CN105129859A - Preparation method of octagonal Mn3O4 nano particles - Google Patents
Preparation method of octagonal Mn3O4 nano particles Download PDFInfo
- Publication number
- CN105129859A CN105129859A CN201510577465.8A CN201510577465A CN105129859A CN 105129859 A CN105129859 A CN 105129859A CN 201510577465 A CN201510577465 A CN 201510577465A CN 105129859 A CN105129859 A CN 105129859A
- Authority
- CN
- China
- Prior art keywords
- preparation
- octahedra
- nano particle
- water
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of octagonal Mn3O4 nano particles. In the mixed solvent consisting of N-N-dimethylformamide (DMF) and water, potassium permanganate is used as a raw material to prepare an octagonal Mn3O4 catalyst in a one-step hydrothermal method. By controlling the ratio of DMF and water, the hydrothermal reaction temperature and reaction time, the control synthesis of a target product can be realized. The preparation method has advantages of simple process, low cost, short period and the like and is suitable for industrialized production. The prepared octagonal Mn3O4 nano material is regular in shape, uniform in particle distribution and excellent in oxygen reduction catalytic performance.
Description
Technical field
The invention belongs to the synthesis technical field of chemical power source nano material, be specifically related to a kind of octahedra Mn
3o
4the preparation method of nano particle.
Background technology
The energy nano material of specific morphology has noticeable physics and chemical property, is the focus of research always.The nano material of special appearance has unique nanostructure, is widely used in fundamental research and industrial application, such as lithium ion battery, gas sensor, catalysis industry and stored energy.Up to the present, about the method for the nano material of synthesizing special appearance is appeared in the newspapers repeatly, common synthetic method comprises the thermolysis of metal precursor, sol-gel method, hydrothermal method etc.
In transition metal, Mn oxide is the emphasis of research always, and it is widely used, and comprises lithium ion battery, electrocatalysis, molecular adsorption and magneticsubstance etc.Although about the report of the monodispersed Mn oxide nanocrystal of synthesis high quality has a lot, the synthesis condition of a lot of method is harsh, or employs a large amount of toxic raw materials, or productive rate is lower.On the other hand, relevant synthesizing octahedral Mn
3o
4the relevant report of nano particle is fewer.ZhangLichun etc. (Chem.Mater.2009,21,5066-5071) take potassium permanganate as raw material, and with n-Laurylamine-alcohol solvent, sodium sulfate is additive, and under the hydrothermal condition of 180 DEG C, reaction just obtains Mn in 48 hours
3o
4octahedron, the method is complex process not only, and the reaction times is long especially, is very unfavorable for suitability for industrialized production; ZhangPengqu etc. (NanoRes.2010,3,235-243) have adopted soft template method to synthesize in the octahedra Mn of quadrangle distortion
3o
4, the method adopts two step line synthesizing octahedral Mn
3o
4, the first step is coprecipitation presoma Mn (OH)
2, second step is that sintering process is to obtain octahedra Mn
3o
4, due to co-precipitation chronic (24h), the control ratio of processing condition is harsher.
On the other hand, owing to having cheap price and higher electro catalytic activity, Mn oxide substitutes precious metal and does the focus that oxygen reduction catalyst is research always.Focused mostly at doping or load carbon material about the research of Mn oxide to put forward electroconductibility in recent years, and the Mn oxide synthesizing special appearance may have and exposes crystal face especially, greatly may promote that oxygen is in the absorption of oxide surface, at present about the octahedra Mn of the specific exposed crystal face of synthesis
3o
4report as aluminium-air cell air electrode catalyst is few.The present invention devises a kind of relatively mild technology of preparing and has synthesized the Mn of shape of octahedron
3o
4nano particle, is applied to aluminium-air cell positive pole, and this material shows excellent hydrogen reduction electro catalytic activity.
Summary of the invention
It is simple that object of the present invention proposes a kind of technique, with low cost, is suitable for the Mn of large-scale production
3o
4octahedral preparation method.
The object of the present invention is achieved like this, the octahedra Mn of described one
3o
4the preparation method of nano particle, is characterized in that, comprises the following steps:
(1) potassium permanganate is joined in the mixing solutions containing N-N-dimethyl formamide and water, stir;
(2) transfer in autoclave by the mixed solution that step (1) obtains, reactor is inserted in air dry oven again, reacts, and naturally cools to room temperature after completion of the reaction, takes out;
(3) filtration, washing, drying, finally grinding obtains product.
Described N-N-dimethyl formamide and H
2the volume ratio of O is 0.1-1.
Water described in above-mentioned steps (1) is deionized water or distilled water.
Temperature of reaction in described autoclave is 100 DEG C-250 DEG C.
Reaction times in described autoclave is 6 hours-15 hours.
Decompress filter is filtered into described in above-mentioned steps (3).
Drying described in above-mentioned steps (3) is vacuum-drying.
Described vacuum-drying temperature 60-100 DEG C, 10-24 hours time.
The pure phase Mn that the above-mentioned method of the present invention is obtained
3o
4,described pure phase Mn
3o
4for the regular octahedron of pattern rule, particle diameter is 400-500nm.
The octahedra Mn of one of the present invention
3o
4nano particle prepares the method for air electrode, comprises the steps: pure phase Mn obtained for above-mentioned arbitrary described method
3o
4or above-mentioned pure phase Mn
3o
4fully mix by 3:3:1:3 mass ratio with gac, acetylene black and binding agent PTFE, take dehydrated alcohol as solvent, ultrasonic disperse is after 30 minutes, be transferred in 90 DEG C of water-baths and obtain rubber pureed mixture after removing ethanol, be rolled into the catalytic film that thickness is 0.2mm again, waterproof membrane adopts the method preparation same with catalytic film, and its thickness is similarly 0.2mm; Wherein the massfraction of acetylene black is 40%, and the massfraction of binding agent PTFE emulsion is 60%, take nickel foam as collector, according to waterproof membrane, collector, the order of catalytic film is hot pressed into air electrode, and 320 DEG C of thermal treatments obtain air electrode finished product in 30 minutes in retort furnace.
Specifically, the octahedra Mn of one of the present invention
3o
4the preparation method of nano particle, comprises the following steps:
(1) potassium permanganate is joined in the mixing solutions containing N-N-dimethyl formamide and water, stir;
(2) to be mixed evenly after, transferred in autoclave, reactor is inserted in air dry oven again, reacts, and naturally cools to room temperature after completion of the reaction, takes out;
(3) filtration, washing, drying, finally grinding obtains product.
Described N-N-dimethyl formamide and H
2the volume ratio of O is 0.1-1.
Water described in step (1) is the one in deionized water or distilled water.
Temperature of reaction in described autoclave is 100 DEG C-250 DEG C.
Reaction times in described autoclave is 6 hours-15 hours.
Decompress filter is filtered into described in step (3).
Drying described in step (3) is vacuum-drying.
Vacuum-drying temperature 60 C-100 DEG C, 10-24 hours time.
The present invention has following distinguishing feature:
1) advantages such as raw material of the present invention is simple, low in the pollution of the environment, has technique simple, with low cost, are applicable to suitability for industrialized production;
2) the octahedra Mn for preparing of the present invention
3o
4pattern rule, and particle size is nano level.
3) the octahedra Mn for preparing of the present invention
3o
4nanoparticle has outstanding hydrogen reduction catalytic performance.
4) positively effect: the present invention adopts water heat transfer to have the Mn of shape of octahedron
3o
4nano material, due to the microtexture that it is special, this material may play its special performance in various fields, as the negative material as lithium ion battery, or the presoma of synthetic lithium manganate, or electrocatalysis material.The present invention will be octahedra Mn
3o
4the further investigation of nano material and commercial application supplying method are from now on supported.
Accompanying drawing explanation
Fig. 1 is the octahedra Mn of embodiment 1 gained
3o
4x ray diffracting spectrum.
Fig. 2 is the octahedra Mn of embodiment 1 gained
3o
4scanning electron microscope (SEM) photograph.
Fig. 3 is embodiment 3 gained Mn
3o
4x ray diffracting spectrum.
Fig. 4 is embodiment 3 gained Mn
3o
4scanning electron microscope (SEM) photograph.
Fig. 5 is the octahedra Mn of embodiment 1 gained
3o
4prepare air electrode at 0 ~-0.6V, scanning speed is the polarization curve under 2mV/s.
Embodiment
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Take 0.4g potassium permanganate for subsequent use, accurately measure 20mlN-N-dimethyl formamide (DMF) and 50ml deionized water, after the two being mixed, add potassium permanganate again.To be mixed evenly after, to be transferred to volume be 100ml is in the autoclave of liner with tetrafluoroethylene, insert in air dry oven, arranging temperature of reaction is 140 DEG C, and the reaction times is 12 hours, reactor is taken out after question response, naturally cool to room temperature, decompress filter, washing, 60 DEG C of vacuum-drying 24 hours, finally grinding obtains product.Products therefrom is carried out XRD sign, and its XRD figure spectrum is shown in Fig. 1, shows that the product adopting the preparation of the present embodiment is pure phase Mn
3o
4.Show the scanning electron microscopic observation (Fig. 2) of product, products obtained therefrom is the regular octahedron of pattern rule, and particle diameter is 400-500nm.
By the pure phase Mn be prepared into
3o
4, gac, acetylene black and binding agent PTFE fully mix in the ratio (3:3:1:3) of certain mass, take dehydrated alcohol as solvent, ultrasonic disperse is after 30 minutes, be transferred in 90 DEG C of water-baths and obtain rubber pureed mixture after removing ethanol, be rolled into the catalytic film of 0.2mm again, it is 0.2mm that waterproof membrane adopts the method same with catalytic film to prepare waterproof membrane thickness, wherein the massfraction of acetylene black is 40%, the massfraction of binding agent PTFE emulsion is 60%, take nickel foam as collector, according to waterproof membrane, collector, the order of catalytic film is hot pressed into air electrode, finally in retort furnace, 320 DEG C of thermal treatments obtain finished product in 30 minutes, then at room temperature test.The electrochemical workstation adopting Shanghai Chen Hua instrument company to produce carries out linear volt-ampere test and half-cell constant-current discharge to material, and the voltage range of its neutral line volt-ampere test is 0.3 ~-0.6V, and sweep velocity is 2mVs
-1, Pt electrode is to electrode, and Hg/HgO is reference electrode, and the polarization curve of gained as shown in Figure 5.
Embodiment 2
Take 0.4g potassium permanganate for subsequent use, accurately measure 35mlN-N-dimethyl formamide (DMF) and 35ml deionized water, after the two being mixed, add potassium permanganate again.To be mixed evenly after, to be transferred to volume be 100ml is in the autoclave of liner with tetrafluoroethylene, insert in air dry oven, arranging temperature of reaction is 140 DEG C, and the reaction times is 12 hours, reactor is taken out after question response, naturally cool to room temperature, decompress filter, washing, 60 DEG C of vacuum-drying 24 hours, finally grinding obtains product.Products obtained therefrom is carried out XRD sign, and result shows that the product adopting the present embodiment to prepare is pure phase Mn
3o
4.Show the scanning electron microscopic observation of product, products obtained therefrom is the regular octahedron of pattern rule, and particle diameter is 400-500nm.
Embodiment 3
Take 0.4g potassium permanganate for subsequent use, accurately measure 20mlN-N-dimethyl formamide (DMF) and 50ml deionized water, after the two being mixed, add potassium permanganate again.To be mixed evenly after, to be transferred to volume be 100ml is in the autoclave of liner with tetrafluoroethylene, insert in air dry oven, arranging temperature of reaction is 120 DEG C, and the reaction times is 12 hours, reactor is taken out after question response, naturally cool to room temperature, decompress filter, washing, 60 DEG C of vacuum-drying 24 hours, finally grinding obtains product.Products obtained therefrom is carried out XRD sign, and its XRD figure spectrum is shown in Fig. 3, and result shows that adopting the product prepared of the present embodiment to be principal phase is Mn
3o
4, parafacies is MnOOH.Show the scanning electron microscopic observation (Fig. 4) of product, products obtained therefrom is the regular octahedron being mainly pattern rule, simultaneously also with a small amount of Rod-like shape.
Embodiment 4
Take 0.4 gram of potassium permanganate for subsequent use, accurately measure 20mlN-N-dimethyl formamide (DMF) and 50ml deionized water, after the two being mixed, add potassium permanganate again.To be mixed evenly after, to be transferred to volume be 100ml is in the autoclave of liner with tetrafluoroethylene, insert in air dry oven, arranging temperature of reaction is 140 DEG C, and the reaction times is 6 hours, reactor is taken out after question response, naturally cool to room temperature, decompress filter, washing, 60 DEG C of vacuum-drying 24 hours, finally grinding obtains product.Products obtained therefrom is carried out XRD sign, and result shows that adopting the product prepared of the present embodiment to be principal phase is Mn
3o
4, parafacies is MnOOH.Show the scanning electron microscopic observation of product, products obtained therefrom is the regular octahedron being mainly pattern rule, simultaneously also with a small amount of Rod-like shape.
Claims (10)
1. an octahedra Mn
3o
4the preparation method of nano particle, is characterized in that, comprises the following steps:
Potassium permanganate is joined in the mixing solutions containing N-N-dimethyl formamide and water, stir;
Transfer in autoclave by the mixed solution that step (1) obtains, reactor is inserted in air dry oven again, reacts, and naturally cools to room temperature after completion of the reaction, takes out;
Filtration, washing, drying, finally grinding obtains product.
2. octahedra Mn according to claim 1
3o
4the preparation method of nano particle, is characterized in that, described N-N-dimethyl formamide and H
2the volume ratio of O is 0.1-1.
3. octahedra Mn according to claim 1
3o
4the preparation method of nano particle, is characterized in that, the water described in step (1) is deionized water or distilled water.
4. octahedra Mn according to claim 1
3o
4the preparation method of nano particle, is characterized in that, the temperature of reaction in described autoclave is 100 DEG C-250 DEG C.
5. the octahedra Mn according to claim 1 or 4
3o
4the preparation method of nano particle, is characterized in that, the reaction times in described autoclave is 6 hours-15 hours.
6. octahedra Mn according to claim 1
3o
4the preparation method of nano particle, is characterized in that, is filtered into decompress filter described in step (3).
7. the octahedra Mn according to claim 1 or 2 or 3 or 4 or 5 or 6
3o
4the preparation method of nano particle, is characterized in that, the drying described in step (3) is vacuum-drying.
8. octahedra Mn according to claim 7
3o
4the preparation method of nano particle, is characterized in that, vacuum-drying temperature 60-100 DEG C, 10-24 hours time.
9. the pure phase Mn that the arbitrary described method of claim 1-8 is obtained
3o
4,described pure phase Mn
3o
4for the regular octahedron of pattern rule, particle diameter is 400-500nm.
10. an octahedra Mn
3o
4nano particle prepares the method for air electrode, comprises the steps: pure phase Mn obtained for arbitrary for claim 1-8 described method
3o
4or pure phase Mn according to claim 9
3o
4, gac, acetylene black and binding agent PTFE fully mix by 3:3:1:3 mass ratio, take dehydrated alcohol as solvent, ultrasonic disperse is after 30 minutes, be transferred in 90 DEG C of water-baths and obtain rubber pureed mixture after removing ethanol, be rolled into the catalytic film that thickness is 0.2mm again, waterproof membrane adopts the method preparation same with catalytic film, and its thickness is similarly 0.2mm; Wherein the massfraction of acetylene black is 40%, and the massfraction of binding agent PTFE emulsion is 60%, take nickel foam as collector, according to waterproof membrane, collector, the order of catalytic film is hot pressed into air electrode, and 320 DEG C of thermal treatments obtain air electrode finished product in 30 minutes in retort furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577465.8A CN105129859A (en) | 2015-09-11 | 2015-09-11 | Preparation method of octagonal Mn3O4 nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577465.8A CN105129859A (en) | 2015-09-11 | 2015-09-11 | Preparation method of octagonal Mn3O4 nano particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105129859A true CN105129859A (en) | 2015-12-09 |
Family
ID=54715521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510577465.8A Pending CN105129859A (en) | 2015-09-11 | 2015-09-11 | Preparation method of octagonal Mn3O4 nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105129859A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548696A (en) * | 2021-07-13 | 2021-10-26 | 浙江大学 | Preparation method of high-purity manganous-manganic oxide octahedral particles, product and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165964A (en) * | 2007-09-20 | 2008-04-23 | 复旦大学 | Asymmetric secondary air fuel battery |
| CN102157742A (en) * | 2011-03-18 | 2011-08-17 | 北京中航长力能源科技有限公司 | Catalyst for preparing air electrode and preparation method thereof as well as air electrode and preparation method thereof |
| CN103127929A (en) * | 2011-12-01 | 2013-06-05 | 百泽(常州)新能源科技有限公司 | Lithium air cell by utilizing graphene/oxide composite material as air electrode catalyst |
| CN103151530A (en) * | 2012-12-21 | 2013-06-12 | 中国科学院大连化学物理研究所 | Negative electrode for metal air battery and preparation method thereof |
| 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 |
-
2015
- 2015-09-11 CN CN201510577465.8A patent/CN105129859A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165964A (en) * | 2007-09-20 | 2008-04-23 | 复旦大学 | Asymmetric secondary air fuel battery |
| CN102157742A (en) * | 2011-03-18 | 2011-08-17 | 北京中航长力能源科技有限公司 | Catalyst for preparing air electrode and preparation method thereof as well as air electrode and preparation method thereof |
| CN103127929A (en) * | 2011-12-01 | 2013-06-05 | 百泽(常州)新能源科技有限公司 | Lithium air cell by utilizing graphene/oxide composite material as air electrode catalyst |
| CN103151530A (en) * | 2012-12-21 | 2013-06-12 | 中国科学院大连化学物理研究所 | Negative electrode for metal air battery and preparation method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| YULIANG ZHANG, ET AL.: "Structural evolution of Manganese oxides via surfactant-free solvothermal routes", 《ADVANCED MATERIALS RESEARCH》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548696A (en) * | 2021-07-13 | 2021-10-26 | 浙江大学 | Preparation method of high-purity manganous-manganic oxide octahedral particles, product and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104045113A (en) | Preparation method of octahedral Mn3O4 nanoparticles | |
| Chen et al. | Simple preparation of ZnCo2O4 porous quasi-cubes for high performance asymmetric supercapacitors | |
| CN102891016B (en) | A kind of cobalt acid nickel graphene composite material and application thereof and preparation method | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN104941674A (en) | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst | |
| CN102745752A (en) | Method of synthesizing mesoporous nickel cobalt oxide nanowire using hydrothermal method and application thereof | |
| CN110970630B (en) | CuO nanosheet and top-down preparation method and application thereof | |
| CN104577145B (en) | Air electrode catalyst for aluminum-air cell and preparation method of air electrode catalyst | |
| WO2021104087A1 (en) | Metal oxide nanoparticles, and preparation method therefor and application thereof | |
| CN111634954B (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| KR20130079735A (en) | Method of manufacturing graphene/metal oxide nanocomposites through microwaved-assisted synthesis | |
| Wang et al. | Plant polyphenols induced the synthesis of rich oxygen vacancies Co3O4/Co@ N-doped carbon hollow nanomaterials for electrochemical energy storage and conversion | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN102502610A (en) | Simple method for preparing a large amount of graphene | |
| CN105140494A (en) | Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material | |
| CN115044935B (en) | Preparation method and application of nano high-entropy oxide | |
| CN106745337A (en) | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method | |
| CN104649327A (en) | Controlled preparation method of nano-manganese oxide | |
| CN109671574B (en) | MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor | |
| CN112408487B (en) | Ramsdellite type manganese dioxide @ C composite material and preparation method and application thereof | |
| JP6449592B2 (en) | Low alkaline nickel lithium metal composite oxide powder and method for producing the same | |
| Ji et al. | Microwave-assisted hydrothermal synthesis of sphere-like C/CuO and CuO nanocrystals and improved performance as anode materials for lithium-ion batteries | |
| CN106825553B (en) | A kind of preparation method of cobalt-nitrogen-carbon nucleocapsid hybrid hollow porous carbon ball | |
| CN109231276A (en) | Sulfamic acid restores potassium permanganate and prepares α-MnO2The method and application of nano wire | |
| CN113186560A (en) | Ni-rich alloy3+Nickel cobaltate modified carbon ball electrode catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151209 |