma-assisted formation of these coordination polymers is reported. The obtained materials were examined by X-ray diffraction, Fourier-transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy (SEM). These analyses confirmed that the desired phases had formed, along with small amounts of oxide byproducts (α-Fe₂O₃, CuO) arising from the erosion of the electrodes. Photocatalytic activity was evaluated through the degradation of organic dyes (Reactive Red 6C, Rhodamine B, and Methylene Blue) under UV-light irradiation. Both catalysts achieved complete dye degradation within 90 min of UV irradiation (after an initial 30 min dark adsorption step, total experiment time 120 min). Notably, selective performance was observed: PB exhibited higher activity toward the cationic dye Methylene Blue, while Cu-PBA was more effective for the anionic dye Reactive Red 6C. This selectivity is attributed to the specific oxide impurities forming heterojunctions that facilitate charge separation and generate distinct reactive oxygen species. The plasma–liquid method offers a rapid and environmentally benign route to functional PBA-based composites, with potentially scalable characteristics pending further engineering optimization. These findings highlight the potential of utilizing synthesis-induced impurities to tailor photocatalytic selectivity for water purification applications. Full article

This study employed a metakaolin-based geopolymer (GP) to solidify potassium copper hexacyanoferrate after its saturation with adsorbed Cs⁺. The experiment was designed using response surface methodology (RSM) in the Design–Expert 13 software, targeting the compressive strength and cumulative leaching fraction of the solidified form. A regression model was developed to achieve the multi-objective optimization of the comprehensive performance of the GP solidified product. Regression analysis identified the optimal mix proportion as Na₂O/Al₂O₃ = 0.84, SiO₂/Al₂O₃ = 2.8, and H₂O/Na₂O = 10.23. Under these conditions, the experimentally measured compressive strength was 23.41 MPa. The 42-day cumulative leaching fractions at 25 °C and 40 °C were 7.906 × 10⁻⁴ cm and 1.5923 × 10⁻³ cm, respectively, both significantly below the national standard threshold (Standard Code GB7023-2011) of 2.6 × 10⁻¹ cm. The percentage error remained within 10%, indicating strong agreement with predicted values. These results suggest that metakaolin-based GP exhibits promising potential for the immobilization of radionuclides. Full article

Artificial enzymes or nanozymes (NZs) are gaining significant attention in biotechnology due to their stability and cost-effectiveness. NZs can offer several advantages over natural enzymes, such as enhanced stability under harsh conditions, longer shelf life, and reduced production costs. The booming interest in NZs is likely to continue as their potential applications expand. In our previous studies, we reported the “green” synthesis of copper hexacyanoferrate (gCuHCF) using the oxidoreductase flavocytochrome b₂ (Fcb₂). Organic–inorganic micro-nanoparticles were characterized in detail, including their structure, composition, catalytic activity, and electron-mediator properties. An SEM analysis revealed that gCuHCF possesses a flower-like structure well-suited for concentrating and stabilizing Fcb₂. As an effective peroxidase (PO) mimic, gCuHCF has been successfully employed for H₂O₂ detection in amperometric sensors and in several oxidase-based biosensors. In the current study, we demonstrated the uniqueness of gCuHCF that lies in its multifunctionality, serving as a PO mimic, a chemosensor for ammonium ions, a biosensor for L-lactate, and exhibiting perovskite-like properties. This exceptional ability of gCuHCF to enhance fluorescence under blue light irradiation is being reported for the first time. Using gCuHCF as a PO-like NZ, novel oxidase-based sensors were developed, including an optical biosensor for L-arginine analysis and electrochemical biosensors for methanol and glycerol determination. Thus, gCuHCF, synthesized via Fcb₂, presents a promising platform for the development of amperometric and optical biosensors, bioreactors, biofuel cells, solar cells, and other advanced devices. The innovative approach of utilizing biocatalysts for nanoparticle synthesis highlights a groundbreaking direction in materials science and biotechnology. Full article

Prussian blue PB analogues (K;Mg)_xM[Fe(CN)₆] were obtained via the co-precipitation method. Manganese, iron, cobalt, nickel, copper and zinc were selected to obtain the metal hexacyanoferrates (MHCFs) of these metals and to systematically study their structural and electrochemical properties as cathode materials. The obtained substances were characterized via X-ray powder analysis, scanning electron microscopy, thermogravimetric analysis and elemental analysis. An electrochemical study of the obtained cathode materials relative to a platinum anode in an aqueous medium and a magnesium anode in a nonaqueous medium was carried out, and the cycling parameters were determined. The influence of 3d-metal nature on the composition–structure–properties of hexacyanoferrates was demonstrated. MHCFs are promising cathode materials for Mg²⁺ intercalation/deintercalation in aqueous electrolytes. Full article

This paper reports the use of nanoparticles (NPs)-modified voltammetric sensors for the rapid determination of glycerol in the presence of ethanol and methanol, which are used in the transesterification reaction of biodiesel production. Two different modified electrodes have been prepared to form the electronic tongue (ET): copper hexacyanoferrate NPs obtained by chemical synthesis and mixed into graphite/epoxy (GEC) electrode, and nickel hydroxide NPs electrodeposited in reduced graphene oxide onto a GEC electrode. The response characteristics of these electrodes were first evaluated by building the respective calibration against glycerol, ethanol, and methanol. The electrodes demonstrated good stability during their analytical characterization, while principal component analysis confirmed the differentiated response against the different alcohols. Finally, the quantification of mixtures of these substances was achieved by a genetic algorithm-artificial neural networks (GA-ANNs) model, showing satisfactory agreement between expected and obtained values. Full article

This article presents a study of the synthesis and characterization of new biphasic hybrid composite materials consisting of intercalated complexes (ICC) of natural mineral bentonite with copper hexaferrocyanide (phase I), which are incorporated into the bulk of the polymer matrix (phase II). It has been established that the sequential modification of bentonite with copper hexaferrocyanide and introduction of acrylamide and acrylic acid cross-linked copolymers into its volume by means of in situ polymerization promote the formation of a heterogeneous porous structure in the resulting hybrid material. The sorption abilities of prepared hybrid composite toward radionuclides of liquid radioactive waste (LRW) have been studied, and the mechanism for binding radionuclide metal ions with the components of the hybrid composition have been described. Full article

In this work, we have developed novel beads based on carboxymethyl cellulose (CMC) encapsulated copper oxide-titanium oxide (CuO-TiO₂) nanocomposite (CMC/CuO-TiO₂) via Al⁺³ cross-linking agent. The developed CMC/CuO-TiO₂ beads were applied as a promising catalyst for the catalytic reduction of organic and inorganic contaminants; nitrophenols (NP), methyl orange (MO), eosin yellow (EY) and potassium hexacyanoferrate (K₃[Fe(CN)₆]) in the presence of reducing agent (NaBH₄). CMC/CuO-TiO₂ nanocatalyst beads exhibited excellent catalytic activity in the reduction of all selected pollutants (4-NP, 2-NP, 2,6-DNP, MO, EY and K₃[Fe(CN)₆]). Further, the catalytic activity of beads was optimized toward 4-nitrophenol with varying its concentrations and testing different concentrations of NaBH₄. Beads stability, reusability, and loss in catalytic activity were investigated using the recyclability method, in which the CMC/CuO-TiO₂ nanocomposite beads were tested several times for the reduction of 4-NP. As a result, the designed CMC/CuO-TiO₂ nanocomposite beads are strong, stable, and their catalytic activity has been proven. Full article

Copper hexacyanoferrate (CuHCF) has become an attractive Zn²⁺ insertion material as a positive electrode in aqueous zinc-ion batteries thanks to its high reversibility towards Zn²⁺ (de-)insertion, its simple, inexpensive and easily scalable synthesis route, its low toxicity, and its high working potential. It is known that the physiochemical properties of CuHCF can be modified by manipulating its synthesis parameters. However, the effect of these parameters on the material’s electrochemical performance and cycle life needs further investigation. Here, the structure and composition of CuHCF treated at different temperatures are studied through crystallographic, compositional, and thermogravimetric analyses. The resulting CuHCF powders were galvanostatically cycled to assess their electrochemical performance in relation to their annealing temperature. The results showed that the annealed CuHCF electrodes exhibited longer cycle life while maintaining a coulombic efficiency ≥ 99.5%. The longest cycle life was achieved by annealing the CuHCF electrodes at 100 °C. Full article

In this study, a copper hexacyanoferrate nanoparticle with excellent oxidase-mimetic behaviour has been synthesized through a simple precipitation method. The synthesized copper hexacyanoferrate nanoparticle has intrinsic oxidase-like activity, which can catalyze the chromogenic reaction of 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) through an O₂^•− reactive oxygen-species-participated process. On the other hand, K₃[Fe(CN)₆] can be reduced by ascorbic acid (AA) to produce K₄[Fe(CN)₆], thereby inhibiting the formation of the copper hexacyanoferrate nanoparticles. Furthermore, ascorbate oxidase (AAO) can catalyze the oxidation of AA to produce dehydroascorbic acid, which cannot reduce K₃[Fe(CN)₆]. Thus, a system for an AAO-regulated in situ formation of copper hexacyanoferrate nanoparticles was constructed by coupling a prepared copper hexacyanoferrate nanozyme with AA for the detection of AAO activity. This colorimetric sensing assay shows high sensitivity and selectivity for the detection of AAO activity (the limit of detection is 0.52 U/L) with a linear range of 1.1–35.7 U/L. Finally, the developed method was applied to detect the activity of AAO in normal human serum with a satisfactory sample spiked recovery (87.4–108.8%). In short, this study provides a good strategy for the construction of nanozyme-based multi-enzyme cascade-signal amplification assay. Full article

Laccase is a copper-containing enzyme that does not require hydrogen peroxide as a co-substrate or additional cofactors for an enzymatic reaction. Nanomaterials of various chemical structures are usually applied to the construction of enzyme-based biosensors. Metals, metal oxides, semiconductors, and composite NPs perform various functions in electrochemical transformation schemes as a platform for the enzyme immobilization, a mediator of an electron transfer, and a signal amplifier. We describe here the development of amperometric biosensors (ABSs) based on laccase and redox-active micro/nanoparticles (hereafter—NPs), which were immobilized on a graphite electrode (GE). For this purpose, we isolated a highly purified enzyme from the fungus Trametes zonatus, and then synthesized bi- and trimetallic NPs of noble and transition metals, as well as hexacyanoferrates (HCF) of noble metals; these were layered onto the surfaces of GEs. The electroactivity of many of the NPs immobilized on the GEs was characterized by cyclic voltammetry (CV) experiments. The most effective mediators of electron transfer were selected as the platform for the development of laccase-based ABSs. As a result, a number of catechol-sensitive ABSs were constructed and characterized. The laccase/CuCo/GE was demonstrated to possess the highest sensitivity to catechol (4523 A·M⁻¹·m⁻²) among the tested ABSs. The proposed ABSs may be promising for the analysis of phenolic derivatives in real samples of drinking water, wastewater, and food products. Full article

There are limited data on amperometric biosensors (ABSs) for L-arginine (Arg) determination based on oxidases that produce hydrogen peroxide (H₂O₂) as a byproduct of enzymatic reaction, and artificial peroxidases (POs) for decomposition of H₂O₂. The most frequently proposed Arg-sensitive oxidase-based ABSs contain at least two enzymes in the bioselective layer; this complicates the procedure and increases the cost of analysis. Therefore, the construction of a one-enzyme ABS for Arg analysis is a practical problem. In the current work, fabrication, and characterization of three ABS types for the direct measurement of Arg were proposed. L-arginine oxidase (ArgO) isolated from the mushroom Amanita phalloides was co-immobilized with PO-like nanozymes (NZs) on the surface of graphite electrodes. As PO mimetics, chemically synthesized NZs of CeCu (nCeCU) and NiPtPd (nNiPtPd), as well as green-synthesized hexacyanoferrate of copper (gCuHCF), were used. The novel ABSs exhibited high sensitivity and selectivity to Arg, broad linear ranges and good storage stabilities. Two ABSs were tested on real samples of products containing Arg, including the pharmaceutical preparation “Tivortine”, juices, and wine. A high correlation (R = 0.995) was demonstrated between the results of testing “Tivortine” and juice using nCeCU/GE and nNiPtPd/GE. It is worth mentioning that only a slight difference (less than 1%) was observed for “Tivortin” between the experimentally determined content of Arg and its value declared by the producer. The proposed ArgO-NZ-based ABSs may be promising for Arg analysis in different branches of science, medicine, and industry. Full article

The use of Prussian blue analogues (PBA) materials in electrochemical energy storage and harvesting has gained much interest, necessitating the further clarification of their electrochemical characteristics. However, there is no well-defined technique for manufacturing PBA-based microelectrochemical devices because the PBA film deposition method has not been well studied. In this study, we developed the following deposition method for growing copper hexacyanoferrate (CuHCFe) thin film: copper thin film is immersed into a potassium hexacyanoferrate solution, following which the redox reaction induces the spontaneous deposition of CuHCFe thin film on the copper thin film. The film grown via this method showed compatibility with conventional photolithography processes, and the micropattern of the CuHCFe thin film was successfully defined by a lift-off process. A microelectrochemical device based on the CuHCFe thin film was fabricated via micropatterning, and the sodium ion diffusivity in CuHCFe was measured. The presented thin film deposition method can deposit PBAs on any surface, including insulating substrates, and it can extend the utilization of PBA thin films to various applications. Full article

Prussian blue analogs (PBAs) are well-known artificial enzymes with peroxidase (PO)-like activity. PBAs have a high potential for applications in scientific investigations, industry, ecology and medicine. Being stable and both catalytically and electrochemically active, PBAs are promising in the construction of biosensors and biofuel cells. The “green” synthesis of PO-like PBAs using oxido-reductase flavocytochrome b₂ is described in this study. When immobilized on graphite electrodes (GEs), the obtained green-synthesized PBAs or hexacyanoferrates (gHCFs) of transition and noble metals produced amperometric signals in response to H₂O₂. HCFs of copper, iron, palladium and other metals were synthesized and characterized by structure, size, catalytic properties and electro-mediator activities. The gCuHCF, as the most effective PO mimetic with a flower-like micro/nano superstructure, was used as an H₂O₂-sensitive platform for the development of a glucose oxidase (GO)-based biosensor. The GO/gCuHCF/GE biosensor exhibited high sensitivity (710 A M⁻¹m⁻²), a broad linear range and good selectivity when tested on real samples of fruit juices. We propose that the gCuHCF and other gHCFs synthesized via enzymes may be used as artificial POs in amperometric oxidase-based (bio)sensors. Full article

Nanozymes (NZs) are catalytically active nanomaterials that have enzyme-like activity but possess increased stability and greater availability due to the fact of their simpler preparation technologies. Nanozymes as nanoscale artificial enzymes demonstrate various catalytic specificities as oxidoreductases, such as peroxidase, catalase, laccase, and others as well as hydrolases, proteases, endonucleases, DNA-ases, NO synthases, etc. A broad variety of NZs exhibits dual- or multienzyme mimetic activity. Nanozymes as stable, low-cost mimetics of natural enzymes have a high potential for application in different branches of biotechnology including scientific investigations, industry, and ecology. Nanozymes can be applied in medicine as diagnostic tools and components of therapeutic drugs. Since NZs have high catalytic activity and chemical and biological stability, they are very promising in the construction of biosensors and biofuel cells. For these reasons, the search for simple methods of synthesis and characterization of different NZs is a very important and real problem. The “green” synthesis of Prussian blue analogous as peroxidase-like NZs using oxido-reductases is described in this study. The obtained green-synthesized hexacyanoferrates (gHCFs) of transition metals were characterized by structure, size, composition, catalytic properties, electro-mediator activities, and substrate specificity. Copper hexacyanoferrate (gCuHCF) was studied in more detail. When immobilized on a graphite electrode (GE), gCuHCF under special conditions of pH and tension gave amperometric signals on hydrogen peroxide and can be used as a peroxidase mimetic in oxidase-based biosensors. Under other conditions, gCuHCF/GE reacts to other analytes. We propose that gHCFs of transition metals synthesized via enzymes may become prospect platforms for the construction of multi-functional amperometric (bio)sensors. Full article

A Microbial Fuel Cell (MFC) is a process in which a microorganism respires and captures the electrons that normally passes through the electron transport system of the organism and produces electricity. This work intends to present the different operating parameters affecting the efficiency of a Microbial Fuel Cell (MFC) process. To study the performance of the process, various materials for the cathode and anode rods with similar size and chape including, copper, aluminum, carbon cloth, steel and brass were considered to determine the combination that leads to the best results. Moreover, different oxidizing agents such as Copper Sulphate and Potassium Hexacyanoferrate were considered. Furthermore, the effects of shapes, sizes and distance between electrodes on the current and voltage were investigated. The power outputs between electrochemical and microbial cells were recorded. In addition, the power, whether expressed as voltage or current, was measured at different conditions and different cell combinations. The power is directly related to the area, volume of the bacterial solution and supplying air and stirring. Full article