Copper Sulfide Research Articles

Genesis of the Hajibolagh-Zalibolagh Cu-(Ag) intermediate-sulfidation epithermal deposit, Urumieh-Dokhtar magmatic arc, Iran: Evidence from ore geology, fluid inclusions, and stable isotopes

The Hajibolagh-Zalibolagh deposit located northeast of the city of Saveh in the central part of the Urumieh-Dokhtar magmatic arc of Iran, demonstrates vein and breccia vein style copper-(silver) mineralization hosted by Eocene volcano-sedimentary rocks. The main mineralization stage can be divided into four phases, respectively (1) jasperoid + quartz veins, chalcopyrite, and pyrite; (2) quartz veins along with chalcopyrite, bornite, chalcocite, arsenopyrite, and pyrite; (3) quartz-barite veins along with chalcopyrite, bornite, chalcocite and pyrite; and (4) veins of quartz, calcite, hematite, and oligist along with a small number of copper sulfides. The main stages of mineralization are cut by barren post-ore quartz and calcite veinlets. As a result of supergene processes, minerals are oxidized, and malachite, azurite, chrysocolla, chalcocite, covellite, goethite, and hematite are formed, presenting an important exploration guide. The hydrothermal alteration from the center of the vein-veinlets to the outside includes, respectively, silicification, sericitization, intermediate argillic, and propylitic. The average salinity and homogenization temperature (Th) of fluid inclusions is 14.2 wt% NaCl equiv. and 288 °C, respectively. The coexistence of the vapor phase, liquid-rich phase, and halite-bearing fluid inclusions is a sign of boiling in this hydrothermal system, which has contributed to copper saturation. Sulfur isotope values for pyrite, chalcopyrite, chalcocite, and bornite are mainly from –0.16 to 2.98 ‰, indicating a probable magmatic source for sulfur. Boiling, dilution, and mixing are the mechanisms for the ore deposition and facilitated the mineralization. The Hajibolagh-Zalibolagh deposit shows the highest similarity to intermediate-sulfidation epithermal deposits. The best environment for mineralization and fluid circulation in these epithermal deposits is the intersection of faults with the Eocene subvolcanic rocks.

Enhanced performance of a Na3.5Co4[Bi2Co2W19.75O70(H2O)6]/porous graphitic carbon nitride heterojunction based photocatalyst realized by the addition of copper sulfide nanoparticles.

Photocatalytic hydrogen (H2) evolution can effectively solve the global energy problem, in which the key factor is the synthesis of efficient photocatalytic materials. In this study, we successfully synthesized a novel photocatalyst, BiWCo/CuS/PGCN, by functionalizing porous graphitic carbon nitride (PGCN) with sandwich-type polyoxometalate Na3.5Co4[Bi2Co2W19.75O70(H2O)6]·39.5H2O (BiWCo) and introducing copper sulfide (CuS) nanoparticles as a cocatalyst. This approach was aimed at enhancing the built inner electric field between interfaces, resulting in a significant improvement in photocatalytic H2 evolution performance. This research adopts a step-by-step method to synthesize BiWCo/CuS/PGCN composites with p-n heterojunctions, which has high visible light absorption and a synergistic effect of multiple elements. PGCN with a high specific surface area contributes to the uniform distribution of active sites. In addition, the nano-CuS cocatalyst provides abundant active sites and more electron transfer pathways for photocatalysis. Therefore, the H2 production efficiency of BiWCo/CuS/PGCN is 6.3 times that of PGCN, 4.5 times that of BiWCo and 2.5 times that of BiWCo/PGCN under visible light. The H2 production rate of BiWCo/CuS/PGCN reaches 3477.58 μmol g-1 h-1. At the same time, the ternary photocatalyst shows high stability after 30 hours and 5 cycles. This work demonstrates that BiWCo/CuS/PGCN has good application prospects in H2 evolution, and provides a new strategy for the design of efficient ternary photocatalytic materials.

In-situ non destructive investigation of contemporary outdoor bronze sculptures

Indoor investigations are commonly used to assess the causes and extent of damage to bronze artwork and cultural heritage items; however, these methods typically involve destructive sampling and outdoor bronze sculptures are typically heavy and large, hindering their transport. In this study, 16 contemporary bronze sculptures exposed to outdoor environments for a period exceeding 20 years were evaluated in-situ to develop a non-destructive prediction model that can identify types of corrosion and quantify the amount of corrosion on bronze sculptures that cannot be easily transported. The sculptures were classified into three groups according to their patina chromaticity, reflectivity, and chemical composition. The corrosion characteristics were found to be copper oxide and sulfide patinas. Chromaticity and reflectivity investigations revealed that the chemical composition changes of the patinas corresponded to the formation of corrosion products, thus showing a high potential for the identification of the type of corrosion. Portable XRF spectroscopy showed that the low error rate of Cu make its compositional behavior a good indicator in identifying the type of corrosion of sulfide and chloride patinas. Portable Raman spectroscopy was able to detect basic sulfides such as brochantite, antlerite, and cuprite. The corrosion types and corrosion products on the bronze sculptures could be identified using chromaticity and reflectivity, portable X-ray fluorescence, and portable Raman spectroscopy. The rapid insitu diagnosis of these corrosion attributes is expected to contribute to establishing conservation treatment plans in the future.

Copper sulfide mineral performs non-enzymatic anaerobic ammonium oxidation through a hydrazine intermediate.

Anaerobic ammonium oxidation (anammox)-the biological process that activates ammonium with nitrite-is responsible for a significant fraction of N2 production in marine environments. Despite decades of biochemical research, however, no synthetic models capable of anammox have been identified. Here we report that a copper sulfide mineral replicates the entire biological anammox pathway catalysed by three metalloenzymes. We identified a copper-nitrosonium {CuNO}10 complex, formed by nitrite reduction, as the oxidant for ammonium oxidation that leads to heterolytic N-N bond formation from nitrite and ammonium. Similar to the biological process, N2 production was mediated by the highly reactive intermediate hydrazine, one of the most potent reductants in nature. We also found another pathway involving N-N bond heterocoupling for the formation of hybrid N2O, a potent greenhouse gas with a unique isotope composition. Our study represents a rare example of non-enzymatic anammox reaction that interconnects six redox states in the abiotic nitrogen cycle.

Synthesis of S-Allyl-O, O′-Dibutyl Phosphorodithioate and Its Adsorption Mechanism on Chalcopyrite Surface

The demand for non-ferrous copper metals has increased dramatically with the development of the global economy; accordingly, some refractory copper sulfide ores with low grade and their associated minerals are beginning to be utilized, making the flotation separation of copper concentrates exceptionally difficult, especially the separation of chalcopyrite and pyrite. In this paper, S-allyl-O, O′-dibutyl phosphorodithioate (ADTP) was synthesized by a one-pot method and used as a chalcopyrite collector in the flotation separation of chalcopyrite and pyrite. Flotation experiments results have shown that ADTP exhibits better selectivity and greater collecting power for chalcopyrite under neutral or weak base conditions. The 95% recovery of chalcopyrite can be achieved at pH 8.0 and 8.0 mg/L ADTP. From the analysis results of the contact angle, the SEM-EDS spectrogram, and elemental mapping, it was found that ADTP adsorbed uniformly on a chalcopyrite surface and made a significant contribution to the hydrophobicity of the surface. Confirmed by FTIR and XPS analysis, ADTP was able to form P–S–Cu bonds on a chalcopyrite surface, proving that it was adsorbed on the chalcopyrite surface in the form of chemisorption.

Sulfated Chitosan-Modified CuS Nanocluster: A Versatile Nanoformulation for Simultaneous Antibacterial and Bone Regenerative Therapy in Periodontitis.

Periodontitis, a prevalent chronic inflammatory disease worldwide, is triggered by periodontopathogenic bacteria, resulting in the progressive destruction of periodontal tissue, particularly the alveolar bone. To effectively address periodontitis, this study proposed a nanoformulation known as CuS@MSN-SCS. This formulation involves coating citrate-grafted copper sulfide (CuS) nanoparticles with mesoporous silica (MSNs), followed by surface modification using amino groups and sulfated chitosan (SCS) through electrostatic interactions. The objective of this formulation is to achieve efficient bacteria removal by inducing ROS signaling pathways mediated by Cu2+ ions. Additionally, it aims to promote alveolar bone regeneration through Cu2+-induced pro-angiogenesis and SCS-mediated bone regeneration. As anticipated, by regulating the surface charges, the negatively charged CuS nanoparticles capped with sodium citrate were successfully coated with MSNs, and the subsequent introduction of amine groups using (3-aminopropyl)triethoxysilane was followed by the incorporation of SCS through electrostatic interactions, resulting in the formation of CuS@MSN-SCS. The developed nanoformulation was verified to not only significantly exacerbate the oxidative stress of Fusobacterium nucleatum, thereby suppressing bacteria growth and biofilm formation in vitro, but also effectively alleviate the inflammatory response and promote alveolar bone regeneration without evident biotoxicity in an in vivo rat periodontitis model. These findings contribute to the therapeutic effect on periodontitis. Overall, this study successfully developed a nanoformulation for combating bacteria and facilitating alveolar bone regeneration, demonstrating the promising potential for clinical treatment of periodontitis.

Highly Stable Solid Contact Calcium Ion-Selective Electrodes: Rapid Ion-Electron Transduction Triggered by Lipophilic Anions Participating in Redox Reactions of CunS Nanoflowers.

Solid contact (SC) calcium ion-selective electrodes (Ca2+-ISEs) have been widely applied in the analysis of water quality and body fluids by virtue of the unique advantages of easy operation and rapid response. However, the potential drift during the long-term stability test hinders their further practical applications. Designing novel redox SC layers with large capacitance and high hydrophobicity is a promising approach to stabilize the potential stability, meanwhile, exploring the transduction mechanism is also of great guiding significance for the precise design of SC layer materials. Herein, flower-like copper sulfide (CunS-50) composed of nanosheets is meticulously designed as the redox SC layer by modification with the surfactant (CTAB). The CunS-50-based Ca2+-ISE (CunS-50/Ca2+-ISE) demonstrates a near-Nernstian slope of 28.23 mV/dec for Ca2+ in a wide activity linear range of 10-7 to 10-1 M, with a low detection limit of 3.16 × 10-8 M. CunS-50/Ca2+-ISE possesses an extremely low potential drift of only 1.23 ± 0.13 μV/h in the long-term potential stability test. Notably, X-ray absorption fine-structure (XAFS) spectra and electrochemical experiments are adopted to elucidate the transduction mechanism that the lipophilic anion (TFPB-) participates in the redox reaction of CunS-50 at the solid-solid interface of ion-selective membrane (ISM) and redox inorganic SC layer (CunS-50), thereby promoting the generation of free electrons to accelerate ion-electron transduction. This work provides an in-depth comprehension of the transduction mechanism of the potentiometric response and an effective strategy for designing redox materials of ion-electron transduction triggered by lipophilic anions.

Dual‐Stoichiometry Copper Sulphide Nanoparticles by Laser Ablation in DMSO: Synthesis and Biomedical Applications for Enhanced Photothermal Therapy and Photoacoustic Imaging

Copper sulphide nanoparticles are synthesized by laser ablation of a copper target in DMSO by a 527 nm nanosecond pulsed laser. These nanoparticles have double stoichiometry (CuS and Cu1.8S) and crystalline structures, sizes under 30 nm, and they present substantial absorbance in the second near‐infrared window and photoluminescence in the visible region. The nanoparticles are used as photothermal and photoacoustic agents at 1080 nm and 1064 nm, respectively. Utilizing as a photothermal agent, these nanoparticles rapidly exhibit local heating, photothermal stability, and a temperature change of 52.2 ◦C within 300 s at 1 mg mL‐1 concentration and 3.23 W cm‐2 laser intensity. On the other hand, while employed as a photoacoustic agent, they enhanced the contrast significantly and increased the brightness proportional to their concentrations when compared to ultrasound imaging. Additionally, the biocompatibility properties of these nanoparticles were tested with cancer cells, and they were subjected to laser ablation to assess their photothermal effects. In this article, we demonstrate that copper sulphide nanoparticles synthesized by pulsed laser ablation hold great promise for photothermal and photoacoustic applications, especially in biomedical applications.

An Examination of Bronze Vessel Technology in the Unified Silla Period: Case Study on the Bronzes Excavated from Gwanbuk-ri Site in Buyeo

Archaeological excavations in Buyeo had revealed Bronze vessels interred within a hole in the building at the Gwanbuk-ri site. These bronze vessels are dated to the Unified silla period (9-10th centuries). To identify the bronze vessels’ manufacturing technology, metallurgical analyses were carried out using Optical Microscopy, SEM-EDS and EPMA. The results allowed a reconstruction of the manufacturing process of bronze vessels in the Unified silla. It proved that bronze vessels were manufactured with Cu-Sn alloy with varying tin contents, which may be related to the application of uncontrolled procedures in making the bronze alloys. Also a casting process was used to shape the bronze vessels and the strength and hardness of the container were improved through a quenching process. Twins were observed in one of the samples, so it was assumed that hot working had been attempted. Non-metallic inclusions in bronze vessels have circular or polygonal shapes, and Cu and S were detected. The presence of Cu-S inclusions showed the probable use of copper sulphide ores for metal production and smelting. Se and Te in the inclusions of the bronze vessels show that the copper ore is different. From the results of metallurgical analyses of bronze vessels excavated from other regions of the same era, casting and quenching treatments were confirmed, and the sequential relationship of the technological system was revealed.

Glycyrrhizin functionalized CuS Nanoprobes for NIR Light-based therapeutic mitigation of acne vulgaris.

Acne Vulgaris or Acne is a multifactorial bacterial infection caused by Propionibacterium acne, leading to inflammation and decreased quality of life, especially in adolescence. Currently, antibiotics and retinoids are preferred for treating acne. However, their continuous usage may lead to anti-microbial resistance and other side effects. Therefore, research on developing effective strategies to reduce antimicrobial resistance and improve acne healing is ongoing. The current work reports the synthesis and evaluation of near-infrared light-absorbing copper sulfide (CuS) nanoparticles loaded with a biomolecule, Glycyrrhizin (Ga). The photothermal efficacy studies, and in-vitro and in-vivo experiments indicated that the Ga-CuS NPs generated localized hyperthermia in acne-causing bacteria, leading to their complete growth inhibition. The results indicated that the Ga-Cus NPs possess excellent antibacterial and anti-inflammatory properties in the acne and inflammatory models. This could be from the synergistic effect of CuS NPs mediated mild Photothermal effect and inherent pharmacological properties of Ga. Further detailed studies of the formulations can pave the way for application in cosmetic clinics for the effective and minimally invasive management of Acne-like conditions.

Synthesis and characterization of CuxCd1‐xS nanocrystals into functionalized nitrile butadiene rubber matrix

AbstractIntroductionPolymetallic sulfides and heterostructures like CdIn2S4, CdZnS2, CuxS‐NiySz, Cu2CoSnS4, CoNi2S4, Zn0.76Co0.24S have been fabricated with various shapes and forms for new applications. Ternary copper cadmium sulfides (CuCdS2) are a p‐type semiconductor with a direct band gap of about 2.4 eV forms very good nanocrystals like copper sulfide could be potentially applied to optical and electronic applications. Knowing that the SILAR synthesis, optical, paramagnetic, dielectric properties, and annealing of copper cadmium sulfides have not been sufficiently investigated, they are extensively analyzed and studied in the present work.ObjectivesCuxCd1−xS (x = 0, 0.5, and 1) nanoparticles have been synthesized on the base of functionalized nitrile butadiene rubber by SILAR method and characterized using scanning electron microscopy, x‐ray diffractometer, UV–visible spectroscopy, Fourier‐transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy. Effects of cycles, reaction time, and precursor concentration on the particle size, crystal growth and structure, bandgap energy, dielectric and paramagnetic properties, elemental composition, and morphology were investigated.MethodsThe synthesis of CuxCd1−xS nanocrystals was carried out into the obtained functional polymer matrix by SİLAR method. The functional polymer (FNBR) is a dark brown powder which contains ‐PO(OH)2 and ‐OPO(OH)2 functional groups and does not dissolve in organic and inorganic solvents, can be used as a very good stabilizer of nanostructures. The synthesis of CuxCd1−xS/FNBR nanocompsite was carried out in 3, 5, and 15 cycles.Results and discussionIn the process of ternary sulfide formation, the nucleation rate of CdS was high at the beginning of the reaction, while the growth rate and stability of CuS were high in the later course of the reaction. The average crystallite size of the nancrystallites has been increased from 1.13 nm to 7.39 nm by the increasing of the number of cycles from 5 to 15, respectively. It is explained by the inclusion of copper in the composition and getting more stable material. Copper cadmium sulfide nanostructures demonstrate wide band gap energy (~3.7 eV) in this work which is explained by the formation of nanosized particles in a limited volume of FNBR matrix.ConclusionsThe synthesis of CuxCd1‐xS nanocrystals was carried out into the obtained functional polymer matrix by SİLAR method. Strong diffraction peaks corresponding to cubic CdS are found with low SILAR cycles. SEM images of CuxCd1−xS/FNBR nanocomposite show that the atomic percentage of Cu and Cd into the ternary sulfide is 20.19% and 0.61%, respectively. It is explained by the inclusion of copper in the composition and getting more stable material with low solubility products (Ksp) which is in good agreement with XRD results. The calculated band gaps are higher than that of bulk CdS, CuS, and CuCdS2. Larger band gap is usually reported for defects or structural disorders, which is in good agreement with XRD and Raman results.

Enhanced chalcopyrite leaching by mechanical activation: New insights from microstructure

Bioleaching is an effective technique for treating low-grade copper sulfide ore, but low leaching rate limit its industrial application of chalcopyrite bioleaching. Many passivation film compositions have been hypothesized to explain the difficulty of chalcopyrite leaching, but the essential reason remain unclear. Mechanical activation can not only reduce the solid particle size, but also result in lattice defects and induce redox reactions, and even affect the electronic structure of the solid. Therefore, the mechanical activation enhanced chalcopyrite leaching and its influence mechanism was investigated. The main conclusions are as follows: mechanical activation can significantly reduce chalcopyrite particle size, simultaneously, microscopic strain and cell volume increased; the mechanical activation changed the energy band structure of chalcopyrite—the positions of the conduction band and the valence band were positively shifted, implying that Fe3+ could more easily capture electrons from the chalcopyrite surface to be reduced, thus the leaching rate of chalcopyrite increased significantly in in Fe3+ solution. The results show that the passivation film may affect the leaching of chalcopyrite, but the structural characteristics of chalcopyrite is the essential reason for the difficulty of chalcopyrite leaching.

Product development and characterization of the Ayurvedic herbo-mineral-metallic compound- Hridayarnava Rasa

BackgroundHerbo-mineral-metallic formulations are an inseparable part of the Ayurveda system of traditional medicine. Hridayarnava Rasa (HR) is a preparation containing metals like copper, sulphur, and mercury in processed forms and other herbs that do not produce toxic effects and adverse drug reactions when taken in appropriate dosage. Ayurveda practitioners use it in treating cardiac diseases like hypertension, cardiotoxicity and many more. The rasa-aushadhis possess characteristics such as rapid efficacy, little dosage required, and extensive therapeutic applicability. Hridayarnava Rasa [AFI Part-1, 20:55] has been employed for the treatment of various diseases from ancient times. A systematic study of these formulations manufacturing is required to maintain their quality, safety, and efficacy is a need of time to protect the immense faith of patients in Ayurveda. ObjectivesThe present study aimed to prepare HR as per standard operating procedures mentioned in the classical text and to characterize it physio-chemically using advanced analytical techniques. Materials and MethodsHR was prepared and physicochemical analyses and assay of elements by ICP-AES were carried out as per Ayurvedic Pharmacopoeia of India (API). Powder X-ray diffraction (XRD), Field emission gun scanning electron microscopy with energy dispersive spectroscopy (FEG SEM, EDAX), CHNS-O analysis, Fourier Transform Infrared Spectroscopy (FTIR), Thermo-gravimetric analysis (TGA), Particle size distribution analysis (PSD) was carried out. ResultsThe XRD analysis of HR showed the presence of unreacted sulphur and sulfides of copper and mercury. FEG SEM revealed the particles in the form of aggregates as nanocrystallites in the range of 100–1000 nm. Elemental analysis showed the presence of copper, sulphur, and mercury in major, along with traces of iron, calcium, sodium, potassium, and magnesium. In FTIR analysis, 18 peaks were observed, which strongly suggests the presence of various organic groups. In the TGA, four peaks were seen, which can be attributed to sulphur volatilization and oxidative changes in mercury. In PSD analysis, 50% of the material was found below 16.40 μm. ConclusionTo establish a piece of fundamental knowledge and ensure uniformity of these rasa-aushadhis, it is imperative to conduct an analysis of their characteristics as per classical texts and modern analytical techniques. Additionally, it is crucial to investigate the significance of each procedural step included in the preparation process. The inferences drawn are helpful as an essential aid for quality assurance and standardization of this herbo-mineral-metallic formulation.

Hollow drop bubbles: A preliminary study of simplified prototype for improving copper(II) extraction with ACORGA® M5640 using coated bubble swarm

There are two well-defined processes for the types of copper ores. One for the processing of copper sulfides and another for the processing of the copper oxides. There are similarities between the two, particularly in the preparation stage of the run of mine (ROM) such as the crushing. However, significant differences exist in how to concentrate the elements of interest. Flotation is the most used concentration process to separate copper sulfide minerals from other minerals using air bubbles. For oxides, after the dissolution of copper, the solvent extraction (SX) process is the preferred path using two immiscible liquids to separate the copper.A line of investigation for solvent extraction is the use of a bubble coated with solvent to extract the metal of interest from the aqueous solution, some devices have been built and tested for this purpose using different principles to generate a coated bubble swarm. However, those equipments have been tested on laboratory and have not been scaled up to an industry level.The Hollow Drop (HD) concept was born from the idea of building a device to generate coated bubbles in a continuous swarm that could be scalable to an industry level. In this paper two columns were built and operated: a proof-of-concept column and a scale-up attempt for the extraction of Cu(II) fom an aqueous solution of 2.5 g L−1 using ACORGA® M5640 (25% v/v) in the Kerosene.The results show that we could generate a bubble swarm and conduct the solvent extraction process at a 97% recovery using our proposed coated bubble generator. However, in our scaled prototype test only a 70% recovery was achieved, which shows that our column is working but the scaling-up needs more investigation regarding the dimensions and flows of the process.

Morphological studies, photocatalytic degradation of organic dyes and anticancer potential of copper sulfide nanoparticles prepared from bis(diallyl dithiocarbamato)copper(II) complex

Bis(diallyl dithiocarbamato)copper(II) complex was synthesized and characterized by single crystal X-ray crystallography. The molecular structure revealed dimeric copper(II) complex consisting of two copper(II) ions that coordinate two molecules of diallydithiocarbamato anions in bidentate chelating modes and the centrosymmetrically related diallydithiocarbamato anions bridges the S-atom of the adjacent chelating ligand to formed square pyramidal geometry around the copper(II) ions. Copper sulfide nanoparticles were prepared at 160 °C by thermolysis of the copper(II) complex in dodecylamine (DDA), hexadecylamine (HDA), and octadecylamine (ODA) to study the effect of capping agents on the structural morphologies, photocatalytic properties, and anticancer potential of the as-prepared copper sulfides nanoparticles. Powder X-ray diffraction patterns confirmed Cu9S5 digenite crystalline phases for CuS-DDA and CuS-HDA while CuS-ODA is covellite crystalline phase. HRTEM images showed spherical particles with particle sizes in the range 2–25 nm. The copper sulfide nanophotocatalysts are efficient for the degradation of bromophenol blue with the highest photocatalytic efficiency of 95.14 % for CuS-DDA followed by CuS-HDA with 94.52 % and 93.95 % for CuS-ODA. The anticancer potentials of the compounds showed that CuS-HDA is the most potent with IC50 values of 1.22 µg/mL against HEK293 and 28.78 µg/mL against HeLa.

Constructing Cu9S5@CuSe heterostructures under microwave irradiation for rechargeable magnesium batteries

Copper chalcogenides are believed as the prospective cathode materials for rechargeable magnesium batteries. However, their practical application is seriously restricted by slow diffusion and reaction kinetics due to the large charge/radius ratio of divalent Mg2+ ions. Herein, a simple two-step microwave-assisted synthesis method is rationally developed to construct Cu9S5@CuSe heterostructures as the capable cathode materials for rechargeable magnesium batteries. Two-dimensional CuSe nanosheets are vertically grown on the surface of single-crystal Cu9S5 substrate through selenation reaction under microwave irradiation to form the mixed-dimensional heterostructures. Electrochemical measurements reveal that the as-synthesized Cu9S5@CuSe heterostructures show high reversible capacity of 240 mAh/g and good long-term cyclic stability with approximate 0.013 % capacity decay per cycle at 500 mA g−1 within 1000 cycles. Furthermore, the obviously enhanced rate capability can be achieved in comparison with that of single-crystal Cu9S5 substrate and CuSe nanoparticles. Ex-situ X-ray photoelectron spectroscopy and X-ray diffraction characterizations reveal favourable electrochemical conversion reaction over the Cu9S5@CuSe heterostructure cathode. The superior electrochemical properties are attributed to the optimized diffusion kinetics within the unique heterostructure. This research offers a valuable strategy to develop high-performance cathode materials with favourable kinetics for magnesium batteries.

Implications of renewable energy sources in metallurgy: Utilization of concentrated solar energy in recycling metallurgical wastes

Solar energy, when it is concentrated, can reach temperatures as high as 3000 °C and generate heat without producing pollutants such as carbon dioxide or other harmful agents. Additionally, solar energy is virtually free and can be utilized in remote areas not connected to the electrical grid. However, slags, a by-product of metallurgical industries, are not commonly used due to the cost of processing them. This manuscript proposes studying the use of concentrated solar energy to extract metals from four types of slags: basic oxygen furnace (BOF) slag, copper slag, silicomanganese slag, and ferromanganese slag, each containing important metals. Experimental work at the Odeillo solar furnace suggests that iron oxides in the BOF slag transform into magnetic phases, while copper slag experiences changes in fayalite (that partially transforms into magnetite) and copper oxides and sulfides (that also convert into metallic copper nodules). The ferromanganese and silicomanganese slags become more refractory, making the extraction of manganese more challenging. Overall, the study suggests that at least part of the metals might be collected in a usable form.

Glutathione-mediated copper sulfide nanoplatforms with morphological and vacancy-dependent photothermal catalytic activity for multi-model tannic acid assays

Interface engineering and vacancy engineering play an important role in the surface and electronic structure of nanomaterials. The combination of the two provides a feasible way for the development of efficient photocatalytic materials. Here, we use glutathione (GSH) as a coordination molecule to design a series of CuxS nanomaterials (CuxS-GSH) rich in sulfur vacancies using a simple ultrasonic-assisted method. Interface engineering can induce amorphous structure in the crystal while controlling the formation of porous surfaces of nanomaterials, and the formation of a large number of random orientation bonds further increases the concentration of sulfur vacancies in the crystal structure. This study shows that interface engineering and vacancy engineering can enhance the light absorption ability of CuxS-GSH nanomaterials from the visible to the near-infrared region, improve the efficiency of charge transfer between CuxS groups, and promote the separation and transfer of optoelectronic electron-hole pairs. In addition, a higher specific surface area can produce a large number of active sites, and the synergistic and efficient photothermal conversion efficiency (58.01%) can jointly promote the better photocatalytic performance of CuxS-GSH nanomaterials. Based on the excellent hot carrier generation and photothermal conversion performance of CuxS-GSH under illumination, it exhibits an excellent ability to mediate the production of reactive oxygen species (ROS) through peroxide cleavage and has excellent peroxidase activity. Therefore, CuxS-GSH has been successfully developed as a nanoenzyme platform for detecting tannic acid (TA) content in tea, and convenient and rapid detection of tannic acid is achieved through the construction of a multi-model strategy. This work not only provides a new way to enhance the enzyme-like activity of nanomaterials but also provides a new prospect for the application of interface engineering and vacancy engineering in the field of photochemistry.

Copper Sulfide-based Hollow Nanoarchitectonics for Augmented Photothermal, Chemodynamic, and Chemotherapeutic Modalities

Cancer has become one of the dreadful ailments, accounting for millions of mortalities every year. Despite the advancements, it remains one of the appalling diseases, with numerous casualties due to delayed prognosis and poor survival rate. To this end, combinatorial strategies have garnered enormous interest in improved performance. This study aims to investigate the fabrication of transition metal-based hollow nanoarchitectures for synergistic augmented photothermal (PTT), chemodynamic (CDT), and chemotherapeutic (CT) modalities. Initially, copper sulfide nanoparticles with hollow cavities (hCuS) are synthesized using the facile sacrificial templating-based approach and subsequently loaded with the CT agent (Doxorubicin, DOX), referred to shortly as hCuS-DOX. These hCuS-DOX nanoarchitectures are systematically characterized using various techniques to successfully explore the physicochemical properties. The DOX molecules are encapsulated in hCuS containers through the electrostatic interactions due to their contrary charges and coordination interactions between copper in CuS and nitrogen in DOX molecules. These innovative nanoarchitectures showed pH-responsive release of DOX molecules from the hollow cavities, specifically in the tumor, which could be through the protonation of DOX and progressive degradation of hCuS. In addition, these architectures exhibited substantial PTT properties, on the one hand, by raising the temperature to over 60 °C. On the other hand, the released DOX molecules supported the CDT effect by generating enormous levels of deadly free radical species intracellularly, significantly reducing the viability of 4T1 cells. Finally, the apoptosis assay based on calcein AM/propidium iodide staining using various combinations validated the synergistic therapeutic modalities. In summary, these nanoarchitectures potentiated the synergistic therapeutic efficacy against breast carcinoma towards their ability in pharmaceutics.

Highly enhanced thermoelectric and mechanical performance of copper sulfides via natural mineral in-situ phase separation

Highly enhanced thermoelectric and mechanical performance of copper sulfides via natural mineral <i>in-situ</i> phase separation