CN104261478B - A kind of Mn3o4nano wire or the preparation method of nanometer rods - Google Patents
A kind of Mn3o4nano wire or the preparation method of nanometer rods Download PDFInfo
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- CN104261478B CN104261478B CN201410480565.4A CN201410480565A CN104261478B CN 104261478 B CN104261478 B CN 104261478B CN 201410480565 A CN201410480565 A CN 201410480565A CN 104261478 B CN104261478 B CN 104261478B
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- C01G45/00—Compounds of manganese
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of Mn3O4Nano wire or the preparation method of nanometer rods, comprise the following steps: joins in lower alcohol by manganous salt and sodium acetate, and stirring obtains clear solution；Above-mentioned clear solution employing solvent-thermal method is prepared Mn3O4Nano wire or nanometer rods；Centrifugation after reaction, washing, obtain Mn3O4Nano wire or nanometer rods.The present invention utilizes solvent-thermal method one-step synthesis Mn3O4Nano wire or nanometer rods, by changing reaction condition, the Mn obtaining required draw ratio that can be controlled3O4Nano wire or nanometer rods.Preparation technology of the present invention is simple, efficient, low raw-material cost, production cost are low, to Mn3O4Nano wire or the mass industrialized production of nanometer rods and reality thereof are applied significant.Products therefrom yield is high, purity high, pattern is homogeneous, narrow size distribution, has preferable magnetic, has a wide range of applications at catalysis, solaode, the aspect such as heavy metal ion adsorbed.
Description
Technical field
The present invention relates to a kind of Mn3O4Nano wire or the preparation method of nanometer rods, be specifically related to a kind of adjustable Mn of draw ratio3O4Nano wire or the preparation method of nanometer rods.
Background technology
Mn3O4Nano material can have the effect of reversible color due to it from brown to yellow, can apply the electrochromic material in anode material, it is also possible to applies in oxidation or reduction reaction as catalyst.One-dimensional Mn3O4Nano material, due to the physicochemical properties of its uniqueness, is generally of preferable optics, electricity and mechanical characteristic, has a wide range of applications at catalysis, solaode, the aspect such as heavy metal ion adsorbed.
Report prepares one-dimensional Mn both at home and abroad3O4Nano material is not a lot.CN 200810103467.3 discloses one and utilizes chemical vapour deposition technique to prepare Mn3O4The method of nano wire, is placed on Mn powder in aluminium sesquioxide crucible, places plated film silicon chip in surface, is passed through argon thermal treatment and obtains the Mn of tetragonal3O4Nano wire.Document " Odair P. Ferreira, Larissa
Otubo, Ricardo Romano, and Oswaldo L. Alves. Crystal Growth & Design, 2006,
6 (2), 601-606 " report the MnOOH nanometer rods of preparation has been thermally treated resulting in MnO2, Mn2O3,
Mn3O4Nanometer rods.Document " Wenzhong Wang and Ling Ao. Crystal Growth & Design,
2008,8 (1), 358-362 " report by presoma in the environment of sodium chloride by being thermally treated resulting in Mn3O4Nano wire.
At present, synthesizing one-dimensional Mn3O4The preparation process major part of nano material is required for heat treatment and higher temperature, and some method also needs to protection or the after-treatment of noble gas.Operating process is relative complex, relatively costly, is unfavorable for being accurately controlled and industrialized production.
Summary of the invention
The present invention is directed to the deficiency that existing method exists, it is provided that a kind of Mn3O4Nanometer rods or the preparation method of nano wire.This preparation method is simple to operate, one-step synthesis, it is not necessary to inert gas shielding, and the prices of raw materials are cheap, and product draw ratio is adjustable, and controllability is strong.
The present invention, with manganous salt for manganese source, mixes with sodium acetate and is made into clear solution, then uses solvent-thermal method to obtain Mn3O4Nano wire or nanometer rods.The method can be relatively simple, controlled the Mn obtaining required draw ratio3O4Nano wire or nanometer rods, have good industrial applications prospect.
Concrete technical scheme is as follows:
A kind of Mn3O4Nano wire or the preparation method of nanometer rods, comprise the following steps:
(1) joining in lower alcohol by manganous salt and sodium acetate, stirring obtains clear solution；
(2) above-mentioned clear solution employing solvent-thermal method is prepared Mn3O4Nano wire or nanometer rods；
(3) centrifugation, washing after reaction, obtains Mn3O4Nano wire or nanometer rods.
In said method, the nanometer rods of indication, be diameter at 500nm or following, draw ratio exists20Following material；The nano wire of indication, refer to diameter at 500nm or following, draw ratio material more than 30.
By means of the invention it is also possible to be easily obtained Mn3O4Nano wire or nanometer rods, gained Mn3O4A diameter of 70-500 nm of nano wire, draw ratio is 30-240；Mn3O4A diameter of 70-500 nm of nanometer rods, draw ratio is7-20。
In above-mentioned steps (1), bivalence water-soluble manganese salt is 1:4-20 with the mol ratio of sodium acetate.Manganese salt is to control Mn with the mol ratio of sodium acetate3O4One of key factor of pattern.When other experiment conditions keep constant, manganese salt is relatively low with the mol ratio of sodium acetate, when being in 1:4-9 scope, and available Mn3O4Nanometer rods；When manganese salt is higher with the mol ratio of sodium acetate, when being in 1:10-20 scope, available Mn3O4Nano wire.The relative amount of sodium acetate is the highest, Mn3O4The length of nanostructured is the longest.
In above-mentioned steps (1), described lower alcohol is methanol, ethanol, propanol, butanol or isopropanol.
In above-mentioned steps (1), the described nitrate that bivalence water-soluble manganese salt is manganese or halogenide.
In above-mentioned steps (1), bivalence water-soluble manganese salt concentration in clear solution is 0.06-0.15 mol/L.
In above-mentioned steps (2), the temperature of solvent-thermal method is 160-190 DEG C.
In above-mentioned steps (2), the response time of solvent-thermal method is 8-30 h, preferably 14-30 h.
In said method of the present invention, by changing reaction condition, the Mn of different draw ratio can be obtained3O4Nano wire or nanometer rods, controllability is strong.Manganese salt and the mol ratio of sodium acetate, and the dicyandiamide solution (alcohol system) used by reaction is to Mn3O4Pattern be formed with important function, by their cooperation, nano wire or the nanorod structure of required pattern can be obtained.Additionally, the Mn of different draw ratio can be obtained by the adjustment concentration of manganese salt, the temperature and time of solvent-thermal method3O4Nano wire or nanometer rods, the selection of these conditions can also make that the pattern of product is the most regular, distribution of sizes is narrower.
The present invention utilizes solvent-thermal method one-step synthesis Mn3O4Nano wire or nanometer rods, by changing the conditions such as manganese salt and the mol ratio of sodium acetate, the concentration of manganese salt, reaction temperature, response time, the Mn obtaining required draw ratio that can be controlled3O4Nano wire or nanometer rods.Preparation technology of the present invention is simple, efficient, low raw-material cost, production cost are low, can regulate and control to obtain the Mn of different draw ratios by controlling reaction condition3O4Nano wire or nanometer rods, to Mn3O4Nano wire or the mass industrialized production of nanometer rods and reality thereof are applied significant.Products therefrom yield is high, purity high, pattern is homogeneous, narrow size distribution, has preferable magnetic, has a wide range of applications at catalysis, solaode, the aspect such as heavy metal ion adsorbed.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) picture of the manganic manganous oxide nanometer wire of the embodiment of the present invention 1 synthesis.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the manganic manganous oxide nanometer wire of the embodiment of the present invention 1 synthesis.
Fig. 3 is hysteresis curve (VSM) collection of illustrative plates of the manganic manganous oxide nanometer wire of the embodiment of the present invention 1 synthesis.
Fig. 4 is scanning electron microscope (SEM) picture of the trimanganese tetroxide nano rod of the embodiment of the present invention 3 synthesis.
Fig. 5 is scanning electron microscope (SEM) picture of the mangano-manganic oxide structure of comparative example 1 of the present invention synthesis.
Detailed description of the invention
Below by embodiment, the present invention will be further elaborated, and its content, only for explaining the present invention, is not defined by the description below.
Embodiment
1
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 2.914 g are joined in 25 mL ethanol and stir to clarify by 1.1；
Above-mentioned solution is transferred in reactor by 1.2, reacts 16 h at 180 DEG C；
After 1.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 80-130 nm, draw ratio is the Mn of 65-853O4Nano wire.The SEM of product schemes as it is shown in figure 1, it can be seen that products obtained therefrom pattern is regular, single, smooth surface.The XRD figure of product is as in figure 2 it is shown, XRD result keeps consistent with standard x RD card (24-0734), it was demonstrated that the crystalline phase of products therefrom is Mn3O4Phase.The hysteresis curve of product is as shown in Figure 3, it can be seen that the magnetic performance of product is good, and its magnetic saturation intensity is 0.0236 emu/g, and coercivity is 98.7 Oe.
Embodiment
2
The four nitric hydrate manganese of 0.628 g, the sodium acetate of 4.100 g are joined in 40 mL methanol and stir to clarify by 2.1；
Above-mentioned solution is transferred in reactor by 2.2, reacts 25 h at 190 DEG C；
After 2.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 380-430 nm, draw ratio is the Mn of 92-1103O4Nano wire.
Embodiment
3
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 1.457 g are joined in 25 mL ethanol and stir to clarify by 3.1；
Above-mentioned solution is transferred in reactor by 3.2, reacts 16 h at 180 DEG C；
After 3.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 130-160 nm, draw ratio is the Mn of 15-183O4Nanometer rods, the SEM of product schemes as shown in Figure 4, it can be seen that products obtained therefrom is club shaped structure, smooth surface.
Embodiment
4
The four nitric hydrate manganese of 0.628 g, the sodium acetate of 3.076 g are joined in 17 mL propanol and stir to clarify by 4.1；
Above-mentioned solution is transferred in reactor by 4.2, reacts 9 h at 160 DEG C；
After 4.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 75-110 nm, draw ratio is the Mn of 80-1023O4Nano wire.
Embodiment
5
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 2.060 g are joined in 20 mL butanol and stir to clarify by 5.1；
Above-mentioned solution is transferred in reactor by 5.2, reacts 29 h at 170 DEG C；
After 5.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 175-210 nm, draw ratio is the Mn of 52-743O4Nano wire.
Embodiment
6
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 1.840 g are joined in 30 mL isopropanols and stir to clarify by 6.1；
Above-mentioned solution is transferred in reactor by 6.2, reacts 8 h at 170 DEG C；
After 6.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 95-120 nm, draw ratio is the Mn of 12-163O4Nanometer rods.
Embodiment
7
The four nitric hydrate manganese of 0.628 g, the sodium acetate of 1.330 g are joined in 17 mL methanol and stir to clarify by 7.1；
Above-mentioned solution is transferred in reactor by 7.2, reacts 24 h at 170 DEG C；
After 7.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 180-195 nm, draw ratio is the Mn of 14-173O4Nanometer rods.
Embodiment
8
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 0.83 g are joined in 40 mL butanol and stir to clarify by 8.1；
Above-mentioned solution is transferred in reactor by 8.2, reacts 10 h at 180 DEG C；
After 8.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 165-178 nm, draw ratio is the Mn of 10-133O4Nanometer rods.
Embodiment
9
The four nitric hydrate manganese of 0.628 g, the sodium acetate of 1.025 g are joined in 22 mL isopropanols and stir to clarify by 9.1；
Above-mentioned solution is transferred in reactor by 9.2, reacts 28 h at 190 DEG C；
After 9.3 reactions terminate, through centrifugation and washing, obtaining a diameter of 220-245 nm, draw ratio is the Mn of 9-133O4Nanometer rods.
Comparative example
1
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 0.728 g are joined in 25 mL ethanol and stir to clarify by 1.1；
Above-mentioned solution is transferred in reactor by 1.2, reacts 16 h at 180 DEG C；
After 1.3 reactions terminate, through centrifugation and washing, obtain the Mn that pattern mixes3O4Structure, as it is shown in figure 5, product Mn3O4Microscopic appearance be granule and one-dimentional structure coexists.
Comparative example
2
The four nitric hydrate manganese of 0.628 g, the sodium hydroxide of 0.725 g are joined in 30 mL methanol and stir to clarify by 2.1；
Above-mentioned solution is transferred in reactor by 2.2, reacts 16 h at 170 DEG C；
After 2.3 reactions terminate, through centrifugation and washing, the product obtained is irregular granule, distribution of sizes heterogeneity.
Comparative example
3
The four chloride hydrate manganese of 0.495 g, the sodium acetate of 1.640 g are joined in 25 mL water and stir to clarify by 3.1；
Above-mentioned solution is transferred in reactor by 3.2, reacts 20 h at 170 DEG C；
After 3.3 reactions terminate, through centrifugation and washing, the product obtained is octahedral structure, pattern rule, smooth surface.
Claims (4)
1. a Mn3O4Nano wire or the preparation method of nanometer rods, is characterized in that comprising the following steps:
(1) joining in lower alcohol by manganous salt and sodium acetate, stirring obtains clear solution；
(2) above-mentioned clear solution employing solvent-thermal method is prepared Mn3O4Nano wire or nanometer rods；
(3) centrifugation, washing after reaction, obtains Mn3O4Nano wire or nanometer rods；
In step (1), manganous salt is 1:4-20 with the mol ratio of sodium acetate；
In step (1), described lower alcohol is methanol, ethanol, propanol, butanol or isopropanol；
In step (1), manganous salt concentration in clear solution is 0.06-0.15 mol/L；
In step (2), the temperature of solvent-thermal method is 160-190 DEG C, and the time is 8-30 h.
Preparation method the most according to claim 1, is characterized in that: in step (1), when the mol ratio of manganous salt Yu sodium acetate is 1:4-9, and gained Mn3O4Structure is Mn3O4Nanometer rods；When the mol ratio of manganous salt Yu sodium acetate is 1:10-20, gained Mn3O4Structure is Mn3O4Nano wire.
Preparation method the most according to claim 1 and 2, is characterized in that: in step (1), and described manganous salt is nitrate or the halogenide of manganese.
Preparation method the most according to claim 1 and 2, is characterized in that: Mn3O4A diameter of 70-500 nm of nano wire, draw ratio is 30-240；Mn3O4A diameter of 70-500 nm of nanometer rods, draw ratio is 7-20.
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| CN105797698B (en) * | 2016-04-13 | 2018-06-26 | 同济大学 | A kind of petal-shaped MoS2-Mn3O4The preparation method and application of nanowire magnetic composite material |
| CN107555480B (en) * | 2017-09-19 | 2019-04-05 | 济南大学 | A kind of wax crayon shape Mn3O4The preparation method and products obtained therefrom of microstructure |
| CN108273518B (en) * | 2018-01-17 | 2021-03-02 | 济南大学 | Flower-shaped composite structure SnS2/Mn3O4Synthetic method of (2) and the resulting product |
| CN110040783B (en) * | 2019-05-20 | 2021-09-10 | 新乡医学院 | Manganous-manganic oxide nano material, preparation method and application thereof |
| CN111087030A (en) * | 2019-12-20 | 2020-05-01 | 佛山科学技术学院 | LiNi0.5Mn1.5O4Method for producing materials and use thereof |
| CN115028202B (en) * | 2022-01-13 | 2022-12-27 | 渤海大学 | Preparation of high saturation magnetization Mn 3 O 4 Method for magnetic nano rod |
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