CN103570072A - Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough - Google Patents

Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough Download PDF

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Publication number
CN103570072A
CN103570072A CN201210263078.3A CN201210263078A CN103570072A CN 103570072 A CN103570072 A CN 103570072A CN 201210263078 A CN201210263078 A CN 201210263078A CN 103570072 A CN103570072 A CN 103570072A
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preparation
manganese
consumption
trimethylammonium bromide
cetyl trimethylammonium
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陈小芳
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BYD Co Ltd
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BYD Co Ltd
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Abstract

The invention provides a trimanganese tetroxide preparation method. The preparation method comprises the following steps: 1, mixing and dissolving a manganese source, cetyltrimethylammonium bromide, polyvinylpyrrolidone and an alkaline precipitating agent to obtain an aqueous solution; 2, introducing an oxidative atmosphere or adding H2O2 to the aqueous solution obtained in step 1 for reacting to obtain a manganese-containing solid oxide; and 3, sequentially washing and drying the manganese-containing solid oxide obtained in step 2 to obtain a trimanganese tetroxide product. The invention also provides trimanganese tetroxide. The preparation method has the advantages of simplicity, simple operation, environmental protection, and the trimanganese tetroxide product has the advantages of regular morphology and good dispersibility.

Description

The trimanganese tetroxide that a kind of preparation method of trimanganese tetroxide and the method prepare
Technical field
The invention belongs to manganic compound synthesis technical field, relate in particular to a kind of preparation method of trimanganese tetroxide.
Background technology
Mn 3o 4be a kind of stable Mn oxide, in catalyzer, battery material and electromagnetism storing unit, be widely used.
Aspect battery, Mn 3o 4have and LiMn 2o 4identical spinel structure, therefore adopts Mn 3o 4as presoma sintering, prepare LiMn 2o 4can reduce the time of crystal conversion, greatly shorten the time of solid state sintering.Meanwhile, Mn 3o 4pattern systematicness and the particle dispersion of presoma, have decisive influence to the pattern of sintered product and dispersiveness.Therefore, the good spinel LiMn of processability 2o 4, require Mn 3o 4presoma has good pattern systematicness and particle dispersion.
Mn 3o 4preparation method mainly contain electrolytic metal manganese powder suspension catalytic oxidation, roasting method, reduction method.But the power consumption of electrolytic metal manganese powder suspension catalytic oxidation is high, roasting method power consumption is high, and reduction method technological operation difficulty is large, therefore all to be improved.In recent years, develop a kind of low temperature liquid polymerization process and prepare Mn 3o 4, take manganese salt as raw material, under inert atmosphere, with alkaline precipitating agent, make Mn (OH) 2precipitation, then its oxidation is made to Mn 3o 4, energy consumption is low, low for equipment requirements, but operation steps is many, long reaction time.
Patent CN200710193538.9 discloses the preparation method of the controlled mangano-manganic oxide nanocrystalline of a kind of size and dimension, manganese source and organic coating agent are joined to heating for dissolving in toluene, the aqueous solution that adds alkaline matter, under 25-280 ℃ of condition, react 10min-240h, reaction is carried out under normal pressure or in autoclave, manganese source hydrolysis under the condition of heating, the nuclei of crystallization form and process of growth, finally form the mangano-manganic oxide nanocrystalline of organic ligand coated.This patent has adopted the organic solvents such as toluene, and toluene is that poisonous and hazardous volatile substances is unfavorable for operational safety and HUMAN HEALTH.
Patent CN200910051641.9 discloses a kind of preparation method of manganic manganous oxide nano-material of nano magnetic material technical field, comprises the configuration manganous acetate aqueous solution and the polyvinylpyrrolidone aqueous solution; Preparation is containing manganese solid salt and carrying out washing treatment and drying treatment.But the method adopts seal pot to react at >100 ℃, belongs to High Temperature High Pressure hydro-thermal reaction, and operation is difficult for.
Summary of the invention
The present invention is directed to prior art above shortcomings, a kind of preparation method of trimanganese tetroxide is provided, the method step is simple, have easy and simple to handle, Environmental Safety, the advantage of product pattern rule and good dispersity.
The present invention is achieved by the following technical solutions, the present invention includes step: 1) manganese source, cetyl trimethylammonium bromide, Polyvinylpyrolidone (PVP) and alkaline precipitating agent mixed dissolution are obtained to the aqueous solution; 2) logical oxidizing atmosphere or interpolation H in the aqueous solution obtaining toward step 1) 2o 2reaction, obtains containing manganese soild oxide; 3) by step 2) obtain carry out successively carrying out washing treatment and drying treatment containing manganese soild oxide, obtain trimanganese tetroxide product.
The present invention also provides a kind of trimanganese tetroxide, by preparation method of the present invention, is prepared.
The present invention is at CTAB(cetyl trimethylammonium bromide) and PVP(Polyvinylpyrolidone (PVP)) acting in conjunction under, between crystal grain, form certain steric hindrance, for particle provides enough free growth spaces, thereby be conducive to dispersiveness and the pattern systematicness of crystal grain.
The present invention directly prepares the method for regular morphology trimanganese tetroxide with manganese salt solution, single stage method makes the regular morphology Mn of submicron order 3o 4crystal, saves Mn (OH) 2settling step, technique is simple, easy and simple to handle, energy consumption is low, raw material is cheap and easy to get, product pattern rule and good dispersity.
Accompanying drawing explanation
Fig. 1 is the nano particle electron scanning micrograph that embodiment 1 prepares;
Fig. 2 is the nano particle electron scanning micrograph that embodiment 2 prepares;
Fig. 3 is the nano particle electron scanning micrograph that embodiment 3 prepares;
Fig. 4 is the nano particle electron scanning micrograph that embodiment 4 prepares;
Fig. 5 is the nano particle electron scanning micrograph that comparative example 1 is prepared;
Fig. 6 is the nano particle electron scanning micrograph that comparative example 2 is prepared.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The preparation method who the invention provides a kind of trimanganese tetroxide, comprises step: 1) manganese source, cetyl trimethylammonium bromide, Polyvinylpyrolidone (PVP) and alkaline precipitating agent mixed dissolution are obtained to the aqueous solution; 2) in the aqueous solution obtaining toward step 1), logical oxidizing atmosphere or interpolation H2O2 reaction, obtain containing manganese soild oxide; 3) by step 2) obtain carry out successively carrying out washing treatment and drying treatment containing manganese soild oxide, obtain trimanganese tetroxide product.Reaction system of the present invention can be reacted under static state, also can adopt the dynamically lower reaction such as mechanical stirring, magnetic agitation, and more preferably static reaction, is so more conducive to crystal free growth under unperturbed.
The method for washing and processing that carrying out washing treatment of the present invention is known to the skilled person, can be: will be dispersed in pure water containing manganese soild oxide is ultrasonic, then adopt whizzer centrifugation 3-4 time, each 3-4 minute.The centrifugation of described whizzer refers to that the rotating speed of whizzer is 3000-5000rpm.The conventional drying that drying treatment of the present invention is known to the skilled person is processed.
The present inventor finds by a large amount of experiments, after CTAB and PVP are combined with, in CTAB, four ammonia cation groups more than needed can be adsorbed on the negative charge place in particle surface gap, and hydrophobic grouping is wherein distributed in water, thereby reduced the wetting ability in particle surface gap, induction produces the infiltration of wicking action and large water gaging.In crystal growing process, the carbonyl in the pyrrolidone ring in PVP can form PVP-metal complexes with metal, has increased repulsive energy and has reduced Van der Waals'attractive force, thereby increased the steric hindrance between regular nano particle.Under the acting in conjunction of above-mentioned CTAB and PVP, can reduce product and reunite, greatly improved dispersiveness, be conducive to the systematicness of granule-morphology simultaneously.If it is serious to adopt separately CTAB or PVP product to reunite, be unfavorable for particle growth.
According to the present invention, described alkaline precipitating agent is preferably weakly alkaline precipitation agent, as urea, hexamethylene tetraammonia, thioacetamide.Alkalescence is more weak, and precipitin reaction is slower, is more conducive to the growth of nucleus, is conducive to the systematicness of surface topography.In the water of heating, the hydrolysis rate of urea is very slow, from urea, starts hydrolysis to the generation of Mn3O4, because the step speed of hydrolysis of urea is the slowest, thereby is the control step of whole reaction.At the beginning of reaction, solution is transparence, and under certain heating condition, urea is slowly hydrolyzed the NH of generation 3with Mn 2+reaction generates Mn3O4, when Mn3O4 concentration reaches certain degree of supersaturation in solution, slowly separates out Mn in solution 3o 4nucleus, the Mn of follow-up generation 3o 4can diffuse on nucleus and grow.Because each nucleus particle is minimum, surface can be larger, and according to minimum energy principle, each nucleus particle has reunion to form together the tendency of coacervate, and nucleus particle is more, and the proneness of reunion is larger.The slow hydrolysis rate of urea, has slowed down Mn 3o 4formation speed, thereby reduced Mn in solution 3o 4degree of supersaturation, degree of supersaturation is brilliant caryogenic motivating force, more megacryst karyogenesis is more for degree of supersaturation, the tendency that nucleus is reunited is larger.The present inventor finds by a large amount of experiments, and the participation role of urea can reduce degree of supersaturation, thereby has indirectly reduced nucleus reunion proneness.
CTAB and PVP can increase intergranular steric hindrance, and urea can reduce degree of supersaturation, reduce intergranular reunion motivating force, under three's mating reaction, have effectively avoided the intergranular reunion of nucleus, make nucleating surface have growing space more freely.
Alkaline precipitating agent of the present invention is preferably urea.Hexamethylene tetraammonia is hydrolyzed and can produces formaldehyde in water, and thioacetamide hydrolysis produces H 2s, all unfavorable to human body or environment, therefore do not advise using.
Described alkaline precipitating agent urea is slowly hydrolyzed and generates NH in water 3and then cause precipitation, for crystal growth provides time enough, be conducive to granule-morphology systematicness.This hydrolytic process is utmost point process slowly, along with temperature raises, correspondingly increases.
According to the present invention, described manganese source is water-soluble manganese salt, is not particularly limited, and is known to the skilled person, preferably, described manganese source is selected from one or more in manganous sulfate, manganous nitrate, manganese acetate, dodecyl sodium sulfonate manganese, lauric acid manganese, manganese stearate or manganese oleate.Acid manganese, nitric acid
According to the present invention, preferably, described oxidizing atmosphere is a kind of in air, oxygen, ozone, air-oxygen mixture, nitrogen-oxygen mixture, nitrogen-air Mixture, more preferably the low gas of oxygen concn such as air, nitrogen-oxygen mixture, nitrogen-air Mixture.Can adopt and be purged into oxidizing gas mode or add H 2o 2etc. mode, be preferably the oxidizing gas mode that is purged into, oxidizing gas safety non-toxic, easy to operate, easily controls flow, speed flexibly.
According to the present invention, preferably, the consumption in described manganese source is 1-20mmol/L, and when the consumption in manganese source is less than 1mmol/L, productive rate is too low; When the consumption in manganese source is greater than 20mmol/L, make reaction rate accelerates, increase Mn 3o 4degree of supersaturation, thereby increase nucleation rate, the tendency of reuniting that attracts each other between each nucleus strengthens, and easily makes final product reunite and seriously and is not too beneficial to pattern regularity.
According to the present invention, preferably, the consumption of described cetyl trimethylammonium bromide is 1-50mmol/L, when the consumption of cetyl trimethylammonium bromide is less than 1mmol/L, thereby easily make final product reunite, seriously causes pattern irregular; When the consumption of cetyl trimethylammonium bromide is greater than 50mmol/L, too much tensio-active agent easily makes Mn 3o 4steric hindrance between nucleus increases, and hinders the mass transfer in liquid phase of crystal grain, causes the speed of growth of nucleus to be less than its formation speed, and final product is superfine little, and when washing away tensio-active agent, small-particle is reunited serious.
According to the present invention, preferably, the consumption of described Polyvinylpyrolidone (PVP) is 0.01-0.5mmol/L, when the consumption of Polyvinylpyrolidone (PVP) is less than 0.01mmol/L, is difficult to bring into play dissemination, and final product is reunited serious and pattern is irregular; When the consumption of Polyvinylpyrolidone (PVP) is greater than 0.5mmol/L, can make product particle tiny and reunite serious.
According to the present invention, preferably, the consumption of described alkaline precipitating agent is consumption that 50-200mmol/L works as alkaline precipitating agent while being less than 50mmol/L, and productive rate is too low; When the consumption of alkaline precipitating agent is greater than 200mmol/L, easily make reaction rate accelerates, increase Mn 3o 4degree of supersaturation, thereby increase nucleation rate, the tendency of reuniting that attracts each other between each nucleus strengthens, and makes final product reunite serious and be unfavorable for pattern regularity.
Further preferably, the consumption in described manganese source is 5-10mmol/L, and the consumption of cetyl trimethylammonium bromide is 10-35mmol/L, and the consumption of Polyvinylpyrolidone (PVP) is 0.05-0.2mmol/L, and the consumption of alkaline precipitating agent is 100-150mmol/L.
According to the present invention, preferably, the mol ratio of described manganese source and cetyl trimethylammonium bromide is 1:1-10.
According to the present invention, preferably, the mol ratio of described manganese source and cetyl trimethylammonium bromide is 1:1-5.
According to the present invention, preferably, the mol ratio of described cetyl trimethylammonium bromide and Polyvinylpyrolidone (PVP) is 100-300:1.
According to the present invention, preferably, the mol ratio of described cetyl trimethylammonium bromide and Polyvinylpyrolidone (PVP) is 150-200:1.
According to the present invention, preferably, the temperature of reacting under described oxidizing atmosphere is 75-100 ℃, and the reaction times is 8-30h.Temperature of reaction of the present invention, for the temperature of precipitation oxidation occurs, is preferably 75-100 ℃, if be less than 75 ℃, the hydrolysis rate of urea is very slow, easily causes system oxidation precipitation speed very slow, thereby greatly extends the reaction times; If be greater than 100 ℃, having relatively high expectations to equipment correspondingly.
According to the present invention, further preferably, the temperature of reacting under described oxidizing atmosphere is 80-95 ℃, and the reaction times is 16-24h.
According to the present invention, preferably, described trimanganese tetroxide is of a size of 100-500nm, is shaped as Polygons, more preferably octahedra.The steady state of thermodynamics of Mn3O4 crystal is spinel octahedral structure.Wherein, the speed of growth of (111) crystal face is slower, the octahedral structure that each (111) face of the final formation of crystal growth is staggered to form.At crystal free growth state, on each crystal face, do not stop the material of crystal face growth, according to minimum energy principle, crystal can grow the most stable state, and Mn3O4 is more easily partial to be grown to spinel octahedral structure.
The present invention also provides a kind of trimanganese tetroxide preparing by preparation method of the present invention.
Low temperature liquid polymerization process of the present invention is prepared the preparation method of Mn3O4, and technique is simple, easy and simple to handle, energy consumption is low, raw material is cheap and easy to get, product pattern rule and good dispersity.
Below in conjunction with embodiment, the present invention is further explained to explanation.In embodiment and comparative example, the raw material that adopts is all commercially available, and the present invention is not particularly limited.
Embodiment 1
Take respectively 0.189gMnSO 4h 2o, 1.218gCTAB, 0.180gPVP (1w), 1.335g urea, add after 200ml water stirring and dissolving, and 80 ℃ of lower surfaces are blown into after air reaction 24h, with drying 6h at after distilled water centrifuge washing 60 ℃, obtain Mn 3o 4sample S1.
Embodiment 2
Compare with embodiment 1, difference is: " 80 ℃ of lower surfaces are blown into air reaction 24h " changed into " 95 ℃ of lower surfaces are blown into oxygen reaction 8h ", and all the other are all identical with embodiment 1, obtain Mn 3o 4sample S2.
Embodiment 3
Compare with embodiment 1, difference is: " 80 ℃ of lower surfaces are blown into air reaction 24h " changed into " 70 ℃ of lower surfaces are blown into after nitrogen-air mixed solid/liquid/gas reactions 30h ", " at 60 ℃, drying 8h " changed into " at 50 ℃, drying 11h ", and all the other are all identical with embodiment 1, obtain Mn 3o 4sample S3.
Embodiment 4
Take respectively 0.662gMnSO 4h 2o, 3.046gCTAB, 0.760gPVP (1w), 2.136g urea, add after 200ml water stirring and dissolving said components, and 75 ℃ of lower surfaces are blown into after nitrogen-air mixed solid/liquid/gas reactions 22h, with 60 ℃ of oven dry 10h after distilled water centrifuge washing, obtains Mn 3o 4sample S4.
Comparative example 1
Take respectively 0.189gMnSO4.H2O, 2.437gCTAB, 1.335g urea, add after 200ml water stirring and dissolving, surface is blown into air reaction 24h.Dry with conventional method after distilled water centrifuge washing, obtain Mn 3o 4sample DS1.
Comparative example 2
Take respectively 0.189gMnSO4.H2O, 1.26gPVP (1w), 1.335g urea, add after 200ml water stirring and dissolving, surface is blown into air reaction 24h.With conventional drying after distilled water centrifuge washing, obtain Mn 3o 4sample DS2.
performance test
Electron-microscope scanning
The SEM figure that Fig. 1-4 are respectively sample S1-S4, can find out: adopt preparation method provided by the invention, use CTAB and PVP combination, can make the submicron order Mn of regular octahedral structure, good dispersity 3o 4.
Fig. 5, Fig. 6 are respectively the SEM figure of sample DS1, DS2, can find out: adopt separately CTAB or PVP, product is reunited serious.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (15)

1. a preparation method for trimanganese tetroxide, comprises step: 1) manganese source, cetyl trimethylammonium bromide, Polyvinylpyrolidone (PVP) and alkaline precipitating agent mixed dissolution are obtained to the aqueous solution; 2) logical oxidizing atmosphere or interpolation H in the aqueous solution obtaining toward step 1) 2o 2reaction, obtains containing manganese soild oxide; 3) by step 2) obtain carry out successively carrying out washing treatment and drying treatment containing manganese soild oxide, obtain trimanganese tetroxide product.
2. preparation method according to claim 1, is characterized in that, described alkaline precipitating agent is urea.
3. preparation method according to claim 1, is characterized in that, described manganese source is selected from one or more in manganous sulfate, manganous nitrate, manganese acetate, dodecyl sodium sulfonate manganese, lauric acid manganese, manganese stearate or manganese oleate.
4. preparation method according to claim 1, is characterized in that, described oxidizing atmosphere is a kind of in air, oxygen, ozone, air-oxygen mixture, nitrogen-oxygen mixture, nitrogen-air Mixture.
5. preparation method according to claim 1, it is characterized in that, the consumption in described manganese source is 1-20mmol/L, and the consumption of cetyl trimethylammonium bromide is 1-50mmol/L, the consumption of Polyvinylpyrolidone (PVP) is 0.01-0.5mmol/L, and the consumption of alkaline precipitating agent is 50-200mmol/L.
6. preparation method according to claim 5, it is characterized in that, the consumption in described manganese source is 5-10mmol/L, the consumption of cetyl trimethylammonium bromide is 10-35mmol/L, the consumption of Polyvinylpyrolidone (PVP) is 0.05-0.2mmol/L, and the consumption of alkaline precipitating agent is 100-150mmol/L.
7. preparation method according to claim 5, is characterized in that, the mol ratio of described manganese source and cetyl trimethylammonium bromide is 1:1-10.
8. preparation method according to claim 7, is characterized in that, the mol ratio of described manganese source and cetyl trimethylammonium bromide is 1:1-5.
9. preparation method according to claim 5, is characterized in that, the mol ratio of described cetyl trimethylammonium bromide and Polyvinylpyrolidone (PVP) is 100-300:1.
10. preparation method according to claim 9, is characterized in that, the mol ratio of described cetyl trimethylammonium bromide and Polyvinylpyrolidone (PVP) is 150-200:1.
11. preparation methods according to claim 1, is characterized in that, the temperature of reacting under described oxidizing atmosphere is 75-100 ℃, and the reaction times is 8-30h.
12. preparation methods according to claim 11, is characterized in that, the temperature of reacting under described oxidizing atmosphere is 80-95 ℃, and the reaction times is 16-24h.
13. preparation methods according to claim 1, is characterized in that, described mangano-manganic oxide nanocrystalline body is of a size of 100-500nm, is shaped as Polygons.
14. preparation methods according to claim 13, is characterized in that, described Polygons is octahedra.
15. 1 kinds of trimanganese tetroxides, is characterized in that, by preparation method described in claim 1-14 any one, are prepared.
CN201210263078.3A 2012-07-27 2012-07-27 Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough Pending CN103570072A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104045113A (en) * 2014-06-06 2014-09-17 长沙飞博化工科技有限公司 Preparation method of octahedral Mn3O4 nanoparticles
CN104261477A (en) * 2014-09-19 2015-01-07 济南大学 Preparation method of Mn3O4 octahedral structure
CN106477634A (en) * 2016-10-13 2017-03-08 中国人民解放军后勤工程学院 One kind prepares Mn3O4Nanosphere and MnO2The method of nanometer sheet
CN106495226A (en) * 2016-11-07 2017-03-15 江苏理工学院 A kind of octahedra Mn3O4 and its microwave synthesis method
CN108751335A (en) * 2018-05-04 2018-11-06 中山大学 A kind of method of antibiotic in light-Fenton-like system concerted catalysis oxidative degradation water environment
CN109502649A (en) * 2019-01-04 2019-03-22 西北工业大学 A kind of octahedron Mn3O4The preparation method of particle
CN110776015A (en) * 2019-11-05 2020-02-11 江西智锂科技有限公司 Synthesis method of battery-grade trimanganese tetroxide

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440213B1 (en) * 1999-10-28 2002-08-27 The Regents Of The University Of California Process for making surfactant capped nanocrystals
JP2004292264A (en) * 2003-03-27 2004-10-21 Toda Kogyo Corp Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method
WO2009116755A2 (en) * 2008-03-15 2009-09-24 서울대학교 산학협력재단 Magnetic resonance imaging t1 contrast media containing manganese tetroxide nanoparticles and manufacturing method thereof
CN101565208A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing manganic manganous oxide nano-material
CN102060333A (en) * 2011-02-18 2011-05-18 中山火炬职业技术学院 Method for preparing manganese oxide nano-material
CN102328960A (en) * 2011-09-02 2012-01-25 上海大学 Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure
TW201210113A (en) * 2010-08-06 2012-03-01 Delta Electronics Inc Manufacturing method for porous material
CN102502849A (en) * 2011-10-31 2012-06-20 上海理工大学 Method for preparing Mn3O4 and composite nano material thereof by using manganous salt as raw material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440213B1 (en) * 1999-10-28 2002-08-27 The Regents Of The University Of California Process for making surfactant capped nanocrystals
JP2004292264A (en) * 2003-03-27 2004-10-21 Toda Kogyo Corp Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method
WO2009116755A2 (en) * 2008-03-15 2009-09-24 서울대학교 산학협력재단 Magnetic resonance imaging t1 contrast media containing manganese tetroxide nanoparticles and manufacturing method thereof
CN101565208A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing manganic manganous oxide nano-material
TW201210113A (en) * 2010-08-06 2012-03-01 Delta Electronics Inc Manufacturing method for porous material
CN102060333A (en) * 2011-02-18 2011-05-18 中山火炬职业技术学院 Method for preparing manganese oxide nano-material
CN102328960A (en) * 2011-09-02 2012-01-25 上海大学 Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure
CN102502849A (en) * 2011-10-31 2012-06-20 上海理工大学 Method for preparing Mn3O4 and composite nano material thereof by using manganous salt as raw material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PENGQU ZHANG ET AL.: ""Shape-controlled synthesis of Mn3O4 nanocrystals and their catalysis of the degradation of methylene blue"", 《NANO RESEAECH》 *
张鹏曲: ""MnOx微纳米结构形貌控制合成及其催化动力学研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104045113A (en) * 2014-06-06 2014-09-17 长沙飞博化工科技有限公司 Preparation method of octahedral Mn3O4 nanoparticles
CN104261477A (en) * 2014-09-19 2015-01-07 济南大学 Preparation method of Mn3O4 octahedral structure
CN104261477B (en) * 2014-09-19 2016-04-13 济南大学 A kind of Mn 3o 4the preparation method of octahedral structure
CN106477634A (en) * 2016-10-13 2017-03-08 中国人民解放军后勤工程学院 One kind prepares Mn3O4Nanosphere and MnO2The method of nanometer sheet
CN106495226A (en) * 2016-11-07 2017-03-15 江苏理工学院 A kind of octahedra Mn3O4 and its microwave synthesis method
CN108751335A (en) * 2018-05-04 2018-11-06 中山大学 A kind of method of antibiotic in light-Fenton-like system concerted catalysis oxidative degradation water environment
CN109502649A (en) * 2019-01-04 2019-03-22 西北工业大学 A kind of octahedron Mn3O4The preparation method of particle
CN109502649B (en) * 2019-01-04 2020-10-27 西北工业大学 Octahedron Mn3O4Process for the preparation of granules
CN110776015A (en) * 2019-11-05 2020-02-11 江西智锂科技有限公司 Synthesis method of battery-grade trimanganese tetroxide

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Application publication date: 20140212