Cobalt–copper based catalysts for higher terminal alcohols synthesis via Fischer–Tropsch reaction

The production of higher terminal alcohols through CO hydrogenation according to the Fischer–Tropsch(F–T) process has been a topic of interest since the Institut Fran?ais du Pétrole(IFP) demonstrated shortchain C_1–C_6mixed alcohols production over cobalt–copper based catalysts. A number of catalyst formulations were screened for their suitability at that time. In particular, the addition of Cr, Zn, Al, Mn and V to Co Cu was investigated. In a number of patents, it was shown that catalyst preparation is crucial in these catalyst formulations and that high alcohols selectivity can only be achieved by carefully respecting the procedures and recipes. This short critical review highlights recent developments in Co Cu-based catalysts for higher terminal alcohols synthesis via F–T synthesis. Special attention will be given to catalyst preparation which according to developments in our group is based on oxalate precipitation. This way we show that the close association of Co and Cu on the one hand and promoter/dispersant on the other are of utmost importance to ensure high performance of the catalysts. We shall concentrate on 'Co Cu Mn','Co Cu Mo' and 'Co Cu Nb' catalyst formulations, all prepared via oxalate precipitation and combined with'entrainment techniques' if necessary, and show high total alcohols selectivity can be obtained with tunable Anderson-Schulz-Flory chain-lengthening probability. Either long-chain C_8–C_(14)terminal alcohols as feedstock for plasticizers, lubricants and detergents, or short-chain C_2–C_5alcohols as 'alkanol' fuels or fuel additives can be formed this way.

A core-shell copper oxides-cobalt oxides heterostructure nanowire arrays for nitrate reduction to ammonia with high yield rate

Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.

Copper Metabolism and Cuproptosis:Molecular Mechanisms and Therapeutic Perspectives in Neurodegenerative Diseases

Copper is an essential trace element,and plays a vital role in numerous physiological processes within the human body.During normal metabolism,the human body maintains copper homeostasis.Copper deficiency or excess can adversely affect cellular function.Therefore,copper homeostasis is stringently regulated.Recent studies suggest that copper can trigger a specific form of cell death,namely,cuproptosis,which is triggered by excessive levels of intracellular copper.Cuproptosis induces the aggregation of mitochondrial lipoylated proteins,and the loss of iron-sulfur cluster proteins.In neurodegenerative diseases,the pathogenesis and progression of neurological disorders are linked to copper homeostasis.This review summarizes the advances in copper homeostasis and cuproptosis in the nervous system and neurodegenerative diseases.This offers research perspectives that provide new insights into the targeted treatment of neurodegenerative diseases based on cuproptosis.

Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

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.

Editorial Commentary:Copper Homeostasis in Neurodegenerative Diseases

Copper,as an essential trace nutrient,plays a crucial role in biological processes such as mitochondrial respiration,antioxidant stress response,and the synthesis of biomolecules.Typically,cellular copper concentrations are maintained at very low levels,a pattern also observed in cancer cells to prevent adverse consequences of copper overload,such as cuproptosis.This involves copper dependency,accumulation of lipidated proteins,and a reduction in Fe-S cluster proteins[1].Various neurodegenerative diseases are associated with imbalances in copper homeostasis.

Detection of Al, Mg, Ca, and Zn in copper slag by LIBS combined with calibration curve and PLSR methods

The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was utilized for the spectral analysis of copper slag samples at a distance of 2.5 m. The composition of copper slag was then analyzed using both the calibration curve(CC) method and the partial least squares regression(PLSR) analysis method based on the characteristic spectral intensity ratio. The performance of the two analysis methods was gauged through the determination coefficient(R^(2)), average relative error(ARE), root mean square error of calibration(RMSEC), and root mean square error of prediction(RMSEP). The results demonstrate that the PLSR method significantly improved both R^(2) for the calibration and test sets while reducing ARE, RMSEC, and RMSEP by 50% compared to the CC method. The results suggest that the combination of LIBS and PLSR is a viable approach for effectively detecting the elemental concentration in copper slag and holds potential for online detection of the elemental composition of high-temperature molten copper slag.

Interphase migration and enrichment of lead and zinc during copper slag depletion

An interphase migration and enrichment model of lead and zinc during molten copper slag depletion was established.The occurrence of various components in copper slag was predicted using sulfur-oxygen potential calculations and confirmed through high-temperature experiments.The recovery rate of copper can reach 90.13%under the optimal conditions of 1200°C,an iron to silicon mass ratio of 1.0,3 wt.%ferrous sulfide,and a duration of 45 min.Lead(54.07 wt.%)and zinc(17.42 wt.%)are found in the flue dust as lead sulfate,lead sulfide,and zinc oxide,while copper matte contains lead(14.44 wt.%)and zinc sulfide(1.29 wt.%).The remaining lead and zinc are encapsulated as oxides within the fayalite phase.

The component-activity interrelationship of cobalt-based bifunctional electrocatalysts for overall water splitting:Strategies and performance

Cobalt-based electrocatalysts take advantage of potentially harmonizable microstructure and flexible coupling effects compared to commercial noble metal-based catalytic materials.However,conventional water electrolysis systems based on cobalt-based monofunctional hydrogen evolution reaction(HER)or oxygen evolution reaction(OER)catalysts have certain shortcomings in terms of resource utilization and universality.In contrast,cobalt-based bifunctional catalysts(CBCs)have attracted much attention in recent years for overall water splitting systems because of their practicality and reduced preparation cost of electrolyzer.This review aims to address the latest development in CBCs for total hydrolysis.The main modification strategies of CBCs are systematically classified in water electrolysis to provide an overview of how to regulate their morphology and electronic configuration.Then,the catalytic performance of CBCs in total-hydrolysis is summarized according to the types of cobalt-based phosphides,sulfides and oxides,and the mechanism of strengthened electrocatalytic ability is emphasized through combining experiments and theoretical calculations.Future efforts are finally suggested to focus on exploring the dynamic conversion of reaction intermediates and building near-industrial CBCs,designing advanced CBC materials through micro-modulation,and addressing commercial applications.

Structural and magnetic properties of micropolycrystalline cobalt thin films fabricated by direct current magnetron sputtering

Pure cobalt(Co)thin films were fabricated by direct current magnetron sputtering,and the effects of sputtering power and pres-sure on the microstructure and electromagnetic properties of the films were investigated.As the sputtering power increases from 15 to 60 W,the Co thin films transition from an amorphous to a polycrystalline state,accompanied by an increase in the intercrystal pore width.Simultaneously,the resistivity decreases from 276 to 99μΩ·cm,coercivity increases from 162 to 293 Oe,and in-plane magnetic aniso-tropy disappears.As the sputtering pressure decreases from 1.6 to 0.2 Pa,grain size significantly increases,resistivity significantly de-creases,and the coercivity significantly increases(from 67 to 280 Oe),which can be attributed to the increase in defect width.Corres-pondingly,a quantitative model for the coercivity of Co thin films was formulated.The polycrystalline films sputtered under pressures of 0.2 and 0.4 Pa exhibit significant in-plane magnetic anisotropy,which is primarily attributable to increased microstress.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

MOF-Derived Iron-Cobalt Phosphide Nanoframe as Bifunctional Electrocatalysts for Overall Water Splitting

Transition metal phosphides(TMPs)have emerged as an alternative to precious metals as efficient and low-cost catalysts for water electrolysis.Elemental doping and morphology control are effective approaches to further improve the performance of TMPs.Herein,Fe-doped CoP nanoframes(Fe-CoP NFs)with specific open cage configuration were designed and synthesized.The unique nano-framework structured Fe-CoP material shows overpotentials of only 255 and 122 mV at 10 mA cm^(−2)for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER),respectively,overwhelming most transition metal phosphides.For overall water splitting,the cell voltage is 1.65 V for Fe-CoP NFs at a current density of 10 mA cm^(−2),much superior to what is observed for the classical nanocubic structures.Fe-CoP NFs show no activity degradation up to 100 h which contrasts sharply with the rapidly decaying performance of noble metal catalyst reference.The superior electrocatalytic performance of Fe-CoP NFs due to abundant accessible active sites,reduced kinetic energy barrier,and preferable*O-containing intermediate adsorption is demonstrated through experimental observations and theoretical calculations.Our findings could provide a potential method for the preparation of multifunctional material with hollow structures and offer more hopeful prospects for obtaining efficient earth-abundant catalysts for water splitting.

High-Voltage and Fast-Charging Lithium Cobalt Oxide Cathodes: From Key Challenges and Strategies to Future Perspectives

Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.

Modification,application and expansion of electrode materials based on cobalt telluride

Metal(Li,Na,K,Al)-ion batteries and lithium-sulfur and lithium-tellurium batteries are gaining recognition for their eco-friendly characteristics,substantial energy density,and sustainable attributes.However,the overall performance of rechargeable batteries heavily depends on their electrode materials.Transition metal tellurides have recently gained significant attention due to their high electrical conductivity and density.Cobalt telluride has received the most extensive research due to its catalytic activity,unique magnetic properties,and diverse composition and crystal structure.Nevertheless,its limited conductivity and significant volume variation contribute to electrode structural deterioration and rapid capacity decline.This review comprehensively summarizes recent advances in rational design and synthesis of modified cobalt telluride-based electrodes,encompassing defect engineering(Te vacancies,cation vacancies,heterointerfaces,and homogeneous interfaces)and composite engineering(derived carbon from precursors,carbon fibers,Mxene,graphene nanosheets,etc.).Particularly,the intricate evolution mechanisms of the conversion reaction process during cycling are elucidated.Furthermore,these modified strategies applied to other transitional metal tellurides,such as iron telluride,nickel telluride,zinc telluride,copper telluride,molybdenum telluride,etc.,are also thoroughly summarized.Additionally,their application extends to emerging aqueous zinc-ion batteries.Finally,potential challenges and prospects are discussed to further propel the development of transition metal tellurides electrode materials for next-generation rechargeable batteries.

Role of copper chelating agents: between old applications and new perspectives in neuroscience

The role of copper element has been an increasingly relevant topic in recent years in the fields of human and animal health, for both the study of new drugs and innovative food and feed supplements. This metal plays an important role in the central nervous system, where it is associated with glutamatergic signaling, and it is widely involved in inflammatory processes. Thus, diseases involving copper(Ⅱ) dyshomeostasis often have neurological symptoms, as exemplified by Alzheimer's and other diseases(such as Parkinson's and Wilson's diseases). Moreover, imbalanced copper ion concentrations have also been associated with diabetes and certain types of cancer, including glioma. In this paper, we propose a comprehensive overview of recent results that show the importance of these metal ions in several pathologies, mainly Alzheimer's disease, through the lens of the development and use of copper chelators as research compounds and potential therapeutics if included in multi-target hybrid drugs. Seeing how copper homeostasis is important for the well-being of animals as well as humans, we shortly describe the state of the art regarding the effects of copper and its chelators in agriculture, livestock rearing, and aquaculture, as ingredients for the formulation of feed supplements as well as to prevent the effects of pollution on animal productions.

OsMYB84,a transcriptional regulator of OsCOPT2 and OsHMA5,modulates copper uptake and transport and yield production in rice

Transcription factors regulating crop uptake and translocation of the micronutrient Cu have not been identified.We isolated a novel R2R3-MYB transcription factor,OsMYB84,and showed that it was a positive regulator involved in uptake and transport of Cu via activation of OsCOPT2 and OsHMA expression.OsMYB84 was highly expressed in roots and anthers and induced by Cu.Overexpression of OsMYB84 promoted uptake and root-to-shoot translocation of Cu in rice,facilitated Cu distribution into grain and increased grain yield.In contrast,mutation of OsMYB84 reduced Cu concentration in xylem sap.OsMYB84 bound to the promoter region of OsCOPT2 and OsHMA5 and upregulated their expression.OsCOPT2 mutants showed reduced uptake of Cu and OsHMA5 overexpression lines showed increased root-to-shoot translocation of Cu.

Purification of copper foils driven by single crystallization

High-purity copper(Cu) with excellent thermal and electrical conductivity, is crucial in modern technological applications, including heat exchangers, integrated circuits, and superconducting magnets. The current purification process is mainly based on the zone/electrolytic refining or anion exchange, however, which excessively relies on specific integrated equipment with ultra-high vacuum or chemical solution environment, and is also bothered by external contaminants and energy consumption. Here we report a simple approach to purify the Cu foils from 99.9%(3N) to 99.99%(4N) by a temperature-gradient thermal annealing technique, accompanied by the kinetic evolution of single crystallization of Cu.The success of purification mainly relies on(i) the segregation of elements with low effective distribution coefficient driven by grain-boundary movements and(ii) the high-temperature evaporation of elements with high saturated vapor pressure.The purified Cu foils display higher flexibility(elongation of 70%) and electrical conductivity(104% IACS) than that of the original commercial rolled Cu foils(elongation of 10%, electrical conductivity of ~ 100% IACS). Our results provide an effective strategy to optimize the as-produced metal medium, and therefore will facilitate the potential applications of Cu foils in precision electronic products and high-frequency printed circuit boards.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

A Multi-Stage Differential-Multifactorial Evolutionary Algorithm for Ingredient Optimization in the Copper Industry

Ingredient optimization plays a pivotal role in the copper industry,for which it is closely related to the concentrate utilization rate,stability of furnace conditions,and the quality of copper production.To acquire a practical ingredient plan,which should exhibit long duration time with sufficient utilization and feeding stability for real applications,an ingredient plan optimization model is proposed in this study to effectively guarantee continuous production and stable furnace conditions.To address the complex challenges posed by this integer programming model,including multiple coupling feeding stages,intricate constraints,and significant non-linearity,a multi-stage differential-multifactorial evolution algorithm is developed.In the proposed algorithm,the differential evolutionary(DE)algorithm is improved in three aspects to efficiently tackle challenges when optimizing the proposed model.First,unlike traditional time-consuming serial approaches,the multifactorial evolutionary algorithm is utilized to optimize multiple complex models contained in the population of evolutionary algorithm caused by the feeding stability in a parallel manner.Second,a repair algorithm is employed to adjust infeasible ingredient lists in a timely manner.In addition,a local search strategy taking feedback from the current optima and considering the different positions of global optimum is developed to avoiding premature convergence of the differential evolutionary algorithm.Finally,the simulation experiments considering different planning horizons using real data from the copper industry in China are conducted,which demonstrates the superiority of the proposed method on feeding duration and stability compared with other commonly deployed approaches.It is practically helpful for reducing material cost as well as increasing production profit for the copper industry.

Breaking the Fe_(3)O_(4)-wrapped copper microstructure to enhance copper-slag separation

The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of copper concentrates.Herein,the commercial powdery pyrite or anthracite is replaced with pyrite-anthracite pellets as the reductants to remove a large amount of Fe_(3)O_(4)particles in the molten slag,resulting in a deep fracture in the Fe_(3)O_(4)-wrapped copper microstructure and the full exposure of the copper matte cores.When 1wt%composite pellet is used as the reductant,the copper matte droplets are enlarged greatly from 25μm to a size observable by the naked eye,with the copper content being enriched remarkably from 1.2wt%to 4.5wt%.Density functional theory calculation results imply that the formation of the Fe_(3)O_(4)-wrapped copper structure is due to the preferential adhesion of Cu_(2)S on the Fe_(3)O_(4)particles.X-ray photoelectron spectroscopy,Fourier transform infrared spectrometer(FTIR),and Raman spectroscopy results all reveal that the high-efficiency conver-sion of Fe_(3)O_(4)to FeO can decrease the volume fraction of the solid phase and promote the depolymerization of silicate network structure.As a consequence,the settling of copper matte droplets is enhanced due to the lowered slag viscosity,contributing to the high efficiency of copper-slag separation for copper recovery.The results provide new insights into the enhanced in-situ enrichment of copper from mol-ten slag.