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
Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensiona...Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensional metal oxide electromagnetic wave absorbers.In this study,Manganese dioxide intercalated with alkali metal ions was prepared by a simple molten salt method.The pre-intercalation of ions not only enhances the polarization loss at the heterogeneous interface between cations(point sites)and man-ganese dioxide(face sites)but also alters the energy band structure of manganese oxide and enhances its electrical conductivity,which in turn enhances the conductive loss of the manganese dioxide.Due to the synergistic effect of multiple polarizations and conductive losses,NaMO exhibits superb electromag-netic wave absorption properties and an effective absorption bandwidth of 5.36 GHz at thinner matched thicknesses.In addition,the RCS simulation result further verifies the excellent electromagnetic wave ab-sorption capability of NaMO.Under the positive incidence of electromagnetic waves,the electromagnetic wave reflection intensity of the metal plate coated with NaMO is effectively reduced.Finally,this work establishes a new way to modulate the electromagnetic properties.展开更多
Ceramic foams were prepared using red mud and fly ash as raw materials with sodium borate as sintering aid agent,starchand MnO2as foaming agent,respectively.The influence of the amount of starch or MnO2on the crystall...Ceramic foams were prepared using red mud and fly ash as raw materials with sodium borate as sintering aid agent,starchand MnO2as foaming agent,respectively.The influence of the amount of starch or MnO2on the crystalline phase,pore morphologyand physical–chemical porosities was studied.The results showed that the main crystal phases of samples with starch addition andMnO2addition were sodalite phase Na6(AlSiO4)6and Na8(SiAlO4)6MnO4,respectively.The SEM images showed that the variation ofporous structure was mainly dominated by the addition of foaming agent.With the increase of foaming agent,the samples exhibitedbetter comprehensive properties:bulk density of0.59?0.96g/cm3,porosity of41.82%?63.51%,water absorption of3.16%?9.17%,compressive strength of4.22?8.38MPa,flexural strength of2.44?5.82MPa,acid resistance of95.59%?99.60%,alkali resistance of99.82%?99.99%.Based on these properties,the ceramic foams can be used in building field.展开更多
In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnOnanoparticles(α-MnO@C) for use as cathodes of aqueous zinc-ion batteries(ZIBs) for the first time. α-MnO@C was prepared via a g...In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnOnanoparticles(α-MnO@C) for use as cathodes of aqueous zinc-ion batteries(ZIBs) for the first time. α-MnO@C was prepared via a gel formation, using maleic acid(CHO) as the carbon source, followed by annealing at low temperature of 270 °C. A uniform carbon network among the α-MnOnanoparticles was observed by transmission electron microscopy. When tested in a zinc cell, the α-MnO@C exhibited a high initial discharge capacity of 272 m Ah/g under 66 m A/g current density compared to 213 m Ah/g, at the same current density, displayed by the pristine sample. Further, α-MnO@C demonstrated superior cycleability compared to the pristine samples. This study may pave the way for the utilizing carbon-coated MnOelectrodes for aqueous ZIB applications and thereby contribute to realizing high performance eco-friendly batteries.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
Chemical Manganese Dioxide （CMD） was prepared by an alkali-oxidation method. There are several virtues to this environmental friendly and clean process, including the nontoxic and harmless reagents and products, eas...Chemical Manganese Dioxide （CMD） was prepared by an alkali-oxidation method. There are several virtues to this environmental friendly and clean process, including the nontoxic and harmless reagents and products, easy operations, no pollutants, easily obtained raw materials and moderate reaction conditions. The synthesized manganese dioxide was characterized by XRD and SEM. The particles were small, consisting primarily of α-MnO2 and γ-MnO2. Experimental results showed that the optimum conditions were： MnSOa.H20 to NaOH ratio, 1.0：2.4; catalyst concentration （catalyst TF-2）, 6% of the MnSO4; initial solution pH, 11; reaction time and temperature, 20 min and 80 ℃; air flow, 0.20 m3/h; and, agitation rate, 700 r/rain. The conversion of MnSO4 can exceed 80% under these optimum conditions.展开更多
Hydrous manganese dioxide （HMO） synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb（Ⅱ） removal.The specific surface area,pore volume and BJH pore diameter of the H...Hydrous manganese dioxide （HMO） synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb（Ⅱ） removal.The specific surface area,pore volume and BJH pore diameter of the HMO were 79.31m2/g,0.07cm3/g and 3.38 nm,respectively.The adsorption equilibrium at 298K could be well described by the Langmuir isotherm equation with q max value of 352.55mg/g.The negative values of G and the positive values of H and S indicated the adsorption process was spontaneous and endothermic.The pseudo second-order equation could best fit the adsorption data.The value of the calculated activation energy for Pb（Ⅱ） adsorption onto the HMO was 38.23 kJ/mol.The uptake of Pb（Ⅱ） by HMO was correlated with increasing surface hydroxyl group content and the main adsorbed speciation was PbOH＋.The final chemical state of Pb（Ⅱ） on the surface of HMO was similar to PbO.HMO was a promising candidate for Pb（Ⅱ） removal from aqueous solution.展开更多
The oxidation of a,b-unsaturated primary and secondary alcohols to corresponding aldehydes and ketones by manganese dioxide in ionic liquids as a safe recyclable and accelerative reaction medium under mild conditions ...The oxidation of a,b-unsaturated primary and secondary alcohols to corresponding aldehydes and ketones by manganese dioxide in ionic liquids as a safe recyclable and accelerative reaction medium under mild conditions are described. The rate of the oxidation reaction is faster and the yield is higher than that with conventional procedures.展开更多
The authors reported a facile method for the synthesis of manganese dioxide without any template and catalyst at a low-temperature. The prepared sample was characterized with X-ray diffraction（XRD）, scanning electro...The authors reported a facile method for the synthesis of manganese dioxide without any template and catalyst at a low-temperature. The prepared sample was characterized with X-ray diffraction（XRD）, scanning electron microscopy（SEM）, Brunauer-Emmett-Teller（BET） surface analysis, Fourier transform infrared（FTIR） spectrometry, cyclic voltammetry, alternative current（AC） impedance test and battery discharge test. It is found that the prepared sample belongs to α-MnO2 and has a microsphere morphology and a large BET surface area. The electrochemical characterization indicates that the prepared sample displays a larger electrochemical capacitance than the commercial electrolytic manganese dioxides（EMD） in Na2SO4 solution, and exhibits larger discharge capacity than EMD, especially at a high rate discharge condition when it is used as cathode of alkaline Zn/MnO2 battery.展开更多
Objective To study the anticlastogenic effect of redistilled cow＇s urine distillate （RCUD） in human peripheral lymphocytes （HLC） challenged with manganese dioxide and hexavalent chromium. Methods The anticlastoge...Objective To study the anticlastogenic effect of redistilled cow＇s urine distillate （RCUD） in human peripheral lymphocytes （HLC） challenged with manganese dioxide and hexavalent chromium. Methods The anticlastogenic activity of redistilled cow＇s urine distillate was studied in human polymorphonuclear leukocytes （HPNLs） and human peripheral lymphocytes in vitro challenged with manganese dioxide and hexavalent chromium as established genotoxicants and clastogens which could cause induction of DNA strand break, chromosomal aberration and micronucleus. Three different levels of RCUD： 1 μL/mL, 50 μL/mL and 100 μL/mL, were used in the study. Results Manganese dioxide and hexavalent chromium caused statistically significant DNA strand break, chromosomal aberration and micronucleus formation, which could be protected by redisfilled cow＇s urine distillate. Conclusion The redistilled cow＇s urine distillate posseses strong anfigenotoxic and antielastogenic properties against HPNLs and HLC treated with Cr^＋6 and MnO2. This property is mainly due to the antioxidants present in RCUD.展开更多
Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were d...Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.展开更多
<div style="text-align:justify;"> In this study a novel manganese dioxide modified nanofiber was facile prepared using the electrospinning technique. The as-prepared manganese dioxide/poly(vinyl alcoho...<div style="text-align:justify;"> In this study a novel manganese dioxide modified nanofiber was facile prepared using the electrospinning technique. The as-prepared manganese dioxide/poly(vinyl alcohol)/poly (acrylic acid) (briefly as MnO<sub>2</sub>-PVA/PAA) was firstly characterized by SEM, FT-IR, XRD, stress-strain test and secondly tested as an adsorbent to remove uranium from aqueous solution. Effect of pH, ionic strength, initial uranium concentration, mixing time, temperature on the adsorption, reusability and adsorption mechanism were illustrated. The theoretical adsorption amount of MnO<sub>2</sub>-PVA/PAA calculated as 398.85 mg/g was competitive compared with the reported values. The study proved MnO<sub>2</sub>-PVA/PAA is promising in the uranium removal from aqueous medium. </div>展开更多
Photodynamic therapy(PDT) has emerged as a potential clinical strategy for tumor therapy. It can generate reactive oxygen species(ROS) to cause the chemical damage of tumor cells and promote the immune killing effects...Photodynamic therapy(PDT) has emerged as a potential clinical strategy for tumor therapy. It can generate reactive oxygen species(ROS) to cause the chemical damage of tumor cells and promote the immune killing effects of T cells on tumor cells in the presence of enough oxygen and PDT drugs. However, most solid tumors are in a state of oxygen deficiency, which seriously limit the efficacy of PDT in generation enough ROS. Besides, few safe PDT drugs with ideal pharmacokinetic behavior are available in the clinic,which severely limits the clinical transformation and application of PDT. Herein, we utilized manganese chloride to mineralize the hydrophilic indocyanine green/albumin polyplexes(ICG@BSA@MnO_(2)) by using bio-mineralized method to solve these problems of PDT. These ICG@BSA@MnO_(2)nanoparticles could circulate in the blood for a long period other than quickly removed from body after 30 min like free ICG.When accumulated at the tumor site, ICG was responsively released in the presence of hydrogen peroxide. Apart this, the tumor hypoxia microenvironment was also reversed owing to enhanced O_(2)generation by the reaction of MnO_(2)with hydrogen peroxide. Benefits from the rich accumulation of ICG and ameliorated tumor hypoxia in the tumor sites, the enhanced generation of ROS could successfully promote the distribution of CD3^(+) and CD8^(+)T cells inside the tumors, which then lead to the amplified efficacy of PDT in both CT26 and B16 F10 tumor models without causing any side effects.展开更多
The effects of temperature and the concentration of sulfuric acid on the cell voltage, the anode current efficiency of electrodeposition and the particle size of grainy electrolytic manganese dioxide （EMD） were inve...The effects of temperature and the concentration of sulfuric acid on the cell voltage, the anode current efficiency of electrodeposition and the particle size of grainy electrolytic manganese dioxide （EMD） were investigated. The structure, particle size and appearance of grainy EMD were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrograph measurements. As the concentration of sulfuric acid increases, both the cell voltage and the average anode current efficiency decrease. With the increase of electrolysis temperature in the range of 30-60℃, the cell voltage, average anode current efficiency and particle size decrease. The optimum temperature of 30℃ and concentration of sulfuric acid of 2.5 mol/L for electrodeposition of the grainy EMD were obtained. XRD patterns show that the grainy EMD electrodeposited under the optimum conditions consists of γ-MnO2 and has an orthorhombic lattice structure. According to the results of SEM, the grainy EMD has a spherical or sphere-like appearance and a narrow particle size distribution with an average size of about 7μm. The grainy EMD is a promising cathode of rechargeable alkaline batteries for high energy density and a prospective precursor for production of the LiMn2O4 cathode of lithium ion batteries.展开更多
Aqueous zinc-ion battery has attracted much attention due to its low price, high safety, and high theoretical specific capacity. However, most of their performances are limited by the unsatisfied architecture of catho...Aqueous zinc-ion battery has attracted much attention due to its low price, high safety, and high theoretical specific capacity. However, most of their performances are limited by the unsatisfied architecture of cathodes. Herein, we fabricated amorphous manganese dioxide by an in situ deposition method. The amorphous manganese dioxide can directly serve as the cathode of an aqueous zinc-ion battery without a binder. The resultant cathode exhibits a high specific capacity of 133.9 mAh/g at 200 mA/g and a capacity retention of 82% over 50 cycles at 1 A/g.展开更多
Precipitation was carried out to obtain manganese carbonate by adding a precipitating agent, sodium carbonate (NaCO<sub>3</sub>). This was followed by calcination of the manganese carbonate (MnCO<sub>...Precipitation was carried out to obtain manganese carbonate by adding a precipitating agent, sodium carbonate (NaCO<sub>3</sub>). This was followed by calcination of the manganese carbonate (MnCO<sub>3</sub>) to obtain manganese dioxide (MnO<sub>2</sub>). For precipitation tests, a pH ranging from 8 to 10, a time of one to two hours, and a temperature of 25°C and 50°C are the parameters that are considered. The calcination of MnCO<sub>3</sub> is carried out under the following conditions: time (1, 2, 3, and 4 hours) and temperature (370°C, 420°C, and 470°C). It should be noted that the temperature range selected for the calcination tests is based on thermodynamic data obtained using the HSC CHEMISTRY software. The results obtained show an effective recovery of manganese at 25°C, in one hour, with a pH of 8.5 with a precipitation yield and manganese content in the precipitate around 98.43% and 24.21%, respectively. During calcination tests, results show an increase in mass loss, for a constant calcination time, as temperature increases. On the other hand, increasing the calcination time at a given temperature causes an increase in mass loss. However, a significant decrease in mass loss is noted at 3 hours of calcination. The highest mass loss is obtained at a temperature of 470°C after 4 hours of calcination.展开更多
The treatment of refractory bone defects is a major clinical challenge,especially in steroid-associated osteonecrosis(SAON),which is characterized by insufficient osteogenesis and angiogenesis.Herin,a microenvironment...The treatment of refractory bone defects is a major clinical challenge,especially in steroid-associated osteonecrosis(SAON),which is characterized by insufficient osteogenesis and angiogenesis.Herin,a microenvironment responsiveness scaffold composed of poly-L-lactide(PLLA),and manganese dioxide(MnO_(2))nanoparticles is designed to enhance bone regeneration by scavenging endogenous reactive oxygen species(ROS)and modulating immune microenvironment in situ.A catalase-like catalytic reaction between MnO_(2)and endogenous hydrogen peroxide(H_(2)O_(2))generated at the bone defect area,which typically becomes acidic and ROS-rich,triggers on-demand release of oxygen and M^(n2+),significantly ameliorating inflammatory response by promoting M2-type polarization of macrophages,reprograming osteoimmune microenvironment conducive to angiogenesis and osteogenesis.Furthermore,the fundamental mechanisms were explored through transcriptome sequencing analysis,revealing that PLLA/MnO_(2)scaffolds(PMns)promote osteogenic differentiation by upre-gulating the TGF-β/Smad signaling pathway in human bone marrow mesenchymal stem cells(hBMSCs).Overall,the PMns exhibit superior immunomodulatory,excellent osteogenic-angiogenic properties and promising can-didates as bone graft substitutes for therapy clinical refractory bone defects.展开更多
In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation...In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation mechanism.However,the strong coulomb interaction between Zn^(2+)andδ-MnO_(2)results in the slow diffusion dynamics of Zn^(2+)in the electrochemical process,which affects the structural stability of the cathode.Herein,we report a structural design that stabilizes theδ-MnO_(2)-layered structure by preintercalation of Cu^(2+)to expand the layer spacing,and thus improve H^(+)-transfer kinetics.Compared with the bulkδ-MnO_(2),the modified cathode showed excellent electrochemical performances,including a highly reversible capacity of 280 mA h g^(-1)at 1 A g^(-1)and 62.5%capacity retention after 1500 cycles at 5 A g^(-1).The results shown above confirmed the possibility of increasing the capacity contribution of H^(+)through structural design,and provides a novel idea for the development of high-performance cathode materials.展开更多
The effects of manganese dioxide (MnO 2 ) additives on the electrical characteristics of the Al-doped ZnO varistors are investigated. The leakage current densities of the samples decrease first and then increase again...The effects of manganese dioxide (MnO 2 ) additives on the electrical characteristics of the Al-doped ZnO varistors are investigated. The leakage current densities of the samples decrease first and then increase again with the increase of the amount of MnO 2 additives. Correspondingly, the nonlinear coefficients of the samples keep on increasing and then decrease. In addition, the donor densities increase monotonously with the amount of the doped MnO 2 increasing. The effects of MnO 2 additives on the electrical characteristics of the samples are different from the conclusion of previous literatures. The reasons of the distinct effects are supposed to be related with the donor and interface state densities of the samples.展开更多
A novel composite adsorbent, hydroxyapatite/ manganese dioxide （HAp/MnO2）, has been developed for the purpose of removing lead ions from aqueous solutions. The combination of HAp with MnO2 is meant to increase its a...A novel composite adsorbent, hydroxyapatite/ manganese dioxide （HAp/MnO2）, has been developed for the purpose of removing lead ions from aqueous solutions. The combination of HAp with MnO2 is meant to increase its adsorption capacity. Various factors that may affect the adsorption efficiency, including solution pH, coexistent substances such as humic acid and competing cations （Ca2＋, Mg2＋）, initial solute concentration, and the duration of the reaction, have been investigated. Using this composite adsorbent, solution pH and coexistent calcium or magnesium cations were found to have no significant influence on the removal of lead ions under the experi- mental conditions. The adsorption equilibrium was described well by the Langmuir isotherm model, and the calculated maximum adsorption capacity was 769 mg. gl. The sorption processes obeyed the pseudo-second-order kinetics model. The experimental results indicate that HAp/MnO2 composite may be an effective adsorbent for the removal of lead ions from aqueous solutions.展开更多
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supported by the Jiangxi Provincial Natural Science Foundation(No.20232BAB202036).
文摘Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides,injecting unlimited energy into the design of advanced two-dimensional metal oxide electromagnetic wave absorbers.In this study,Manganese dioxide intercalated with alkali metal ions was prepared by a simple molten salt method.The pre-intercalation of ions not only enhances the polarization loss at the heterogeneous interface between cations(point sites)and man-ganese dioxide(face sites)but also alters the energy band structure of manganese oxide and enhances its electrical conductivity,which in turn enhances the conductive loss of the manganese dioxide.Due to the synergistic effect of multiple polarizations and conductive losses,NaMO exhibits superb electromag-netic wave absorption properties and an effective absorption bandwidth of 5.36 GHz at thinner matched thicknesses.In addition,the RCS simulation result further verifies the excellent electromagnetic wave ab-sorption capability of NaMO.Under the positive incidence of electromagnetic waves,the electromagnetic wave reflection intensity of the metal plate coated with NaMO is effectively reduced.Finally,this work establishes a new way to modulate the electromagnetic properties.
基金Project(K1003027-11) supported by the Key Project Foundation of Science and Technology Plans of Changsha,China
文摘Ceramic foams were prepared using red mud and fly ash as raw materials with sodium borate as sintering aid agent,starchand MnO2as foaming agent,respectively.The influence of the amount of starch or MnO2on the crystalline phase,pore morphologyand physical–chemical porosities was studied.The results showed that the main crystal phases of samples with starch addition andMnO2addition were sodalite phase Na6(AlSiO4)6and Na8(SiAlO4)6MnO4,respectively.The SEM images showed that the variation ofporous structure was mainly dominated by the addition of foaming agent.With the increase of foaming agent,the samples exhibitedbetter comprehensive properties:bulk density of0.59?0.96g/cm3,porosity of41.82%?63.51%,water absorption of3.16%?9.17%,compressive strength of4.22?8.38MPa,flexural strength of2.44?5.82MPa,acid resistance of95.59%?99.60%,alkali resistance of99.82%?99.99%.Based on these properties,the ceramic foams can be used in building field.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIP)(2014R1A2A1A10050821)
文摘In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnOnanoparticles(α-MnO@C) for use as cathodes of aqueous zinc-ion batteries(ZIBs) for the first time. α-MnO@C was prepared via a gel formation, using maleic acid(CHO) as the carbon source, followed by annealing at low temperature of 270 °C. A uniform carbon network among the α-MnOnanoparticles was observed by transmission electron microscopy. When tested in a zinc cell, the α-MnO@C exhibited a high initial discharge capacity of 272 m Ah/g under 66 m A/g current density compared to 213 m Ah/g, at the same current density, displayed by the pristine sample. Further, α-MnO@C demonstrated superior cycleability compared to the pristine samples. This study may pave the way for the utilizing carbon-coated MnOelectrodes for aqueous ZIB applications and thereby contribute to realizing high performance eco-friendly batteries.
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National Natural Science Foundation of China (No50704036)the Natural Science Foundation of Hunan Province (No08JJ3027) for their financial support
文摘Chemical Manganese Dioxide （CMD） was prepared by an alkali-oxidation method. There are several virtues to this environmental friendly and clean process, including the nontoxic and harmless reagents and products, easy operations, no pollutants, easily obtained raw materials and moderate reaction conditions. The synthesized manganese dioxide was characterized by XRD and SEM. The particles were small, consisting primarily of α-MnO2 and γ-MnO2. Experimental results showed that the optimum conditions were： MnSOa.H20 to NaOH ratio, 1.0：2.4; catalyst concentration （catalyst TF-2）, 6% of the MnSO4; initial solution pH, 11; reaction time and temperature, 20 min and 80 ℃; air flow, 0.20 m3/h; and, agitation rate, 700 r/rain. The conversion of MnSO4 can exceed 80% under these optimum conditions.
基金supported by the Fundamental Research Funds for the Central Universities(No.TD2010-5)the National Natural Science Research Fund(No.51078034,51278051)Beijing Forestry University Young Scientist Fund(No.BLX2009018)
文摘Hydrous manganese dioxide （HMO） synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb（Ⅱ） removal.The specific surface area,pore volume and BJH pore diameter of the HMO were 79.31m2/g,0.07cm3/g and 3.38 nm,respectively.The adsorption equilibrium at 298K could be well described by the Langmuir isotherm equation with q max value of 352.55mg/g.The negative values of G and the positive values of H and S indicated the adsorption process was spontaneous and endothermic.The pseudo second-order equation could best fit the adsorption data.The value of the calculated activation energy for Pb（Ⅱ） adsorption onto the HMO was 38.23 kJ/mol.The uptake of Pb（Ⅱ） by HMO was correlated with increasing surface hydroxyl group content and the main adsorbed speciation was PbOH＋.The final chemical state of Pb（Ⅱ） on the surface of HMO was similar to PbO.HMO was a promising candidate for Pb（Ⅱ） removal from aqueous solution.
文摘The oxidation of a,b-unsaturated primary and secondary alcohols to corresponding aldehydes and ketones by manganese dioxide in ionic liquids as a safe recyclable and accelerative reaction medium under mild conditions are described. The rate of the oxidation reaction is faster and the yield is higher than that with conventional procedures.
基金Supported by the National Natural Science Foundation of China(No.20873046)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.200805740004)+1 种基金the Natural Science Foundation of Guangdong Province,China(No.10351063101000001)the Fund of Guangdong Province Cooperation of Producing, Studying and Researching,China (No.2011B090400317)
文摘The authors reported a facile method for the synthesis of manganese dioxide without any template and catalyst at a low-temperature. The prepared sample was characterized with X-ray diffraction（XRD）, scanning electron microscopy（SEM）, Brunauer-Emmett-Teller（BET） surface analysis, Fourier transform infrared（FTIR） spectrometry, cyclic voltammetry, alternative current（AC） impedance test and battery discharge test. It is found that the prepared sample belongs to α-MnO2 and has a microsphere morphology and a large BET surface area. The electrochemical characterization indicates that the prepared sample displays a larger electrochemical capacitance than the commercial electrolytic manganese dioxides（EMD） in Na2SO4 solution, and exhibits larger discharge capacity than EMD, especially at a high rate discharge condition when it is used as cathode of alkaline Zn/MnO2 battery.
文摘Objective To study the anticlastogenic effect of redistilled cow＇s urine distillate （RCUD） in human peripheral lymphocytes （HLC） challenged with manganese dioxide and hexavalent chromium. Methods The anticlastogenic activity of redistilled cow＇s urine distillate was studied in human polymorphonuclear leukocytes （HPNLs） and human peripheral lymphocytes in vitro challenged with manganese dioxide and hexavalent chromium as established genotoxicants and clastogens which could cause induction of DNA strand break, chromosomal aberration and micronucleus. Three different levels of RCUD： 1 μL/mL, 50 μL/mL and 100 μL/mL, were used in the study. Results Manganese dioxide and hexavalent chromium caused statistically significant DNA strand break, chromosomal aberration and micronucleus formation, which could be protected by redisfilled cow＇s urine distillate. Conclusion The redistilled cow＇s urine distillate posseses strong anfigenotoxic and antielastogenic properties against HPNLs and HLC treated with Cr^＋6 and MnO2. This property is mainly due to the antioxidants present in RCUD.
文摘Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.
文摘<div style="text-align:justify;"> In this study a novel manganese dioxide modified nanofiber was facile prepared using the electrospinning technique. The as-prepared manganese dioxide/poly(vinyl alcohol)/poly (acrylic acid) (briefly as MnO<sub>2</sub>-PVA/PAA) was firstly characterized by SEM, FT-IR, XRD, stress-strain test and secondly tested as an adsorbent to remove uranium from aqueous solution. Effect of pH, ionic strength, initial uranium concentration, mixing time, temperature on the adsorption, reusability and adsorption mechanism were illustrated. The theoretical adsorption amount of MnO<sub>2</sub>-PVA/PAA calculated as 398.85 mg/g was competitive compared with the reported values. The study proved MnO<sub>2</sub>-PVA/PAA is promising in the uranium removal from aqueous medium. </div>
基金supported by the National Natural Science Foundation of China (Nos. 22007042, 31800833, 21977081, 81874094, 81974397 and 82003697)Zhejiang Provincial Natural Science of Foundation of China (No. LZ19H180001)。
文摘Photodynamic therapy(PDT) has emerged as a potential clinical strategy for tumor therapy. It can generate reactive oxygen species(ROS) to cause the chemical damage of tumor cells and promote the immune killing effects of T cells on tumor cells in the presence of enough oxygen and PDT drugs. However, most solid tumors are in a state of oxygen deficiency, which seriously limit the efficacy of PDT in generation enough ROS. Besides, few safe PDT drugs with ideal pharmacokinetic behavior are available in the clinic,which severely limits the clinical transformation and application of PDT. Herein, we utilized manganese chloride to mineralize the hydrophilic indocyanine green/albumin polyplexes(ICG@BSA@MnO_(2)) by using bio-mineralized method to solve these problems of PDT. These ICG@BSA@MnO_(2)nanoparticles could circulate in the blood for a long period other than quickly removed from body after 30 min like free ICG.When accumulated at the tumor site, ICG was responsively released in the presence of hydrogen peroxide. Apart this, the tumor hypoxia microenvironment was also reversed owing to enhanced O_(2)generation by the reaction of MnO_(2)with hydrogen peroxide. Benefits from the rich accumulation of ICG and ameliorated tumor hypoxia in the tumor sites, the enhanced generation of ROS could successfully promote the distribution of CD3^(+) and CD8^(+)T cells inside the tumors, which then lead to the amplified efficacy of PDT in both CT26 and B16 F10 tumor models without causing any side effects.
基金This work was financially supported by the National Natural Science Foundation of China (No. 50302016) and the PostdoctoralScience Foundation of Central South University.
文摘The effects of temperature and the concentration of sulfuric acid on the cell voltage, the anode current efficiency of electrodeposition and the particle size of grainy electrolytic manganese dioxide （EMD） were investigated. The structure, particle size and appearance of grainy EMD were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrograph measurements. As the concentration of sulfuric acid increases, both the cell voltage and the average anode current efficiency decrease. With the increase of electrolysis temperature in the range of 30-60℃, the cell voltage, average anode current efficiency and particle size decrease. The optimum temperature of 30℃ and concentration of sulfuric acid of 2.5 mol/L for electrodeposition of the grainy EMD were obtained. XRD patterns show that the grainy EMD electrodeposited under the optimum conditions consists of γ-MnO2 and has an orthorhombic lattice structure. According to the results of SEM, the grainy EMD has a spherical or sphere-like appearance and a narrow particle size distribution with an average size of about 7μm. The grainy EMD is a promising cathode of rechargeable alkaline batteries for high energy density and a prospective precursor for production of the LiMn2O4 cathode of lithium ion batteries.
文摘Aqueous zinc-ion battery has attracted much attention due to its low price, high safety, and high theoretical specific capacity. However, most of their performances are limited by the unsatisfied architecture of cathodes. Herein, we fabricated amorphous manganese dioxide by an in situ deposition method. The amorphous manganese dioxide can directly serve as the cathode of an aqueous zinc-ion battery without a binder. The resultant cathode exhibits a high specific capacity of 133.9 mAh/g at 200 mA/g and a capacity retention of 82% over 50 cycles at 1 A/g.
文摘Precipitation was carried out to obtain manganese carbonate by adding a precipitating agent, sodium carbonate (NaCO<sub>3</sub>). This was followed by calcination of the manganese carbonate (MnCO<sub>3</sub>) to obtain manganese dioxide (MnO<sub>2</sub>). For precipitation tests, a pH ranging from 8 to 10, a time of one to two hours, and a temperature of 25°C and 50°C are the parameters that are considered. The calcination of MnCO<sub>3</sub> is carried out under the following conditions: time (1, 2, 3, and 4 hours) and temperature (370°C, 420°C, and 470°C). It should be noted that the temperature range selected for the calcination tests is based on thermodynamic data obtained using the HSC CHEMISTRY software. The results obtained show an effective recovery of manganese at 25°C, in one hour, with a pH of 8.5 with a precipitation yield and manganese content in the precipitate around 98.43% and 24.21%, respectively. During calcination tests, results show an increase in mass loss, for a constant calcination time, as temperature increases. On the other hand, increasing the calcination time at a given temperature causes an increase in mass loss. However, a significant decrease in mass loss is noted at 3 hours of calcination. The highest mass loss is obtained at a temperature of 470°C after 4 hours of calcination.
基金financially supported by the National Natural Science Foundation of China(81871767)Shenzhen Medical Research Funds(B2302050)+4 种基金Guangdong Basic and Applied Basic Research Foundation(No.2022B1515120046,2023A1515010087,2023A1515011315)Shenzhen Key Laboratory of Digital Surgical Printing Project(ZDSYS201707311542415)Shenzhen Science and Technology Program(JCYJ20220818103417037,JCYJ20210324115814040,JCYJ 20210324102206016,JSGG20210629144538010,KJZD20230923115200002)Shenzhen Development and Reform Program(XMHT20220106001)the Shenzhen Basic Research General Project(JCYJ20220531100408019).
文摘The treatment of refractory bone defects is a major clinical challenge,especially in steroid-associated osteonecrosis(SAON),which is characterized by insufficient osteogenesis and angiogenesis.Herin,a microenvironment responsiveness scaffold composed of poly-L-lactide(PLLA),and manganese dioxide(MnO_(2))nanoparticles is designed to enhance bone regeneration by scavenging endogenous reactive oxygen species(ROS)and modulating immune microenvironment in situ.A catalase-like catalytic reaction between MnO_(2)and endogenous hydrogen peroxide(H_(2)O_(2))generated at the bone defect area,which typically becomes acidic and ROS-rich,triggers on-demand release of oxygen and M^(n2+),significantly ameliorating inflammatory response by promoting M2-type polarization of macrophages,reprograming osteoimmune microenvironment conducive to angiogenesis and osteogenesis.Furthermore,the fundamental mechanisms were explored through transcriptome sequencing analysis,revealing that PLLA/MnO_(2)scaffolds(PMns)promote osteogenic differentiation by upre-gulating the TGF-β/Smad signaling pathway in human bone marrow mesenchymal stem cells(hBMSCs).Overall,the PMns exhibit superior immunomodulatory,excellent osteogenic-angiogenic properties and promising can-didates as bone graft substitutes for therapy clinical refractory bone defects.
基金supported by the National Natural Science Foundation of China(52225204,52173233,52002059 and 52202085)Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-03-E00109)+3 种基金Natural Science Foundation of Shanghai(23ZR1479200)“Shuguang Program”supported by the Shanghai Education Development Foundation and Shanghai Municipal Education Commission(20SG33)DHU Distinguished Young Professor Program(LZA2022001 and LZB2023002)the Fundamental Research Funds for Central Universities(2232023G-07,2232024Y-01).
文摘In aqueous zinc-ion batteries(AZIB),layered manganese dioxide(δ-MnO_(2))is considered to be a suitable cathode material due to its high theoretical capacity,suitable operating voltage and Zn^(2+)/H^(+)cointercalation mechanism.However,the strong coulomb interaction between Zn^(2+)andδ-MnO_(2)results in the slow diffusion dynamics of Zn^(2+)in the electrochemical process,which affects the structural stability of the cathode.Herein,we report a structural design that stabilizes theδ-MnO_(2)-layered structure by preintercalation of Cu^(2+)to expand the layer spacing,and thus improve H^(+)-transfer kinetics.Compared with the bulkδ-MnO_(2),the modified cathode showed excellent electrochemical performances,including a highly reversible capacity of 280 mA h g^(-1)at 1 A g^(-1)and 62.5%capacity retention after 1500 cycles at 5 A g^(-1).The results shown above confirmed the possibility of increasing the capacity contribution of H^(+)through structural design,and provides a novel idea for the development of high-performance cathode materials.
基金supported by the National Natural Science Foundations of China (Grant No. 50737001)
文摘The effects of manganese dioxide (MnO 2 ) additives on the electrical characteristics of the Al-doped ZnO varistors are investigated. The leakage current densities of the samples decrease first and then increase again with the increase of the amount of MnO 2 additives. Correspondingly, the nonlinear coefficients of the samples keep on increasing and then decrease. In addition, the donor densities increase monotonously with the amount of the doped MnO 2 increasing. The effects of MnO 2 additives on the electrical characteristics of the samples are different from the conclusion of previous literatures. The reasons of the distinct effects are supposed to be related with the donor and interface state densities of the samples.
基金This work was supported by the National Natural Science Foundation of China （Grant No. 41372241）.
文摘A novel composite adsorbent, hydroxyapatite/ manganese dioxide （HAp/MnO2）, has been developed for the purpose of removing lead ions from aqueous solutions. The combination of HAp with MnO2 is meant to increase its adsorption capacity. Various factors that may affect the adsorption efficiency, including solution pH, coexistent substances such as humic acid and competing cations （Ca2＋, Mg2＋）, initial solute concentration, and the duration of the reaction, have been investigated. Using this composite adsorbent, solution pH and coexistent calcium or magnesium cations were found to have no significant influence on the removal of lead ions under the experi- mental conditions. The adsorption equilibrium was described well by the Langmuir isotherm model, and the calculated maximum adsorption capacity was 769 mg. gl. The sorption processes obeyed the pseudo-second-order kinetics model. The experimental results indicate that HAp/MnO2 composite may be an effective adsorbent for the removal of lead ions from aqueous solutions.
