CN103232070A - Method for preparing rod-like basic type manganese oxide nanometer material - Google Patents
Method for preparing rod-like basic type manganese oxide nanometer material Download PDFInfo
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- CN103232070A CN103232070A CN2013101635411A CN201310163541A CN103232070A CN 103232070 A CN103232070 A CN 103232070A CN 2013101635411 A CN2013101635411 A CN 2013101635411A CN 201310163541 A CN201310163541 A CN 201310163541A CN 103232070 A CN103232070 A CN 103232070A
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- manganese oxide
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- alkali formula
- nanometer material
- oxide nanometer
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Abstract
The invention provides a method for preparing a rod-like basic type manganese oxide nanometer material. The method comprises the following steps of: with manganese acetate tetrahydrate and ammonium peroxydisulfate serving as raw materials, preparing 0.1mol.L-1 Mn(CH3COO)2 solution and 0.1mol.L-1 (NH4)2S2O8 solution; directly carrying out hydrothermal reaction for 24 hours at 160 DEG C in a stainless steel reaction kettle which is provided with a teflon inner tank under the condition that the molar ratio of manganese acetate tetrahydrate to ammonium peroxydisulfate is not less than 2, so as to obtain a basic manganese oxide nanometer material; washing the product with distilled water and absolute ethyl alcohol three times, respectively; and drying at room temperature, thus obtaining the rod-like basic manganese oxide nanometer material, wherein the product has crystal diameter ranging from 30 nm to 300nm and crystal length ranging from 3 microns to 8 microns, and has uniform and dense morphology. The method is simple and convenient to operate, hardly causes the environment pollution, and is short in reaction time and good in reaction repeatability. The method does not need a surface active agent, can realize large-scale preparation, and is convenient for industrial production and technology promotion.
Description
Technical field:
The invention belongs to material chemistry technical field, relate in particular to a kind of chemical process for preparing bar-shaped alkali formula manganese oxide nano material.
Background technology:
Nanoscale science and technology is cross-centennial new subject, will develop into the gordian technique of 21 century.The nanoscale science and technology field comprises nanoelectronics, nanomaterial science, nanobiology, nanomechanics, nanometer micrology and nanometer manufacturing etc.As seen, nanoscale science and technology is the cross-section subject of a multidisciplinary intersection, be to be born on the basis that modern physics and advanced engineering combine, and be the novel science and technology that a subject and hi-tech are combined closely.The connotation of " nanometer " not only refers to space scale, the more important thing is to propose a kind of new way of thinking, and namely the mankind will utilize more and more forr a short time, and fine techniques manufactures a finished product more and more accurately, to satisfy high-level demand.Progress in recent years shows that scientists has realized the manipulation to single atom.Certainly, making the product with specific function still needs the time.Carrying out nanoscale science and technology research, is the potential information of an exploitation material and the Important Project of structure potentiality.It will make the ability of the long-pending material storage of monomer and process information realize leap again, cause the ability of human knowledge and reforming world important breakthrough to occur, thereby national economy is produced far-reaching influence.
In the last few years, monodimension nanometer material as nanometer rod, nano wire, nanotube etc., because it has novel chemistry and physical property and the potential application aspect nano-device, and had caused the research interest that people are strong.At present, the synthetic method of monodimension nanometer material has many kinds, as template, adopts carbon nanotube, porous alumina formwork to wait the synthesizing one-dimensional nano material.Solution method synthesizing one-dimensional nano material, existing bibliographical information so far, wherein, hydrothermal method is a kind of relatively more popular solution synthetic method, has been used to the nanometer rod, nano wire, nanotube of synthetic multiple material etc.Consider that from application point of view it is more gentle to explore preparation condition, method is more simple, and suitable mass-produced technology of preparing with monodimension nanometer material of good crystal formation remains long-term challenge.
Alkali formula manganese oxide (MnOOH) is a kind of very important solid matter, it all has a very wide range of applications at aspects such as soft magnetic materials, electrochemical material, electrochromic material, catalytic material, ion-exchange materials, thereby is attracting the eyeball of researcher always.Recent studies show that one-dimensional material in peculiar property and application prospect that fields such as light, electricity, magnetic, catalysis show, makes the extremely numerous investigators' of preparation research the concern of one dimension alkali formula manganese oxide, and MnOOH can be used as Li-Mn-O spinel structure and MnO
2Wait the presoma of other manganese and oxygen compounds, and manganese and oxygen compound is also having very superior performance aspect secondary cell, molecular sieve and the catalysis, a lot of bibliographical informations are arranged in this respect in recent years, as simple calcining γ-MnOOH nanometer rod in air such as Yang, obtained α-MnO
2, β-MnO
2And Mn
3O
4Nanometer rod.Recently, about branched manganese and oxygen compound synthetic a spot of report is arranged.David etc. have synthesized six branch MnO with o, and Zhong etc. have obtained multiple-limb dumbbell shape MnO, and usefulness low temperature reflux methods such as Zheng have been synthesized branched α-MnO
2For a long time, manganese and oxygen compound is subjected to scientific circles always and pays close attention to widely, tradition upper body phase MnOOH generally can be by electrochemical production but with the development of nano materials research, various preparation methods are also further optimized, and prepare the MnOOH monodimension nanometer material with additive method, bibliographical information is also arranged, for example, Dong Yanxi etc. utilize reverse micelle method to prepare diameter about 10nm, the polycrystalline MnOOH nano wire of length about 200nm.Sharma etc. and Sun etc. have synthesized the MnOOH monocrystal nano rod in the auxiliary hydro-thermal down of tensio-active agent.Zhang etc. with Xi etc. with potassium permanganate as the manganese source, with inorganic salt (NH
4Cl, KIO
3) synthesized the MnOOH monocrystal nano rod as reductive agent in the auxiliary hydro-thermal down of surfactant-free.But these methods all more or less experiment condition is had certain requirement, therefore, seeking a kind of more simple and convenient preparation method, prepare a kind of good reproducibility, success ratio height, alkali formula manganese oxide nano material that pattern is good, is the problem that presses for solution.
Summary of the invention
Problem to be solved by this invention is: overcome that present preparation alkali formula manganese oxide nano material method relies on that tensio-active agent, treatment step are loaded down with trivial details, product shortcoming such as pure and mild complex process not, a kind of chemical process that can easy synthetic alkali formula manganese oxide nano material is provided.The present invention adopts cheap four water manganous acetates, ammonium peroxydisulfate, can generate the nano material with bar-shaped alkali formula manganese oxide through hydrothermal reaction process.This method is simple to operate, raw material is cheap, environmentally friendly, need not loaded down with trivial details post-processing operation, only need Mn (CH
3COO)
2Solution and (NH
4)
2S
2O
8Solution places the stainless steel cauldron of polytetrafluoroethylliner liner according to a certain percentage, reacts and takes out product after 24 hours, carry out centrifugal, clean with distilled water and absolute ethanol washing, dry getting final product under the room temperature.Product purity height, densification and the good reproducibility of gained.
The technical scheme that the present invention takes the problem that will solve is:
A kind of method for preparing bar-shaped alkali formula manganese oxide nano material, it is characterized in that: with four water manganous acetates, ammonium peroxydisulfate be raw material in stainless steel cauldron directly hydro-thermal reaction obtain the nanocrystal of bar-shaped alkali formula manganese oxide, the crystal diameter scope is 30nm～300nm, length range is 3 μ m～8 μ m, and pattern is even and fine and close.
Its concrete preparation process is followed successively by:
1) be raw material with four water manganous acetates, ammonium peroxydisulfate, preparation 0.1molL
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution;
2) pipette the Mn (CH of 14ml respectively
3COO)
2(the NH of solution and 7ml
4)
2S
2O
8Solution is in the reactor of 25ml in volume, and four water manganous acetates and ammonium peroxydisulfate molar weight ratio 〉=2 get togather reactor and transfer to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven;
3) it is centrifugal to react products therefrom, respectively washs 3 times with deionized water and dehydrated alcohol, and drying at room temperature namely gets alkali formula manganese oxide nano crystal material, and the crystal diameter scope is 30nm～300nm, and length range is 3 μ m～8 μ m, and pattern is even and fine and close.
In the technical scheme of the present invention, the concentration of four water manganous acetates and ammonium peroxydisulfate is 0.1molL
-1, this concentration mainly is in order to save medicine, the product that obtains under this concentration can satisfy the demand of various detections.
In the technical scheme of the present invention, described container is the stainless steel cauldron with polytetrafluoroethylliner liner, and volume is 25mL, uses tap water, distilled water repeated washing clean before it uses successively, oven dry again.
In the technical scheme of the present invention, Mn (CH
3COO)
2Solution and (NH4
) 2S
2O
8The molar weight ratio of solution is more than 2: 1 or 2: 1, is accompanied by the increase of the two molar weight ratio, and the color of prepared alkali formula manganese oxide also changes pale brown look into by black gradually, changes yellow again into.
Advantage of the present invention:
1, the preparation method is simple.With Mn (CH
3COO)
2Solution and (NH
4)
2S
2O
8Solution is that feed molar amount ratio is more than 2: 1 or 2: 1, and directly hydro-thermal reaction just can obtain alkali formula manganese oxide nano material.
2, reaction good reproducibility, product easily becomes crystalline form, and this experiment uses hydro-thermal reaction directly to obtain product, and the nanocrystal pattern of the bar-shaped alkali formula manganese oxide of gained is even, length-to-diameter ratio big, uniform particle diameter degree height
3, raw material cheapness belongs to environmentally friendly reaction, applied range.Raw materials used all nontoxic in the reaction process, can reduce environmental pollution, reduce the harm to human body; And need not to use tensio-active agent, and can mass preparation, be convenient to suitability for industrialized production and technology popularization.
Description of drawings:
The scanning electron photomicrograph of the MnOOH nano material of Fig. 1-1, embodiment 1 preparation;
X-ray powder diffraction instrument (XRD) collection of illustrative plates of the MnOOH nano material of Fig. 1-2, embodiment 1 preparation;
The scanning electron photomicrograph of the MnOOH nano material of Fig. 2-1, embodiment 2 preparations;
X-ray powder diffraction instrument (XRD) collection of illustrative plates of the MnOOH nano material of Fig. 2-2, embodiment 2 preparations;
The scanning electron photomicrograph of the MnOOH nano material of Fig. 3-1, embodiment 3 preparations;
X-ray powder diffraction instrument (XRD) collection of illustrative plates of the MnOOH nano material of Fig. 3-2, embodiment 3 preparations;
The scanning electron photomicrograph of the MnOOH nano material of Fig. 4-1, embodiment 4 preparations;
X-ray powder diffraction instrument (XRD) collection of illustrative plates of the MnOOH nano material of Fig. 4-2, embodiment 4 preparations.
Embodiment:
Further specify bar-shaped alkali formula manganese oxide preparation of nanomaterials below by embodiment.
Embodiment 1
1, preparation work: the volumetric flask preparation 0.1molL that at first utilizes electronic balance, 100ml
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution, the stainless steel cauldron (volume is 25mL) that will have polytetrafluoroethylliner liner is used tap water, distilled water wash 3 times successively, and oven dry is used tap water, distilled water wash 3 times with the transfer pipet of 10ml, successively again with waiting to get the liquid rinse again;
2, reactions steps: pipette 14mlMn (CH respectively with transfer pipet
3COO)
2Solution and 7ml (NH
4)
2S
2O
8Solution after closing, is transferred to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven in the reactor of 25ml;
3, aftertreatment: after reaction finishes, product is carried out centrifugal, wash 3 times drying under the room temperature with distilled water and dehydrated alcohol respectively.The outward appearance of product is uniform black, determines that with x-ray powder diffraction instrument (XRD) it has only alkali formula manganese oxide, does not have impurity.Observe down its microtexture in scanning electronic microscope (SEM) and be one-dimensional array nanocrystalline (length range of rod is 3-8 μ m) closely.Scanning electron photomicrograph is seen Fig. 1-1, and the XRD figure spectrum is seen Fig. 1-2.
Embodiment 2
1, preparation work: the volumetric flask preparation 0.1molL that at first utilizes electronic balance, 100ml
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution, the stainless steel cauldron (volume is 20mL) that will have polytetrafluoroethylliner liner is used tap water, distilled water wash 3 times successively, and oven dry is used tap water, distilled water wash 3 times with the transfer pipet of 10ml, successively again with waiting to get the liquid rinse again;
2, reactions steps: pipette 12mlMn (CH respectively with transfer pipet
3COO)
2Solution and 3ml (NH
4)
2S
2O
8Solution after closing, is transferred to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven in the reactor of 25ml;
3, aftertreatment: with embodiment 1.Product is uniform pale brown look, and observing its microtexture under scanning electronic microscope is that one-dimensional array is nanocrystalline.Scanning electron photomicrograph is seen Fig. 2-1, and the XRD figure spectrum is seen Fig. 2-2,
Embodiment 3
1, preparation work: the volumetric flask preparation 0.1molL that at first utilizes electronic balance, 100ml
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution, the stainless steel cauldron (volume is 25mL) that will have polytetrafluoroethylliner liner is used tap water, distilled water wash 3 times successively, and oven dry is used tap water, distilled water wash 3 times with the transfer pipet of 10ml, successively again with waiting to get the liquid rinse again;
2, reactions steps: pipette 20mlMn (CH respectively with transfer pipet
3COO)
2Solution and 4ml (NH
4)
2S
2O
8Solution after closing, is transferred to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven in the reactor of 25ml;
3, aftertreatment: with embodiment 1.Product is uniform pale brown look, and observing its microtexture under scanning electronic microscope is that one-dimensional array is nanocrystalline.Scanning electron photomicrograph is seen Fig. 3-1, and the XRD figure spectrum is seen Fig. 3-2.
Embodiment 4
1, preparation work: the volumetric flask preparation 0.1molL that at first utilizes electronic balance, 100ml
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution, the stainless steel cauldron (volume is 50mL) that will have polytetrafluoroethylliner liner is used tap water, distilled water wash 3 times successively, and oven dry is used tap water, distilled water wash 3 times with the transfer pipet of 10ml, successively again with waiting to get the liquid rinse again;
2, reactions steps: pipette 40mlMn (CH respectively with transfer pipet
3COO)
2Solution and 5ml (NH
4)
2S
2O
8Solution after closing, is transferred to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven in the reactor of 25ml;
3, aftertreatment: with embodiment 1.Product is yellow uniformly, and observing its microtexture under scanning electronic microscope is that one-dimensional array is nanocrystalline.Scanning electron photomicrograph is seen Fig. 4-1, and the XRD figure spectrum is seen Fig. 4-2.
The present invention uses Mn (CH
3COO)
2Solution and (NH
4)
2S
2O
8Solution is that the direct hydro-thermal reaction of raw material (the molar weight ratio of the two is more than 2: 1 or 2: 1) just can obtain alkali formula manganese oxide nano material.Of no use to toxic substances such as any additive and tensio-active agents, belong to environmentally friendly reaction.Do not need subsequent purification step, easy to operate, reaction is quick, is convenient to suitability for industrialized production and technology popularization.
Claims (1)
1. method for preparing bar-shaped alkali formula manganese oxide nano material, it is characterized in that: with four water manganous acetates, ammonium peroxydisulfate be raw material in stainless steel cauldron directly hydro-thermal reaction obtain the nanocrystal of bar-shaped alkali formula manganese oxide, the crystal diameter scope is 30nm～300nm, length range is 3 μ m～8 μ m, and pattern is even and fine and close.
2 a kind of methods that prepare bar-shaped alkali formula manganese oxide nano material according to claim 1 is characterized in that its preparation process is followed successively by:
1) be raw material with four water manganous acetates, ammonium peroxydisulfate, preparation 0.1molL
-1Mn (CH
3COO)
2Solution and 0.1molL
-1(NH
4)
2S
2O
8Solution;
2) pipette the Mn (CH of 14ml respectively
3COO)
2(the NH of solution and 7ml
4)
2S
2O
8Solution is in the reactor of 25ml in volume, and four water manganous acetates and ammonium peroxydisulfate molar weight ratio 〉=2 get togather reactor and transfer to 160 ℃ of hydro-thermal 24h in the constant temperature air dry oven;
3) it is centrifugal to react products therefrom, respectively washs 3 times with deionized water and dehydrated alcohol, and drying at room temperature namely gets alkali formula manganese oxide nano crystal material, and the crystal diameter scope is 30nm～300nm, and length range is 3 μ m～8 μ m, and pattern is even and fine and close.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055621A (en) * | 2017-03-06 | 2017-08-18 | 符策煌 | Trimanganese tetroxide nano granular materials of size tunable of normal temperature synthesis and preparation method thereof |
| CN110540242A (en) * | 2019-09-06 | 2019-12-06 | 辽宁星空新能源发展有限公司 | method for preparing two-dimensional basic manganese oxide nanosheet through rapid precipitation |
| CN113155919A (en) * | 2021-05-10 | 2021-07-23 | 南京海关工业产品检测中心 | Based on MnO2Method for detecting pentachlorophenol in wood product by using nano-rod |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
| CN102765759A (en) * | 2011-05-02 | 2012-11-07 | 三星康宁精密素材株式会社 | Manganese oxide nanowire, rechargeable battery including the same and method of producing manganese oxide |
-
2013
- 2013-05-07 CN CN2013101635411A patent/CN103232070A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765759A (en) * | 2011-05-02 | 2012-11-07 | 三星康宁精密素材株式会社 | Manganese oxide nanowire, rechargeable battery including the same and method of producing manganese oxide |
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
Non-Patent Citations (1)
| Title |
|---|
| CHI-CHANG HU ET AL.: "Low-Temperature Hydrothermal Synthesis of Mn3O4 and MnOOH Single Crystals: Determinant Influence of Oxidants", 《CHEM. MATER.》, vol. 20, 16 April 2008 (2008-04-16), pages 2890 - 2894 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055621A (en) * | 2017-03-06 | 2017-08-18 | 符策煌 | Trimanganese tetroxide nano granular materials of size tunable of normal temperature synthesis and preparation method thereof |
| CN110540242A (en) * | 2019-09-06 | 2019-12-06 | 辽宁星空新能源发展有限公司 | method for preparing two-dimensional basic manganese oxide nanosheet through rapid precipitation |
| CN113155919A (en) * | 2021-05-10 | 2021-07-23 | 南京海关工业产品检测中心 | Based on MnO2Method for detecting pentachlorophenol in wood product by using nano-rod |
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Application publication date: 20130807 |