CN105858732B - The regulation and control method and manganese sesquioxide managnic oxide powder of manganese sesquioxide managnic oxide nanostructured - Google Patents
The regulation and control method and manganese sesquioxide managnic oxide powder of manganese sesquioxide managnic oxide nanostructured Download PDFInfo
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Abstract
The invention discloses the regulation and control method and manganese sesquioxide managnic oxide powder of a kind of manganese sesquioxide managnic oxide nanostructured, the method is comprised the following steps：By [Mn (BTO) (H2O)2]nPowder paving is dispersed in rectangle alumina crucible, and crucible is pushed in tube furnace, and 10~25min is persistently purged under a shielding gas；300~600 DEG C are warming up to the heating rate of 5~30 DEG C/min and are incubated 1~5h at such a temperature, all carried out under protective gas protection in heating and insulating process；After the completion of calcining, room temperature is cooled to the rate of temperature fall of 5~30 DEG C/min, is carried out under protective gas protection in cooling procedure, you can obtain the manganese sesquioxide managnic oxide powder of different nanostructureds.This method regulates and controls to obtain the manganese sesquioxide managnic oxide powder of different nanostructureds by atmosphere, and preparation method is simple, and environmental protection and economy is conducive to preparing manganese sesquioxide managnic oxide different-shape particle on a large scale.
Description
Technical field
The invention belongs to metal oxide materials field, and in particular to a kind of regulation and control method of manganese sesquioxide managnic oxide nanostructured
And manganese sesquioxide managnic oxide powder, the regulation and control method be related to calcining atmosphere regulation and control obtain different nanostructured manganese sesquioxide managnic oxides.
Background technology
In recent years, flourishing with nanometer technology, caused people and widely ground using nano material as adsorbent
Study carefully interest, this is mainly due to the inherent advantage of nano material such as small size, big specific surface area, chemism high
Find that Mn oxide has stronger dirt-removing power Deng researchs, using more in terms of wastewater treatment.So the manganese oxidation of synthesis
Thing nano material turns into the study hotspot in the field.
At present, the preparation method of nano manganese oxide is concentrated mainly on mangano-manganic oxide and manganese dioxide, its preparation method
Also synthesize simply by hydro-thermal, synthetic method is relative complex, and it is less efficient.In addition, for the nanometer of manganese sesquioxide managnic oxide
Structure preparation method is more rare.In recent years, a kind of novel preparation method is progressed into the middle of nm regime --- calcination method.
The method can reach the purpose of nanostructured regulation and control by temperature and control climate, and comparatively more economical, green
Color.So the present invention is based on calcination method, [Mn (BTO) (H is utilized2O)2]nMany nitrogen class energy-containing compounds, are carried out under different atmosphere
Calcining and decomposing, synthesizes the manganese sesquioxide managnic oxide material of different nanostructureds.
The content of the invention
It is an object of the invention to provide a kind of regulation and control method of manganese sesquioxide managnic oxide nanostructured.
It is a further object to provide three oxidations two of the different nanostructureds obtained using above-mentioned regulation and control method
Manganese powder body.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme：
A kind of regulation and control method of manganese sesquioxide managnic oxide nanostructured, comprises the following steps：
Step one：Calcined precursors [Mn (BTO) (H2O)2]nTreatment：By [Mn (BTO) (H2O)2]nPowder paving is dispersed in rectangular
In shape alumina crucible, crucible is pushed in tube furnace, 10~25min is persistently purged under a shielding gas；
Step 2：Calcining [Mn (BTO) (H2O)2]n：300~600 DEG C are warming up to the heating rate of 5~30 DEG C/min simultaneously
1~5h is incubated at such a temperature, is all carried out under protective gas protection in heating and insulating process；
Step 3：The treatment of product after calcining：After the completion of calcining, room temperature is cooled to the rate of temperature fall of 5~30 DEG C/min,
Carried out under protective gas protection in cooling procedure, you can obtain the manganese sesquioxide managnic oxide powder of different nanostructureds.
Further technical scheme is, described [Mn (BTO) (H2O)2]nPreparation method it is as follows：
Step A：Prepare 5,5'- bistetrazole -1,1'- dioxy hydroxylammonium salt solutions：By 5,5'- bistetrazole -1,1'- dioxy hydroxylammoniums
Salt is mixed to form troubled liquor with deionized water, is then heated to 50~70 DEG C of temperature and stirs at such a temperature to 5,5'- connection
Tetrazolium -1,1'- dioxy hydroxyl ammonium salts are completely dissolved；
Step B：Prepare metal manganese salt solution：Metal manganese salt is mixed with deionized water, is added until completely dissolved certain
The absolute ethyl alcohol of amount；
Step C：Prepare separation layer mixed liquor：Absolute ethyl alcohol is taken according to certain volume ratio and water mixes, it is mixed as separation layer
Close liquid；
Step D：Prepare [Mn (BTO) (H2O)2]nCrystal：5,5'- bistetrazole -1,1'- dioxies hydroxylammonium salt solution is instilled and is tried
Guan Zhong, is then added dropwise separation layer mixed liquor, and metal manganese salt solution is then added dropwise, and being placed in constant incubator culture a couple of days obtains [Mn
(BTO)(H2O)2]nCrystal.
Further technical scheme is that described metal manganese salt is selected from manganese sulfate, manganese nitrate, manganese chloride, manganese acetate or second
Acyl acetone manganese.
Further technical scheme is that the ratio between volume of absolute ethyl alcohol and water is 2 in described separation layer mixed liquor:1、1:
1 or 1:2.
Further technical scheme is that the temperature of described constant incubator is 30~50 DEG C.
Further technical scheme is that 5,5'- bistetrazole -1 is added dropwise in step D, 1'- dioxies hydroxylammonium salt solution, separation layer
When mixed liquor or metal manganese salt solution, burette exit port is maintained at 5~7mm with the distance of liquid level.
Further technical scheme is that described protective gas is nitrogen or argon gas.
Further technical scheme is that described protective gas is air or oxygen.
The present invention also provides manganese sesquioxide managnic oxide obtained in the regulation and control method for using above-mentioned manganese sesquioxide managnic oxide nanostructured, when
When protective gas is argon gas or nitrogen, described manganese sesquioxide managnic oxide is the rectangular manganese sesquioxide managnic oxide of nano particle with micropore
Powder.
The present invention also provides manganese sesquioxide managnic oxide obtained in the regulation and control method for using above-mentioned manganese sesquioxide managnic oxide nanostructured, when
When protective gas is air or oxygen, described manganese sesquioxide managnic oxide is the monodispersed manganese sesquioxide managnic oxide powder of 10-20nm.
Explanation that the present invention will be further explained below.
To [Mn (BTO) (H before calcining2O)2]nTreatment, the precursor material homogeneous its object is to obtain molecule rank,
It is easy to produce homogeneous metal oxide products during calcining.
Calcining [Mn (BTO) (H2O)2]nDuring, 300~600 DEG C are warming up to certain heating rate, if temperature is less than
300 DEG C of oxide form of the manganese for then generating unformed shape；If temperature is higher than 600 DEG C, the form of mangano-manganic oxide is generated；
Therefore temperature for 300~600 DEG C be suitable.According to a preferred embodiment of the invention, described temperature is 400~500 DEG C.
In calcination process, temperature undetermined is warming up to the heating rate of 5~30 DEG C/min, if heating rate less than 5 DEG C/
Min, then calcined product is incomplete, generates other accessory substances；If heating rate is higher than 30 DEG C/min, reacting excessively acutely causes
Yield is too low；Therefore it is suitable to be warming up to temperature undetermined with the heating rate of 5~30 DEG C/min.Preferred reality of the invention
Example is applied, described heating rate is 15~25 DEG C/min.
After calcining terminates, temperature is cooled to the rate of temperature fall of 5~30 DEG C/min, and enter under the protection of protective gas
OK, its reason is to prevent the generation of accessory substance.
In the method for the invention, the protective gas of described step one, step 2 and step 3 is same protection gas
Body.
When protective gas is argon gas or nitrogen, obtained manganese sesquioxide managnic oxide is rectangular with mesoporous nano particle
Manganese sesquioxide managnic oxide powder, its principle is that BTO parts are slowly decomposed, and produces a certain amount of gas, but be insufficient to allow manganese sesquioxide managnic oxide
Nano particle is separated, so formed having mesoporous manganese sesquioxide managnic oxide powder.
When protective gas is air or oxygen, obtained manganese sesquioxide managnic oxide is monodispersed three oxidation two of 10-20nm
Manganese powder is last, and when its principle is that the oxygen for having abundance is provided, BTO parts decompose the very violent of change, produce in a short time a large amount of
Gas, by the manganese sesquioxide managnic oxide of nano particle dispel separate, obtain single uniform nano particle.
The present invention compared with prior art, with following beneficial effect：
This method regulates and controls to obtain the manganese sesquioxide managnic oxide powder of different nanostructureds by atmosphere, and preparation method is simple, environmental protection
Economy, is conducive to preparing manganese sesquioxide managnic oxide different-shape particle on a large scale.Obtained manganese sesquioxide managnic oxide powder has ratio higher
Surface area, specific surface area is up to 50.2m2/ g and different exterior appearances.
Brief description of the drawings
Fig. 1 is [Mn (BTO) (H obtained in embodiment 12O)2]nThe scanning electron microscope (SEM) photograph of crystal；
Fig. 2 is [Mn (BTO) (H obtained in embodiment 22O)2]nCrystal TG-DSC figures under nitrogen atmosphere；
Fig. 3 is [Mn (BTO) (H2O)2]nThe monocrystalline figure of crystal；
Fig. 4 is the SEM figures of the nano particle rectangle manganese sesquioxide managnic oxide powder with micropore prepared by embodiment 6；
Fig. 5 is the SEM figures of the monodispersed manganese sesquioxide managnic oxide powder of 10~20nm prepared by embodiment 9.
Specific embodiment
With reference to embodiments of the invention, the invention will be further elaborated.
[Mn(BTO)(H2O)2]nPreparation embodiment：
Embodiment 1：
(1) 20.0mg 5 is weighed, 5'- bistetrazole -1,1'- dioxies hydroxyl ammonium salt is simultaneously transferred in clean measuring cup, to weighing
Bottle in add 4mL deionized water formed troubled liquor, be then heated to temperature 60 C and be stirred continuously at such a temperature until
5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts are completely dissolved.
(2) weigh the manganese sulfate monohydrate of 16.9mg and be transferred in clean measuring cup, to addition 1mL deionizations in measuring cup
Water, adds 3mL absolute ethyl alcohols until completely dissolved.
(3) according to 1:1 volume ratio prepares the absolute ethyl alcohol of 4mL and the mixing liquid of water as separation layer mixed liquor.
(4) an a diameter of 1.1cm is taken, is highly the clean tube of 15cm, insertion is placed in the rack for test tube of level table simultaneously
Keep test tube vertical with table top.It is molten that fine droplets pipe with length not less than 15cm draws 5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts
Liquid, stretches into dropper test tube to bottom and slowly extrudes liquid.The clean dropper for changing one draws separation layer mixed liquor and by dropper
Test tube is stretched into, burette exit port is dropwise added dropwise ethanol and water mixed liquid when reaching at ullage 5mm.As the rising of liquid level is real-time
Adjustment dropper stretches into depth, and burette exit port will remain at 5mm or so with the distance of liquid level.Rate of addition is upper and lower not produce
Two kinds of liquid mixing are advisable.The clean dropper for changing one draws manganese sulfate solution and dropper is stretched into test tube, in an identical manner
Dropwise it is added dropwise.There are two high-visible liquid surfaces to be located at two liquid junctions after being added dropwise to complete.
5th, test tube is sealed with diaphragm seal, and test tube is placed in 40 DEG C of constant incubator.In sealing and transfer process
Careful operation is answered to avoid test tube from shake occur and cause liquid to mix in advance.When this diffusion system stands 9 in constant incubator
Larger [Mn (BTO) (H is can obtain after it2O)2]nCrystal.
Embodiment 2：
(1) 20.0mg 5 is weighed, 5'- bistetrazole -1,1'- dioxies hydroxyl ammonium salt is simultaneously transferred in clean measuring cup, to weighing
Bottle in add 4ml deionized water formed troubled liquor, be then heated to temperature 60 C and be stirred continuously at such a temperature until
5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts are completely dissolved.
(2) weigh the manganese nitrate of 12.0mg and be transferred in clean measuring cup, to addition 1ml deionized waters in measuring cup,
3ml absolute ethyl alcohols are added until completely dissolved.
(3) according to 2:1 volume ratio prepares the absolute ethyl alcohol of 4ml and the mixing liquid of water.
(4) an a diameter of 1.1cm is taken, is highly the clean tube of 15cm, insertion is placed in the rack for test tube of level table simultaneously
Keep test tube vertical with table top.It is molten that fine droplets pipe with length not less than 15cm draws 5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts
Liquid, stretches into dropper test tube to bottom and slowly extrudes liquid.The clean dropper for changing one is drawn ethanol and water mixed liquid and will be dripped
Pipe stretches into test tube, and burette exit port is dropwise added dropwise ethanol and water mixed liquid when reaching at ullage 5mm.With the rising reality of liquid level
When adjustment dropper stretch into depth, burette exit port will remain at 5mm or so with the distance of liquid level.Rate of addition is not producing
Lower two kinds of liquid mixing is advisable.The clean dropper for changing one draws manganese sulfate solution and dropper is stretched into test tube, with identical side
Formula is dropwise added dropwise.There are two high-visible liquid surfaces to be located at two liquid junctions after being added dropwise to complete.
5th, test tube is sealed with diaphragm seal, and test tube is placed in 50 DEG C of constant incubator.In sealing and transfer process
Careful operation is answered to avoid test tube from shake occur and cause liquid to mix in advance.When this diffusion system stands 9 in constant incubator
Larger [Mn (BTO) (H is can obtain after it2O)2]nCrystal.
Embodiment 3：
(1) 20.0mg 5 is weighed, 5'- bistetrazole -1,1'- dioxies hydroxyl ammonium salt is simultaneously transferred in clean measuring cup, to weighing
Bottle in add 4ml deionized water formed troubled liquor, be then heated to temperature 60 C and be stirred continuously at such a temperature until
5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts are completely dissolved.
(2) weigh the manganese chloride of 12.5mg and be transferred in clean measuring cup, to addition 1ml deionized waters in measuring cup,
3ml absolute ethyl alcohols are added until completely dissolved.
(3) according to 1:2 volume ratio prepares the absolute ethyl alcohol of 4ml and the mixing liquid of water.
(4) an a diameter of 1.1cm is taken, is highly the clean tube of 15cm, insertion is placed in the rack for test tube of level table simultaneously
Keep test tube vertical with table top.It is molten that fine droplets pipe with length not less than 15cm draws 5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts
Liquid, stretches into dropper test tube to bottom and slowly extrudes liquid.The clean dropper for changing one is drawn ethanol and water mixed liquid and will be dripped
Pipe stretches into test tube, and burette exit port is dropwise added dropwise ethanol and water mixed liquid when reaching at ullage 5mm.With the rising reality of liquid level
When adjustment dropper stretch into depth, burette exit port will remain at 5mm or so with the distance of liquid level.Rate of addition is not producing
Lower two kinds of liquid mixing is advisable.The clean dropper for changing one draws manganese sulfate solution and dropper is stretched into test tube, with identical side
Formula is dropwise added dropwise.There are two high-visible liquid surfaces to be located at two liquid junctions after being added dropwise to complete.
5th, test tube is sealed with diaphragm seal, and test tube is placed in 50 DEG C of constant incubator.In sealing and transfer process
Careful operation is answered to avoid test tube from shake occur and cause liquid to mix in advance.When this diffusion system stands 9 in constant incubator
Larger [Mn (BTO) (H is can obtain after it2O)2]nCrystal.
Embodiment 4：
(1) 20.0mg 5 is weighed, 5'- bistetrazole -1,1'- dioxies hydroxyl ammonium salt is simultaneously transferred in clean measuring cup, to weighing
Bottle in add 4ml deionized water formed troubled liquor, be then heated to temperature 60 C and be stirred continuously at such a temperature until
5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts are completely dissolved.
(2) weigh the manganese acetate of 17.3mg and be transferred in clean measuring cup, to addition 1ml deionized waters in measuring cup,
3ml absolute ethyl alcohols are added until completely dissolved.
(3) according to 1:1 volume ratio prepares the absolute ethyl alcohol of 4ml and the mixing liquid of water.
(4) an a diameter of 1.1cm is taken, is highly the clean tube of 15cm, insertion is placed in the rack for test tube of level table simultaneously
Keep test tube vertical with table top.It is molten that fine droplets pipe with length not less than 15cm draws 5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts
Liquid, stretches into dropper test tube to bottom and slowly extrudes liquid.The clean dropper for changing one is drawn ethanol and water mixed liquid and will be dripped
Pipe stretches into test tube, and burette exit port is dropwise added dropwise ethanol and water mixed liquid when reaching at ullage 5mm.With the rising reality of liquid level
When adjustment dropper stretch into depth, burette exit port will remain at 5mm or so with the distance of liquid level.Rate of addition is not producing
Lower two kinds of liquid mixing is advisable.The clean dropper for changing one draws manganese sulfate solution and dropper is stretched into test tube, with identical side
Formula is dropwise added dropwise.There are two high-visible liquid surfaces to be located at two liquid junctions after being added dropwise to complete.
5th, test tube is sealed with diaphragm seal, and test tube is placed in 30 DEG C of constant incubator.In sealing and transfer process
Careful operation is answered to avoid test tube from shake occur and cause liquid to mix in advance.When this diffusion system stands 9 in constant incubator
Larger [Mn (BTO) (H is can obtain after it2O)2]nCrystal.
Embodiment 5：
(1) 20.0mg 5 is weighed, 5'- bistetrazole -1,1'- dioxies hydroxyl ammonium salt is simultaneously transferred in clean measuring cup, to weighing
Bottle in add 4ml deionized water formed troubled liquor, be then heated to temperature 60 C and be stirred continuously at such a temperature until
5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts are completely dissolved.
(2) weigh the manganese acetylacetonate of 31.0mg and be transferred in clean measuring cup, to addition 1ml deionizations in measuring cup
Water, adds 3ml absolute ethyl alcohols until completely dissolved.
(3) according to 1:1 volume ratio prepares the absolute ethyl alcohol of 4ml and the mixing liquid of water.
(4) an a diameter of 1.1cm is taken, is highly the clean tube of 15cm, insertion is placed in the rack for test tube of level table simultaneously
Keep test tube vertical with table top.It is molten that fine droplets pipe with length not less than 15cm draws 5,5'- bistetrazole -1,1'- dioxy hydroxyl ammonium salts
Liquid, stretches into dropper test tube to bottom and slowly extrudes liquid.The clean dropper for changing one is drawn ethanol and water mixed liquid and will be dripped
Pipe stretches into test tube, and burette exit port is dropwise added dropwise ethanol and water mixed liquid when reaching at ullage 5mm.With the rising reality of liquid level
When adjustment dropper stretch into depth, burette exit port will remain at 5mm or so with the distance of liquid level.Rate of addition is not producing
Lower two kinds of liquid mixing is advisable.The clean dropper for changing one draws manganese sulfate solution and dropper is stretched into test tube, with identical side
Formula is dropwise added dropwise.There are two high-visible liquid surfaces to be located at two liquid junctions after being added dropwise to complete.
5th, test tube is sealed with diaphragm seal, and test tube is placed in 30 DEG C of constant incubator.In sealing and transfer process
Careful operation is answered to avoid test tube from shake occur and cause liquid to mix in advance.When this diffusion system stands 9 in constant incubator
Larger [Mn (BTO) (H is can obtain after it2O)2]nCrystal.
The preparation embodiment of manganese sesquioxide managnic oxide nanometer powder：
Embodiment 6
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace, 15min is purged with nitrogen atmosphere.Sample is heated with the heating rate of 5 DEG C/min to descend and protect to 500 degree
Temperature 1 hour.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is dropped with 5 DEG C/min after the completion of experiment
Warm speed is cooled to room temperature, and pouring for corresponding purging nitrogen is kept during cooling.It is that to can obtain 20-30 micro- to take out crucible and collect sample
The manganese sesquioxide managnic oxide powder sample of the nano particle rectangle aggregation with micropore of rice.
Embodiment 7
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with argon gas atmosphere.With the heating rate of 10 DEG C/min heat sample under 400 degree simultaneously
Insulation 1 hour.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 10 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purging argon gas is kept during cooling.It is that can obtain 20-30 to take out crucible and collect sample
The manganese sesquioxide managnic oxide powder sample of the nano particle rectangle aggregation with micropore of micron.
Embodiment 8
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with air atmosphere.With the heating rate of 20 DEG C/min heat sample under 300 degree simultaneously
Insulation 1 hour.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 20 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purging air is kept during cooling.It is that can obtain 20-30 to take out crucible and collect sample
The manganese sesquioxide managnic oxide powder sample of the nano particle rectangle aggregation with micropore of micron.
Embodiment 9
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with oxygen atmosphere.With the heating rate of 20 DEG C/min heat sample under 300 degree simultaneously
Insulation 5 hours.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 20 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purge oxygen is kept during cooling.It is that can obtain 10-20 to take out crucible and collect sample
The monodispersed manganese sesquioxide managnic oxide powder sample of nanometer.
Embodiment 10
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with oxygen atmosphere.With the heating rate of 30 DEG C/min heat sample under 400 degree simultaneously
Insulation 2 hours.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 30 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purge oxygen is kept during cooling.It is that can obtain 10-20 to take out crucible and collect sample
The monodispersed manganese sesquioxide managnic oxide powder sample of nanometer.
Embodiment 11
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with oxygen atmosphere.With the heating rate of 20 DEG C/min heat sample under 400 degree simultaneously
Insulation 3 hours.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 20 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purge oxygen is kept during cooling.It is that can obtain 10-20 to take out crucible and collect sample
The monodispersed manganese sesquioxide managnic oxide powder sample of nanometer.
Embodiment 12
Take a certain amount of [Mn (BTO) (H2O)2]nUniformly paving is dispersed in rectangle alumina crucible powder (embodiment 1), will
In crucible push-in tube furnace.15min is purged with oxygen atmosphere.With the heating rate of 30 DEG C/min heat sample under 400 degree simultaneously
Insulation 5 hours.Heating and insulating process are carried out under all being protected in corresponding nitrogen.Sample is with 30 DEG C/min after the completion of experiment
Rate of temperature fall is cooled to room temperature, and pouring for corresponding purge oxygen is kept during cooling.It is that can obtain 10-20 to take out crucible and collect sample
The monodispersed manganese sesquioxide managnic oxide powder sample of nanometer.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferably implementation method, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementation methods, and these modifications and implementation method will fall in principle disclosed in the present application
Within scope and spirit.
Claims (6)
1. a kind of regulation and control method of manganese sesquioxide managnic oxide nanostructured, its feature is being comprised the following steps：
Step one：Calcined precursors [Mn (BTO) (H2O)2]nTreatment：By [Mn (BTO) (H2O)2]nPowder paving is dispersed in rectangle oxidation
In aluminium crucible, crucible is pushed in tube furnace, 10~25min is persistently purged under a shielding gas；
Step 2：Calcining [Mn (BTO) (H2O)2]n：300~600 DEG C are warming up to the heating rate of 5~30 DEG C/min and at this
At a temperature of be incubated 1~5h, heating and insulating process in all protective gas protection under carry out；
Step 3：The treatment of product after calcining：After the completion of calcining, room temperature is cooled to the rate of temperature fall of 5~30 DEG C/min, cooled down
During carried out under protective gas protection, you can obtain the manganese sesquioxide managnic oxide powder of different nanostructureds；
Step one, step 2, the protective gas of step 3 are same protective gas, described protective gas is nitrogen, argon gas,
Air or oxygen；
When protective gas is argon gas or nitrogen, obtained manganese sesquioxide managnic oxide is with mesoporous rectangular three oxygen of nano particle
Change two manganese powders end；
When protective gas is air or oxygen, obtained manganese sesquioxide managnic oxide is the monodispersed manganese sesquioxide managnic oxide powder of 10-20nm
End.
2. the regulation and control method of manganese sesquioxide managnic oxide nanostructured according to claim 1, it is characterised in that described [Mn
(BTO)(H2O)2]nPreparation method it is as follows：
Step A：Prepare 5,5'- bistetrazole -1,1'- dioxy hydroxylammonium salt solutions：By 5,5'- bistetrazoles -1,1'- dioxies hydroxyl ammonium salt with
Deionized water is mixed to form troubled liquor, be then heated to 50~70 DEG C of temperature and stir at such a temperature to 5,5'- bistetrazoles-
1,1'- dioxy hydroxyl ammonium salts are completely dissolved；
Step B：Prepare metal manganese salt solution：Metal manganese salt is mixed with deionized water, is added until completely dissolved a certain amount of
Absolute ethyl alcohol；
Step C：Prepare separation layer mixed liquor：Absolute ethyl alcohol is taken according to certain volume ratio and water mixes, as separation layer mixed liquor；
Step D：Prepare [Mn (BTO) (H2O)2]nCrystal：5,5'- bistetrazole -1,1'- dioxies hydroxylammonium salt solution is instilled into test tube
In, separation layer mixed liquor is then added dropwise, metal manganese salt solution is then added dropwise, being placed in constant incubator culture a couple of days obtains [Mn
(BTO)(H2O)2]nCrystal.
3. the regulation and control method of manganese sesquioxide managnic oxide nanostructured according to claim 2, it is characterised in that described manganese metal
Salt is selected from manganese sulfate, manganese nitrate, manganese chloride, manganese acetate or manganese acetylacetonate.
4. the regulation and control method of manganese sesquioxide managnic oxide nanostructured according to claim 2, it is characterised in that described separation layer
The ratio between volume of absolute ethyl alcohol and water is 2 in mixed liquor:1、1:1 or 1:2.
5. the regulation and control method of manganese sesquioxide managnic oxide nanostructured according to claim 2, it is characterised in that described constant temperature training
The temperature for supporting case is 30~50 DEG C.
6. the regulation and control method of manganese sesquioxide managnic oxide nanostructured according to claim 2, it is characterised in that be added dropwise 5 in step D,
5'- bistetrazole -1, when 1'- dioxies hydroxylammonium salt solution, separation layer mixed liquor or metal manganese salt solution, burette exit port and liquid level away from
From being maintained at 5~7mm.
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