Search Results (93)

Magnesium metal has a high theoretical volume capacity and abundant reserves. Magnesium ion battery is theoretically secure and eco-friendly. In recent years, magnesium ion battery has attracted wide attention and is expected to become a competitive energy storage candidate in the next generation. However, due to the large polarization effect and slow migration kinetics of magnesium ions, magnesium ions are hard to insert/desert in cathode materials, resulting in a poor cycle and rate performance. CoHCF, a typical Prussian blue analog, has an open frame structure and double REDOX sites, and it is regarded as a candidate for rechargeable ion battery. Herein, a Ni-doping method was utilized to improve the performance of CoHCF. Compared with the original CoHCF, the maximum specific discharge capacity of the Ni-doped CoHCF at 50 mA/g charging and discharging current increased from 70 mAh/g to 89 mAh/g, and the cyclic performance and rate performance improved. These improvements result from the fact that the electrode reaction process of Ni-doped CoHCF changes from diffusion-driven to reaction-driven. The Ni-doped CoHCF is more stable, and the lattice changes during Mg²⁺ (de-)intercalation are smaller. This study can provide a reference for the development of Prussian blue analogs as cathode materials for magnesium ion batteries. Full article

An electrochemical sensor was developed for the detection of hydrogen peroxide (H₂O₂) based on the in situ formation of a nickel hexacyanoferrate complex on the electrode surface. Screen-printed carbon electrodes were modified with nickel-doped carbon nanodots (Ni-CNDs), and a nickel hexacyanoferrate complex was electrogenerated over the nickel carbon nanodots. Ni-CNDs were synthetized “a la carte” in one step by including nickel (II) acetate as precursor and characterized using different techniques: transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy, atomic force microscopy (AFM), and infrared spectroscopy (FTIR). The electrocatalytic activity toward H₂O₂ reduction and the oxidation of the resulting modified electrodes was studied. The developed sensor had a strong electrocatalytic effect on the oxidation and reduction of H₂O₂, yielding detection limits of 3.22 and 0.49 μM, respectively. The H₂O₂ content of a tap water sample was determined, confirming the viability of the developed electrochemical sensor. Full article

Amperometric biosensors (ABSs) and enzymatic biofuel cells (BFCs) share several fundamental principles in their functionality, despite serving different primary purposes. Both devices rely on biorecognition, redox reactions, electron transfer (ET), and advanced electrode materials, including innovative nanomaterials (NMs). ABSs and BFCs, utilizing microbial oxidoreductases in combination with electroactive NMs, are both efficient and cost-effective. In the current study, several laboratory prototypes of BFCs have been developed with bioanodes based on yeast flavocytochrome b₂ (Fcb₂) and alcohol oxidase (AO), and a cathode based on fungal laccase. For the first time, BFCs have been developed featuring anodes based on Fcb₂ co-immobilized with redox NMs on a glassy carbon electrode (GCE), and cathode-utilizing laccase combined with gold–cerium–platinum nanoparticles (nAuCePt). The most effective lactate BFC, which contains gold–hexacyanoferrate (AuHCF), exhibited a specific power density of 1.8 µW/cm². A series of BFCs were developed with an AO-containing anode and a laccase/nAuCePt/GCE cathode. The optimal configuration featured a bioanode architecture of AO/nCoPtCu/GCE, achieving a specific power density of 3.2 µW/cm². The constructed BFCs were tested using lactate-containing food product samples as fuels. Full article

In an enzyme-based fuel cell system, glucose oxidase and laccase were immobilized on carbon paper as the anode and cathode electrodes. A conductive polymer (polypyrrole) was added to improve conductivity. The mediator and enzymes were mixed in a phosphate-buffer solution for entrapment. A Nafion 212 membrane separated the two half-cells. Power density measurements were taken at a glucose concentration of 10 mM across different operating voltages. Potassium hexacyanoferrate III was used as a redox mediator in the anode and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) in the cathode to boost power output. The biofuel cells, constructed from acrylic (40 × 50 × 50 mm) with a working volume of 20 × 30 × 40 mm, were assembled using a rubber gasket to secure the Nafion membrane. The use of micropore tape covering the electrodes extended the system’s operational lifespan. Without the micropore tape, the maximum power density was 57.6 μW/cm² at 0.24 V. With the micropore tape, the cell achieved a maximum power density of 324.9 μW/cm² at 0.57 V, sustaining performance for 20 days. Thus, micropore tape effectively enhances enzyme retention and biofuel cell performance. 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

Layered double hydroxides (LDH) containing various exchangeable anions were studied to show how X-ray Photoelectron Spectroscopy (XPS) can provide information on the local environments of the different elements within the interlayer anionic groups and their possible influence on the LDH interlayer hydroxide surfaces. As such, XPS can potentially provide additional information about these systems that cannot be obtained by other common spectroscopic methods, such as infrared and Raman spectroscopy. A Mg₆Al₂X(OH)₁₆. 4H₂O with X representing interlayer anions CO₃²⁻, PO₄³⁻, SO₄²⁻, MoO₄²⁻, CrO₄³⁻, Fe(CN)₆⁴⁻, and Fe(CN)₆³⁻ was studied. The hydroxide layer structure is characterized by the Mg 2p and Al 2p with a binding energy of around 50.1 and 74.5 eV for the normal CO₃²⁻ containing LDH. The O 1s contained three peaks related to the layer OH-groups at 531.6 eV, interlayer CO₃²⁻ at 530.5 eV and interlayer water at 532.4 eV. Similar observations were made for the other interlayer anions showing characteristic P 2p, S 2p, and Mo 3d peaks. Intercalation with CrO₄³⁻ shows that a significant amount of the Cr⁶⁺ has been reduced to Cr³⁺. Finally, the intercalation of hexacyanoferrate in hydrotalcite showed the potential of XPS in detecting changes in the oxidation state of Fe upon intercalation in the LDH with a change in the Fe 2p peaks with a shift in binding energy and the possibility of determining the amount of reduction of Fe(III) to Fe(II). In general, the XPS high-resolution scans of P 2p, S 2p, Mo 3d, and Cr 2p show that slightly lower binding energies are observed compared to the binding energy values for the corresponding anionic groups as part of a rigid crystal structure, such as in minerals. Overall, the influence of the nature of the interlayer anion on the binding energy of the elements (Mg, Al, O) in the layered double hydroxide structure is minimal and considered to be within the experimental error of XPS. A detailed analysis of XPS data in combination with infrared and Raman spectroscopy shows how XPS can provide additional information that is not readily available via vibrational spectroscopy. XPS can simultaneously account for both surface and bulk properties of LDH that are not available through common vibrational spectroscopic methods. Full article

This research presents a simple procedure for chemically modifying yeast (Saccharomyces cerevisiae) cells with nickel hexacyanoferrate (NiHCF) and ferric hexacyanoferrate, also known as Prussian blue (PB), to increase the conductivity of the yeast cell wall. Using linear sweep voltammetry, NiHCF-modified yeast and PB-modified yeast (NiHCF/yeast and PB/yeast, respectively) were found to have better cell wall conductivity in [Fe(CN)₆]³⁻ and glucose-containing phosphate-buffered solution than unmodified yeast. Spectrophotometric analysis showed that the modification of yeast cells with NiHCF had a less harmful effect on yeast cell viability than the modification of yeast cells with PB. The use of NiHCF/yeast and PB/yeast cells in the construction of a yeast-based fuel cell allowed the maximum power densities of 62.66 mW/m² and 94.09 mW/m² to be achieved. These values were much higher than those obtained using unmodified yeast cells (42.25 mW/m²). NiHCF/yeast and PB/yeast fuel cells were renewed by replenishing the yeast suspension in the anolyte or the FeCl₃ salt in the catholyte. This allowed 77.4% and 50.1% of the initial maximum power density of the fuel cells to be achieved. Full article

Magnetic resonance imaging (MRI) is a technique that employs strong magnetic fields and radio frequencies to generate detailed images of the body’s interior. In oncology patients, gadolinium-based contrast agents (GBCAs) are frequently administered to enhance the visualization of tumors. Those contrast agents are gadolinium chelates, characterized by high stability that prevents the release of the toxic gadolinium ion into the body. This work is part of the research for alternative nanoscaled GBCAs. Following the synthesis and characterization of zinc hexacyanoferrate nanoparticles, gadolinium ions were successfully incorporated into a hexacyanoferrate-based matrix, deposited on FTO-coated glass used as working electrode in a gadolinium salt solution, by applying a fixed potential determined through cyclic voltammetry studies. The presence of gadolinium inside the matrix was confirmed by EDX. Full article

The structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting N-benzylyridinium-4-oxime cation (BPA4⁺) and electron donating hexacyanoferrate (II) are reported. The study of reversible stimuli-induced transformation between hydrated reddish-brown (BPA4)₄[Fe(CN)₆]·10H₂O and anhydrous blue (BPA4)₄[Fe(CN)₆] revealed the origin of observed hydrochromic behavior. The comparison of the crystal structures of decahydrate and anhydrous phase showed that subsequent exclusion/inclusion of lattice water molecules induces structural relocation of one BPA4⁺ that alter the donor-to-acceptor charge-transfer states, resulting in chromotropism seen as reversible reddish-brown to blue color changes. The decreased donor-acceptor distance in (BPA4)₄[Fe(CN)₆] enhanced charge-transfer interaction allowing charge separation via one-electron transfer, as evidenced by in-situ ESR and FTIR spectroscopies. The reversibility of hydrochromic behavior was demonstrated by in-situ HT-XRPD, hot-stage microscopic and in situ diffuse-reflectance spectroscopic analyses. The insight into electronic structural features was obtained with density functional theory calculations, employed to elucidate electronic structure for both compounds. The electrical properties of the phases during dehydration process were investigated by temperature-dependent impedance spectroscopy. Full article

Sodium-ion batteries offer an attractive alternative to lithium-based chemistries due to the lower cost and abundance of sodium compared to lithium. Using solid electrolytes instead of liquid ones in such batteries may help improve safety and energy density, but they need to combine easy processing with high stability toward the electrodes. Herein, we describe a new class of solid electrolytes that are accessible by room-temperature, aqueous synthesis. The materials exhibit a garnet-type zinc hexacyanoferrate framework with large diffusion channels for alkaline ions. Specifically, they show superionic behavior and allow for facile processing into pellets. We compare the structure, stability, and transport properties of lithium-, sodium-, and potassium-containing zinc hexacyanoferrates and find that Na₂Zn₃[Fe(CN)₆]₂ achieves the highest ionic conductivity of up to 0.21 mS/cm at room temperature. In addition, the electrochemical performance and stability of the latter solid electrolyte are examined in solid-state sodium-ion batteries. Full article

Prussian blue analogs (PBAs) are appealing cathode materials for sodium-ion batteries because of their low material cost, facile synthesis methods, rigid open framework, and high theoretical capacity. However, the poor electrical conductivity, unavoidable presence of [Fe(CN)₆] vacancies and crystalline water within the framework, and phase transition during charge–discharge result in inferior electrochemical performance, particularly in terms of rate capability and cycling stability. Here, cobalt-free PBAs are synthesized using a facile and economic co-precipitation method at room temperature, and their sodium-ion storage performance is boosted due to the reduced crystalline water content and improved electrical conductivity via the high-entropy and component stoichiometry tuning strategies, leading to enhanced initial Coulombic efficiency (ICE), specific capacity, cycling stability, and rate capability. The optimized HE-HCF of Fe_0.60Mn_0.10-hexacyanoferrate (referred to as Fe_0.60Mn_0.10-HCF), with the chemical formula Na_1.156Fe_0.599Mn_0.095Ni_0.092Cu_0.109Zn_0.105 [Fe(CN)₆]_0.724·3.11H₂O, displays the most appealing electrochemical performance of an ICE of 100%, a specific capacity of around 115 and 90 mAh·g⁻¹ at 0.1 and 1.0 A·g⁻¹, with 66.7% capacity retention observed after 1000 cycles and around 61.4% capacity retention with a 40-fold increase in specific current. We expect that our findings could provide reference strategies for the design of SIB cathode materials with superior electrochemical performance. 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

In this work, iron hexacyanoferrate (FeHCF—Prussian blue) particles have been grown onto a reduced graphene oxide substrate through a pulsed electrodeposition process. Thus, the prepared FeHCF electrode exhibits a specific volumetric capacitance of 88 F cm⁻³ (specific areal capacitance of 26.6 mF cm⁻²) and high cycling stability with a capacitance retention of 93.7% over 10,000 galvanostatic charge–discharge cycles in a 1 M KCl electrolyte. Furthermore, two identical FeHCF electrodes were paired up in order to construct a symmetrical supercapacitor, which delivers a wide potential window of 2 V in a 1 M KCl electrolyte and demonstrates a large energy density of 27.5 mWh cm⁻³ at a high power density of 330 W cm⁻³. Full article

Aqueous zinc-ion batteries (AZiBs) have emerged as a promising alternative to lithium-ion batteries as energy storage systems from renewable sources. Manganese hexacyanoferrate (MnHCF) is a Prussian Blue analogue that exhibits the ability to insert divalent ions such as Zn²⁺. However, in an aqueous environment, MnHCF presents weak structural stability and suffers from manganese dissolution. In this work, zinc doping is explored as a strategy to provide the structure with higher stability. Thus, through a simple and easy-to-implement approach, it has been possible to improve the stability and capacity retention of the cathode, although at the expense of reducing the specific capacity of the system. By correctly balancing the amount of zinc introduced into the MnHCF it is possible to reach a compromise in which the loss of capacity is not critical, while better cycling stability is obtained. Full article