CN102060333B - Method for preparing manganese oxide nano-material - Google Patents
Method for preparing manganese oxide nano-material Download PDFInfo
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Abstract
The invention discloses a method for preparing a manganese oxide nano-material. The method comprises the following steps of: with manganous salt and weak basic salt as raw materials, dissolving the manganous salt and the weak basic salt into glycol solvent respectively; mixing two obtained solutions, and uniformly stirring to form a uniform dark brown solution; adding water into the brown solution and stirring until brown precipitate occurs; separating and drying the precipitate to obtain superfine nanowires manganese hydroperoxide; calcining the prepared manganese hydroperoxide nanowires at the temperature of between 400 and 1,050 DEG C under atmosphere or nitrogen condition to obtain a manganese oxide nano-wire material and a manganese oxide nano-particle material. The manganese hydroperoxide has a superfine nanowire structure with diameter less than 10nm and length of about 1mu m, so that the calcined manganese oxide nano-wire or nano-particle material has uniform size and higher specific area; and the preparation method is simple, has mild condition, is beneficial to the reduction of production cost, is convenient to operate, and has the advantages of high yield and low energy consumption.
Description
Technical field
The present invention relates to a kind of method for preparing the Mn oxide nano material.
Background technology
Nano material is a new material technology priority fields of study in this century, to nano material carry out size, pattern at three dimension scale, the valence state regulation and control are one of inorganic chemist most important.Mn oxide has multiple variable valence state; The outer orbit electronics can efficiently exchange at surface, interface and other material; And possess the transmission of interface quantum and excite required smallest dimension characteristic, so become nearest focus gradually for their research with redox couple.In addition, attracted a large amount of investigators' concern owing to its unique electronics, magnetics, catalytic property and in potential application such as aspect electronics, electrochemistry, biological chemistry sensing, the catalysis.
In recent years, the wet-chemical reduction method is simple gentle with it, be convenient to, product evenly and help advantage such as mass preparation and extensively be used in the preparation of manganese oxide nanostructure material, and obtained great success.But wet chemical method synthetic manganese oxide nanostructure material only limits to trimanganese tetroxide, manganic oxide etc., and is also comparatively rare comparatively speaking to the preparation research of water manganese stone up to the present.In addition; The solution methods of having reported perhaps needs to use the high-temperature high-voltage reaction environment, perhaps need be by tensio-active agent (like Vinylpyrrolidone polymer) as structure directing agent, and the preparation process is very loaded down with trivial details; Generally need complicated follow-up template to remove operation, productive rate is lower.This breadboard preparation method is unfavorable for the heavy industrialization application of Mn oxide nano wire.At present; Main both at home and abroad use electrolytic process prepares Mn oxide material; Wang Hongtai discloses main electrolytic metal manganese powder (sheet) the suspension-s oxidation style that adopts both at home and abroad and has produced Mn oxide on 2006 the 26th volumes of magazine " Shanxi chemical industry " the 3rd phase " the production technique present situation and the developing direction of domestic trimanganese tetroxide "; Advantages such as this method is simple with its technology, pollution is little are adopted by most of manufacturers, have become the main flow of suitability for industrialized production.But shortcoming that it is outstanding such as with low content of technology, production cost be high have been restricted it and has further developed.
On March 3rd, 2010, publication number was the method that 101659447 Chinese invention patent application discloses synthesizing manganese oxide nano-particles in one step; This method may further comprise the steps: press manganese salt: tensio-active agent: the proportioning of solvent 1-octadecylene is (0.5-2) mmol: (2-4) mL: (5-10) mL; Choose manganese salt, tensio-active agent and 1-octadecylene, subsequent use; Manganese salt, tensio-active agent and 1-octadecylene are mixed, place there-necked flask, adopt the anhydrous and oxygen-free technology to remove the air of system, under nitrogen protection, be stirred to solid under the room temperature and dissolve fully; Be heated to 280-330 ℃ then, after solution produces muddiness, react 5-60min again, be cooled to room temperature; After washing 2-3 time with normal hexane and alcoholic acid mixed solution again, vacuum-drying obtains manganese oxide nano-particles.But this method also exists processing requirement high, the shortcoming that operation is complicated.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art for preparing technology, a kind of method for preparing the Mn oxide nano material is provided, this method uses easy processing condition to prepare the Mn oxide nano material that size is even, specific surface area is big; Working condition is simple; Easy to operate, productive rate is high, and it is low to consume energy; Production cost is low, and application promise in clinical practice is arranged.
The objective of the invention is to realize like this:
The present invention prepares the method for Mn oxide nano material, may further comprise the steps:
A. be raw material with manganous salt and weakly alkaline salt, terepthaloyl moietie is solvent, and manganous salt and weakly alkaline salt are dissolved in respectively in the ethylene glycol solvent, two kinds of solution of gained is mixed again and stirs to the dark red brown solution that forms homogeneous; B. in the gained red tan solution, add entry and stirring, the brown precipitate thing occurs; C. the separation of gained brown precipitate thing, drying can be obtained the superfine nano line of water manganese stone; D. the water manganese stone nano wire of preparing obtains Mn oxide nano-material and manganese oxide nano-particles material in 400 ℃ of-1050 ℃ of roastings under air conditions or condition of nitrogen gas.
The preferred manganous acetate of said manganous salt, the preferred ammonium hydrogencarbonate of weakly alkaline salt.
As preferably, said manganous salt and weakly alkaline salt mol ratio are 1:10-10:1.
As preferably, add the water yield and ethylene glycol solvent volume ratio at 1:1-1:100.
Water manganese stone nano wire with said preparation is a raw material, under air atmosphere, prepares the manganic manganous oxide nanometer wire material more than 3 hours in 400 ℃ of-550 ℃ of roastings.
Water manganese stone nano wire with said preparation is a raw material, and the manganic oxide nano-material is prepared in 600 ℃ of-750 ℃ of roastings more than 3 hours under air atmosphere.
Water manganese stone nano wire with said preparation is a raw material, and 800 ℃ of-1050 ℃ of roastings are equipped with the trimanganese tetroxide nano particulate material more than 3 hours under air atmosphere.
Water manganese stone nano wire with said preparation is a raw material, and the manganic manganous oxide nanometer wire material is prepared in 400 ℃ to 600 ℃ roastings more than 3 hours under condition of nitrogen gas.
Water manganese stone nano wire with said preparation is a raw material, and 800 ℃ of-1050 ℃ of roasting systems are equipped with the trimanganese tetroxide nano particulate material more than 3 hours under condition of nitrogen gas.
The invention has the beneficial effects as follows:
Because the water manganese stone that this method obtained is the superfine nano line structure, diameter is about 1 μ m less than 10nm, so Mn oxide nano wire that after calcination process, is obtained or particulate material size homogeneous have higher specific surface area; Because the preparation method is simple, mild condition helps reducing production costs, and easy to operate, and productive rate is high, and it is low to consume energy; Owing to adopt terepthaloyl moietie as reaction solvent, water is the initiator of reaction, production process environmental protection.
Description of drawings
Below in conjunction with accompanying drawing the present invention is done and to describe in further detail:
Fig. 1: the microscopic appearance figure of water manganese stone nano wire;
Fig. 2: the X ray diffracting spectrum of water manganese stone;
Fig. 3: the microscopic appearance figure of 400 ℃ of trimanganese tetroxides that make in the air;
Fig. 4: the microscopic appearance figure of 600 ℃ of manganic oxides that make in the air;
Fig. 5: the microscopic appearance figure of the trimanganese tetroxide that makes more than 800 ℃ in the air;
Fig. 6: the microscopic appearance figure of 400 ℃ of trimanganese tetroxides that make in the nitrogen;
Fig. 7: the microscopic appearance figure of 600 ℃ of trimanganese tetroxides that make in the nitrogen;
Fig. 8: the microscopic appearance figure of 800 ℃ of trimanganese tetroxides that make in the nitrogen;
Fig. 9: the X ray diffracting spectrum of Mn oxide.
Embodiment
The present invention is a raw material with manganous salt and weakly alkaline salt, and terepthaloyl moietie is solvent, respectively manganous salt and weakly alkaline salt is dissolved in respectively in the ethylene glycol solvent, two kinds of solution of gained is mixed again and stirs to the dark red brown solution that forms homogeneous.Add entry and stirring in the gained red tan solution, brown precipitate occurs.With the superfine nano line (diameter is about 1 μ m less than 10nm) that the gained throw out separates, drying can obtain water manganese stone.The water manganese stone nano wire of preparing carries out calcination process, makes Mn oxide nano wire (the about 20nm of diameter is about 400nm) and nano particle (the about 100nm of diameter).Respectively at 400 ℃, 600 ℃, 800 ℃, 1050 ℃ roastings, product is respectively the nanometer particle material of manganic manganous oxide nanometer wire, manganic oxide nano wire and trimanganese tetroxide under air conditions.Under condition of nitrogen gas, all obtain manganic manganous oxide nano-material in the roasting temperature that is higher than 400 ℃, at the pattern that can keep nano wire below 600 ℃, higher temperature melts forms nano particle.
Be the embodiment for preparing the method for Mn oxide nano material below.
With manganous acetate, ammonium hydrogencarbonate is raw material, through following steps and prepared water manganese stone nano wire:
(1) manganous acetate and ammonium hydrogencarbonate are dissolved in respectively in the ethylene glycol solvent, the two mol ratio of control manganous acetate, ammonium hydrogencarbonate is about 1:10;
(2) the said two kinds of solution of step (1) are mixed to the dark red brown solution that forms homogeneous;
(3) in the described dark red brown solution of step (2), add entry.Here, water is reaction initiator.Add the water yield and ethylene glycol solvent volume ratio about 1:1, keep in the time of adding stirring, the brown precipitate thing occurs.
(4) resulting throw out is separated, drying promptly obtains the nano wire of water manganese stone.
The two the not special restriction of mol ratio of manganous acetate in the foregoing description, ammonium hydrogencarbonate, the scope of preferred 1:10-10:1; The also not special restriction of the water yield and ethylene glycol solvent volume ratio, the scope of preferred 1:1-1:100.
The nano wire microscopic appearance of gained water manganese stone is as shown in Figure 1, and the X ray diffracting spectrum of water manganese stone is as shown in Figure 2, proves that it is water manganese stone and the nano-scale that can observe its homogeneous.
With above-mentioned prepared water manganese stone nano wire is raw material, preparation Mn oxide nano material under following different complete processing:
Embodiment one: under air atmosphere, under 400 ℃ of conditions, roasting is more than 3 hours, prepare manganic manganous oxide nanometer wire (as Fig. 3, Fig. 9 a).
Embodiment two: under air atmosphere, under 550 ℃ of conditions, roasting was prepared the manganic manganous oxide nanometer wire material more than 3 hours.
Embodiment three: under air atmosphere, under 600 ℃ of conditions, roasting was prepared manganic oxide nano wire (like the e of Fig. 4, Fig. 9) more than 3 hours.
Embodiment four: under air atmosphere, under 750 ℃ of conditions, roasting was prepared the manganic oxide nano-material more than 3 hours.
Embodiment five: under air atmosphere, under 800 ℃ of conditions, roasting was prepared the trimanganese tetroxide nano particle, i.e. nanoparticle more than 3 hours.(like Fig. 5, Fig. 9 b).
Embodiment six: under air atmosphere, under 1050 ℃ of conditions, roasting was prepared the trimanganese tetroxide nano particle, i.e. nanoparticle more than 3 hours.
Embodiment seven: under nitrogen atmosphere, under 400 ℃ of conditions, roasting was prepared manganic manganous oxide nanometer wire (like the c of Fig. 6, Fig. 9) more than 3 hours.
Embodiment eight: under nitrogen atmosphere, under 600 ℃ of conditions, roasting was prepared manganic manganous oxide nanometer wire (like the d of Fig. 7, Fig. 9) more than 3 hours.
Embodiment nine: under nitrogen atmosphere, more than 800 ℃, roasting was prepared the trimanganese tetroxide nano particle more than 3 hours, i.e. nanoparticle (like Fig. 8).
Embodiment ten: under nitrogen atmosphere, under 1050 ℃ of conditions, roasting was prepared the trimanganese tetroxide nano particle, i.e. nanoparticle more than 3 hours.
The X ray diffracting spectrum of the Mn oxide that is obtained is as shown in Figure 9, and wherein a-d is the XRD figure spectrum of trimanganese tetroxide, and e is the XRD figure spectrum of manganic oxide, and this figure proof product is respectively trimanganese tetroxide and manganic oxide.
Roasting is the routine techniques in present technique field in the foregoing description, have no special requirements, roasting time 3 hours or surpass 3 hours all can, need not exceed during actually operating 3 hours too many, preferred 3 hours, can save energy consumption like this.
The microscopic appearance figure of observation intermediate product water manganese stone nano wire and the finished product Mn oxide nano material uses electron-microscope scanning in the foregoing description, and equipment is Hitachi S4800 CFE-SEM; The detecting instrument that the X ray diffracting spectrum of detection intermediate product water manganese stone and the finished product Mn oxide uses in the foregoing description is Rigaku Goniometer PMG-A2.
Claims (9)
1. method for preparing the Mn oxide nano material may further comprise the steps:
A. be raw material with manganous salt and weakly alkaline salt, terepthaloyl moietie is solvent, and manganous salt and weakly alkaline salt are dissolved in respectively in the ethylene glycol solvent, two kinds of solution of gained is mixed again and stirs to the dark red brown solution that forms homogeneous;
B. in the gained red tan solution, add entry and stirring, the brown precipitate thing occurs;
C. the separation of gained brown precipitate thing, drying can be obtained the superfine nano line of water manganese stone;
D. the water manganese stone nano wire of preparing obtains Mn oxide nano-material or manganese oxide nano-particles material in 400 ℃ of-1050 ℃ of roastings under air conditions or condition of nitrogen gas.
2. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that manganous salt is a manganous acetate, and weakly alkaline salt is ammonium hydrogencarbonate.
3. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, manganous salt and weakly alkaline salt mol ratio are 1:10-10:1.
4. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, adds the water yield and ethylene glycol solvent volume ratio at 1:1-1:100.
5. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, is raw material with the water manganese stone nano wire of said preparation, under air atmosphere, prepares the manganic manganous oxide nanometer wire material more than 3 hours in 400 ℃ of-550 ℃ of roastings.
6. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, is raw material with the water manganese stone nano wire of said preparation, and the manganic oxide nano-material is prepared in 600 ℃ of-750 ℃ of roastings more than 3 hours under air atmosphere.
7. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, is raw material with the water manganese stone nano wire of said preparation, and the trimanganese tetroxide nano particulate material is prepared in 800 ℃ of-1050 ℃ of roastings more than 3 hours under air atmosphere.
8. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, is raw material with the water manganese stone nano wire of said preparation, and the manganic manganous oxide nanometer wire material is prepared in 400 ℃ to 600 ℃ roastings more than 3 hours under condition of nitrogen gas.
9. the method for preparing the Mn oxide nano material according to claim 1 is characterized in that, is raw material with the water manganese stone nano wire of said preparation, and 800 ℃ of-1050 ℃ of roasting systems are equipped with the trimanganese tetroxide nano particulate material more than 3 hours under condition of nitrogen gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102219263B (en) * | 2011-05-20 | 2012-12-12 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
| CN102689929A (en) * | 2012-06-12 | 2012-09-26 | 东华大学 | Method for preparing ultralong MnO2 nanowire supercapacitor material |
| CN103570072A (en) * | 2012-07-27 | 2014-02-12 | 比亚迪股份有限公司 | Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough |
| CN103496745B (en) * | 2013-10-09 | 2015-04-29 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| CN106430317A (en) * | 2016-09-18 | 2017-02-22 | 陕西科技大学 | Preparation method of flaky nano-Mn3O4 |
| CN112516998B (en) * | 2020-12-17 | 2023-04-07 | 广东工业大学 | Volatile organic pollution gas purification catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
| WO2007006585A2 (en) * | 2005-07-14 | 2007-01-18 | Elsper Ruediger | Synthesis of a porous and/or stratified structure manganese oxide |
| CN101306800A (en) * | 2008-07-04 | 2008-11-19 | 中国科学院化学研究所 | Method for preparing metallic oxide nano granules |
| CN101693599A (en) * | 2009-09-18 | 2010-04-14 | 杭州电子科技大学 | Method for preparing trimanganese tetroxide film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
| WO2007006585A2 (en) * | 2005-07-14 | 2007-01-18 | Elsper Ruediger | Synthesis of a porous and/or stratified structure manganese oxide |
| CN101306800A (en) * | 2008-07-04 | 2008-11-19 | 中国科学院化学研究所 | Method for preparing metallic oxide nano granules |
| CN101693599A (en) * | 2009-09-18 | 2010-04-14 | 杭州电子科技大学 | Method for preparing trimanganese tetroxide film |
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