CN101851008A - Method for preparing MnOOH nano rods - Google Patents
Method for preparing MnOOH nano rods Download PDFInfo
- Publication number
- CN101851008A CN101851008A CN 201010218620 CN201010218620A CN101851008A CN 101851008 A CN101851008 A CN 101851008A CN 201010218620 CN201010218620 CN 201010218620 CN 201010218620 A CN201010218620 A CN 201010218620A CN 101851008 A CN101851008 A CN 101851008A
- Authority
- CN
- China
- Prior art keywords
- mnooh
- preparing
- nano rods
- temperature
- solid
- 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.)
- Granted
Links
- 229910003174 MnOOH Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002073 nanorod Substances 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 6
- 238000009776 industrial production Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910008090 Li-Mn-O Inorganic materials 0.000 description 1
- 229910006369 Li—Mn—O Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing MnOOH nano rods, which prepares the MnOOH nano rods through a solvent thermal reaction of potassium permanganate and N,N-dimethylformamide , namely prepares the MnOOH nano rods through the following steps of: dissolving the potassium permanganate in the N,N-dimethylformamide according to a weight to volume ratio of 1:50 to 1:100 (g/ml); performing the solvent thermal reaction for 2 to 24 hours at the temperature of between 100 and 200 DEG C; then carrying out solid-liquid separation on a reaction product; washing the separated solid by using distilled water, absolute ethyl alcohol or acetone sequentially; and finally drying the washed solid at the temperature of between 30 and 100 DEG C to obtain the MnOOH nano rods. The invention aims to provide the method for preparing the MnOOH nano rods, which does not need a surface active agent or a template, has the advantages of high purity and uniform particle size distribution of the product and is suitable for industrial production. The method of the invention has simple process and simple and convenient operation and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method of the MnOOH of preparation nanometer rod.
Background technology
Alkali formula manganese oxide (MnOOH) is a kind of very important material, and it has crucial purposes in fields such as electrochemistry, battery, electrochromism.MnOOH can be used as the presoma of preparation Li-Mn-O spinel structure, Manganse Dioxide and other manganese and oxygen compound.Tradition upper body phase MnOOH generally can pass through electrochemical production.In recent years, also some bibliographical informations are arranged hydrothermal method, reverse micelle method prepare MnOOH.
Chinese patent literature CN101428860A discloses a kind of method for preparing high purity MnOOH, and this method is hydrothermal method, and it is to use MnO
2And Mn
3O
4As the reaction precursor body, earlier with MnO
2And Mn
3O
4After the mixing, add entry, reaction 0.5～60 hour is promptly down in room temperature～100 ℃.The deficiency of this method is: MnO
2And Mn
3O
4Solubleness is smaller in water, and solid state reaction is not too even, sneaks into impurity in the product easily, and has used 2 kinds of manganese sources, and its product does not have specific pattern yet.
The 35th volume S2 phase of " Rare Metals Materials and engineering " August in 2006 discloses one piece " the low temperature neutralisation prepares the research of nanometer MnOOH under the low-intensity magnetic field ", and this method is sodium hydroxide to be reacted with manganous nitrate obtain Mn (OH) being connected with
2, and under magnetic field condition, make Mn (OH)
2Change MnOOH gradually into.The deficiency of this method is: complex operation, magnetic field need be set, and also to feed nitrogen, be unsuitable for suitability for industrialized production.
2004 the 62nd the 24th phases of volume of chemistry journal disclose one piece " reverse micelle method preparation and sign of MnOOH nanometer rod ", and this method is to adopt the aqueous solution/CTAB/ propyl carbinol/heptane four components to form reversed phase micelle system and MnCl
2Making diameter is the MnOOH nanometer rod that 10nm, length are about 200nm.The deficiency of this method is: need reversed phase micelle as template, and need to adopt tensio-active agent.
Summary of the invention
The object of the present invention is to provide a kind of tensio-active agent and template of need not, product purity height, size distribution are even, are suitable for the method for preparing the MnOOH nanometer rod of suitability for industrialized production.
The technical scheme that realizes the object of the invention is: a kind of method of the MnOOH of preparation nanometer rod, it is that dinethylformamide carries out solvent thermal reaction and obtains the MnOOH nanometer rod with potassium permanganate and N.
Specifically: according to 1: 50～1: weightmeasurement ratio 100(g/ml) is dissolved in N with potassium permanganate, in the dinethylformamide, under 100 ℃～200 ℃ temperature, carry out solvent thermal reaction 2h～24h, then reacted product is carried out solid-liquid separation, solid after separating with distilled water, dehydrated alcohol or washing with acetone successively, drying solid obtains the MnOOH nanometer rod under 30 ℃～100 ℃ temperature at last.The temperature of drying solid is preferably 50 ℃～90 ℃.
The positively effect that the present invention has: (1) method of the present invention need not add tensio-active agent and not have the effect of template, but adopt not only as reductive agent but also as the N of solvent, dinethylformamide and potassium permanganate carry out solvent thermal reaction, finally obtain the MnOOH nanometer rod that size distribution is even, purity is high.(2) method technology of the present invention is simple, easy and simple to handle, is suitable for suitability for industrialized production.
Description of drawings
Transmission electron microscope (TEM) figure of the MnOOH nanometer rod that Fig. 1 makes for embodiments of the invention 1;
X-ray diffraction (XRD) figure of the MnOOH nanometer rod that Fig. 2 makes for embodiments of the invention 1.
Embodiment
(embodiment 1)
Take by weighing the potassium permanganate of 0.2g, it is dissolved in the N of 15mL, in the dinethylformamide, in confined conditions, make the temperature of reaction system rise to 120 ℃, under 120 ℃ temperature, carry out solvent thermal reaction 10h by temperature controlling system control reaction system, this reaction also is a redox reaction, principal product wherein is an alkali formula manganese oxide (MnOOH), and alkali formula manganese oxide is solid, and all the other products are dissolved in the liquid system.Post reaction mixture is carried out solid-liquid separation by the mode or the filtering mode of centrifugation, remove fluent meterial, stay solid alkali formula manganese oxide, use distilled water and absolute ethanol washing solid then successively, last solid 2-3 hour after vacuum-drying washing under 80 ℃ the temperature, air pressure in the loft drier is 0.01-0.03MPa, and obtaining diameter is 8nm～12nm, and length is the MnOOH nanometer rod of 50nm～500nm.
(embodiment 2～embodiment 5)
Each embodiment is substantially the same manner as Example 1, and difference sees Table 1.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Potassium permanganate | 0.2g | 0.2g | 0.2g | 0.2g | 0.2g |
| N, dinethylformamide | 15mL | 18mL | 20mL | 15mL | 16mL |
| Temperature of reaction | 120℃ | 140℃ | 140℃ | 110℃ | 130℃ |
| Reaction times | 10h | 12h | 12h | 20h | 8h |
| |
80 |
60℃ | 70℃ | 90℃ | 50℃ |
| Diameter | 8nm～12nm | 6nm～10nm | 10nm～15nm | 7nm～10nm | 8nm～11nm |
| Length | 50nm～500nm | 40nm～400nm | 60nm～600nm | 40nm～450nm | 55nm～550nm |
Claims (3)
1. method for preparing the MnOOH nanometer rod is characterized in that: with potassium permanganate and N, dinethylformamide carries out solvent thermal reaction and obtains the MnOOH nanometer rod.
2. the method for preparing the MnOOH nanometer rod according to claim 1, it is characterized in that: according to 1: 50～1: weightmeasurement ratio 100(g/ml) is dissolved in N with potassium permanganate, in the dinethylformamide, under 100 ℃～200 ℃ temperature, carry out solvent thermal reaction 2h～24h, then reacted product is carried out solid-liquid separation, solid after separating with distilled water, dehydrated alcohol or washing with acetone successively, drying solid obtains the MnOOH nanometer rod under 30 ℃～100 ℃ temperature at last.
3. the method for preparing the MnOOH nanometer rod according to claim 2 is characterized in that: the temperature of drying solid is 50 ℃～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102186204A CN101851008B (en) | 2010-07-06 | 2010-07-06 | Method for preparing MnOOH nano rods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102186204A CN101851008B (en) | 2010-07-06 | 2010-07-06 | Method for preparing MnOOH nano rods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101851008A true CN101851008A (en) | 2010-10-06 |
| CN101851008B CN101851008B (en) | 2011-11-23 |
Family
ID=42802725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102186204A Expired - Fee Related CN101851008B (en) | 2010-07-06 | 2010-07-06 | Method for preparing MnOOH nano rods |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101851008B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001709A (en) * | 2010-12-24 | 2011-04-06 | 江苏技术师范学院 | Preparation method of basic manganese oxide nanorods |
| CN102041553A (en) * | 2010-12-21 | 2011-05-04 | 浙江大学 | Preparation method and application of crystalline-state beta-MnOOH nanowire |
| CN102092789A (en) * | 2011-04-07 | 2011-06-15 | 青岛科技大学 | Preparation method of beta-MnOOH hexagonal nanosheet |
| CN103496745A (en) * | 2013-10-09 | 2014-01-08 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| 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 |
| CN104383920A (en) * | 2014-11-18 | 2015-03-04 | 安徽师范大学 | Preparation method and application of MnOOH/Ag nano-composite material |
| CN104386756A (en) * | 2014-10-20 | 2015-03-04 | 中国科学院海洋研究所 | Mimic enzyme material as well as preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215006A (en) * | 2008-01-08 | 2008-07-09 | 北京科技大学 | Method for preparing high quality manganese oxides by using mixed manganese oxides as predecessor |
| CN101428860A (en) * | 2008-12-08 | 2009-05-13 | 北京科技大学 | Method for producing high purity MnOOH |
-
2010
- 2010-07-06 CN CN2010102186204A patent/CN101851008B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215006A (en) * | 2008-01-08 | 2008-07-09 | 北京科技大学 | Method for preparing high quality manganese oxides by using mixed manganese oxides as predecessor |
| CN101428860A (en) * | 2008-12-08 | 2009-05-13 | 北京科技大学 | Method for producing high purity MnOOH |
Non-Patent Citations (3)
| Title |
|---|
| 《J Mater Sci》 20070906 Fu Zhou et al. Synthesis of gamma-MnOOH nanorods and their isomorphous transformation into beta-MnO2 and alpha-Mn2O3 nanorods 第9978-9982页 1-3 第42卷, 2 * |
| 《人工晶体学报》 20060831 张元广等 水热法生长棒状MnOOH和MnO2晶体 第705－708页 1－3 第35卷, 第4期 2 * |
| 《无机化学学报》 20061231 糜裕宏等 多枝状gamma-MnOOH的低温水热合成与表征 第2242-2246页 1-3 第22卷, 第12期 2 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041553A (en) * | 2010-12-21 | 2011-05-04 | 浙江大学 | Preparation method and application of crystalline-state beta-MnOOH nanowire |
| CN102041553B (en) * | 2010-12-21 | 2012-06-27 | 浙江大学 | Preparation method and application of crystalline-state beta-MnOOH nanowire |
| CN102001709A (en) * | 2010-12-24 | 2011-04-06 | 江苏技术师范学院 | Preparation method of basic manganese oxide nanorods |
| CN102092789A (en) * | 2011-04-07 | 2011-06-15 | 青岛科技大学 | Preparation method of beta-MnOOH hexagonal nanosheet |
| CN102092789B (en) * | 2011-04-07 | 2012-01-25 | 青岛科技大学 | Preparation method of beta-MnOOH hexagonal nanosheet |
| CN103496745A (en) * | 2013-10-09 | 2014-01-08 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| CN103496745B (en) * | 2013-10-09 | 2015-04-29 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| 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 |
| CN104386756A (en) * | 2014-10-20 | 2015-03-04 | 中国科学院海洋研究所 | Mimic enzyme material as well as preparation and application thereof |
| CN104386756B (en) * | 2014-10-20 | 2015-10-21 | 中国科学院海洋研究所 | A kind of analogue enztme material and Synthesis and applications |
| CN104383920A (en) * | 2014-11-18 | 2015-03-04 | 安徽师范大学 | Preparation method and application of MnOOH/Ag nano-composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101851008B (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101851008B (en) | Method for preparing MnOOH nano rods | |
| CN103058278B (en) | Preparation method of tin antimony oxide nano-powder | |
| CN104129810A (en) | Preparation of pure monoclinic phase thorny-sphere-like lanthanum carbonate oxide (La2O2CO3) three-dimensional multi-stage structure | |
| CN107792887A (en) | A kind of high-specific surface area ZnMn2O4Preparation method | |
| CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
| CN102030371A (en) | Preparation method of manganese dioxide nanowire with high aspect ratio | |
| CN106698527A (en) | Hydrothermal method for preparing nanometer nickel cobaltate by taking ethylene glycol and water as solvent system | |
| CN108948368B (en) | Method for rapidly preparing nickel-based metal organic framework material | |
| CN103482689B (en) | Method for preparing nano lead stannate powder by microwave hydrothermal/solvothermal process | |
| CN105329948A (en) | Novel preparation method for gamma-MnOOH of net structure | |
| CN105562704A (en) | Method for preparing cobalt nanometer magnetic material through hydrothermal synthesis method | |
| Zeng et al. | Facile synthesis of self-assembled porous NiO nanostructures and their application to supercapacitor electrodes | |
| CN103432973A (en) | Method for preparing graphene-ferric oxide nano-particle composite material | |
| CN108262051B (en) | Method for synthesizing cerium dioxide-bismuthyl carbonate nano composite by mechanical ball milling heat treatment two-step method | |
| CN103071479A (en) | Preparation method for double-rare earth element lanthanum and gadolinium codoped titanium dioxide nanotube | |
| CN107459063B (en) | A kind of manganese molybdate micro Nano material and its preparation method and application | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres | |
| CN102001709B (en) | Preparation method of basic manganese oxide nanorods | |
| CN106082298A (en) | A kind of preparation method of cerium bismuth composite oxide nano-bar material | |
| CN103771490B (en) | A kind of simple and easy stirring at room temperature prepares the method for micro-/ nano zinc oxide | |
| CN106082363B (en) | Iron-doped Nickel Oxide composite hollow ball array films and preparation method thereof | |
| CN109231276A (en) | Sulfamic acid restores potassium permanganate and prepares α-MnO2The method and application of nano wire | |
| CN105129834A (en) | Preparation method for nanoscale rare earth oxide powder | |
| CN105439213B (en) | A kind of nano nickel cobalt oxide and preparation method thereof | |
| CN104909409A (en) | Preparation method of one-dimensional Euphorbia-milii-shaped WO3 microcrystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU UNIVERSITY OF TECHNOLOGY Effective date: 20130903 Owner name: JIANGSU TIANHENG NANOMETER TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: JIANGSU TECHNOLOGY NORMAL COLLEGE Effective date: 20130903 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 213001 CHANGZHOU, JIANGSU PROVINCE TO: 226600 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130903 Address after: 226600 Nantong, Haian, east of the town of East China Sea Road (East), No. 18, No. Patentee after: Jiangsu Tianheng Nanometer Technology Co., Ltd. Patentee after: Jiangsu University of Technology Address before: 213001 Changzhou Province in the Clock Tower District, Jiangsu, Wu Road, No. 1801 Patentee before: Jiangsu Teachers University of Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111123 Termination date: 20170706 |