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

In situ phase separation precipitates play an important role in enhancing the thermoelectric properties of copper sulfides by suppressing phonon transmission.In this study,Cu1.8S composites were fabricated by melting reactions and spark plasma sintering.The complex structures,namely,micron-PbS,Sb_(2)S_(3),nano-FeS,and multiscale pores,originate from the introduction of FePb_(4)Sb_(6)S_(14)into the Cu1.8S matrix.Using effective element(Fe)doping and multiscale precipitates,the Cu_(1.8)S+0.5 wt%FePb_(4)Sb_(6)S_(14)bulk composite reached a high dimensionless figure of merit(ZT)value of 1.1 at 773 K.Furthermore,the modulus obtained for this sample was approximately 40.27 GPa,which was higher than that of the pristine sample.This study provides a novel strategy for realizing heterovalent doping while forming various precipitates via in situ phase separation by natural minerals,which has been proven to be effective in improving the thermoelectric and mechanical performance of copper sulfides and is worth promoting in other thermoelectric systems.

Improved electrical transport properties and optimized thermoelectric figure of merit in lithium-doped copper sulfides

Copper sulfide Cu2S is a p-type semiconducting compound that has attracted great attentions in the thermoelectric （TE） community most recently. Considering the intrinsic ultralow lattice thermal conductivity, the enhancement of TE performance in CuzS should be achieved through improving its electrical transport properties. To achieve this goal, lithium element was doped into CuzS in this study. A series of Cu2_xLixS samples with different Li contents （x = 0, 0.005, 0.010, 0.050, and 0.100） was synthesized by the melting-annealing method. When x 〈 0.05, the Cuz_xLixS samples are stable and pure phases, having the same monoclinic structure with the pristine Cu2S at room temperature. The electrical conductivities in the Cu2_xLixS samples are greatly improved with the Li-doping content increasing due to the enhanced carrier concentrations. Meanwhile, doping Li into CuzS increases the ionic activation energy and lessens the influence of mobile Cu ions on the heat-carrying phonons. Thus, the thermal conductivities of the Li-doped Cu2S samples increase. A maximal figure of merit （zT） of 0.84 at 900 K is obtained in Cul.99Lio.018, about 133% improvement as compared with that in Cu2S matrix.

Copper Indium Sulfide Enables Li-CO_(2)Batteries with Boosted Reaction Kinetics and Cycling Stability

High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of the discharge product Li_(2)CO_(3)is one of the main problems that limit its application,resulting in poor cycling stability and severe polarization.Herein,copper indium sulfide(CIS),a semiconducting non-precious metal sulfide,is fabricated as cathode catalysts for high-performance Li-CO_(2)batteries.Combined with the synergistic effect of bimetallic valence bonding and coordinated electron transfer,Li-CO_(2)batteries using CIS cathodes exhibit high full specific discharge capacity,excellent rate capability and cycle stability,namely it delivers a high specific full discharge capacity of 8878μAh cm^(-2),runs steadily from 10 to 100μA cm^(-2),and performs a stable long-term cycling behavior(>1050 h)under a high energy efficiency of 84%and a low charge voltage of approximately 3.4 V at 20μA cm^(-2)within 100μAh cm^(-2).In addition,a flexible Li-CO_(2)pouch cell is constructed to reveal the potential of employing CIS to fabricate flexible high energy storage devices in practical applications.This work shows a promising development pathway toward next-generation sustainable energy storage devices.

Construction of 3D porous Cu_(1.81)S/nitrogen-doped carbon frameworks for ultrafast and long-cycle life sodium-ion storage

Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.

High area-capacity Mg batteries enabled by sulfur/copper integrated cathode design

Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.

Bioleaching of low-grade copper sulfide ores by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

The grown conditions of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans were investigated,and then experiments were conducted to research the bioleaching behaviors of crude ore of copper sulfide and hand-picked concentrates of chalcopyrite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans.The experimental results show that the bacteria grow best when the temperature is(30±1) °C and the pH value is 2.0.The bacteria concentration is 2.24×107 mL-1 in this condition.It is found that the copper extraction yield is affected by the inoculum size and the pulp density and the extraction yield increases as the inoculum size grows.The bioleaching rates reach their highest point in sulfide copper and chalcopyrite with a pulp density of 5% and 10%,respectively.Column flotation experiments of low-grade copper sulfide ores show that the bioleaching recovery reaches nearly 45% after 75 days.

Acid equilibrium during bioleaching of alkaline low-grade sulfide copper ore

This article reports the study on acid equilibrium during bioleaching of alkaline low-grade copper sulfide ore. Adding auxiliary agents 1# （sulfur） and 2# （pyrite） makes bacterial leaching of copper and acid production carried out simultaneously because the auxiliary agents can be oxidized by bacteria and the oxidation products involve acid. The acid required for dissolving alkaline gangue during bacterial leaching is produced, and acid equilibrium is reached during the ore bio-leaching. The recovery of copper reaches more than 95%.

Bioleaching of low-grade copper sulfide ore by extremely thermoacidophilic consortia at 70℃in column reactors

The effects of introducing M.sedula derivatives having different Cu^2+-resistance on bioleaching capacity of a defined consortium(consisting of A.brierleyi DSM1651 and M.hakonensis HO1-1)were studied in column reactors at 70℃.Introducing M.sedula copA mutant,a copper sensitive derivative,only had negligible effects on bioleaching.While introducing M.sedula ARS50-2,a Cu^2+resistant strain,substantially consolidated bioleaching process,with 27.77%more copper recovered after 58 d of bioleaching.Addition of M.sedula ARS50-2 likely enhanced the sulfur oxidation capacity of consortium after the 24th day under the Cu^2+stress.The majority of extreme thermoacidophiles were attached on minerals surface as indicated by quantitative PCR(qPCR)data.Successions of microbial community of extremely thermoacidophilic consortia that attached on surface of minerals were different from those in leachate.M.hakonensis HO1-1 was the dominant species attached on minerals surface in each column reactor throughout bioleaching process.The sessile M.sedula ARS50-2 remained as a major species till the 34th day.A.brierleyi DSM1651 was the most abundant planktonic species in leachate of each column reactor.These results highlight that higher Cu^2+-resistance is a beneficial trait for extreme thermoacidophiles to process copper minerals.

STUDY ON GREY FORECASTING MODEL OF COPPER EXTRACTION RATE WITH BIOLEACHING OF PRIMARY SULFIDE ORE

A model GM （grey model） （1,1） for forecasting the rate of copper extraction during the bioleaching of primary sulphide ore was established on the basis of the mathematical theory and the modeling process of grey system theory. It was used for forecasting the rate of copper extraction from the primary sulfide ore during a laboratory microbial column leaching experiment. The precision of the forecasted results were examined and modified via ＂posterior variance examination＂. The results show that the forecasted values coincide with the experimental values. GM （1,1） model has high forecast accuracy; and it is suitable for simulation control and prediction analysis of the original data series of the processes that have grey characteristics, such as mining, metallurgical and mineral processing, etc. The leaching rate of such copper sulphide ore is low. The grey forecasting result indicates that the rate of copper extraction is approximately 20% even after leaching for six months.

Recent advances in the utilization of copper sulfide compounds for electrochemical CO2 reduction

Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.

Enhanced copper recovery from low grade copper sulfide ores through bioleaching using residues produced by fermentation of agricultural wastes

Effects of residues produced by agricultural wastes fermentation(AWF)on low grade copper sulfide ores bioleaching,copper recovery,and microbial community were investigated.The results indicated that adding appropriate bulk of AWF made contributions to low grade copper sulfide ores bioleaching,which may be mainly realized through reducing the passivation layer formed by Fe3+hydrolysis.Improved copper recovery(78.35%)and bacteria concentration(9.56×10^(7)cells·mL^(−1))were yielded in the presence of 5 g·L^(−1)AWF.The result of 16S rDNA analysis demonstrated that microbial community was differentiated by adding AWF.Bacteria proportion,such as Acidithiobacillus ferrooxidans,Moraxella osloensis,and Lactobacillus acetotolerans changed distinctly.Great difference between samples was showed according to beta diversity index,and the maximum value reached 0.375.Acidithiobacillus ferrooxidans accounted for the highest proportion throughout the bioleaching process,and that of sample in the presence of 5 g·L^(−) AWF reached 28.63%.The results should show reference to application of agricultural wastes and low grade copper sulfide ores.

Influence of copper on quality of hot strips by EAF-CSP process

Electron microscopy and X-ray Energy Dispersive Spectroscopy (XEDS) study on influence of Cu on low carbon hot strips produced by CSP (Compact Strip Production) process has been carried out. The results indicated that copper segregation and enrichment at interfacial layer between oxidized surface and steel matrix is the key factor, which results in microcracks and edge flaws on the strips. The primary considerations to prevent detrimental effects from Cu include controlling copper content in proper level, higher soaking temperature and non-oxidizable atmosphere during soaking. Copper sulfide precipitates with nanometers in size were observed, they may be beneficial to the properties of CSP products, and influence of Cu on quality of CSP hot strips is discussed.

Well-controlled column bioleaching of a low-grade copper ore by a novel equipment

For the low-grade copper sulfide ores with 0.99% of copper, of which 41.5% was primary copper sulfide, and 54.5% was secondary copper sulfide, well-controlled column bioleaching on a novel equipment was carried out to investigate the optimal conditions of pre-leaching, particle sizes of ores, temperature, spray intensity and strain consortium. Results show that copper extraction of 91.11% can be obtained after 90 d with the optimal p H value of pre-leaching of 0.8; the p H values of pre-leaching significantly affect the final copper extractions. Copper extractions of 93.11%, 91.04% and 80.45% can be obtained for the bioleaching of ores with particles size of 5-8 mm, 5-15 mm and 5-20 mm, respectively. Copper extractions are 83.77% and 91.02% for bioleaching under the conditions of room temperature and 35 oC. Copper extractions are 77.25%, 85.45% and 91.12% for the bioleaching when flow rate of spray was 5 L/（h·m2）, 10 L/（h·m2） and 15 L/（h·m2）, respectively. Additionally, the strain consortium C3 is the best among the four strain consortia in bioleaching. By considering the energy consumption, the optimal conditions of bioleaching in this work are determined as p H of pre-leaching of 0.8, particles size of 5-15 mm, temperature of 35 ℃, spray intensity of 15 L/（h·m2）, and strain consortium C3.

The Mechanism of Structural Control of Ore Formation and Geochemical Characteristics in the Massive Sulfide Deposits of the Wushan Copper Ore Field,Jiangxi

The ore-controlling mechanism of the bedding fault system in the massive sulfide deposits of the Wushancopper orefield may be generalized as the control of ore deposition by optimum surface in an ore-formingstructural trap. The mechanism has three major features: (1) timing of mineralization; (2) positioning of hostformation; and (3) dependence of ore-controlling structure on properties of rocks. The 'optimum surface' is adivisional structural plane which marks obvious difference in physical, chemical and mechanical properties andis favorable for mineralization. It is also a unity of structures. lithofacies and orebodies. The structural and geochemical characteristics of the ore deposits indicate the migration trend of the ma-jor characteristic clements in the ore-controlling fault belt: elements with a small radius (Si, Fe, Mg and Al)moved towards and concentrated at the center of the belt while large-radius ones (Ca, K and Na) were remotefrom the center.

Mild-temperature Synthesis of Covellite Copper Sulfide Hexagonal Nanoplatelets via the Hydrothermal Route

Covellite CuS hexagonal nanoplatelets were prepared by a simple hydrothermal process at mild temperature, using sodium dodecyl benzene sulfonate （SDBS） as an assisting reagent. The products were characterized by X-ray powder diffraction （XRD）, transmission electron microscopy （TEM） and UV-vis absorption spectroscopy. An energy-dispersive X-ray spectrometer （EDS） was used to analyze the elementary compositions of the intermediate products. A possible formation mechanism of hexagonal nanoplatelets is discussed, using TEM observations.

L-Cysteine-assisted Synthesis of Copper Gallium Sulfide Microspheres

An effective L-cysteine-assisted synthetic route has been successfully developed to prepare copper gallium sulfide（CuGaS2） microspheres under solvothermal conditions with CuCI2.2HzO, GaC13 and L-cysteine as source materials, in which L-cysteine was used as the sulfide source and complexing molecule. The experiments revealed that the synthesized sample was of a typical CuGaS2 tetragonal structure. Moreover, the prepared CuGaS2 crystals consisting of microspheres made up of nanoflakes, and the diameter of the nanoflakes was about 20 nm. Raman spectrum of the obtained CuGaS2 exhibits a high-intensity peak of the A1 mode at 306 cm^-1. Meanwhile, a possible growth mechanism was proposed based on the investigations.

Influence of copper on quality of hot strips by EAF-CSP process

Electron microscopy and X-ray Energy Dispersive Spectroscopy (XEDS) study oninfluence of Cu on low carbon hot strips produced by CSP (Compact Strip Production) process has beencarried out. The results indicated that copper segregation and enrichment at interfacial layerbetween oxidized surface and steel matrix is the key factor, which results in microcracks and edgeflaws on the strips. The primary considerations to prevent detrimental effects from Cu includecontrolling copper content in proper level, higher soaking temperature and non-oxidizable atmosphereduring soaking. Copper sulfide precipitates with nanometers in size were observed, they may bebeneficial to the properties of CSP products, and influence of Cu on quality of CSP hot strips isdiscussed.

Isothermal precipitation behavior of copper sulfide in ultra low carbon steel

Copper and sulfur are typical residual elements or impurity elements in steel.Sufficient removal of them during steelmaking process is difficult for copper and costly for sulfur.Utilization of copper and sulfur in steel, especially in steel scrap,has been an important issue for a long period for metallurgists.Copper and sulfur may combine to form copper sulfide,which may provide a prospect to avoid the detrimental effects of copper and sulfur in steel.Unfortunately the formation mechanism of copper sulfide in steel has not been completely clarified so far. In the present paper,solution treatment of samples containing copper and sulfur are firstly performed at 1623 K for 2.7×10~3 s followed by quenching into water.The samples are then isothermally heat-treated at 673 K,873 K, 1073 K,1273 K and 1373K for different time followed by quenching into water again.The size,morphology, constituent and crystallography of sulfide precipitates in these samples are investigated by scanning electron microscope(SEM) and TEM equipped with EDS.Fine copper sulfides(less than 100 nm) are observed to coexist with silicon oxide in samples even isothermally heat-treated at 1 373 K for 1.44×10~4 s;Film-like copper sulfides are generally observed to co-exist with iron sulfide in all samples;Plate-like copper sulfides are observed especially in sample isothermally heat-treated at 1 073 K for 1.44×10~4 s.The formation mechanisms of these copper sulfides have been discussed.

Precise phase adjustment and antibacterial property of copper sulfide particles in confined mesoporous silica nanoreactor

Bacteria-caused wound infection greatly threatens human health,thus developing an efficient and safe antibacterial agent without drug resistance is still a great challenge.Herein,a confined vulcanization strategy is proposed to construct copper sulfides-loaded dual-mesoporous silica nanospheres(Cux-Sy@DMSNs)with various crystal phases for reactive oxygen species(ROS)-mediated and photothermal antibacterial application.With the pore confinement of DMSNs,the crystal phases of copper sulfides including CuS,Cu_(9)S_(5)and Cui.96S can be easily controlled by changing the vulcanization temperature.The relationships between the crystal phases and photothermal properties as well as peroxidase-like activity of copper sulfides were systematically investigated.Results show that the obtained CuS@DMSNs exhibited higher photothermal ability with remarkable photothermal conversion efficiency of 36.86%in the second near-infrared region(NIR-II)and better peroxidase-like activity,compared to those of Cu_(9)S_(5)@DMSNs and Cu_(1.96)S@DMSNs.As a result,the in vitro experiments showed the good antibacterial effect against both gram-negative E.coli and gram-positive S.aureus under 1064 nm laser irradiation and the presence of H_(2)O_(2).Besides,the CCK-8 assay indicated that CuS@p-DMSNs have minimal cytotoxicity against normal human umbilical vein endothelial cells at the ranged concentrations.Therefore,the resultant CuS@p-DMSNs could act as a promising antibacterial agent for deep wound bacterial infection treatment.

Combination losartan with hyaluronic acid modified diethyldithiocarbamate loaded hollow copper sulfide nanoparticles for the treatment of breast cancer and metastasis

The application of photothermal therapy(PTT)is greatly limited by the low accumulation of photothermal agents,uneven photothermal distribution,and heat endurance of cancer cells.Worse still,despite PTT enhances immunogenicity,the anti-tumor immune efficacy is still unsatisfactory due to the inefficient immunogenic cell death(ICD)induction and poor infiltration of immune cells.To solve the above problems of PTT,we developed hyaluronic acid(HA)modified hollow copper sulfide nanoparticles encapsulating diethyldithiocarbamate(DDTC)to construct a breast tumor targeting and near infrared(NIR)photo-responsive drug delivery system(D-HCuS@HA),which further combined with losartan to improve the accumulation and penetration in the tumor site.Upon irradiation,D-HCuS@HA realized enhanced PTT and released cytotoxic Cu(DDTC)_(2)to eliminate heat endurance tumor cells,thereby enhancing antitumor effect and inducing effective ICD.Moreover,the combination with losartan could remodel the tumor microenvironment,allowing more T cells to infiltrate into the tumor,and significantly inhibiting the occurrence and development of metastatic tumors.In vitro/vivo results revealed the great potential of D-HCuS@HA combined with losartan,which provides a new paradigm for anti-tumor and anti-metastases.