Search Results (819)

This study presents the synthesis and electrochemical characterization of meso-tetracyanobutadiene (TCBD)-functionalized diphenylporphyrin (DPP) complexes incorporating copper (Cu) and nickel (Ni) metals. These push–pull metallo diphenylporphyrin–TCBD complexes were synthesized via a [2 + 2] cycloaddition–retroelectrocyclization reaction between 5-bromo-15-formyl-10,20-diphenylporphyrin metal(II) complexes (M = Cu, Ni) and tributyl(phenylethynyl)stannate, followed by tetracyanoethylene (TCNE) addition. The resulting TCBD-functionalized porphyrins were obtained in moderate yields (70–75%) and thoroughly characterized by ¹H and ¹³C NMR, UV-Vis spectroscopy, MALDI-TOF-MS, and single-crystal XRD. Although the single-crystal X-ray structure of NiDPP was solved, DFT calculations were used to determine the structures of the donor–acceptor MDPP-TCBD systems and to visualize their electronic structures. HOMO on the porphyrin π system and LUMO on the TCBD entity were observed, and energy level diagrams clearly laid out the electron donor and acceptor parts of the molecular systems. As expected, these novel donor–acceptor porphyrinoid assemblies exhibited enhanced push–pull properties in both the ground and excited states. Femtosecond transient absorption studies revealed that both NiDPP-TCBD and CuDPP-TCBD populate the charge-transfer state upon photoexcitation, with lifetimes of 383.1 ps and 484.7 ps, respectively, in benzonitrile. The charge-transfer states populated the triplet or doublet states (in the case of CuDPP) before returning to the ground state. Full article

3D electrodeposition printing is an emerging process for fabricating metallic parts with controllable geometry, yet the coupled influences of electrochemical kinetics, ion transport, and tool motion on layer height remain difficult to interpret. This work presents a physics-based process model that links key process inputs, current density, electrolyte concentration, the inter-electrode gap, and tool scanning speed, to the resulting layer height in 3D electrodeposition printing of nickel-based structures. The model combines species transport in the inter-electrode gap with Butler–Volmer kinetics, under carefully stated assumptions regarding current efficiency, overpotential, and lateral spreading. Model predictions are validated against experimentally reported layer heights over a range of process conditions, yielding average errors (9–15%) and root-mean-square errors (0.13–0.28 µm) that demonstrate good agreement and highlight the impact of simplifying assumptions. Systematic parametric studies reveal how each process input monotonically influences layer height in ways consistent with Faraday’s law and diffusion-controlled growth, while also quantifying the relative sensitivity to different parameters. Building on these results, we introduce a dimensionless 3D Electrodeposition Printing Index that consolidates the key process and material parameters into a single scalar describing the geometric growth regime. The index enables construction of process maps that capture how combinations of current density, scan speed, concentration, and gap affect achievable layer height within the validated operating window. The scope and limitations of the proposed modeling framework and the index, particularly regarding other materials, more complex geometries, and pulsed or strongly convective regimes, are explicitly discussed, providing a basis for future model extensions and experimental validation. Full article

The accelerating transition to low carbon energy systems has intensified the demand for nickel and cobalt from low-grade (<1.5 wt.%) refractory lateritic ores. These low-grade laterites are however not amenable to conventional beneficiation due to their complex mineralogy, eclectic physicochemical properties, and fine Ni–Co dissemination. This review examines recent advances made in the extraction of nickel and cobalt from complex low-grade lateritic ores, emphasizing the interplay between ore mineralogy, chemistry, beneficiation, pretreatment, and processing route selection. Developments in selective ore comminution–classification have led to the generation of Ni-rich fine fractions (undersize) and Co-rich coarse fractions (oversize), enabling differentiated extraction strategies that improve resource utilization, frugal energy use, and process efficiency. Mechanical activation via stirred media milling, thermal calcination-induced structural disorder, and dehydroxylate goethite products, are shown to significantly enhance Ni–Co leaching kinetics under both atmospheric and heap leaching conditions. A critical comparison of pyrometallurgical (rotary-kiln electric furnace) and hydrometallurgical (HPAL, EPAL, heap, atmospheric, bioleaching) routes demonstrates that ore-specific optimization is essential to balance recovery, acid consumption, and greenhouse gas emissions. The novel resin in moist mix (RIMM) process, which integrates ambient leaching and in situ ion exchange selective recovery, is shown to offer potential for sustainable values extraction from sub-economic resources. Furthermore, the review highlights the key innovation challenges and concomitant opportunities for enhanced critical battery metal recovery from complex laterite ores. Full article

A novel distilled alcoholic beverage was produced by fermenting yellow and red prickly pear (Opuntia ficus-indica) fruits with two Cypriot grape varieties (Mavro and Xynisteri), followed by traditional distillation. Two spirit variants (45% and 59% v/v alcohol) were prepared and assessed for physicochemical properties, antioxidant capacity, methanol, phenolic and flavonoid content, mineral composition, volatile profile, and sensory characteristics. Both spirits exhibited a pH of 3.83, total titratable acidity of 0.113% (expressed as citric acid), and methanol content between 0.38–1.85 g/hL of 100% v/v alcohol. Prickly pear addition enhanced the bioactive composition, with the yellow variant showing the highest flavonoid content (5.56 mg/L quercetin) compared to control zivania. Antioxidant activity (FRAP assay) ranged from 1.00 to 1.49 mg FeSO₄/L. Mineral analysis revealed elevated manganese, cobalt, and nickel in yellow (59% v/v) spirits, while red variants contained higher aluminum, platinum and magnesium. Volatile profiling showed increased ester and alcohol levels in 59% v/v beverages, with yellow spirits enriched in fruity esters (e.g., ethyl acetate). Sensory testing confirmed a greater consumer preference for prickly pear beverages, particularly yellow (59% v/v), which achieved a score of 9.7/10 for overall acceptability. These findings highlight the potential of prickly pear to contribute to the chemical composition and sensory complexity of grape-based distilled spirits. Full article

Superhydrophilic micro/nano-porous media have extensive applications in electronic thermal management and energy storage systems. Predicting two-phase pressure drop in complex porous structures is of great importance for system design and optimization while remaining highly challenging. This study systematically investigates the two-phase flow resistance characteristics of bi-porous microstructures with multiple particle sizes and porosities under varying boiling regimes. Experimentally, porous samples were fabricated via vacuum sintering using nickel powders and pore-forming agents (CaCl₂), which exhibit superhydrophilicity and enhanced wicking characteristics. A visualized experimental platform was constructed to investigate the impact of pore size combinations, flow velocities, and boiling states on pressure drop. The dataset obtained through multi-factor saturated boiling experiments was further used to derive a semi-empirical model for the two-phase flow pressure drop based on the classic Kozeny-Carman (K-C) and Akagi-Chisholm (A-C) correlations. Results show that the pore size combinations and boiling states have a significant impact on the resistance performance. The proposed model achieves an average prediction deviation below 15.7%, confirming its reliability and its effectiveness as a design framework for optimizing high-capillary-force porous wicks in advanced thermal management systems. Full article

Trace metal contamination in lotic freshwater systems exhibits pronounced heterogeneity arising from coupled hydrological connectivity, geochemical partitioning, and anthropogenic forcing, complicating exposure characterization in urban and peri-urban catchments. Addressing this complexity requires integrative analytical approaches capable of deciphering system-level controls, prompting an investigation of the environmental structuring and governing controls of dissolved trace metal signatures in a human-impacted stream using a system-oriented computational framework. To capture temporal variability associated with seasonal hydrological contrasts and heterogeneous pollution inputs, a station-based, season-resolved sampling strategy was implemented during the wet and dry seasons. Physicochemical gradients (pH, temperature, dissolved oxygen, and electrical conductivity), inorganic nitrogen species (NH₃, NO₂⁻, and NO₃⁻), and phosphorus fractions (total phosphorus, TP; total orthophosphate, TOP; soluble reactive P, SRP) were jointly analyzed with dissolved concentrations of chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), cadmium (Cd), mercury (Hg), and arsenic (As). Regression-based machine learning models were used to quantify element-specific sensitivities to hydrochemical drivers under wet–dry periods and to identify optimal predictive configurations. Predictive performance was consistently high for trace metals (R² generally >0.95), with Random Forest providing the best accuracy for Cr, Ni, Pb, Cd, As, and Hg, whereas Cu was most reliably captured by an XGBoost tree ensemble (R² = 0.994). Explainability analyses revealed heterogeneous, metal-specific control regimes: Cr was primarily driven by temperature, Ni by NO₂⁻ and redox-sensitive conditions, Cd by NH₃ and temperature, and As by Hg in combination with phosphorus-related and redox-linked proxies, while Pb showed comparatively lower predictability relative to other metals. Trace metal distributions are therefore structured primarily by differential environmental sensitivity rather than uniform source-driven inputs, reinforcing the need for integrative computational frameworks when interpreting freshwater contamination under intensifying anthropogenic and climatic pressures. Full article

Understanding hydrological, agricultural, and environmental processes in soils relies on accurately measuring volumetric water content (θ), matric potential (h), and hydraulic conductivity (K). These parameters are fundamental for quantifying plant-available water, optimizing irrigation scheduling in precision agriculture, modeling watershed responses, and studying the impacts of climate change in complex ecosystems. Among these parameters, θ is truly indispensable, as it represents the primary indicator of the water status of soils and a prerequisite for interpreting the other hydraulic variables. In recent years, capacitive sensors have become one of the most widely adopted technologies for θ estimation, owing to their favorable balance between accuracy, robustness, and affordability. These sensors infer soil moisture by measuring dielectric permittivity of soils, which is strongly governed by water content, making them particularly suitable for distributed monitoring and IoT-based environmental applications. The present study aimed to develop a low-cost capacitive sensor for θ estimation. This sensor can be made using 3D printing technology combined with conductive, nickel-based paint, which (once applied on the 3D-printed guides) forms the capacitive electrode. The capacitive component operates at an operational frequency of 60 MHz. The system was subjected to a rigorous testing protocol, including calibration and validation phases under laboratory conditions using three soils of different textures. Its performance was specifically compared with the time-domain reflectometry (TDR) technique, which is widely recognized in Soil Physics and Soil Hydrology as the reference method for θ estimation due to its reliability and accuracy. These tests confirmed the effective performance of the proposed sensor, which overall exhibited good reliability within the selected validation range, corresponding to a θ range of 0 to 0.40 cm³/cm³. Full article

In critical sectors such as energy, transportation, and high-end manufacturing, components must endure simultaneous exposure to high temperatures, heavy loads, and severe wear, necessitating materials with balanced strength, toughness, and durability. Metal matrix composites (MMCs), enhanced with ceramic reinforcements, offer a promising solution to these multifaceted demands. While conventional techniques like casting and powder metallurgy often struggle with limited design freedom and uniform reinforcement distribution, additive manufacturing (AM) enables the production of complex, graded components with tailored microstructures and unlocks new possibilities for materials operating under extreme service conditions. This review systematically examines recent advances in AM-processed MMCs—focusing on aluminum-, titanium-, nickel-, and steel-based systems—for applications in coupled extreme environments. It provides a detailed analysis of their high-temperature mechanical performance and wear resistance, emphasizing the roles of reinforcement selection, microstructural design, and AM processing parameters in governing key properties. Furthermore, the underlying strengthening and wear mechanisms are discussed, along with current challenges and future opportunities. This work aims to serve as a foundational reference for the development of next-generation AM MMCs tailored for high-performance engineering applications. Full article

Although powder metallurgy (PM) is known as a near-net-shape fabrication process, a large number of PM parts need to be machined for dimensional conformance or to produce complex geometrical features that cannot be achieved through compaction. However, due mainly to the presence of porosity, the machinability of PM steels is difficult compared to that of wrought steels and can add 20% or more to the overall fabrication cost of PM parts. Among the various measures known to improve the machinability of PM steels, the addition of machining aids, either as admixed or pre-alloyed constituents, is the most popular. Manganese sulfide (MnS) is by far the most common machinability-enhancing additive used in the PM steel industry. Although it is extremely efficient in improving the machining response of PM steels, MnS is known to have detrimental effects on mechanical properties and corrosion resistance. Thus, the use of MnS involves a compromise between obtaining good machinability at the expense of lower mechanical properties and corrosion resistance. In this study, free graphite particles are introduced as a new additive that not only noticeably improves the machinability of PM steel components but also does not affect their mechanical properties or corrosion resistance. It was found that it is possible to obtain free graphite particles in press-and-sintered PM steel components by coating graphite particles with a metallic layer. This coating prevents graphite from diffusing into the iron matrix while creating metallurgical bonds with the surrounding steel matrix during sintering. In this research, graphite particles were coated with nickel and copper through a cementation process. A heat treatment was then performed on this newly developed material to obtain a more uniform single-layer coating and achieve dimensional changes during sintering that are similar to those measured when MnS is used as a machinability enhancer. The results showed that the tensile properties as well as the fatigue resistance of components made of FC-0208-type PM steel containing admixed copper/nickel-coated graphite particles are not affected by the presence of the latter. Moreover, the corrosion resistance of the samples containing copper/nickel-coated graphite was found to be the same as that of samples without the additive, which is a significant improvement on the case where MnS is used. The performance of the newly developed additive in terms of machinability was also characterized in drilling. It was found that this new additive has an identical machinability-enhancing performance to admixed MnS. Full article

The electrochemical stability of redox-active polymers based on Ni(II)–Salen complexes is of critical importance for their application as electrode materials for supercapacitors and lithium-ion batteries. This study presents a systematic analysis of the influence of fluoride, chloride, and bromide anions on the redox behavior of two polymeric films: poly[Ni(Salen)] and sterically protected poly[Ni(Saltmen)]. Using cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), and X-ray photoelectron spectroscopy (XPS), we identify two distinct degradation mechanisms: (1) axial coordination of halide ions to the Ni(II) center followed by demetallation, which disrupts the conjugated system and reduces conductivity, and (2) oxidative halogenation of the ligand. In the presence of chloride ions, both poly[Ni(Salen)] and poly[Ni(Saltmen)] lose approximately 70% of their initial capacity over 50 cycles, indicating progressive electrochemical degradation. In contrast, both polymers demonstrate high electrochemical stability in bromide-containing electrolytes, retaining most of their capacity under identical conditions. Fluoride coordinates without compromising redox performance, serving as a model for electrochemically inert ligands. The results highlight the critical role of both electrolyte composition and ligand design in ensuring the long-term stability of nickel–Salen polymers in energy storage devices. Full article

Black shale represents a distinctive and critical mineral resource in China, harboring approximately 90% of the nation’s recoverable vanadium reserves while concurrently containing abundant strategic metal elements such as nickel and molybdenum. However, the complex occurrence states of vanadium, nickel, and molybdenum within black shale pose significant challenges to their efficient extraction. Conventional metallurgical processes—including calcination-leaching and hydrometallurgical leaching—primarily target vanadium recovery, exhibiting limited efficiency for comprehensive utilization of valuable metals. Against the backdrop of green metallurgy and carbon neutrality objectives, bioleaching techniques have garnered extensive research attention. This study developed a specialized consortium of ore-leaching microorganisms, designated WZ-Q, tailored to the mineralogical characteristics of black shale, demonstrating effective leaching capabilities for vanadium, nickel, and molybdenum. Furthermore, the enhancing effects of Fe²⁺, elemental sulfur (S⁰), and pyrite as energy substrates on bioleaching efficiency were investigated. Upon incorporating these energy materials, maximum leaching efficiencies reached 66.5% for vanadium, 82.5% for nickel, and 29.7% for molybdenum. Analysis through leaching process monitoring and multi-characterization of both raw ore and residues revealed that supplemental energy substrates intensify shifts in solution potential and pH, thereby promoting elemental oxidation and mineral decomposition. Nevertheless, critical impediments to leaching efficiency include the encapsulation of target elements within silicate matrices and incomplete dissolution of oxidized species. Subsequent research should prioritize methodologies to intensify silicate mineral dissolution and enhance the release of oxidized compounds during microbial leaching processes. Full article

Conventional hydrometallurgical processes typically employ inorganic acids as leaching agents; however, these processes are frequently associated with significant environmental pollution and suffer from poor metal selectivity. Oxalic acid, as a green alternative leaching agent, demonstrates considerable application potential owing to its mild acidity, strong reducing capability, and superior complexing properties. This paper presents a systematic review of recent advances in the application of oxalic acid in hydrometallurgy, encompassing the coordination chemistry between oxalic acid and metal ions, its role as a selective leaching agent, and strategies for handling multicomponent oxalate-rich solutions. Furthermore, the industrial prospects of oxalic acid-based leaching technologies are discussed. Research indicates that oxalic acid exhibits high selectivity and efficient leaching performance for critical metals—including vanadium, lithium, cobalt, nickel, and gallium—from both primary ores and solid secondary resources. The underlying leaching mechanism primarily involves the formation of stable chelation complexes between oxalate anions and high charge-density metal ions, or valence state modulation via reduction, enabling selective dissolution and separation of target metals. In multicomponent oxalate systems, where metals predominantly exist as anionic complexes, established enrichment and purification approaches include anion exchange extraction, as well as precipitation techniques based on valence adjustment and double salt crystallization. To advance the industrial implementation of oxalic acid leaching technologies, further in-depth investigation is required into the recycling mechanisms of oxalic acid and the fundamental reaction pathways governing leaching and metal recovery processes. Full article

To address the growing problem of electromagnetic pollution, the development of intelligent, multifunctional electromagnetic shielding materials is essential. The objective of this work is to fabricate an intelligent, low-reflection and high-absorption electromagnetic shielding composite via direct ink writing. In this study, epoxy resin (EP) was employed as the matrix, with nickel powder (Ni), multi-walled carbon nanotubes (MWCNTs), and silver powder (Ag) serving as functional fillers. Direct-ink printing enabled the fabrication of uniformly structured composites and layered gradient-structured composites. By precisely varying the filler content through layer-by-layer printing, the gradient-structured composite exhibited an increasing electrical conductivity gradient and a decreasing magnetic permeability gradient along the direction of electromagnetic wave incidence. Comprehensive characterization of microstructure, electrical, magnetic, and dielectric properties, and electromagnetic shielding effectiveness revealed that the uniformly structured composites exhibited higher total shielding effectiveness (SE_T) and reflection coefficient (R) with increased electrical conductivity. The layered gradient-structured composite achieved an electrical conductivity of 5.44 S/m and an SE_T of 17.74 dB, with the R value reduced to 0.53. Compared to the highly conductive homogeneous composite used in the bottom layer (R = 0.87), this represents a reduction in reflectivity of approximately 39.1%, thereby mitigating secondary pollution from excessive reflection. Under a DC voltage of 200 V, all composites recovered their original shape within 63 s, with shape fixity (R_f) and recovery (R_r) ratios exceeding 92%. This strong shape memory capability supports conformal coating on complex devices and facilitates material recycling, offering a practical foundation for next-generation multifunctional electromagnetic shielding materials. Full article

Polymer films of nickel Schiff-base complexes were investigated to clarify degradation mechanisms induced by coordinating impurities—specifically, the protic solvents methanol and isopropanol. Films of poly[Ni(Salen)] and its sterically protected derivatives were electropolymerized in situ and subjected to cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) measurements in dry acetonitrile electrolyte with 1% vol. alcohol added. In situ monitoring of redox activity and mass changes revealed something. It was revealed that traces of alcohols act as axial ligands to the Ni center. This disrupts the conjugated π-system and conductivity of the polymer. The rate of electrochemical stability strongly depends on the complex structure. The unsubstituted poly[Ni(Salen)] film showed the fastest loss of capacity in both methanol and isopropanol, whereas complexes with methyl substituents in the diimine bridge (poly[Ni(Salpn-1,2)] and poly[Ni(Saltmen)]) exhibited significantly improved stability. EQCM measurements revealed irreversible changes in the mass of all polymer films upon exposure to alcohol-containing electrolytes. These observations are consistent with the axial coordination of alcohol molecules to the Ni centers and the concomitant ingress of solvent species into the polymer matrix. The results demonstrate that molecular design—specifically, introducing steric hindrance around the metal center—markedly enhances resistance to coordinating impurities. Full article

Nickel(II) and palladium(II) ions are capable of forming complexes with macrocyclic terapyrrole structures such as the porphyrin or corrin ring. Many different derivatives of these complexes are synthesized and studied because these compounds have potential numerous applications, including catalysis, various light-driven chemical reactions and processes related to intramolecular and intermolecular energy redistribution. Nickel porphyrins exhibit neither fluorescence nor phosphorescence when excited with light; however, palladium porphyrins, when excited to the singlet state, very quickly transform into the triplet state, and unlike nickel porphyrins, deactivation of the excited states occurs by phosphorescence. Palladium corrin has dual luminescent properties and exhibits both a weak fluorescence and strong phosphorescence. These photophysical differences are based on the complex energetic redistribution of singlet and triplet excited states interacting with each other in the intersystem crossing process. Based on the results of calculations at the DFT/TDDFT and CASSCF/NEVPT2 levels of theory, the structure of electronic excited states of model nickel(II) and palladium(II) complexes with corrin and porphyrin macro-rings was characterized and potential paths of photophysical processes leading to the occupancy of low-lying triplet states were described. In nickel complexes, very low-energy triplet states are the main cause of the rapid radiationless deactivation of excited states via triplet photophysical pathways. Full article