Search Results (147)

Nickel is widely deployed in caustic service, yet its native Ni(OH)₂/NiOOH passive film raises concerns for long service life. Graphene has emerged as a promising corrosion barrier; however, its long-term durability in strongly alkaline media remains largely unexplored. The extended exposure period in a highly caustic solution is a novel aspect of the present work, distinguishing it from previous studies that predominantly examined short-term exposures or focused on neutral and acidic environments. Here, we present the systematic assessment of low-pressure CVD-grown multilayer graphene (MLG) coatings on Ni in highly caustic (0.5 M NaOH) for up to 80 days. Two architectures, a conformal, robust MLG coating (Gr_Ni) and a less robust film (Gr_Ni_DF), were benchmarked against bare Ni. PDP and EIS reveal that Gr_Ni initially delivers nearly 2 orders of magnitude enhancement, as evidenced by the low frequency impedance, accompanied by a broad, high-fidelity capacitive plateau; the impedance still maintains 1.3–1.5 orders of magnitude superior after prolonged exposure. In contrast, Gr_Ni_DF undergoes progressive degradation, affording a modest 2-fold benefit over time, consistent with defect-mediated electrolyte ingress. SEM morphologies further corroborate these trends, confirming the superior structural stability of Gr_Ni under extended alkaline immersion. Full article

The intrinsic electronic and structural properties of the transition metal rhenium (Re) endow it with substantial application potential in electrocatalysis. However, the high cost of Re requires the development of Re-based materials to reduce cost and optimize the performance at the same time. Herein, a one-step high-pressure and high-temperature (HPHT) synthetic strategy is proposed for fabricating Re-C phase gradient composites, presenting a facile and efficient pathway to develop high-performance hydrogen evolution reaction (HER) electrocatalysts. By studying the structural evolution of Re toward ReC and uncovering its intrinsic mechanism, the regulation of the material’s electrocatalytic activity was successfully realized. Experimental results confirm that HPHT conditions of 5 GPa and 1400 °C effectively induce the formation of multiple crystalline phases of Re-C solid solution and ReC in the Re-C composite. These phases have coherent phase boundaries and form the phase gradient composites. Compared with element Re, the synergistic effect of phase gradient composites broadens the electronic state range by increasing electron transfer from Re to C in ReC (increasing the binding energy) and reduces the binding energy in Re-C solid solution. The broad electronic states range in the phase gradient composites exhibits optimal HER overpotentials of 150 mV (acidic electrolyte) and 166 mV (alkaline electrolyte) at 10 mA cm⁻². These findings provide a promising strategy to boost catalysts’ electrocatalytic performance via constructing phase gradient composites. Full article

Waste printed circuit boards (WPCBs) are a highly concentrated secondary source of copper. However, their complex and heterogeneous composition significantly complicates the selective extraction of metals. This study examined the feasibility of direct electrochemical leaching of copper from used PCB fragments in a sulfate–glycine alkaline electrolyte. The PCB fragments were used directly as a composite working electrode, without prior separation of the components or special surface preparation. It has been demonstrated that the electrochemical response of the composite PCB anode is similar to that of a pure copper electrode, which indicates the predominant role of the anodic dissolution of copper. A distinct potential window of 0.30 to 0.40 V relative to the Ag/AgCl electrode has been established, within which copper dissolves efficiently, while the dissolution of the associated metals (Sn, Pb, Ni, Fe) remains strongly inhibited. The maximum selectivity is reached at a potential of approximately 0.35 V. This is due to the formation of soluble and stable copper–glycine complexes, while the other metals remain in an alkaline medium in the form of poorly soluble phases. At more positive potentials (≥0.40–0.50 V), the co-dissolution of the associated metals begins, resulting in a sharp decrease in the selectivity of the process. Real-time potentiostatic experiments have shown that the selective leaching mode at 0.35 V is stable over long periods of operation and is characterized by continuous dissolution of copper with minimal release of other metals in solution. Full article

Soil salinization and alkalinization critically constrain alfalfa (Medicago sativa L.) productivity, yet the regulatory mechanisms underlying its responses to salt–alkali stress are not fully understood. In this study, the alfalfa variety “Zhongmu No. 1” was used as experimental material. The seeds were subjected to salt stress (75 mM NaCl), alkali stress (15 mM NaHCO₃), and combined salt–alkali stress (50 mM NaCl + 5 mM NaHCO₃) in dishes, with ddH₂O serving as the control (CK). After 7 days of germination, the seedlings were transferred to a hydroponic system containing Hoagland nutrient solution supplemented with the corresponding treatments. Following 32 days of stress exposure, leaf and root tissue samples were collected for morphological and physiological measurements, as well as mRNA and miRNA sequencing analyses. Physiological assays revealed significant growth inhibition and increased electrolyte leakage under stress conditions. Transcriptome profiling identified over 5000 common differentially expressed genes (DEGs) in both leaves and roots under stress conditions, mainly enriched in pathways related to “iron ion binding”, “flavonoid biosynthesis”, “MAPK signaling”, and “alpha-Linolenic acid metabolism”. MiRNA sequencing detected 453 miRNAs, including 188 novel candidates, with several differentially expressed miRNAs (DEMs) exhibiting tissue- and stress-specific patterns. Integrated analysis revealed 147, 81, and 140 negatively correlated miRNA–mRNA pairs across three treatment groups, highlighting key regulatory modules in hormone signaling and metabolic pathways. Notably, in the ethylene and abscisic acid signaling pathways, ERF (XLOC_006645) and PP2C (MsG0180000476.01) were found to be regulated by miR5255 and miR172c, respectively, suggesting a post-transcriptional layer of hormonal control. DEM target genes enrichment pathway analyses also identified stress-specific regulation of “Fatty acid degradation”, “Galactose metabolism”, and “Fructose and mannose metabolism”. qRT-PCR validation confirmed the expression trends of selected DEGs and DEMs. Collectively, these findings reveal the complexity of miRNA–mRNA regulatory networks in alfalfa’s response to salt–alkali stress and provide candidate regulators for breeding stress-resilient cultivars. Full article

This paper presents the results of modeling the DC and dynamic characteristics of an alkaline electrolyzer. A model of such an electrolyzer is proposed as a subcircuit for the SPICE software. This model describes DC and dynamic current–voltage characteristics of the electrolyzer, taking into account the effect of solution concentration on the electrolyzer internal resistance and electrolyte capacitance, as well as the resistance and inductance of the leads. Using this model, one can calculate the voltage and current waveforms across the electrolyzer, as well as the gas flow rate produced by the electrolyzer. The correctness of the developed model was experimentally verified by powering the electrolyzer using a DC source and by powering the device using a voltage source, generating a rectangular pulse train with an adjustable frequency and duty cycle. The measurement system is described, and the obtained calculation and measurement results are presented and discussed. It was shown that the obtained calculation results differed minimally from the measurement results across a wide range of frequencies (from 0 to 50 kHz), duty cycles (from 0.3 to 0.7) of the supply voltage, and concentrations of the electrolyte (from 0.1 to 10%). The mean square error, normalized to peak measured values of each considered quantity, does not exceed 4%. Full article

This article focuses on studying the phase transformation of bauxite iron minerals during electrolytic reduction processes in alkaline solutions (400 g/L Na₂O), with the aim of improving aluminum extraction in the subsequent Bayer process. The research employs electrolytic reduction to convert the refractory minerals in unmilled bauxite (alumogoethite (Fe,Al)OOH, alumohematite (Fe,Al)₂O₃, chamosite (Fe²⁺,Mg,Al,Fe³⁺)₆(Si,Al)₄O₁₀(OH,O)₈) into magnetite, elemental iron (Fe) and to minimize aluminum (Al) extraction during electrolysis. Preliminary thermodynamic research suggests that the presence of hematite (α-Fe₂O₃) and chamosite in boehmitic bauxite increases the iron concentration in the solution. Cyclic voltammetry revealed that, in the initial stage of electrolysis, overvoltage at the cathode decreases as metallic iron deposited and conductive magnetite form on the surface of the particles. After 60 min, the reduction efficiency begins to decrease. The proportion of the current used for magnetization and iron deposition on the cathode decreased from 89.5% after 30 min to 67.5% after 120 min. After 120 min of electrolytic reduction, the magnetization rate exceeded 65%; however, more than 60% of the Al was extracted simultaneously. Al extraction after electrolysis and subsequent Bayer leaching exceeded 91.5%. Studying the electrolysis product using SEM-EDS revealed the formation of a dense, iron-containing reaction product on the particles’ surface, preventing diffusion of the reaction products (sodium ferrite and sodium aluminate). Mössbauer spectroscopy of the high-pressure leaching product revealed that the primary iron-containing phases of bauxite residue are maghemite (γ-Fe₂O₃), formed during the hydrolysis of sodium ferrite. Full article

The Bayer process is used to extract alumina from bauxite, resulting in the formation of a highly alkaline solid residue known as bauxite residue (BR). However, such residue contains insufficient iron (<35% Fe) and complex impurity composition for use in blast furnace ironmaking. This study investigates the potential for enhancing the extraction of aluminium (Al) and increasing the concentration of Fe in residue by electrolytical reduction in suspension of BR in a spent Bayer process solution. A maximal current efficiency of 43.7% was obtained during the electroreduction of the coarse fraction of BR. The magnetite-containing residue obtained was further used as an aid in the high-pressure Bayer process leaching of gibbsitic bauxite. Adding the reduced BR increased the Al extraction rate by up to 7.2%. The kinetics of bauxite leaching at 120–160 °C and time interval 0–40 min in the presence of reduced BR were investigated using a shrinking core model (SCM). The results showed that the leaching kinetics of Al correlate well with the intraparticle SCM equation, indicating that the reaction velocity is regulated by the diffusion of the OH⁻ or Al(OH)₄⁻ through the product layer. The apparent activation energy of the process at 140–160 °C was found to be 32.2 kJ/mol. Al in the solid residue is closely associated with Fe, i.e., it is enclosed in a solid matrix of iron minerals. Full article

This work reports the electrochemical behavior of a nickel hydroxide electrode, electrodeposited in a deep eutectic solvent (DES), in alkaline solutions of varying composition, aiming to elucidate the influence of the cation (Na⁺ vs. K⁺), urea, and carbonate ions on the mechanism and kinetics of anodic processes. Cyclic voltammetry and electrochemical impedance spectroscopy were employed to analyze the electrochemical responses of electrode processes in alkaline water electrolysis systems. For the urea oxidation reaction (UOR), the frequency-dependent characteristics were thoroughly characterized, and the impedance response was simulated according to the Armstrong–Henderson equivalent circuit. It was found that the addition of urea significantly transforms the impedance structure, sharply reducing the polarization resistance and increasing the pseudo-capacitive component of the constant phase element at low frequencies, indicating activation of the slow steps of urea oxidation via a direct mechanism and the formation of an extended adsorptive surface. It was demonstrated that, unlike conventional alkaline electrolysis where KOH-based systems are generally more effective, urea-assisted systems exhibit superior performance in NaOH-based electrolytes, which provides more favorable kinetics for the electrocatalytic urea oxidation process. Furthermore, the accumulation of carbonate ions was shown to negatively affect UOR kinetics by increasing polarization resistance and partially blocking surface sites, highlighting the necessity of controlling electrolyte composition in practical systems. These findings open new opportunities for the rational design of efficient urea-assisted electrolyzers for green hydrogen generation. Full article

The study investigates the effect of plasma-electrolytic polishing on the structure and wear resistance of 30KhGSA steel after plasma-electrolytic boriding. Plasma-electrolytic boriding was carried out in a boron-containing electrolyte at a temperature of 900 °C, which ensured the formation of a hardened modified layer consisting of a surface oxide layer, a subsequent zone composed of boride phases FeB and Fe₂B, as well as a transitional martensitic zone. To remove brittle oxide phases and reduce surface roughness, plasma-electrolytic polishing in an alkaline solution was applied, which made it possible to form a smoother and more stable surface. The results showed that plasma-electrolytic boriding increases the microhardness up to 1500–1600 HV_0.1, which is 5–6 times higher compared to untreated steel, and reduces the friction coefficient and wear rate. However, the borided layers exhibit brittleness and surface roughness. Subsequent plasma-electrolytic polishing made it possible to reduce surface roughness by nearly an order of magnitude, decrease the friction coefficient by more than 30%, and almost halve the wear rate. The obtained results confirm the high potential of this combined technology for strengthening structural steel components operating under high loads and severe wear conditions. Full article

This study focuses on enhancing the efficiency of alkaline water electrolysis technology, a key process in green hydrogen production, by leveraging the synergy of magnetic fields and in situ electrode activation. Optimizing AWE efficiency is essential to meet increasing demands for sustainable energy solutions. In this research, nickel mesh electrodes were modified through the application of magnetic fields and the addition of hypo-hyper d-metal (cobalt complexes and molybdenum salt) to the electrolyte. These enhancements improve mass transfer, facilitate bubble detachment, and create a high-surface-area catalytic layer on the electrodes, all of which lead to improved hydrogen evolution rates. The integration of magnetic fields and in situ activation achieved over 35% energy savings, offering a cost-effective and scalable pathway for industrial green hydrogen production. Full article

The decarbonization of hard-to-defossilize sectors, such as international maritime transport, requires innovative, and at times disruptive, energy solutions that combine efficiency, scalability, and climate benefits. Therefore, power-to-liquid (PtL) routes have stood out for their potential to use low-emission electricity for the production of synthetic fuels, via electrolytic hydrogen and CO₂ capture. However, the high energy demand inherent to these routes poses significant challenges to large-scale implementation. Moreover, PtL routes are usually at most neutral in terms of CO₂ emissions. This study evaluates, from a thermo-energetic perspective, the optimization potential of an e-methanol synthesis route through integration with a biomass oxy-fuel combustion process, making use of electrolytic oxygen as the oxidizing agent and the captured CO₂ as the carbon source. From the standpoint of a first-law thermodynamic analysis, mass and energy balances were developed considering the full oxygen supply for oxy-fuel combustion to be met through alkaline electrolysis, thus eliminating the energy penalty associated with conventional oxygen production via air separation units. The balance closure was based on a small-scale plant with a capacity of around 100 kta of methanol. In this integrated configuration, additional CO₂ surpluses beyond methanol synthesis demand can be directed to geological storage, which, when combined with bioenergy with carbon capture and storage (BECCS) strategies, may lead to net negative CO₂ emissions. The results demonstrate that electrolytic oxygen valorization is a promising pathway to enhance the efficiency and climate performance of PtL processes. Full article

Binary metallic nickel–copper nanocatalysts were anchored onto a polyvinylidene fluoride-co-hexafluoropropylene membrane [NiCu/PVdF–HFP] using the electrospinning technique, followed by the chemical reduction of the relevant precursor salts by introducing sodium borohydride to the synthesis mixture. A series of varied Ni:Cu weight % proportions was developed in order to optimize the electroactivity of this binary nanocomposite towards the investigated oxidation process. A number of physicochemical tools were used to ascertain the morphology and chemical structure of the formed metallic species on polymeric films. Cyclic voltammetric studies revealed a satisfactory performance of altered NiCu/PVdF–HFP membranes in alkaline solution. Ethylene glycol molecules were successfully electro-oxidized at their surfaces, showing the highest current intensity [564.88 μA cm⁻²] at the one with Ni:Cu weight ratios of 5:5. The dependence of these metallic membranes’ behavior on the added alcohol concentration to the reaction electrolyte and the adjusted scan rate during the electrochemical measurement was carefully investigated. One hundred repeated scans did not significantly deteriorate the NiCu/PVdF–HFP nanostructures’ durability. Decay percentages of 76.90–87.95% were monitored at their surfaces, supporting the stabilized performance for prolonged periods. A much-decreased R_ct value was estimated at Ni₅Cu₅/PVdF–HFP [392.6 Ohm cm²] as a consequence of the feasibility of the electron transfer step for the electro-catalyzing oxidation process of alcohol molecules. These enhanced study results will hopefully motivate the interested workers to explore the behavior of many binary and ternary combinations of metallic nanomaterials after their deposition onto convenient polymeric films for vital electrochemical reactions. Full article

Anion exchange ionomer (AEI) binders are critical to the performance of alkaline electrochemical devices (i.e., fuel cells, electrolyzers, and batteries), as they facilitate ion transport, provide structural integrity, and improve the overall performance and lifespan of these devices. These binders not only ensure ion transport but also provide mechanical stability to the electrode materials. Recently, there has been significant progress in designing AEIs that are more compatible with existing electrode materials and electrolytes. This review summarizes the different types of AEI binders, focusing on their chemical structure, functionalization, conductivity, and how they affect the performance of alkaline fuel cells, specifically, anion exchange membrane fuel cells (AEMFCs). It also discusses how factors like functional groups, polymer backbone and side-chain flexibility, and ion exchange capacity balance conductivity, mechanical strength, and water uptake (WU). Recent advances in material design, such as polymer blends, composites, and crosslinked ionomers, as well as electrode setup, such as asymmetric ionomer electrodes, are explored as methods for improving stability and ion transport. The main challenges facing AEIs, including water management, alkaline degradation, phase separation, mechanical robustness, and long-term durability, are discussed along with strategies for overcoming them. Finally, we outline future research directions for developing scalable, economical solutions and integrating these binders with new electrode materials to help improve the performance and stability of next-generation AEMFCs. Full article

Room-temperature ionic liquids (RTILs) have attracted attention in engineering electrolytes for electrochemical energy conversion and storage devices. Within the present study, five different RTILs were prepared and subsequently investigated as additives to alkaline aqueous solutions for the oxygen evolution reaction (OER). Studied RTILs were based on dicyanamide ion as a green anion, suitable for electrochemical applications, and included 1-butyl-3-ethylimidazolium dicyanamide, 1,3-dibutylimidazolium dicyanamide, 1-butyl-3-hexylimidazolium dicyanamide, 1-butyl-3-octylimidazolium dicyanamide, and 1,3-diethylimidazolium dicyanamide. The OER studies were performed in 8 M KOH with RTILs (1 vol.%) using linear scan voltammetry, and the current densities were compared to those recorded in 8 M KOH with no RTILs added. Reaction parameters, such as the Tafel slope, were determined, enabling further evaluation and comparison of RTIL-containing electrolyte systems. Moreover, the influence of temperature on the OER efficiency of the system with mixed RTIL-KOH electrolytes was studied. Voltammetric studies were complemented by electrochemical impedance spectroscopy, which revealed a decrease in solution resistance with increasing temperature, as well as by chronoamperometry analysis. Full article

Hydrogen generation has become a popular research subject in light of currently pressing issues, such as the rapidly increasing environmental pollution, the depleting fossil fuel reserves, and the looming energy crisis. Sustainable electrochemical water splitting is regarded as one of the most desirable methods for obtaining green hydrogen. Considering this state of affairs, the water splitting electrocatalytic activity of glassy carbon electrodes modified with birnessite-type K₂Mn₄O₈ and mixed-valence iron phosphate Fe₃(PO₃OH)₄(H₂O)₄ materials were evaluated in electrolyte solutions having different pH values. Both compounds were characterized by X-ray diffraction and FT-IR spectroscopy in order to analyze their phase purity and their structural features. The most catalytically active birnessite-type K₂Mn₄O₈-based electrode was manufactured using a catalyst ink containing only the electrocatalyst dispersed in ethanol and Nafion solution. In 0.1 M H₂SO₄, it exhibited an oxygen evolution reaction (OER) overpotential of 1.07 V and a hydrogen evolution reaction (HER) overpotential of 0.957 V. The Tafel slopes obtained in the OER and HER experiments were 0.180 and 0.142 V/dec, respectively. The most catalytically active mixed-valence iron phosphate Fe₃(PO₃OH)₄(H₂O)₄-based electrode was obtained with a catalyst ink containing the specified material mixed with carbon black and dispersed in ethanol and Nafion solution. In a strongly alkaline medium, it displayed a HER overpotential of 0.515 V and a Tafel slope value of 0.122 V/dec. The two electrocatalysts have not been previously investigated in this way, and the acquired data provide insights into their electrocatalytic activity and improve the scientific understanding of their properties and applicative potential. Full article