Recent progress of advanced manganese oxide-based materials for acidic oxygen evolution reaction: Fundamentals, performance optimization,and prospects

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.

Recent progress of manganese dioxide based electrocatalysts for the oxygen evolution reaction

The oxygen evolution reaction(OER)represents an anodic reaction for a variety of sustainable energy conversion and storage technologies,such as hydrogen production,CO_(2) reduction,etc.To realize the large-scale implementation of these technologies,the sluggish kinetics of the OER resulting from multistep proton/electron transfer and occurring at the gas–liquid–solid triple-phase boundary needs to be accelerated.Manganese oxide-based(MnO_(x))materials,especially MnO_(2),have become promising nonprecious metal electrocatalysts for the OER under acidic conditions due to the good trade-off between catalytic activity and stability.This paper reviews the recent progress of MnO_(2)-based materials to catalyze the OER through either the traditional adsorbent formation mechanism(AEM)or the emerging latticeoxygen-mediated mechanism(LOM).Pure manganese dioxide OER catalysts with different crystalline structures and morphologies are summarized,while MnO2-based composite structures are also discussed,and the application of MnO_(2)-based catalysts in PEMWEs is summarized.Critical challenges and future research directions are presented to hopefully help future research.

Red mud and fly ash-based ceramic foams using starch and manganese dioxide as foaming agent

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.

Carbon-coated manganese dioxide nanoparticles and their enhanced electrochemical properties for zinc-ion battery applications

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.

Recent Advances on Challenges and Strategies of Manganese Dioxide Cathodes for Aqueous Zinc-Ion Batteries

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.

Preparation of chemical manganese dioxide from manganese sulfate

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.

Identification of reversible insertion-type lithium storage reaction of manganese oxide with long cycle lifespan

Recently,MnO2 has gained attention as an electrode material because of its very high theoretical capacity and abundant availability.However,the very high volumetric change caused by its conversion-type reaction results in bad reversibility of charge-discharge.In this study,δ-MnO2 of thickness 8 nm anchored on the surface of carbon nanotubes(CNT)by Mn-O-C chemical bonding is synthesized via a facile hydrothermal method.Numerous ex-situ characterizations of the lithium storage process were performed.Furthermore,density functional theory(DFT)calculations indicated thatδ-MnO2(012)thermodynamically prefers bonding with CNTs.Moreover,the interfacial interaction reinforces the connection of Mn-O and reduces the bond strength of Li-O in lithiated MnO2,which could facilitate an intercalation-type lithium storage reaction.Consequently,the as-synthesizedδ-MnO2 retains an excellent reversible capacity of 577.5 mAh g-1 in 1000 cycles at a high rate of 2 A g-1 between 0.1 V and 3.0 V.The results of this study demonstrate the possibility of employing the cost-effective transition metal oxides as intercalation lithium storage dominant electrodes for advanced rechargeable batteries.

Nanostructured MnO_2 synthesized via methane gas reduction of manganese ore and hydrothermal precipitation methods

A three-stage methane gas （CH4） reduction of manganese ore, dissolution, and precipitation from solution procedure was conducted to synthesize MnO2 nanorods. Methane gas reduction was carried out at 850, 875, 900, 925, and 950℃ for 120 min. Precipitation of the a-MnO2 nanorods was performed in the temperature range of 25-90℃with a constant reaction time of 90 min. The morphology and particle size of the products were determined from scanning electron microscope （SEM） images and X-ray diffraction （XRD） patterns. The BET and BJH of the products were found out by the surface area analyzer. Reduction results indicated that MnO-rich phase is significantly formed at 950℃ as MnO2 phase disappears. Precipitation results also showed an average diameter size of - 50 nm for the embedding a-MnO2 nanorods with BET surface area of 174 m^2/g.

A Facile and Efficient Oxidation of α,β-Unsaturated Alcohols with Manganese Dioxide in Ionic Liquids 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.

Preparation of MnO_2 and calcium silicate hydrate from electrolytic manganese residue and evaluation of adsorption properties

Electrolytic manganese residue(EMR), a high volume byproduct resulting from the electrolytic manganese industry, was used as a cheap and abundant chemical source for preparing MnO2 and EMR-made calcium silicate hydrate(EMR-CSH). The MnO2 is successfully synthesized from the metal cations extracted from EMR, which can effectively recycle the manganese in the EMR. By the combination of XRD, SEM and EDX analysis, the as-prepared MnO2 is found to exhibit a single-phase with the purity of 90.3%. Furthermore, EMR-CSH is synthesized from EMR via hydrothermal method. Based on the detailed analyses using XRD, FT-IR, FE-SEM, EDX and BET surface area measurement, the product synthesized under the optimum conditions(p H 12.0 and 100 °C) is identified to be a calcium silicate hydrate with a specific surface area of 205 m2/g incorporating the slag-derived metals(Al and Mg) in its structure. The as-synthesized material shows good adsorption properties for removal of Mn2+ and phosphate ions diluted in water, making it a promising candidate for efficient bulk wastewater treatment. This conversion process, which enables us to fabricate two different kinds of valuable materials from EMR at low cost and through convenient preparation steps, is surely beneficial from the viewpoint of the chemical and economical use of EMR.

Advances of manganese-oxides-based catalysts for indoor formaldehyde removal

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.

Manganese Dioxide with High Specific Surface Area for Alkaline Battery

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.

Anticlastogenic Effect of Redistilled Cow's Urine Distillate in Human Peripheral Lymphocytes Challenged With Manganese Dioxide and Hexavalent Chromium

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.

Effects of current density on preparation of grainy electrolytic manganese dioxide

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.

Facile Preparation of Novel Manganese Dioxide Modified Nanofiber and Its Uranium Adsorption Performance

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 MnO2-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 MnO2-PVA/PAA calculated as 398.85 mg/g was competitive compared with the reported values. The study proved MnO2-PVA/PAA is promising in the uranium removal from aqueous medium.

Effects of temperature and concentration of sulfuric acid on the electrodeposition of grainy electrolytic manganese dioxide

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.

A Binder-Free Amorphous Manganese Dioxide for Aqueous Zinc-Ion Battery

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.

Manganese Dioxide (MnO2) Gaining by Calcination of Manganese Carbonate (MnCO3) Precipitated from Cobalt Removal Solutions

Precipitation was carried out to obtain manganese carbonate by adding a precipitating agent, sodium carbonate (NaCO3). This was followed by calcination of the manganese carbonate (MnCO3) to obtain manganese dioxide (MnO2). 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 MnCO3 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.

Building Ultra-Stable and Low-Polarization Composite Zn Anode Interface via Hydrated Polyzwitterionic Electrolyte Construction

Aqueous zinc metal batteries are noted for their costeffectiveness,safety and environmental friendliness.However,the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electrochemical deposition remarkably restrict the development of the long-life zinc metal batteries.In this study,zwitterionic sulfobetaine is introduced to copolymerize with acrylamide in zinc perchlorate(Zn(ClO;);)solution.The designed gel framework with hydrophilic and charged groups can firmly anchor water molecules and construct ion migration channels to accelerate ion transport.The in situ generated hybrid interface,which is composed of the organic functionalized outer layer and inorganic Clcontaining inner layer,can synergically lower the mass transfer overpotential,reduce water-related side reactions and lead to uniform Zn deposition.Such a novel electrolyte configuration enables Zn//Zn cells with an ultra-long cycling life of over 3000 h and a low polarization potential(~0.03 V)and Zn//Cu cells with high Coulombic efficiency of 99.18%for 1000 cycles.Full cells matched with MnO;cathodes delivered laudable cycling stability and impressive shelving ability.Besides,the flexible quasi-solid-state batteries which are equipped with the anti-vandalism ability(such as cutting,hammering and soaking)can successfully power the LED simultaneously.Such a safe,processable and durable hydrogel promises significant application potential for long-life flexible electronic devices.

Influences of process parameters on solvent-free toluene oxidation over Au /γ-MnO_2 catalyst

γ-MnO2 nanorobs and Au/γ-MnO2 catalysts were synthesized and characterized by the X-ray powder diffraction XRD the scanning electron microscope SEM and transmission electron microscope TEM . The characterizations show that Au particles are well dispersed on the surface of γ-MnO2 nanorobs with a particle size of about 10 nm.The catalytic performance is evaluated in solvent-free toluene oxidation with oxygen. The influences of several process parameters such as reaction time reaction temperature initial oxygen pressure and catalyst amounts on the catalytic performance are studied.Catalytic results reveal that Au/γ-MnO2 catalyst has a unique selectivity to benzaldehyde and all these factors greatly influence the conversion of toluene and selectivity of bezaldehyde benzoic acid and benzyl benzoate.However these factors have slight influence on the selectivity of benzyl alcohol.