To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Por...To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Portland cement(PO 42.5)with wet-ground electrolytic manganese residue(WEMR),wetground granulated blast-furnace slag(WGBFS),and carbide slag(CS).The mechanical properties,hydration characteristics,microstructure,and carbon emissions of the material were systematically investigated with varying WEMR dosages.The experimental results demonstrates that the wet-grinding process significantly refines the particle size and enhances the reactivity of both EMR and GBFS.As the WEMR dosage increases,the 28-day compressive strength initially rise and then declines.Optimal mechanical performance was achieved with 24%WEMR and 6%CS,yielding a 28-day compressive strength of 48.2 MPa.Advanced analytical techniques,including XRD,TG-DTG,SEM,and MIP,were employed to examine the hydration products.The findings reveal that the wet-grinding-alkali-sulfur synergistic activation system in the multi-solid waste cementitious material effectively utilize EMR to generate abundant hydration products such as AFt and C-(A)-S-H.Additionally,the fine particles of WEMR fill the pores in the mortar,further enhancing compressive strength.The cost and carbon emissions of this multifunctional system are only 65.97%and 46.9% of those of PO 42.5,respectively.This study provides a feasible approach for the efficient utilization of EMR,contributing to sustainable construction practices.展开更多
Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates wi...Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates with varying manganese concentrations(VL-cMn)were prepared through calcium,a calcium-manganese composite,and manganese-based roasting of vanadium slag(VS)to investigate the influence of manganese on vanadium precipitation behavior during hydrolysis precipitation(HP)and ammonium salt precipitation(AP),as well as the microscopic characteristics and purity of the resulting V_(2)O_(5) products.The results showed that increasing the pH mitigated the negative effects of Mn on the V precipitation rate during HP.However,as the manganese concentration increased from 5.69 to 15.38 g/L,the V precipitation rate gradually declined at higher temperatures and longer reaction times.The precipitates exhibited increased microstructural density,which might had contributed to the formation of Mn-bearing phases.Additionally,the average grain size of V_(2)O_(5) was reduced and the particles were increasingly agglomerated,leading to a 2.55%decrease in product purity.For AP,as manganese concentration increased,raising the pH counteracted the negative impact of Mn on the V precipitation rate and reduced the required amount of ammonium sulfate.Moreover,Mn was unevenly adsorbed on the surface of the precipitates.Although V_(2)O_(5) grains gradually shrank and became denser,there was no significant effect on the final product purity,which remained above 99.3%.In conclusion,roasting with added manganese salts influenced the hydrolysis of vanadium but had no significant effect on acidic ammonium salt precipitation.展开更多
In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding o...In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding of their underlying mechanisms.In this study,we systematically explored the evolution of anode electrochemical oscillations during manganese electrolysis and designed a square wave circuit to effectively suppress oscillations and dendrite growth while reducing energy consumption.A novel four-dimensional differential equation was introduced to explore the internal dynamic mechanisms of typical nonlinear behaviors.The experimental results showed that while the evolutionary patterns of current and potential oscillation signals were consistent,their waveform directions were opposite.The square wave current effectively suppressed both electrochemical oscillations and the growth of manganese dendrites.Furthermore,compared to direct current electrolysis,the square wave current improved the current efficiency by 3.6%and reduced the energy consumption by 0.32 kW·h·kg^(−1).展开更多
With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on...With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on the synthesis of porous Fe_(3)O_(4)/C composites that incorporate dielectric and magnetic loss mechanisms via the carbothermal reduction method and optimization of waste ratio to enhance EWA performance.The Fe_(3)O_(4)/C composites with 10wt%soybean residues(Fe_(3)O_(4)/C-10),demonstrated the best EWA performance,achieving the minimum reflection loss of−56.4 dB and a bandwidth of 2.14 GHz at a thickness of 2.23 mm.This enhanced EWA performance is primarily attributable to improved impedance matching and the synergistic effect between dielectric and magnetic losses.Furthermore,radar cross-sectional simulations confirmed the practical feasibility of the porous Fe_(3)O_(4)/C composites.This study proposes a viable strategy for utilizing soybean residue and electrolytic manganese residue,highlighting their potential applications in EWA.展开更多
Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial c...Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.展开更多
This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,u...This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.展开更多
In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidati...In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.展开更多
The elemental segregation,microstructure,and mechanical properties of thermo-mechanical control process(TMCP)treated high-manganese wear-resistant steel(HMWS)were experimentally investigated.Firstly,the initial elemen...The elemental segregation,microstructure,and mechanical properties of thermo-mechanical control process(TMCP)treated high-manganese wear-resistant steel(HMWS)were experimentally investigated.Firstly,the initial elemental segregation in the continuous casting slab of HMWS was characterized using the original position analysis.The results showed that the elemental segregation predominantly occurred near the quarter and the center regions of the slab.The homogenization of manganese(Mn)in the slab was not as obvious as that of other elements after the heating process.Subsequently,a series of hot-rolling tests were carried out on HMWS slab samples under different TMCP conditions,and the elemental segregation and microstructure of the TMCP-treated HMWS were investigated by microscopic analysis methods.The findings demonstrated that the segregations of carbon and silicon were effectively eliminated after the TMCP treatment,while Mn segregation presented a band-shaped arrangement and could be reduced at lower finishing rolling temperatures.The matrix phase of HMWS remained austenite regardless of the TMCP conditions,and the average size of austenite grains increased with the increasing finishing rolling temperature.Carbide particles were observed to form within austenite grains and even along grain boundaries at higher coiling temperatures.Finally,the mechanical tests were performed on the TMCP-treated HMWS at room temperature.The mechanical properties including tensile stress,yield stress,Charpy impact energy,and microhardness were discussed considering the effects of Mn segregation band,microstructure,and carbide precipitation.展开更多
With the boom in electric vehicles(EVs),there is an increasing demand for high-performance lithium-ion batteries.Lithium manganese iron phosphate(LMFP)has emerged as an enhanced variation of LiFePO4(LFP),offering an e...With the boom in electric vehicles(EVs),there is an increasing demand for high-performance lithium-ion batteries.Lithium manganese iron phosphate(LMFP)has emerged as an enhanced variation of LiFePO4(LFP),offering an energy density 10%–20%greater than that of LFP.Structural distortion caused by the Jahn–Teller effect decreases the capacity and voltage platform,thus restricting the commercialization of this material.Herein,ideas to overcome these challenges,including the crystal structure of LMFP and strategies to mitigate the Jahn–Teller distortion,are first explored.Then,the migration pathways of Li+during charging and discharging and the phase transition mechanisms that affect the material’s performance are discussed.Next,the optimal Mn:Fe ratio for achieving the desired performance is described.The influences of various synthesis and modification methods on the morphology and structure of LMFP are reviewed.Additionally,different modification techniques,such as doping and coating,to enhance the performance of LMFP are highlighted.Finally,an overview of the current state of research on the recycling and reuse of LMFP is provided.By addressing these key topics,this paper offers a theoretical foundation for the further development of LMFP,thus contributing to its eventual commercialization.展开更多
Manganese(Mn)has been characterized as an environmental pollutant.Excessive releases of Mn due to human activities have increased Mn levels in the environment over the years,posing a threat to human health and the env...Manganese(Mn)has been characterized as an environmental pollutant.Excessive releases of Mn due to human activities have increased Mn levels in the environment over the years,posing a threat to human health and the environment.Long-term exposure to high concentrations of Mn can induce neurotoxicity.Therefore,toxicological studies on Mn are of paramount importance.Mn induces oxidative stress through affecting the level of reactive oxygen species(ROS),and the overabundance of ROS further triggers ferroptosis.Additionally,Mn^(2+) was found to be a novel activator of the cyclic guanosine-adenosine synthase(cGAS)−stimulator of interferon genes(STING)pathway in the innateimmune system.Thus,we speculate thatMn exposuremay promote ROS production by activating the cGAS−STING pathway,which further induces oxidative stress and ferroptosis,and ultimately triggers Mn neurotoxicity.This review discusses the mechanism between Mn-induced oxidative stress and ferroptosis via activation of the cGAS−STING pathway,which may offer a prospective direction for future in-depth studies on the mechanism of Mn neurotoxicity.展开更多
High manganese steels(HMS),known for their exceptional strength-ductility balance,are increasingly utilized in dynamic loading applications.This review examines the effects of strain rate on their mechanical propertie...High manganese steels(HMS),known for their exceptional strength-ductility balance,are increasingly utilized in dynamic loading applications.This review examines the effects of strain rate on their mechanical properties and microstructural evolution,focusing on strain rate hardening,adiabatic heating softening,and dynamic strain aging(DSA).The influence of strain rate on yield strength,ultimate tensile strength,strain hardening,and ductility is discussed,highlighting both positive and negative sensitivities across different alloy compositions and strain rate regimes.The strain rate response of various deformation mechanisms,including deformation twinning,dislocation slip,and phase transformation,is examined alongside their influence on microstructural evolution,alloy design,and industrial applications.The intricate role of DSA is also analyzed,emphasizing its contribution to strain rate sensitivity.To optimize HMS for dynamic environments,future research should focus on advanced modeling and processing techniques,in-situ characterization methods,and a deeper understanding of thermally activated processes and stacking fault energy-controlled mechanisms.This review provides insights into strain rate effects,guiding alloy design,and technological advancements of the new HMS.展开更多
Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(...Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.展开更多
Original sedimentary manganese(Mn)deposits and supergene Mn ores are important Mn resources in China.However,the geochemical information from Chinese supergene Mn ores is scarce,and the relationship between sedimentar...Original sedimentary manganese(Mn)deposits and supergene Mn ores are important Mn resources in China.However,the geochemical information from Chinese supergene Mn ores is scarce,and the relationship between sedimentary Mn deposits and supergene Mn ores is ambiguous.In this study,we collected the original Mn-bearing dolomitic sandstones(ZK20-3 drillcore)and supergene Mn ores(Longmen Section)from eastern Hebei,North China for systematic petrographic,mineralogical and geochemical analyses.Our new data help us to figure out the transformation from original Mn-bearing deposits to supergene ores.The main minerals of original Mn-bearing dolomitic sandstones are quartz and feldspar,with minor muscovite,dolomite,rhodochrosite,ankerite,and kutnohorite.Supergene Mn-oxide ores only emerged in the middle part of the Longmen(LM)Section,and mainly contain quartz,pyrolusite,cryptomelane,todorokite and occasional dolomite.The possible transformation sequence of Mn minerals is:kutnohorite/rhodochrosite→pyrolusite(Ⅰ)→cryptomelane(todorokite)→todorokite(cryptomelane)→pyrolusite(Ⅱ).For Mn-oxide ores,Fe,Na and Si are enriched but Al,Ca,Mg and K are depleted with the enrichment of Mn.For original and supergene ores,the total rare earth element+ytterbium(∑REY)contents range from 105.68×10^(-6)to 250.56×10^(-6)and from 18.08×10^(-6)to 176.60×10^(-6),respectively.Original Mn ores have similar slightly LREE-enriched patterns,but the purer Mn-oxide ore shows a HREE-enriched pattern.In the middle part of the LM Section,positive Ce anomalies in Mn-oxide ores indicate the precipitation of Ce-bearing minerals.It implies the existence of geochemical barriers,which changed p H and Eh values due to the long-time influence of groundwater.展开更多
A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vana...A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.展开更多
Objective:Osteoporosis is a systemic metabolic disease characterized by decreased bone mass,deterioration of bone microstructure,and increased fracture risk.Its occurrence is closely related to sex,age,and lifestyle f...Objective:Osteoporosis is a systemic metabolic disease characterized by decreased bone mass,deterioration of bone microstructure,and increased fracture risk.Its occurrence is closely related to sex,age,and lifestyle factors.Environmental exposure to heavy metals and metalloids may also influence its development,although existing findings remain inconsistent.The sex differences in the association between mixed metal exposure and osteoporosis are still unclear.This study aims to investigate whether sex differences exist in the associations between cadmium(Cd),lead(Pb),mercury(Hg),selenium(Se),manganese(Mn),and their mixtures and osteoporosis among men aged≥50 years and postmenopausal women,and to analyze the potential moderating effect of dairy product consumption on these associations.Methods:Data from the National Health and Nutrition Examination Survey(NHANES)2013−2014 and 2017−2018 cycles were used.In men and women separately,generalized linear regression models(univariate regression analysis and multivariate logistic regression)were applied to examine the relationships between single-metal exposure and osteoporosis at the femoral neck and vertebrae.A weighted quantile sum(WQS)model was used to construct a weighted index of mixed metal exposure to quantify the joint effects of multiple metals.Bayesian kernel machine regression(BKMR)was used to systematically evaluate the associations between blood Cd,Pb,Hg,Se,Mn,and their mixtures and osteoporosis at different skeletal sites,capturing potential nonlinear relationships and interactions among metals.Participants were further stratified into high dairy consumption(≥7 times/week)and low dairy consumption(<7 times/week)groups to explore the potential moderating effect of dairy consumption on the association between Cd exposure and osteoporosis.Results:Multivariate logistic regression analysis showed that,in the fully adjusted model,Cd was positively associated with femoral neck osteoporosis in men aged≥50 years[odds ratio(OR)=8.563,95%confidence interval(CI)1.888 to 38.845,P<0.05],whereas Se was negatively associated with femoral neck osteoporosis(OR<0.001,95%CI 0 to 0.150,P<0.05).In postmenopausal women,Cd was positively associated with femoral neck osteoporosis risk(OR=2.148,95%CI 1.038 to 4.443,P<0.05),while Se was negatively associated with femoral neck osteoporosis risk(OR=0.027,95%CI 0.001 to 0.986,P<0.05).No significant association was observed between any metal and vertebral osteoporosis(all P>0.05).The WQS model indicated that mixed metal exposure was positively associated with vertebral osteoporosis in men(OR=1.452,95%CI 0.277 to 2.626,P<0.05),whereas no significant association was observed in women.BKMR analysis showed that mixed metal exposure was positively associated with osteoporosis risk at the femoral neck and vertebrae in men,with Cd contributing most to osteoporosis risk,while no association was observed between mixed metal exposure and osteoporosis risk in women.The positive association between mixed blood metal exposure and osteoporosis risk might be partially offset by Se.In stratified analysis,the association between Cd exposure and osteoporosis was stronger in the high dairy consumption group(OR=1.19,95%CI 0.51 to 2.78,P>0.05)than in the low dairy consumption group(OR=3.12,95%CI 1.84 to 5.30,P<0.05),suggesting that frequent dairy consumption may attenuate the positive association between Cd exposure and femoral neck osteoporosis in women.Conclusion:In men aged≥50 years,mixed metal exposure was positively associated with osteoporosis risk at different skeletal sites(femoral neck and vertebra),with Cd contributing most to the risk.In postmenopausal women,no association between mixed metal exposure and osteoporosis risk was observed,indicating clear sex differences.Selenium and dairy consumption may be potential protective factors for osteoporosis in women,whereas such protective effects were not observed in men.展开更多
Calcium ions(Ca^(2+))and manganese ions(Mn^(2+))are essential for sustaining life activities and are key monitoring indicators in drinking water.Developing highly sensitive,selective,and portable detection methods for...Calcium ions(Ca^(2+))and manganese ions(Mn^(2+))are essential for sustaining life activities and are key monitoring indicators in drinking water.Developing highly sensitive,selective,and portable detection methods for Ca^(2+)and Mn^(2+)is significant for water quality monitoring and human health.In this paper,blue fluorescent Ti3C2 MXene-based quantum dots(MQDs,λ_(em)=445 nm)are prepared using Ti_(3)C_(2)MXene as the precursor.Through the chelation effect of ethylene diamine tetraacetic acid(EDTA),a blue and red dual-emission fluorescent probe,MQDs-EDTA-Eu^(3+)-DPA,was constructed.Herein,dipicolinic acid(DPA)acts as an absorbing ligand and significantly enhances the red fluorescence of europium ions(Eu^(3+))at 616 nm through the“antenna effect”.The blue fluorescence of MQDs serves as an internal reference signal.High concentrations of Ca^(2+)can quench the red fluorescence of Eu^(3+)-DPA;Mn^(2+)can be excited to emit purple fluorescence at 380 nm after coordinating with DPA,red fluorescence of Eu^(3+)-DPA serves as the internal reference signal.Based on the above two fluorescence intensity changes,ratiometric fluorescence detection methods for Ca^(2+)and Mn^(2+)are established.The fluorescence intensity ratio(IF_(616)/IF_(445))exhibits a linear relationship with Ca^(2+)in the range of 35-120μmol/L,with a detection limit of 5.98μmol/L.The fluorescence intensity ratio(IF_(380)/IF_(616))shows good linearity with Mn^(2+)in the range of 0-14μmol/L,with a detection limit of 28.6 nmol/L.This method was successfully applied to the quantitative analysis of Ca^(2+)and Mn^(2+)in commercially available mineral water(Nongfu Spring,Ganten,and Evergrande),with recovery rates of 80.6%-117%and relative standard deviations(RSD)of 0.76%-4.6%.Additionally,by preparing MQD-based fluorescent test strips,visual detections of Ca^(2+)and Mn^(2+)are achieved.This work demonstrates the application potential of MQDs in the field of visual fluorescence sensing of ions in water quality.展开更多
The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to ...The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.展开更多
Preparation of electronic grade manganese sulfate from ferromanganese slag, including grinding, leaching and purification, was studied. The impurities, such as Fe3+, Al3+, Ca2+, Mg2+, heavy metal ions and Na+, K+, wer...Preparation of electronic grade manganese sulfate from ferromanganese slag, including grinding, leaching and purification, was studied. The impurities, such as Fe3+, Al3+, Ca2+, Mg2+, heavy metal ions and Na+, K+, were removed from leaching solution by neutralized-hydrolysis, fluorination precipitation, sulfuration precipitation and re-crystallization. Effects of pH of reaction, temperature and dosage of the different additives on removal rates of the metallic ions in leaching solution were investigated, and the suitable temperature, pH and the added amount of precipitating agent were obtained. The prepared manganese sulfate product, of which the mass fractions of Ca2+, Mg2+, Na+, K+ are all smaller than 0.005%, the mass fractions of Fe3+, Al3+ and heavy metal ions are smaller than 0.001%, and the mass fraction of Mn2+ is greater than 32%, can meet the demand of anode materials of lithium-ion batteries.展开更多
Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen at...Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen atom. All the complexes were characterized by analytical and infrared data: for some of them single crystals were obtained, and their molecular structure was determined by X-ray diffraction. The complexes were used in association with methylaluminoxane(MAO) for the polymerization of 1,3-butadiene obtaining active and selective catalysts giving predominantly 1,2 polybutadiene in case of manganese catalysts and exclusively cis-1,4 polybutadiene in case of nickel catalysts.展开更多
By enhancing surface interaction between metal oxide particles and carbon-based materials,it can effectively improve Faraday capacitance and conductivity,ultimately achieving high energy density with sufficient redox ...By enhancing surface interaction between metal oxide particles and carbon-based materials,it can effectively improve Faraday capacitance and conductivity,ultimately achieving high energy density with sufficient redox reactions in supercapacitors.Through a gentle biomineralization process and subsequent thermal reduction strategy,we successfully prepared the graphene oxide(GO)wrapping mixed-valence manganese oxides(MnO_(x))and S,P self-codoped carbon matrix porous composite(MnO_(x)@SPC@reduced graphene oxide(RGO)).During the biomineralization process of engineered Pseudomonas sp.(Ml)cells,GO nanosheets functioned as the'soil'to adsorb Mn^(2+)ion and uniformly disperse biogenic Mn oxides(BMO).After undergoing annealing,the MnO_(x) nanoparticles were evenly wrapped with graphene,resulting in the creation of the MnO_(x)@SPC@RGO3 composite.This composite possesses strong C—O—Mn bond interfaces,numerous electroactive sites,and a uniform pore structure.By optimizing the synergistic interaction between the highly conductive graphene and the remarkable surface capacitance of MnO_(x),the MnO_(x)@SPC@RGO3 electrode,with its intercalation Faraday reactions mechanism of■transformations,exhibits an outstanding specific capacity(448.3 F·g^(-1)at 0.5 A·g^(-1)),multiplying performance(340.5 F·g^(-1)at10 A·g^(-1)),and cycling stability(93.8%retention after 5000 cycles).Moreover,the asymmetric all-solidstate supercapacitors of MnO_(x)@SPC@RGO3//PC exhibit an exceptional energy density of 64.8 W·h·kg^(-1)and power density of 350 W·kg^(-1),as well as a long lifespan with capacitance retention of 92.5%after10000 cycles.In conclusion,the synthetic route utilizing biomineralization and thermal reduction exhibits significant potential for exploiting high-performance electrode materials in all-solid-state supercapacitor applications.展开更多
基金Funded by the Guangxi Key Research and Development Program(Nos.GK AB24010020,and GK AB23026071)the Key Project of Guangxi Natural Science Foundation(No.2025GXNSFDA090046)the Guangxi Science and Technology Base and Talent Special Project(No.GK AD24010062)。
文摘To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Portland cement(PO 42.5)with wet-ground electrolytic manganese residue(WEMR),wetground granulated blast-furnace slag(WGBFS),and carbide slag(CS).The mechanical properties,hydration characteristics,microstructure,and carbon emissions of the material were systematically investigated with varying WEMR dosages.The experimental results demonstrates that the wet-grinding process significantly refines the particle size and enhances the reactivity of both EMR and GBFS.As the WEMR dosage increases,the 28-day compressive strength initially rise and then declines.Optimal mechanical performance was achieved with 24%WEMR and 6%CS,yielding a 28-day compressive strength of 48.2 MPa.Advanced analytical techniques,including XRD,TG-DTG,SEM,and MIP,were employed to examine the hydration products.The findings reveal that the wet-grinding-alkali-sulfur synergistic activation system in the multi-solid waste cementitious material effectively utilize EMR to generate abundant hydration products such as AFt and C-(A)-S-H.Additionally,the fine particles of WEMR fill the pores in the mortar,further enhancing compressive strength.The cost and carbon emissions of this multifunctional system are only 65.97%and 46.9% of those of PO 42.5,respectively.This study provides a feasible approach for the efficient utilization of EMR,contributing to sustainable construction practices.
基金supported by National Natural Science Foundation of China(Nos.52204309,52174277 and 52374300)Fundamental Funds for the Central Universities(No.N2425026)。
文摘Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates with varying manganese concentrations(VL-cMn)were prepared through calcium,a calcium-manganese composite,and manganese-based roasting of vanadium slag(VS)to investigate the influence of manganese on vanadium precipitation behavior during hydrolysis precipitation(HP)and ammonium salt precipitation(AP),as well as the microscopic characteristics and purity of the resulting V_(2)O_(5) products.The results showed that increasing the pH mitigated the negative effects of Mn on the V precipitation rate during HP.However,as the manganese concentration increased from 5.69 to 15.38 g/L,the V precipitation rate gradually declined at higher temperatures and longer reaction times.The precipitates exhibited increased microstructural density,which might had contributed to the formation of Mn-bearing phases.Additionally,the average grain size of V_(2)O_(5) was reduced and the particles were increasingly agglomerated,leading to a 2.55%decrease in product purity.For AP,as manganese concentration increased,raising the pH counteracted the negative impact of Mn on the V precipitation rate and reduced the required amount of ammonium sulfate.Moreover,Mn was unevenly adsorbed on the surface of the precipitates.Although V_(2)O_(5) grains gradually shrank and became denser,there was no significant effect on the final product purity,which remained above 99.3%.In conclusion,roasting with added manganese salts influenced the hydrolysis of vanadium but had no significant effect on acidic ammonium salt precipitation.
基金support from the Fundamental Research Funds for the Central Universities(2022CDJQY-005,2024CDJXY010)the Guangxi Science and Technology Program(AB24010229)is greatly acknowledged.
文摘In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding of their underlying mechanisms.In this study,we systematically explored the evolution of anode electrochemical oscillations during manganese electrolysis and designed a square wave circuit to effectively suppress oscillations and dendrite growth while reducing energy consumption.A novel four-dimensional differential equation was introduced to explore the internal dynamic mechanisms of typical nonlinear behaviors.The experimental results showed that while the evolutionary patterns of current and potential oscillation signals were consistent,their waveform directions were opposite.The square wave current effectively suppressed both electrochemical oscillations and the growth of manganese dendrites.Furthermore,compared to direct current electrolysis,the square wave current improved the current efficiency by 3.6%and reduced the energy consumption by 0.32 kW·h·kg^(−1).
基金supported by the National Natural Science Foundation of China(No.52471221)the Natural Science Foundation of Hunan Province,China(No.2024JJ7145)the National Sustainable Development Agenda Innovation Demonstration Zone Hunan special project,China(No.2022sfq09).
文摘With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on the synthesis of porous Fe_(3)O_(4)/C composites that incorporate dielectric and magnetic loss mechanisms via the carbothermal reduction method and optimization of waste ratio to enhance EWA performance.The Fe_(3)O_(4)/C composites with 10wt%soybean residues(Fe_(3)O_(4)/C-10),demonstrated the best EWA performance,achieving the minimum reflection loss of−56.4 dB and a bandwidth of 2.14 GHz at a thickness of 2.23 mm.This enhanced EWA performance is primarily attributable to improved impedance matching and the synergistic effect between dielectric and magnetic losses.Furthermore,radar cross-sectional simulations confirmed the practical feasibility of the porous Fe_(3)O_(4)/C composites.This study proposes a viable strategy for utilizing soybean residue and electrolytic manganese residue,highlighting their potential applications in EWA.
基金financially supported by the Ten-thousand Talents Programthe K. C. Wong Pioneer Talent Program+3 种基金China Three Gorges Corporation (WWKY-2021–0027)Inner Mongolia Science and Technology Plan (2021ZD0033)the National Natural Science Foundation of China (52202121)funded by China Petroleum&Chemical Corporation (123091)
文摘Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.
基金Funded by the Guangxi Key Research and Development Program(Guike AB23026071 and Guike AB24010020)the Guangxi Science and Technology Base and Talent Project(Guike AD24010062)the Guangxi Beibu Gulf Engineering Research Center for Green Marine Materials。
文摘This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.
基金Project(2022M710619)supported by the Postdoctoral Science Foundation of ChinaProjects(2020YFH0213,2020YFG0039)supported by the Sichuan Science and Technology Program,China+1 种基金Projects(XJ2024001501,KCXTD2023-4)supported by the Basic Scientific Foundation and Innovation Team Funds of China West Normal UniversityProject(CSPC202403)supported by the Open Project Program of Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province,China。
文摘In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.
基金support for this research provided by the High-end Foreign Experts Recruitment Plan of China(Grant No.G2022105011L).
文摘The elemental segregation,microstructure,and mechanical properties of thermo-mechanical control process(TMCP)treated high-manganese wear-resistant steel(HMWS)were experimentally investigated.Firstly,the initial elemental segregation in the continuous casting slab of HMWS was characterized using the original position analysis.The results showed that the elemental segregation predominantly occurred near the quarter and the center regions of the slab.The homogenization of manganese(Mn)in the slab was not as obvious as that of other elements after the heating process.Subsequently,a series of hot-rolling tests were carried out on HMWS slab samples under different TMCP conditions,and the elemental segregation and microstructure of the TMCP-treated HMWS were investigated by microscopic analysis methods.The findings demonstrated that the segregations of carbon and silicon were effectively eliminated after the TMCP treatment,while Mn segregation presented a band-shaped arrangement and could be reduced at lower finishing rolling temperatures.The matrix phase of HMWS remained austenite regardless of the TMCP conditions,and the average size of austenite grains increased with the increasing finishing rolling temperature.Carbide particles were observed to form within austenite grains and even along grain boundaries at higher coiling temperatures.Finally,the mechanical tests were performed on the TMCP-treated HMWS at room temperature.The mechanical properties including tensile stress,yield stress,Charpy impact energy,and microhardness were discussed considering the effects of Mn segregation band,microstructure,and carbide precipitation.
基金supported by National Natural Science Foundation of China(Grant Nos.52302293 and 22272110)Innovation Project of Education Department of Guangdong Province(Grant No.2023KTSCX124)+2 种基金Shenzhen Science and Technology Program(Grant No.KJZD2023092311460401)Guangdong Higher Education Letter(Grant No.[2024]No.30)Shenzhen Key Laboratory of Applied Technologies of Super-Diamond and Functional Crystals(Grant No.ZDSYS20230626091303007).
文摘With the boom in electric vehicles(EVs),there is an increasing demand for high-performance lithium-ion batteries.Lithium manganese iron phosphate(LMFP)has emerged as an enhanced variation of LiFePO4(LFP),offering an energy density 10%–20%greater than that of LFP.Structural distortion caused by the Jahn–Teller effect decreases the capacity and voltage platform,thus restricting the commercialization of this material.Herein,ideas to overcome these challenges,including the crystal structure of LMFP and strategies to mitigate the Jahn–Teller distortion,are first explored.Then,the migration pathways of Li+during charging and discharging and the phase transition mechanisms that affect the material’s performance are discussed.Next,the optimal Mn:Fe ratio for achieving the desired performance is described.The influences of various synthesis and modification methods on the morphology and structure of LMFP are reviewed.Additionally,different modification techniques,such as doping and coating,to enhance the performance of LMFP are highlighted.Finally,an overview of the current state of research on the recycling and reuse of LMFP is provided.By addressing these key topics,this paper offers a theoretical foundation for the further development of LMFP,thus contributing to its eventual commercialization.
基金supported by Lanzhou Youth Science and Technology Talent Innovation Project(No.2023-QN-60)the Startup Fund for the Construction of the Double First-Class Project,Lanzhou University,China(No.561121203)+2 种基金the National Natural Science Foundation of China(No.31802256)the Medical Innovation and Development Project of Lanzhou University(No.lzuyxcx-2022-196)the Science Fund for Distinguished Young Scholars of Gansu Province(No.20JR5RA579).
文摘Manganese(Mn)has been characterized as an environmental pollutant.Excessive releases of Mn due to human activities have increased Mn levels in the environment over the years,posing a threat to human health and the environment.Long-term exposure to high concentrations of Mn can induce neurotoxicity.Therefore,toxicological studies on Mn are of paramount importance.Mn induces oxidative stress through affecting the level of reactive oxygen species(ROS),and the overabundance of ROS further triggers ferroptosis.Additionally,Mn^(2+) was found to be a novel activator of the cyclic guanosine-adenosine synthase(cGAS)−stimulator of interferon genes(STING)pathway in the innateimmune system.Thus,we speculate thatMn exposuremay promote ROS production by activating the cGAS−STING pathway,which further induces oxidative stress and ferroptosis,and ultimately triggers Mn neurotoxicity.This review discusses the mechanism between Mn-induced oxidative stress and ferroptosis via activation of the cGAS−STING pathway,which may offer a prospective direction for future in-depth studies on the mechanism of Mn neurotoxicity.
基金supported by the National Natural Science Foundation(No.52101128)the Jiangsu Provincial Key Research and Development Program(No.BE023059)+1 种基金Postdoctoral Science Foundation(No.2022M710021)the Northeastern University Postdoctoral Research Fund(No.20220202)of China。
文摘High manganese steels(HMS),known for their exceptional strength-ductility balance,are increasingly utilized in dynamic loading applications.This review examines the effects of strain rate on their mechanical properties and microstructural evolution,focusing on strain rate hardening,adiabatic heating softening,and dynamic strain aging(DSA).The influence of strain rate on yield strength,ultimate tensile strength,strain hardening,and ductility is discussed,highlighting both positive and negative sensitivities across different alloy compositions and strain rate regimes.The strain rate response of various deformation mechanisms,including deformation twinning,dislocation slip,and phase transformation,is examined alongside their influence on microstructural evolution,alloy design,and industrial applications.The intricate role of DSA is also analyzed,emphasizing its contribution to strain rate sensitivity.To optimize HMS for dynamic environments,future research should focus on advanced modeling and processing techniques,in-situ characterization methods,and a deeper understanding of thermally activated processes and stacking fault energy-controlled mechanisms.This review provides insights into strain rate effects,guiding alloy design,and technological advancements of the new HMS.
基金supported by the National Natural Science Foundation of China(No.22278041)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K78)+1 种基金Jiangsu Province Key Laboratory of Fine Petrochemical Engineering(No.KF2107)the Advanced Catalysis and Green Manufacturing Collab-orative Innovation Center(No.ACGM2022-10-07)。
文摘Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.
基金supported by the National Key R&D Program of China(No.2022YFF0800200)the NSFC(Nos.U1812402 and 42072131)+6 种基金Most Special Fund(No.MSFGPMR33)from the State Key Laboratory of GPMRthe CUG Scholar Scientific Research Funds(No.2022036)the NSF of Hebei Province(No.D2021334001)Research Project of Talent Engineering Training of Hebei Province(No.B2020005007)Research Project of Postdoctoral Scientific Research Station of HBGMR(No.454-0602-YBN-Z9E4)Natural Science Foundation of Hebei Province(No.D2021334001)the Central Government Guides Local Funds for Scientific and Technological Development(No.236Z7608 G)。
文摘Original sedimentary manganese(Mn)deposits and supergene Mn ores are important Mn resources in China.However,the geochemical information from Chinese supergene Mn ores is scarce,and the relationship between sedimentary Mn deposits and supergene Mn ores is ambiguous.In this study,we collected the original Mn-bearing dolomitic sandstones(ZK20-3 drillcore)and supergene Mn ores(Longmen Section)from eastern Hebei,North China for systematic petrographic,mineralogical and geochemical analyses.Our new data help us to figure out the transformation from original Mn-bearing deposits to supergene ores.The main minerals of original Mn-bearing dolomitic sandstones are quartz and feldspar,with minor muscovite,dolomite,rhodochrosite,ankerite,and kutnohorite.Supergene Mn-oxide ores only emerged in the middle part of the Longmen(LM)Section,and mainly contain quartz,pyrolusite,cryptomelane,todorokite and occasional dolomite.The possible transformation sequence of Mn minerals is:kutnohorite/rhodochrosite→pyrolusite(Ⅰ)→cryptomelane(todorokite)→todorokite(cryptomelane)→pyrolusite(Ⅱ).For Mn-oxide ores,Fe,Na and Si are enriched but Al,Ca,Mg and K are depleted with the enrichment of Mn.For original and supergene ores,the total rare earth element+ytterbium(∑REY)contents range from 105.68×10^(-6)to 250.56×10^(-6)and from 18.08×10^(-6)to 176.60×10^(-6),respectively.Original Mn ores have similar slightly LREE-enriched patterns,but the purer Mn-oxide ore shows a HREE-enriched pattern.In the middle part of the LM Section,positive Ce anomalies in Mn-oxide ores indicate the precipitation of Ce-bearing minerals.It implies the existence of geochemical barriers,which changed p H and Eh values due to the long-time influence of groundwater.
基金finally supported by the National Natural Science Foundation of China (Nos.52204309,52174277,52374300)。
文摘A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.
基金supported by the Science and Technology Innovation Program of Hunan Province(2025RC3061)the Natural Science Foundation of Hunan Province(2022JJ30828)+2 种基金the Grants from Hunan Provincial Clinical Medicine Research Center for Intelligent Management of Chronic Disease(2023SK4042)the Innovation Foundation For Postgraduate of Hunan Province(CX20240310)the Postgraduate Innovative Project of Central South University(2023XQLH183),China。
文摘Objective:Osteoporosis is a systemic metabolic disease characterized by decreased bone mass,deterioration of bone microstructure,and increased fracture risk.Its occurrence is closely related to sex,age,and lifestyle factors.Environmental exposure to heavy metals and metalloids may also influence its development,although existing findings remain inconsistent.The sex differences in the association between mixed metal exposure and osteoporosis are still unclear.This study aims to investigate whether sex differences exist in the associations between cadmium(Cd),lead(Pb),mercury(Hg),selenium(Se),manganese(Mn),and their mixtures and osteoporosis among men aged≥50 years and postmenopausal women,and to analyze the potential moderating effect of dairy product consumption on these associations.Methods:Data from the National Health and Nutrition Examination Survey(NHANES)2013−2014 and 2017−2018 cycles were used.In men and women separately,generalized linear regression models(univariate regression analysis and multivariate logistic regression)were applied to examine the relationships between single-metal exposure and osteoporosis at the femoral neck and vertebrae.A weighted quantile sum(WQS)model was used to construct a weighted index of mixed metal exposure to quantify the joint effects of multiple metals.Bayesian kernel machine regression(BKMR)was used to systematically evaluate the associations between blood Cd,Pb,Hg,Se,Mn,and their mixtures and osteoporosis at different skeletal sites,capturing potential nonlinear relationships and interactions among metals.Participants were further stratified into high dairy consumption(≥7 times/week)and low dairy consumption(<7 times/week)groups to explore the potential moderating effect of dairy consumption on the association between Cd exposure and osteoporosis.Results:Multivariate logistic regression analysis showed that,in the fully adjusted model,Cd was positively associated with femoral neck osteoporosis in men aged≥50 years[odds ratio(OR)=8.563,95%confidence interval(CI)1.888 to 38.845,P<0.05],whereas Se was negatively associated with femoral neck osteoporosis(OR<0.001,95%CI 0 to 0.150,P<0.05).In postmenopausal women,Cd was positively associated with femoral neck osteoporosis risk(OR=2.148,95%CI 1.038 to 4.443,P<0.05),while Se was negatively associated with femoral neck osteoporosis risk(OR=0.027,95%CI 0.001 to 0.986,P<0.05).No significant association was observed between any metal and vertebral osteoporosis(all P>0.05).The WQS model indicated that mixed metal exposure was positively associated with vertebral osteoporosis in men(OR=1.452,95%CI 0.277 to 2.626,P<0.05),whereas no significant association was observed in women.BKMR analysis showed that mixed metal exposure was positively associated with osteoporosis risk at the femoral neck and vertebrae in men,with Cd contributing most to osteoporosis risk,while no association was observed between mixed metal exposure and osteoporosis risk in women.The positive association between mixed blood metal exposure and osteoporosis risk might be partially offset by Se.In stratified analysis,the association between Cd exposure and osteoporosis was stronger in the high dairy consumption group(OR=1.19,95%CI 0.51 to 2.78,P>0.05)than in the low dairy consumption group(OR=3.12,95%CI 1.84 to 5.30,P<0.05),suggesting that frequent dairy consumption may attenuate the positive association between Cd exposure and femoral neck osteoporosis in women.Conclusion:In men aged≥50 years,mixed metal exposure was positively associated with osteoporosis risk at different skeletal sites(femoral neck and vertebra),with Cd contributing most to the risk.In postmenopausal women,no association between mixed metal exposure and osteoporosis risk was observed,indicating clear sex differences.Selenium and dairy consumption may be potential protective factors for osteoporosis in women,whereas such protective effects were not observed in men.
基金The Tertiary Education Scientific Research Project of the Guangzhou Municipal Education Bureau(2024312227)Innovative and Entrepreneurial Projects of Guangzhou University Students(202411078014)+2 种基金Guangzhou University Open Sharing Fund for Instruments and Equipment(2025)National Major Scientific Research Instrument Development Project(22227804)Sub-subject of the National Key Research Project(2023YFB3210100)。
文摘Calcium ions(Ca^(2+))and manganese ions(Mn^(2+))are essential for sustaining life activities and are key monitoring indicators in drinking water.Developing highly sensitive,selective,and portable detection methods for Ca^(2+)and Mn^(2+)is significant for water quality monitoring and human health.In this paper,blue fluorescent Ti3C2 MXene-based quantum dots(MQDs,λ_(em)=445 nm)are prepared using Ti_(3)C_(2)MXene as the precursor.Through the chelation effect of ethylene diamine tetraacetic acid(EDTA),a blue and red dual-emission fluorescent probe,MQDs-EDTA-Eu^(3+)-DPA,was constructed.Herein,dipicolinic acid(DPA)acts as an absorbing ligand and significantly enhances the red fluorescence of europium ions(Eu^(3+))at 616 nm through the“antenna effect”.The blue fluorescence of MQDs serves as an internal reference signal.High concentrations of Ca^(2+)can quench the red fluorescence of Eu^(3+)-DPA;Mn^(2+)can be excited to emit purple fluorescence at 380 nm after coordinating with DPA,red fluorescence of Eu^(3+)-DPA serves as the internal reference signal.Based on the above two fluorescence intensity changes,ratiometric fluorescence detection methods for Ca^(2+)and Mn^(2+)are established.The fluorescence intensity ratio(IF_(616)/IF_(445))exhibits a linear relationship with Ca^(2+)in the range of 35-120μmol/L,with a detection limit of 5.98μmol/L.The fluorescence intensity ratio(IF_(380)/IF_(616))shows good linearity with Mn^(2+)in the range of 0-14μmol/L,with a detection limit of 28.6 nmol/L.This method was successfully applied to the quantitative analysis of Ca^(2+)and Mn^(2+)in commercially available mineral water(Nongfu Spring,Ganten,and Evergrande),with recovery rates of 80.6%-117%and relative standard deviations(RSD)of 0.76%-4.6%.Additionally,by preparing MQD-based fluorescent test strips,visual detections of Ca^(2+)and Mn^(2+)are achieved.This work demonstrates the application potential of MQDs in the field of visual fluorescence sensing of ions in water quality.
基金Project(21376273)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Key Program of Science and Technology of Hunan Province,China
文摘The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.
基金Project(2013ZX0754-001)supported by China National Critical Project for Science and Technology on Water Pollution Prevention and Control
文摘Preparation of electronic grade manganese sulfate from ferromanganese slag, including grinding, leaching and purification, was studied. The impurities, such as Fe3+, Al3+, Ca2+, Mg2+, heavy metal ions and Na+, K+, were removed from leaching solution by neutralized-hydrolysis, fluorination precipitation, sulfuration precipitation and re-crystallization. Effects of pH of reaction, temperature and dosage of the different additives on removal rates of the metallic ions in leaching solution were investigated, and the suitable temperature, pH and the added amount of precipitating agent were obtained. The prepared manganese sulfate product, of which the mass fractions of Ca2+, Mg2+, Na+, K+ are all smaller than 0.005%, the mass fractions of Fe3+, Al3+ and heavy metal ions are smaller than 0.001%, and the mass fraction of Mn2+ is greater than 32%, can meet the demand of anode materials of lithium-ion batteries.
文摘Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen atom. All the complexes were characterized by analytical and infrared data: for some of them single crystals were obtained, and their molecular structure was determined by X-ray diffraction. The complexes were used in association with methylaluminoxane(MAO) for the polymerization of 1,3-butadiene obtaining active and selective catalysts giving predominantly 1,2 polybutadiene in case of manganese catalysts and exclusively cis-1,4 polybutadiene in case of nickel catalysts.
基金supported by the National Natural Science Foundation of China(31900005)the Fund of Science and Technology Department of Henan Province(242102231001,242102320362,242102320157)+1 种基金the Fund of Program for Innovative Research Team(in Science and Technology)in University of Henan Province(23IRTSTHN009)Fund of Key Scientific Research Projects of Higher Education Institutions in Henan Province(22A150048)。
文摘By enhancing surface interaction between metal oxide particles and carbon-based materials,it can effectively improve Faraday capacitance and conductivity,ultimately achieving high energy density with sufficient redox reactions in supercapacitors.Through a gentle biomineralization process and subsequent thermal reduction strategy,we successfully prepared the graphene oxide(GO)wrapping mixed-valence manganese oxides(MnO_(x))and S,P self-codoped carbon matrix porous composite(MnO_(x)@SPC@reduced graphene oxide(RGO)).During the biomineralization process of engineered Pseudomonas sp.(Ml)cells,GO nanosheets functioned as the'soil'to adsorb Mn^(2+)ion and uniformly disperse biogenic Mn oxides(BMO).After undergoing annealing,the MnO_(x) nanoparticles were evenly wrapped with graphene,resulting in the creation of the MnO_(x)@SPC@RGO3 composite.This composite possesses strong C—O—Mn bond interfaces,numerous electroactive sites,and a uniform pore structure.By optimizing the synergistic interaction between the highly conductive graphene and the remarkable surface capacitance of MnO_(x),the MnO_(x)@SPC@RGO3 electrode,with its intercalation Faraday reactions mechanism of■transformations,exhibits an outstanding specific capacity(448.3 F·g^(-1)at 0.5 A·g^(-1)),multiplying performance(340.5 F·g^(-1)at10 A·g^(-1)),and cycling stability(93.8%retention after 5000 cycles).Moreover,the asymmetric all-solidstate supercapacitors of MnO_(x)@SPC@RGO3//PC exhibit an exceptional energy density of 64.8 W·h·kg^(-1)and power density of 350 W·kg^(-1),as well as a long lifespan with capacitance retention of 92.5%after10000 cycles.In conclusion,the synthetic route utilizing biomineralization and thermal reduction exhibits significant potential for exploiting high-performance electrode materials in all-solid-state supercapacitor applications.
