Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during t...Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.展开更多
Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials...Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.展开更多
The hot deformation behavior of a newly designed V micro-alloyed high manganese steel(HMnS)was investigated in order to guide the development of the hot-metal-gas-forming process.Single-pass hot compression experiment...The hot deformation behavior of a newly designed V micro-alloyed high manganese steel(HMnS)was investigated in order to guide the development of the hot-metal-gas-forming process.Single-pass hot compression experiments were conducted in the temperature range of 950–1100°C and the strain rate range of 0.05–10 s^(−1),and the stress–strain curves and the corresponding softening mechanism of the V micro-alloyed HMnS were analyzed.Results show that two types of stress–strain curves,representing the work hardening(WH)-dynamic recovery(DRV)-dynamic recrystallization(DRX)mechanism and the WH–DRV mechanism,respectively,occur during the deformation process.Moreover,the WH–DRV–DRX mechanism gradually transforms into the WH–DRV mechanism with the increasing strain rate and decreasing deformation temperature.Two types of constitutive models considering the softening mechanism difference were established and verified by additional hot-deformation experiments.Hot processing map of the HMnS was established and correlated well with the microstructure evolution result.Based on the constitutive models and processing map,the optimal processing parameter range and flow stress of HMnS for the hot-metal-gas-forming were determined.展开更多
The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of ...The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.展开更多
Manganese-catalyzed C—C bond cleavage of cyclobutanols has attracted great attention due to the high abundance and cheap and eco-friendly behaviour.A manganese-catalyzed ring-opening C—C bond fluorination of cyclobu...Manganese-catalyzed C—C bond cleavage of cyclobutanols has attracted great attention due to the high abundance and cheap and eco-friendly behaviour.A manganese-catalyzed ring-opening C—C bond fluorination of cyclobutanols is reported.Under mild conditions,the reaction provides a straightforward access to γ-fluorinated ketones using 10 mol% Mn(OAc)_(2) as catalyst and electrophilic fluorination reagent,which was generated in situ from HF·Et 3N and PhIO,as fluorine source.The reaction has an excellent functional-group tolerance and displays a broad substrate scope,affording the corresponding products in 50%~76%yields.展开更多
Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In thi...Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.展开更多
The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this ma...The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.展开更多
Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn ...Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.展开更多
Aqueous zinc-ion batteries(AZIBs)are regarded as promising electrochemical energy storage devices owing to its low cost,intrinsic safety,abundant zinc reserves,and ideal specific capacity.Compared with other cathode m...Aqueous zinc-ion batteries(AZIBs)are regarded as promising electrochemical energy storage devices owing to its low cost,intrinsic safety,abundant zinc reserves,and ideal specific capacity.Compared with other cathode materials,manganese dioxide with high voltage,environmental protection,and high theoretical specific capacity receives considerable attention.However,the problems of structural instability,manganese dissolution,and poor electrical conductivity make the exploration of high-performance manganese dioxide still a great challenge and impede its practical applications.Besides,zinc storage mechanisms involved are complex and somewhat controversial.To address these issues,tremendous efforts,such as surface engineering,heteroatoms doping,defect engineering,electrolyte modification,and some advanced characterization technologies,have been devoted to improving its electrochemical performance and illustrating zinc storage mechanism.In this review,we particularly focus on the classification of manganese dioxide based on crystal structures,zinc ions storage mechanisms,the existing challenges,and corresponding optimization strategies as well as structure-performance relationship.In the final section,the application perspectives of manganese oxide cathode materials in AZIBs are prospected.展开更多
The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen ene...The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen energy and mass-scale hydrogen production via water electrolysis,several obstacles,such as the multi-electron transfer OER process with sluggish kinetics and overall high reaction barrier,should be overcome.Manganese oxide-based(MnOx) materials,especially MnO_(2),have emerged as promising non-noble electrocatalysts for water electro-oxidation under acidic conditions due to their wellbalanced properties between catalytic activity and stability.This review introduces the fundamental understanding of the catalytic OER process on MnOx-based materials,including the conventional adsorbate evolution mechanism(AEM) and emerging lattice oxygen oxidation mechanism(LOM).The rational screening and prediction of MnOx-based catalysts that can stably catalyze OER in acid are summarized based on Pourbaix diagram analysis and thermodynamic density functional theory(DFT) calculations.Then,the up-to-date progress of upgrading the OER catalytic performance of MnOx-based catalysts by composite construction is reviewed.Afterward,feasible strategies to improve the electrocatalytic activity and lifetime of MnOx-based catalysts are systemically discussed in terms of crystal structure control,reasonable setting of working potential and electrolyte environment,optimal selection of acid-stable conductive supports,and self-healing engineering.Finally,future scientific challenges and research directions are outlined to guide the construction of advanced MnOx-based electrocatalysts for OER in acid.展开更多
Formaldehyde(HCHO)has been identified as one of the most common indoor pollutions nowadays.Manganese oxides(MnO_(x))are considered to be a promising catalytic material used in indoor HCHO oxidation removal due to thei...Formaldehyde(HCHO)has been identified as one of the most common indoor pollutions nowadays.Manganese oxides(MnO_(x))are considered to be a promising catalytic material used in indoor HCHO oxidation removal due to their high catalytic activity,low-cost,and environmentally friendly.In this paper,the progress in developing MnO_(x)-based catalysts for HCHO removal is comprehensively reviewed for exploring the mechanisms of catalytic oxidation and catalytic deactivation.The catalytic oxidation mechanisms based on three typical theory models(Mars-van-Krevelen,Eley-Rideal and Langmuir-Hinshelwood)are discussed and summarized.Furthermore,the research status of catalytic deactivation,catalysts’regeneration and integrated application of MnO_(x)-based catalysts for indoor HCHO removal are detailed in the review.Finally,the technical challenges in developing MnO_(x)-based catalysts for indoor HCHO removal are analyzed and the possible research direction is also proposed for overcoming the challenges toward practical application of such catalysts.展开更多
The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X...The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.展开更多
Alumina-magnesia dry materials are widely used in induction furnace linings, but they show different kinds of damage when melting different kinds of alloy steel. In this paper, the chemical composition, phase composit...Alumina-magnesia dry materials are widely used in induction furnace linings, but they show different kinds of damage when melting different kinds of alloy steel. In this paper, the chemical composition, phase composition, and microstructure of the post-use dry materials for the working liners melting different kinds of steel were evaluated. Furthermore, the corrosion mechanism of the steel on the furnace lining materials was comprehensively analyzed. The findings reveal a significant ability of the Mn element in the molten steel to diffuse and penetrate into the refractories. Mn oxidizes to form MnO at the steel-refractory interface, and then forms a liquid phase with Al_(2)O_(3). The Cr element is dissolved into corundum and spinel of the refractories, resulting in lattice defects and structural damage of the materials. TiO2reacts with Al_(2)O_(3) to form Al_(2)TiO_(5), which plays a crucial role in preventing crack formation and propagation. Part of Ti4+dissolves into magnesia-alumina(MA), densifying the materials. TiO2also slows down the reaction between the Cr element and refractory components, further improving the corrosion resistance of the materials.展开更多
Manganese-substituted magnetite ferrofluids(FFs)Mnx Fe_(1-x)Fe_(2)O_(4)(x=0–0.8)were prepared in this work through a chemical coprecipitation reaction.The controlled growth of FF nanomaterials for antibacterial activ...Manganese-substituted magnetite ferrofluids(FFs)Mnx Fe_(1-x)Fe_(2)O_(4)(x=0–0.8)were prepared in this work through a chemical coprecipitation reaction.The controlled growth of FF nanomaterials for antibacterial activities is challenging,and therefore,very few reports are available on the topic.This research focuses on stabilizing aqueous FFs with the tetramethylammonium hydroxide surfactant to achieve high homogeneity.Morphological characterization reveals nanoparticles of 5–11 nm formed by the chemical reaction and nanocrystalline nature,as evident from structural investigations.Mn-substituted magnetic FFs are analyzed for their structural,functional,and antibacterial performance according to the Mn-substituent content.Optical studies show a high blue shift for Mn^(2+)-substituted Mnx Fe_(1-x)Fe_(2)O_(4)with the theoretical correlation of optical band gaps with the Mn content.The superparamagnetic nature of substituted FFs causes zero coercivity and remanence,which consequently influence the particle size,cation distribution,and spin canting.The structural and functional performance of the FFs is correlated with the antibacterial activity,finally demonstrating the highest inhibition zone formation for Mnx Fe_(1-x)Fe_(2)O_(4)FFs.展开更多
High manganese steel has wide prospects in industry due to their excellent mechanical and damping properties. The quenching structures of high manganese steel are ε-martensite, γ-austenite and α'-martensite. Re...High manganese steel has wide prospects in industry due to their excellent mechanical and damping properties. The quenching structures of high manganese steel are ε-martensite, γ-austenite and α'-martensite. Researches show that the damping properties of high manganese steel are related to these microstructures. Besides, there are many ways to improve the damping property of damping alloys. This paper reviews the damping mechanism and the influences of the ad-dition of alloying elements, heat treatment, pre-deformation and other factors on their damping performance, hoping to provide methods and ideas for the study of damping properties of high manganese steel. .展开更多
Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesi...Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.展开更多
To explore how manganese affects the antioxidant system and the expression levels of related genes of“Hong yang”seedlings,the leaves of its tissue cultured seedlings were taken as test materials,and single factor tr...To explore how manganese affects the antioxidant system and the expression levels of related genes of“Hong yang”seedlings,the leaves of its tissue cultured seedlings were taken as test materials,and single factor treatment was performed by changing the manganese chloride(MnCl_(2)·4H_(2)O)solution concentration when spraying the leaves.The expression levels of Mn-SOD,POD64 and POD27 genes in leaves were quantitatively analyzed by real-time quantitative PCR(qRT-PCR)at different determination times.Meanwhile,the contents of malondial-dehyde(MDA),hydrogen peroxide(H_(2)O_(2)),the activities of antioxidant enzymes,including catalase(CAT),peroxidase(POD),and superoxide dismutase(SOD).The results showed that the SOD,CAT,POD,ascorbate peroxidase(APX),and reduced glutathione(GSH)activities in leaves were the highest at 12 h post-treatment with 50μM MnCl_(2)·4H_(2)O.Furthermore,the contents of MDA and H_(2)O_(2) in leaves also peaked when the concentration of H_(2)O_(2) is 50μM,which is the minimum value.Additionally at 50μM Mn^(2+),the Mn-SOD and POD27 expression was up-regulated as compared to the control,which promoted the expression of their respective enzyme activities.However,POD64 expression increased with the increasing Mn^(2+) concentration.Therefore,50μM is the optimal concentration of Mn when exogenously applied on“Hong yang”,which improve the antioxidant enzyme activity and regulate the plant’s physiological and biochemical functions.展开更多
基金funds from the National Natural Science Foundation of China(51772082 and 51804106)the Natural Science Foundation of Hunan Province(2023JJ10005)
文摘Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.
基金supported by the grants from the Chinese Academy of Sciences(124GJHZ2023031MI)the National Natural Science Foundation of China(52173274)+1 种基金the National Key R&D Project from the Ministry of Science and Technology(2021YFA1201603)the Fundamental Research Funds for the Central Universities.
文摘Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.
基金the National Natural Science Foundation of China(Grant Nos.52201101 and 52274372)the National Key R&D Program of China(2021YFB3702404)the Fundamental Research Funds for the Central Universities(FRF-TP-22-013A1).
文摘The hot deformation behavior of a newly designed V micro-alloyed high manganese steel(HMnS)was investigated in order to guide the development of the hot-metal-gas-forming process.Single-pass hot compression experiments were conducted in the temperature range of 950–1100°C and the strain rate range of 0.05–10 s^(−1),and the stress–strain curves and the corresponding softening mechanism of the V micro-alloyed HMnS were analyzed.Results show that two types of stress–strain curves,representing the work hardening(WH)-dynamic recovery(DRV)-dynamic recrystallization(DRX)mechanism and the WH–DRV mechanism,respectively,occur during the deformation process.Moreover,the WH–DRV–DRX mechanism gradually transforms into the WH–DRV mechanism with the increasing strain rate and decreasing deformation temperature.Two types of constitutive models considering the softening mechanism difference were established and verified by additional hot-deformation experiments.Hot processing map of the HMnS was established and correlated well with the microstructure evolution result.Based on the constitutive models and processing map,the optimal processing parameter range and flow stress of HMnS for the hot-metal-gas-forming were determined.
基金Funded by the National Natural Science Foundation of China(No.51864012)the Key Projects Supported by Science and Technology in Guizhou Province(No.[2002]KEY020)+2 种基金the Major Special Projects in Guizhou Province(No.[2022]003)the Guizhou Provincial Science Cooperation Program(Nos.[2016]5302,[2017]5788,[2018]5781,[2019]1411,and[2019]2841)the Major Special Projects in Tongren City,Guizhou Province(No.[2021]13)。
文摘The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.
基金Project supported by the National Natural Science Foundation of China(Nos.92156008,22161142016)the Taishan Scholar Program at Shandong Provincethe Natural Science Foundation of Shandong Province(No.ZR2020QB018)。
文摘Manganese-catalyzed C—C bond cleavage of cyclobutanols has attracted great attention due to the high abundance and cheap and eco-friendly behaviour.A manganese-catalyzed ring-opening C—C bond fluorination of cyclobutanols is reported.Under mild conditions,the reaction provides a straightforward access to γ-fluorinated ketones using 10 mol% Mn(OAc)_(2) as catalyst and electrophilic fluorination reagent,which was generated in situ from HF·Et 3N and PhIO,as fluorine source.The reaction has an excellent functional-group tolerance and displays a broad substrate scope,affording the corresponding products in 50%~76%yields.
基金supported by the Key Research and Development Program of Guangxi Province,China (No.AB23075174)the National Natural Science Foundation of China (No.52174386)the Science and Technology Plan Project of Sichuan Province,China (No.2022YFS0459).
文摘Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.
基金supported by Hebei Province Higher Education Science and Technology Research Project(No.ZC2024031).
文摘The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.
基金supported by the National Key Research and Development Program of China(2022YFE0206300)the National Natural Science Foundation of China(22209047,U21A2081,22075074)+2 种基金Natural Science Foundation of Hunan Province(2020JJ5035)Hunan Provincial Department of Education Outstanding Youth Project(23B0037)Macao Science and Technology Development Fund(Macao SAR,FDCT-0096/2020/A2).
文摘Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.
基金supported by the National Natural Science Foundation of China(22279101,5210130199)the Natural Science Basic Research Plan in Shaanxi Province of China(2022JM-090)+2 种基金China Postdoctoral Science Foundation(2021 M693885)Science and Technology Planning Project of Beilin District(GX2111)and Young Talents Supporting Project of Xi'an Science Association(095920221359).
文摘Aqueous zinc-ion batteries(AZIBs)are regarded as promising electrochemical energy storage devices owing to its low cost,intrinsic safety,abundant zinc reserves,and ideal specific capacity.Compared with other cathode materials,manganese dioxide with high voltage,environmental protection,and high theoretical specific capacity receives considerable attention.However,the problems of structural instability,manganese dissolution,and poor electrical conductivity make the exploration of high-performance manganese dioxide still a great challenge and impede its practical applications.Besides,zinc storage mechanisms involved are complex and somewhat controversial.To address these issues,tremendous efforts,such as surface engineering,heteroatoms doping,defect engineering,electrolyte modification,and some advanced characterization technologies,have been devoted to improving its electrochemical performance and illustrating zinc storage mechanism.In this review,we particularly focus on the classification of manganese dioxide based on crystal structures,zinc ions storage mechanisms,the existing challenges,and corresponding optimization strategies as well as structure-performance relationship.In the final section,the application perspectives of manganese oxide cathode materials in AZIBs are prospected.
基金the financial support of the National Natural Science Foundation of China(21962008)the Yunnan Province Excellent Youth Fund Project(202001AW070005)the Yunnan Ten Thousand Talents Plan Young & Elite Talents Project(YNWR-QNBJ-2018-346)。
文摘The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen energy and mass-scale hydrogen production via water electrolysis,several obstacles,such as the multi-electron transfer OER process with sluggish kinetics and overall high reaction barrier,should be overcome.Manganese oxide-based(MnOx) materials,especially MnO_(2),have emerged as promising non-noble electrocatalysts for water electro-oxidation under acidic conditions due to their wellbalanced properties between catalytic activity and stability.This review introduces the fundamental understanding of the catalytic OER process on MnOx-based materials,including the conventional adsorbate evolution mechanism(AEM) and emerging lattice oxygen oxidation mechanism(LOM).The rational screening and prediction of MnOx-based catalysts that can stably catalyze OER in acid are summarized based on Pourbaix diagram analysis and thermodynamic density functional theory(DFT) calculations.Then,the up-to-date progress of upgrading the OER catalytic performance of MnOx-based catalysts by composite construction is reviewed.Afterward,feasible strategies to improve the electrocatalytic activity and lifetime of MnOx-based catalysts are systemically discussed in terms of crystal structure control,reasonable setting of working potential and electrolyte environment,optimal selection of acid-stable conductive supports,and self-healing engineering.Finally,future scientific challenges and research directions are outlined to guide the construction of advanced MnOx-based electrocatalysts for OER in acid.
基金the National Natural Science Foundation of China (NSFC,52070006)BeijingNova Program of Science and Technology (Z191100001119116).
文摘Formaldehyde(HCHO)has been identified as one of the most common indoor pollutions nowadays.Manganese oxides(MnO_(x))are considered to be a promising catalytic material used in indoor HCHO oxidation removal due to their high catalytic activity,low-cost,and environmentally friendly.In this paper,the progress in developing MnO_(x)-based catalysts for HCHO removal is comprehensively reviewed for exploring the mechanisms of catalytic oxidation and catalytic deactivation.The catalytic oxidation mechanisms based on three typical theory models(Mars-van-Krevelen,Eley-Rideal and Langmuir-Hinshelwood)are discussed and summarized.Furthermore,the research status of catalytic deactivation,catalysts’regeneration and integrated application of MnO_(x)-based catalysts for indoor HCHO removal are detailed in the review.Finally,the technical challenges in developing MnO_(x)-based catalysts for indoor HCHO removal are analyzed and the possible research direction is also proposed for overcoming the challenges toward practical application of such catalysts.
基金financially supported by (i) Suranaree University of Technology,(ii) Thailand Science Research and Innovation,and (iii) National Science,Research and Innovation Fund(project codes 90464 and 160363)。
文摘The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.
基金the National Natural Science Foundation of China(52272022)Key Program of Natural Science Foundation of Hubei Province(2021CFA071).
文摘Alumina-magnesia dry materials are widely used in induction furnace linings, but they show different kinds of damage when melting different kinds of alloy steel. In this paper, the chemical composition, phase composition, and microstructure of the post-use dry materials for the working liners melting different kinds of steel were evaluated. Furthermore, the corrosion mechanism of the steel on the furnace lining materials was comprehensively analyzed. The findings reveal a significant ability of the Mn element in the molten steel to diffuse and penetrate into the refractories. Mn oxidizes to form MnO at the steel-refractory interface, and then forms a liquid phase with Al_(2)O_(3). The Cr element is dissolved into corundum and spinel of the refractories, resulting in lattice defects and structural damage of the materials. TiO2reacts with Al_(2)O_(3) to form Al_(2)TiO_(5), which plays a crucial role in preventing crack formation and propagation. Part of Ti4+dissolves into magnesia-alumina(MA), densifying the materials. TiO2also slows down the reaction between the Cr element and refractory components, further improving the corrosion resistance of the materials.
基金the financial assistance provided by the Indian Council of Medical Research in the form of a research associate (No.5/3/8/95/ITR F/2020)。
文摘Manganese-substituted magnetite ferrofluids(FFs)Mnx Fe_(1-x)Fe_(2)O_(4)(x=0–0.8)were prepared in this work through a chemical coprecipitation reaction.The controlled growth of FF nanomaterials for antibacterial activities is challenging,and therefore,very few reports are available on the topic.This research focuses on stabilizing aqueous FFs with the tetramethylammonium hydroxide surfactant to achieve high homogeneity.Morphological characterization reveals nanoparticles of 5–11 nm formed by the chemical reaction and nanocrystalline nature,as evident from structural investigations.Mn-substituted magnetic FFs are analyzed for their structural,functional,and antibacterial performance according to the Mn-substituent content.Optical studies show a high blue shift for Mn^(2+)-substituted Mnx Fe_(1-x)Fe_(2)O_(4)with the theoretical correlation of optical band gaps with the Mn content.The superparamagnetic nature of substituted FFs causes zero coercivity and remanence,which consequently influence the particle size,cation distribution,and spin canting.The structural and functional performance of the FFs is correlated with the antibacterial activity,finally demonstrating the highest inhibition zone formation for Mnx Fe_(1-x)Fe_(2)O_(4)FFs.
文摘High manganese steel has wide prospects in industry due to their excellent mechanical and damping properties. The quenching structures of high manganese steel are ε-martensite, γ-austenite and α'-martensite. Researches show that the damping properties of high manganese steel are related to these microstructures. Besides, there are many ways to improve the damping property of damping alloys. This paper reviews the damping mechanism and the influences of the ad-dition of alloying elements, heat treatment, pre-deformation and other factors on their damping performance, hoping to provide methods and ideas for the study of damping properties of high manganese steel. .
基金supported by the National Natural Science Foundation of China(52164036,U1960201,51764007)the Guizhou Province Graduate Research Fund(YJSKYJJ(2021)003).
文摘Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.
基金supported by the following grants:Science and Technology Support Plan of Guizhou Province:Breeding Research and Demonstration of All-Red Bud Transformation of“GH-1”Clone of“Hong Yang”Kiwifruit(Guizhou Family Combination Support[2021]General 234)Innovation Capacity Construction Project of Scientific Research Institutions in Guizhou Province:Technology R&D and Service Capacity Construction of Fine Fruit(Kiwifruit,Passion Fruit)Industry in Guizhou Province[2019]4004the National Key Research and Development Program“Quality and Efficiency Improvement Technology Integration and Demonstration of Advantageous Characteristic Industries in Guizhou Karst Mountain Area(2021YFD1100300)”Post-Subsidy Fund.
文摘To explore how manganese affects the antioxidant system and the expression levels of related genes of“Hong yang”seedlings,the leaves of its tissue cultured seedlings were taken as test materials,and single factor treatment was performed by changing the manganese chloride(MnCl_(2)·4H_(2)O)solution concentration when spraying the leaves.The expression levels of Mn-SOD,POD64 and POD27 genes in leaves were quantitatively analyzed by real-time quantitative PCR(qRT-PCR)at different determination times.Meanwhile,the contents of malondial-dehyde(MDA),hydrogen peroxide(H_(2)O_(2)),the activities of antioxidant enzymes,including catalase(CAT),peroxidase(POD),and superoxide dismutase(SOD).The results showed that the SOD,CAT,POD,ascorbate peroxidase(APX),and reduced glutathione(GSH)activities in leaves were the highest at 12 h post-treatment with 50μM MnCl_(2)·4H_(2)O.Furthermore,the contents of MDA and H_(2)O_(2) in leaves also peaked when the concentration of H_(2)O_(2) is 50μM,which is the minimum value.Additionally at 50μM Mn^(2+),the Mn-SOD and POD27 expression was up-regulated as compared to the control,which promoted the expression of their respective enzyme activities.However,POD64 expression increased with the increasing Mn^(2+) concentration.Therefore,50μM is the optimal concentration of Mn when exogenously applied on“Hong yang”,which improve the antioxidant enzyme activity and regulate the plant’s physiological and biochemical functions.