Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Extraction and recycling technologies of cobalt from primary and secondary resources:A comprehensive review

Cobalt has excellent electrochemical,magnetic,and heat properties.As a strategic resource,it has been applied in many hightech products.However,the recent rapid growth of the battery industry has substantially depleted cobalt resources,leading to a crisis of cobalt resource supply.The paper examines cobalt ore reserves and distribution,and the recent development and consumption of cobalt resources are summarized as well.In addition,the principles,advantages and disadvantages,and research status of various methods are discussed comprehensively.It can be concluded that the use of diverse sources(Cu-Co ores,Ni-Co ores,zinc plant residues,and waste cobalt products)for cobalt production should be enhanced to meet developmental requirements.Furthermore,in recovery technology,the pyro-hydrometallurgical process employs pyrometallurgy as the pretreatment to modify the phase structure of cobalt minerals,enhancing its recovery in the hydrometallurgical stage and facilitating high-purity cobalt production.Consequently,it represents a promising technology for future cobalt recovery.Lastly,based on the above conclusions,the prospects for cobalt are assessed regarding cobalt ore processing and sustainable cobalt recycling,for which further study should be conducted.

Infrared thermography for prediction of spontaneous combustion of sulfide ores

The method of infrared thermography to predict the temperature of the sulfide ores has a large error. To solve this problem, the temperature of the sulfide ores is measured by thermal infrared imager and recording thermometric instrument contrastively. The main factors, including emissivity, distance, angle and dust concentration that affect the temperature measurement precision, are analyzed. The regression equations about the individual factors and comprehensive factors are obtained by analyzing test data. The application of the regression equations improves the precision of the thermal infrared imager. The geometric information lost in traditional infrared thermometry is determined by visualization grid method and interpolation method, the relationship between the infrared imager and geometry information is established. The geometry location can be measured exactly.

Leaching of nickel-molybdenum sulfide ore in membrane biological reactor

The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that the concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity of Mo to microorganism is decreased in the process of bioleaching.It was also evidenced that there were different leaching rates of Ni and Mo when the concentration of Mo was different.After leaching for 20 d in the MBR at Mo concentration of 395 mg/L,the leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively under the conditions of 100 g/L of mineral density,65 ℃,pH=2 and 1.0 L/min of the aeration rate.While 75.59% Ni and 54.33% Mo were leached out in column without membrane under the same conditions.

Self-heating tendency evaluation of sulfide ores based on nonlinear multi-parameters fusion

In order to reveal the nonlinear dynamics characteristics of unsteady self-heating process of sulfide ores, nine different kinds of sulfide ore samples from a pyrite mine in China were taken as experimental materials and their self-heating characteristics were measured in laboratory. Furthermore, the measured temperature was studied by integrating wavelet transform, nonlinear characteristic parameters extraction and fuzzy comprehensive evaluation. The results indicate that only the ore samples 1, 2, 6 and 9 have obvious self-heating phenomenon, and their self-heating initiative temperatures are 220 ℃, 239 ℃, 220 ℃ and 220 ℃, respectively, which means that they are difficult to produce self-heating under normal mining conditions. The correlation dimension of self-heating process is fraction and the maximum Lyapunov exponent is positive, which means that it is feasible to study the self-heating process based on chaotic dynamics theory. The nonlinearities of self-heating process of these four samples （ore samples 1, 2, 6 and 9） are 0.8227, 0.7521, 0.9401 and 0.8827 respectively and the order of the samples according to these results is： sample 6, sample 9, sample 1, sample 2, which is consistent with the measured results of self-heating characteristics. Therefore, the nonlinearity method can be used to evaluate the self-heating tendency of sulfide ores, and it is an effective verification of the reliability of measured results.

Graphitic Carbon Quantum Dots Modified Nickel Cobalt Sulfide as Cathode Materials for Alkaline Aqueous Batteries

Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.

REE Geochemistry of Sulfides from the Huize Zn-Pb Ore Field, Yunnan Province: Implication for the Sources of Ore-forming Metals

REE abundances in sulfides from the Huize Zn-Pb ore field were determined with the ICPMS after preconcentration. The REE abundances in 26 sulfide samples （including pyrite, galena and sphalerite） are very low, with the ~REE ranging from 1.6×10^-9 to 166.8×10^-9. Their LREE/HREE ratios range from 7.6 to 98, showing LREE enrichment relatively. The JEu values are below 1, indicating that they were deposited from an Eu-depleted and reducing fluid-system. Similar to the ore-hosting carbonate strata, calcite separates from carbonate veinlets filling in the fractures or faults crosscutting the carbonate strata also show clear Eu-depletion. This indicates that the carbonate veinlets and their parent fluid was possibly sourced from the strata and inherited the REE geochemical features of the strata. Therefore, REE-geochemical characteristics of both the sulfides and calcites, which were deposited from an ore-forming hydrothermal system, are similar to those of carbonate strata, and strongly suggest that the ore metals were mainly sourced from carbonate strata.

In-situ growth of vertically aligned nickel cobalt sulfide nanowires on carbon nanotube fibers for high capacitance all-solid-state asymmetric fiber-supercapacitors

Fiber-supercapacitors(FSCs)are promising power sources for miniature portable and wearable electronic devices.However,the development and practical application of these FSCs have been severely hindered by their low volumetric capacitance and narrow operating voltage.In this work,vertically aligned nickel cobalt sulfide(Ni Co2S4)nanowires grown on carbon nanotube(CNT)fibers were achieved through an in-situ two-step hydrothermal reaction method.The as-prepared Ni Co2S4@CNT fiber electrode exhibits a high volumetric capacitance of 2332 F cm-3,benefiting from its superior electric conductivity,large surface area,and rich Faradic redox reaction sites.Furthermore,a Ni Co2S4@CNT//VN@CNT(vanadium nitride nanosheets grown on CNT fibers)asymmetric fiber-supercapacitor(AFSC)was successfully fabricated.The device exhibits an operating voltage up to 1.6 V and a high volumetric energy density of 30.64m Wh cm-3.The device also possesses outstanding flexibility as evidenced by no obvious performance degradation under various bending angles and maintaining high capacitance after 5000 bending cycles.This work promotes the practical application of flexible wearable energy-storage devices.

Cobalt Sulfide Confined in N-Doped Porous Branched Carbon Nanotubes for Lithium-Ion Batteries

Lithium-ion batteries(LIBs) are considered new generation of large-scale energy-storage devices.However,LIBs suffer from a lack of desirable anode materials with excellent specific capacity and cycling stability.In this work,we design a novel hierarchical structure constructed by encapsulating cobalt sulfide nanowires within nitrogen-doped porous branched carbon nanotubes(NBNTs)for LIBs.The unique hierarchical Co9S8@NBNT electrode displayed a reversible specific capacity of 1310 mAhg-1 at a current density of 0.1 Ag-1,and was able to maintain a stable reversible discharge capacity of 1109 mAhg-1 at a current density of 0.5 Ag-1 with coulombic efficiency reaching almost 100% for 200 cycles.The excellent rate and cycling capabilities can be ascribed to the hierarchical porosity of the one-dimensional Co9S8@NBNT internetworks,the incorporation of nitrogen doping,and the carbon nanotube confinement of the active cobalt sulfide nanowires offering a proximate electron pathway for the isolated nanoparticles and shielding of the cobalt sulfide nanowires from pulverization over long cycling periods.

Synthesis of 3D Hexagram-Like Cobalt–Manganese Sulfides Nanosheets Grown on Nickel Foam: A Bifunctional Electrocatalyst for Overall Water Splitting

The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt–manganese sulfide supported on Ni foam(CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co_9S_8 and Mn S, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that ofthe pure Co_9S_8/Ni and Mn S/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a twoelectrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.

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.

Locating method of fire source for spontaneous combustion of sulfide ores

in order to achieve a more efficient way to accurately detect the position of the fire source of spontaneous combustion underground mine, a simple fire source locating method, based on infrared scanning system which can determine the point where the highest temperature on the surface of igniting ores occurs, was proposed. First, the differential equations that describe heat flow in ore body were presented and the relationship between the surface temperature distribution and the depth and intensity of inner fire source was established with a relatively simple heat transfer model. With the solution of equation, the expression of the relationship between the surface temperature distribution and the inner fire source was deduced and the mathematical-physical model of heat transfer process was set up. Then, with the model, visualization of fire source on the basis of MATLAB simulation platform was realized. The results show that： 1） within 10 m, when the detecting depth is less than 2 m, the temperature perturbation on ores surface can change rapidly, and then slowly; after 4 m, in contrast, it changes very little, and is even close to zero at 10 m; 2） When it is close to self-ignition duration and the detective depths are 2, 5 and 10 m, respectively, the maximum temperature differences are correspondingly 0.5, 0.04 and 0.005 ℃ in the scope of 1 m×1 m; under the same condition, the maximum temperature differences are 1.391, 0.136 and 0.018 ℃, respectively, in the scope of 2 m×2 m. Therefore, this system can be used to measure the temperature differences on the surface of ore body and determine the highest temperature point directly. Also, it is possible to determine the depth of fire source and its intensity by locating method of fire source indirectly.

Ore Genesis of the Kalatongke Cu-Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.

Investigation of chemical suppressants for inactivation of sulfideores

In order to investigate the effective control method of sp ontaneous com bustion in the mining of sulfide ore deposits. This paper presents the testing r esults of several selected chemicals (water glass, calcium chloride, calcium oxi de, magnesium oxide and their composites) as oxidation suppressants for sulfide ores. A weight increment scaling method was used to measure suppressant performa nce, and this method proved to be accurate, simple and convenient. Based on a large number of experiments, the test results show that four types of chemical mixtures demonstrate a good performance in reducing the oxidation rate of seven active sulfide ore samples by up to 27% to 100% during an initial 76 d period. T he mixtures of water glass mixed with calcium chloride and magnesium oxide mixed with calcium chloride can also act as fire suppressants when used with fire spr inkling systems.

Evaluation of spontaneous combustion tendency of sulfide ore heap based on nonlinear parameters

To explore a new evaluation method for spontaneous combustion tendency of different areas in sulfide ore heap, ore samples from a pyrite mine in China were taken as experimental materials, and the temperature variations of the measuring points of simulated ore heap were measured. Combined with wavelet transform and nonlinear parameters extraction, a new method for spontaneous combustion tendency of different areas in sulfide ore heap based on nonlinear parameters was proposed and its reliability was verified by field test. The results indicate that temperature field evolution of the simulated ore heap presents significant spatial difference during self-heating process. Area with the maximum increasing extent of temperature in sulfide ore heap changes notably with the proceeding of self-heating reaction. Self-heating of sulfide ore heap is a chaotic evolution process, which means that it is feasible to evaluate spontaneous combustion tendency of different areas by nonlinear analysis method. There is a relatively strong correlation between the maximum Lyapunov exponent and spontaneous combustion tendency with the correlation coefficient of 0.9792. Furthermore, the sort of the maximum Lyapunov exponent is consistent with that of spontaneous combustion tendency. Therefore, spontaneous combustion tendency of different areas in sulfide ore heap can be evaluated by means of the maximum Lyapunov exponent method.

Bioleaching of complex polymetallic sulfide ores by mixed culture

Bacterial leaching of single sulfide minerals and polymetallic sulfide ores was operated in shake flasks and small-scaled columns.The results show that bioleaching of jamesonite is not accessible,the iron extraction rate of pyrrhotite bioleaching reaches 98.2% after 26 d,and the zinc extraction rate of marmatite bioleaching reaches 92.3%,while the corresponding iron extraction reaches only 13.6% after 29 d.Pulp density has a significant effect on metal extraction of pyrrhotite and marmatite bioleaching.The corresponding metal extraction rate decreases with the increase of pulp density.For the polymetallic sulfide ores,zinc extraction of 97.1% is achieved after bioleaching in shake flasks for 10 d,while only 7.8% is obtained after bioleaching in small-scaled column.Analytical results of scanning electron microscopy(SEM) and energy dispersive X-ray analysis(EDX) reveal that large amount of calcium sulfate is formed on the mineral surface.

Mechanism of Mg2+ dissolution from olivine and serpentine: Implication for bioleaching of high-magnesium nickel sulfide ore at elevated pH

To inhibit the dissolution of Mg^2+ during the bioleaching process of high-magnesium nickel sulfide ore, the effect of major bioleaching factors on the dissolution of Mg^2+ from olivine and serpentine was investigated and kinetics studies were carried out. The results indicated that the dissolution rate-controlling steps are chemical reaction for olivine and internal diffusion for serpentine. The most influential factor on the dissolution of Mg^2+ from olivine and serpentine was temperature, followed by p H and particle size. A novel method of bioleaching at elevated pH was used in the bioleaching of Jinchuan ore. The results showed that elevated pH could significantly reduce the dissolution of Mg^2+ and acid consumption along with slightly influencing the leaching efficiencies of nickel and cobalt. A model was used to explain the leaching behaviors of high-magnesium nickel sulfide ore in different bioleaching systems. The model suggested that olivine will be depleted eventually, whereas serpentine will remain because of the difference in the rate-controlling steps. Bioleaching at elevated pH is a suitable method for treating high-magnesium nickel sulfide ores.

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.

Co-extraction of valuable metals and kinetics analysis in chlorination process of low-grade nickel-copper sulfide ore

To efficiently co-extract Ni and Cu from low-grade nickel-copper sulfide ore,chlorination roasting with NH;Cl followed by a water leaching process was investigated.The results show that 98.4%Ni and 98.5%Cu can be synchronously extracted when the ore particle size is 75-80μm,the roasting time is 2 h,the mass ratio of NH;Cl to ore is 1.6:1 and the roasting temperature is 550°C.The evolution behavior of various minerals was elucidated using X-ray diffraction(XRD)coupled with scanning electron microscopy(SEM).The kinetics of the chlorination process based on the differential thermal and thermogravimetric analysis(DTA-TG)data was analyzed by Kissinger method and Flynn-Wall-Ozawa(FWO)method.The chlorination process of low-grade nickel-copper sulfide ore mainly contains two stages:the decomposition of NH;Cl and the chlorination of ore.The maximum apparent activation energies(Ea)at two stages are determined to be 114.8 and 144.6 kJ/mol,respectively.The condensed product of exhaust gas is determined to be ammonium chloride,which can be recycled as the reactant again,making the process economic and clean.