CN102502853A - Method for preparing nanometer manganese dioxide by microwave reflux method - Google Patents
Method for preparing nanometer manganese dioxide by microwave reflux method Download PDFInfo
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Abstract
A method for preparing nanometer manganese dioxide by microwave heating reflux comprises the following steps: (1) preparing a reaction solution by soluble divalent manganese salt and soluble persulfate; (2) putting the reaction solution in a microwave oven with a microwave frequency of 2.45 GHz, a microwave power of 100-850 W, a reaction temperature of 90-100 DEG C and reaction time of 5-30 min; after the reaction, separating, washing and drying the product to obtain a gamma-MnO2 nano-material. In step (1), 1-5 mL concentrated sulfuric acid is added into the reaction solution of soluble divalent manganese salt and soluble persulfate, and the obtained reaction product is a sea urchin-shaped alpha-MnO2 micro-sphere. The manganese dioxide material prepared by the invention is applicable to the fields of super capacitor electrode materials, battery electrode materials, catalysts, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nano-manganese dioxide, particularly a kind of method that adopts the microwave heating backflow to prepare different crystal forms and pattern nano-manganese dioxide.
Background technology
Manganse Dioxide is widely used in fields such as ion(ic)sieve, molecular sieve, biosensor, catalysis, magneticsubstance and energy storage owing to have abundant and unique physics and chemical property.Because it is environmentally friendly, preparation technology is simple, and low in raw material cost is easy to get, and is used as the electrode materials of lithium ion battery, ultracapacitor in recent years.Manganse Dioxide is a kind of oxide compound of crystalline network more complicated, and α is arranged, beta, gamma, multiple crystal formation such as δ.Different crystal forms Manganse Dioxide has identical structural unit: [MnO
6] octahedron.These [MnO
6] between the octahedron through rib altogether or altogether the mode at angle form tunnel-like or layered manganese oxide crystalline compounds.Crystalline structure that it is generally acknowledged material has very big influence to its performance, and the nano material of manganese dioxide of therefore synthetic different crystal forms and different-shape highly significant.At present, the method for synthetic nano material of manganese dioxide mainly comprises: sol-gel method, circumfluence method, hydrothermal method, thermal decomposition method and solid phase method etc.Make a general survey of in the whole bag of tricks of synthetic nano material of manganese dioxide, liquid phase is synthetic to be a kind of means of studying often and can effectively controlling Manganse Dioxide crystal formation and pattern.People such as Villegas (Chem.Mater., 2005,17,1910) adopt circumfluence method to prepare α-MnO
2Nanometer rod, and study its catalytic performance.People such as Yu (Cryst.Growth Des., 2009,9,528) adopt Hydrothermal Preparation to go out sea urchin shape α-MnO
2Micrometre hollow sphere and nanocluster, ε-MnO
2Nanometer ball, and study its chemical property as electrode material for super capacitor.People such as Zeng (J.Mater.Chem., 2010,20,10915.) adopt Hydrothermal Preparation to go out sea urchin shape γ-MnO
2The micron ball, and study its chemical property as lithium ion battery electrode material.But above-mentioned the whole bag of tricks all adopts traditional thermal conduction type of heating, and long reaction time (6～24 hours), energy consumption are high, pattern is wayward, therefore explores a kind of simple and method quickly synthesizing nano Manganse Dioxide is necessary.
Microwave heating is different from traditional type of heating; When microwave penetrates medium, because the rising of the medium temperature that dielectric loss causes makes almost while heat temperature raising of dielectric material inside, outside; Organizer thermal source state; Shortened routine greatly and added the heat conduction time of pining for, system is heated evenly, no lag-effect.The present report that adopts microwave method to prepare nano-manganese dioxide is less.Chinese invention patent 200910019398.2 is a raw material with potassium permanganate and hydrochloric acid, adopts microwave-hydrothermal method, 105～145 ℃ of temperature of reaction, and the reaction times is 0.5～2 hour, prepares the δ-MnO of petal pattern respectively
2Nano material and α-MnO
2Nanotube.Chinese invention patent 201010221314.6 is a raw material with potassium bromate and manganous sulfate, adopts microwave-hydrothermal method, and 70～100 ℃ of temperature of reaction in 0.5～10 hour reaction times, are prepared γ-MnO
2The micron ball.But, all need adopt the reaction vessel of sealing, the operation more complicated, cost is higher, is difficult to scale preparation.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, propose a kind of method that adopts the microwave circumfluence method to prepare different crystal forms and pattern nano-manganese dioxide fast.This method has that technology is simple, the reaction times short (5min), and cost is low, the advantage of controllable product quality, is easy to suitability for industrialized production.
The present invention is achieved through following technical scheme:
A kind of method that adopts the microwave circumfluence method to prepare different crystal forms and pattern nano-manganese dioxide fast, step of preparation process is following:
(1) by the manganous salt of 1: 1 difference of stoichiometric ratio weighing solubility and the persulphate of solubility; And the adding deionized water fully dissolves in described manganous salt and persulphate; The concentration of divalent manganesetion is 0.01～0.1mol/L in the above-mentioned manganous salt solution, then above-mentioned reaction intermediate manganous salt solution is transferred in the there-necked flask.
(2) there-necked flask is placed microwave oven, microwave frequency is 2.45GHz, and the device of external condensing reflux on there-necked flask prevents the reaction solvent evaporation.Microwave power is 100～850W, and temperature of reaction is 90～100 ℃, and the reaction times is 5～30min, adopts magnetic stirrer in the reaction process.Reaction finishes the back and product is separated, washs and drying, promptly obtains γ-MnO
2Nano material.
A kind of method that adopts the microwave circumfluence method to prepare different crystal forms and pattern nano-manganese dioxide fast, step of preparation process is following:
(1) by the manganous salt of 1: 1 difference of stoichiometric ratio weighing solubility and the persulphate of solubility; And the adding deionized water fully dissolves in described manganous salt and persulphate, and the concentration of divalent manganesetion is 0.01～0.1mol/L in the above-mentioned manganous salt solution; The vitriol oil 1～the 5mL of measuring massfraction 95～98% again joins in the described manganous salt solution, then above-mentioned reaction intermediate manganous salt solution is transferred in the there-necked flask.
(2) there-necked flask is placed microwave oven, microwave frequency is 2.45GHz, and the device of external condensing reflux on there-necked flask is to prevent the evaporation of reaction solvent.Microwave power is 100～850W, and temperature of reaction is 90～100 ℃, and the reaction times is 5～30min, adopts magnetic stirrer in the reaction process.Reaction finishes the back and product is separated, washs and drying, promptly obtains sea urchin shape α-MnO
2The micron ball.
The manganous salt of solubility of the present invention is manganous sulfate, manganous nitrate or Manganous chloride tetrahydrate, and the persulphate of described solubility is Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
The chemical equation of above-mentioned reaction is represented as follows:
Mn
2++S
2O
8 2-+2H
2O→MnO
2↓+4H
++2SO
4 2-
The present invention is a raw material with the manganous salt of solubility and the persulphate of solubility, adopts the microwave heating technique of backflow, through adding vitriol oil reagent to reaction soln, synthesizes the nanometer titanium dioxide manganese material with different crystal forms and shape characteristic fast.The present invention has characteristics such as technology is simple, the reaction times is short, cost is low, controllable product quality.The manganese bioxide material of preparation can be used for the fields such as electrode materials, battery electrode material and catalyzer of ultracapacitor.
Description of drawings
Fig. 1 a is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 1;
Fig. 1 b is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 2;
Fig. 1 c is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 3;
Fig. 2 is the field emission scanning electron microscope figure of the Manganse Dioxide of the embodiment of the invention 1;
Fig. 3 a is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 20;
Fig. 3 b is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 21;
Fig. 3 c is the X ray diffracting spectrum of the Manganse Dioxide of the embodiment of the invention 22;
Fig. 4 is the field emission scanning electron microscope figure of the Manganse Dioxide of the embodiment of the invention 20;
Fig. 5 is the transmission electron microscope picture of the Manganse Dioxide of the embodiment of the invention 20.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
Take by weighing 2.7g Potassium Persulphate (analytical pure) and 1.69g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.067mol/L; Above-mentioned reaction intermediate is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 800W, temperature of reaction is 98 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.After reaction finishes with reaction product suction filtration, washing and drying.Fig. 1 and Fig. 2 result for embodiment 1 products therefrom is characterized.Wherein, the curve a among Fig. 1 is depicted as the XRD figure spectrum of product, and the γ that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a γ phase Manganse Dioxide.As shown in Figure 2, the stereoscan photograph of this product shows being made up of the nanoparticle of sheet and filamentary structure for gained γ phase Manganse Dioxide of gained.
Embodiment 2
Take by weighing 4.05g Potassium Persulphate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 10min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.Curve b among Fig. 1 is depicted as the XRD figure spectrum of product, and the γ that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a γ phase Manganse Dioxide.
Embodiment 3
Take by weighing 0.405g Potassium Persulphate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.Curve c among Fig. 1 is depicted as the XRD figure spectrum of product, and the γ that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a γ phase Manganse Dioxide.
Embodiment 4
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 5
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 6
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 7
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 8
Take by weighing 4.05g Potassium Persulphate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 9
Take by weighing 0.405g Potassium Persulphate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 11
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 12
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 13
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 100 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 14
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 15
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 16
Take by weighing 4.05g Potassium Persulphate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 17
Take by weighing 0.405g Potassium Persulphate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 18
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Embodiment 19
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, placed microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is γ-MnO
2
Take by weighing 2.7g Potassium Persulphate (analytical pure) and 1.69g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.067mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 800W, temperature of reaction is 98 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.After reaction finishes with reaction product suction filtration, washing and drying.Fig. 3 and Fig. 4 result for embodiment 2 products therefroms are characterized.Wherein, the curve a among Fig. 3 is depicted as the XRD figure spectrum of product, and the α that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a α phase Manganse Dioxide.Shown in Figure 4 is the stereoscan photograph of this product, and what show gained is the granulometric composition of gained α phase Manganse Dioxide by sea urchin shape three-dimensional structure, and the particulate diameter is 100nm.
Embodiment 21
Take by weighing 4.07g Potassium Persulphate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 500W, temperature of reaction is 95 ℃, the reaction times is 10min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.Curve b among Fig. 3 is depicted as the XRD figure spectrum of product, and the α that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a α phase Manganse Dioxide.
Embodiment 22
Take by weighing 0.407g Potassium Persulphate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 4ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.Curve c among Fig. 3 is depicted as the XRD figure spectrum of product, and the α that has structure in this spectral line and the JCPDS DB spectral line of Manganse Dioxide mutually is very identical, shows that this product is a α phase Manganse Dioxide.
Embodiment 23
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 24
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 25
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 26
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.2535g Manganous sulfate monohydrate (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 27
Take by weighing 0.405g Potassium Persulphate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 28
Take by weighing 4.05g Potassium Persulphate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 29
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 31
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 32
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.2685g manganous nitrate (50% the aqueous solution) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 33
Take by weighing 4.05g Potassium Persulphate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 34
Take by weighing 0.405g Potassium Persulphate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 100 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 35
Take by weighing 0.357g Sodium Persulfate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 36
Take by weighing 3.57g Sodium Persulfate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 37
Take by weighing 0.342g ammonium persulphate (analytical pure) and 0.297g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.01mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, dripped the 1ml vitriol oil again, place microwave oven cavity to heat then, the external condensation reflux unit of there-necked flask.Microwave power 100W, temperature of reaction is 100 ℃, the reaction times is 5min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Embodiment 38
Take by weighing 3.42g ammonium persulphate (analytical pure) and 2.97g four hydration Manganous chloride tetrahydrates (analytical pure) respectively, be dissolved in the 150ml deionized water, divalent manganesetion concentration is 0.1mol/L; The above-mentioned reaction intermediate for preparing is transferred in the there-necked flask, and the Dropwise 5 ml vitriol oil places microwave oven cavity to heat then again, the external condensation reflux unit of there-necked flask.Microwave power 850W, temperature of reaction is 90 ℃, the reaction times is 30min.Adopt magnetic stirrer in the reaction process.Reaction is carried out suction filtration, washing and drying with reaction product after finishing.XRD result shows that products therefrom is α-MnO
2
Claims (3)
1. method that adopts microwave heating to reflux to prepare nano-manganese dioxide, it is characterized in that: its sequence of process steps is following:
(1) by the manganous salt of 1: 1 difference of stoichiometric ratio weighing solubility and the persulphate of solubility; And the adding deionized water fully dissolves; The concentration of divalent manganesetion is 0.01～0.1mol/L in the above-mentioned manganous salt solution, then above-mentioned reaction intermediate is transferred in the there-necked flask;
(2) there-necked flask is placed microwave oven, microwave frequency is 2.45GHz, and the device of external condensing reflux, microwave power are 100～850W, and temperature of reaction is 90～100 ℃, and the reaction times is 5～30min, adopts magnetic stirrer in the reaction process; Reaction finishes the back and product is separated, washs and drying, promptly obtains γ-MnO
2Nano material.
2. method that adopts microwave heating to reflux to prepare nano-manganese dioxide, it is characterized in that: its sequence of process steps is following:
(1) by stoichiometric ratio 1: 1 manganous salt and the persulphate of solubility of weighing solubility respectively, and the adding deionized water fully dissolves, and the concentration of divalent manganesetion is 0.01～0.1mol/L; The vitriol oil 1～the 5mL of measuring massfraction 95～98% again joins in the above-mentioned reaction soln, then reaction soln is transferred in the there-necked flask;
(2) there-necked flask is placed microwave oven, microwave frequency is 2.45GHz, and the device of external condensing reflux, microwave power are 100～850W, and temperature of reaction is 90～100 ℃, and the reaction times is 5～30min, adopts magnetic stirrer in the reaction process; Reaction finishes the back and product is separated, washs and drying, promptly obtains sea urchin shape α-MnO
2The micron ball.
3. microwave heating according to claim 1 and 2 refluxes and prepares the method for nano-manganese dioxide; It is characterized in that: the manganous salt of described solubility is manganous sulfate or manganous nitrate or Manganous chloride tetrahydrate, and the persulphate of described solubility is Potassium Persulphate or Sodium Persulfate or ammonium persulphate.
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| CN104843794A (en) * | 2015-04-17 | 2015-08-19 | 辽宁工业大学 | Gamma-MnO2 preparation method |
| CN105197999A (en) * | 2015-09-10 | 2015-12-30 | 广东工业大学 | Preparation method of sea urchin dendritic gama-MnO2 and electro-catalysis application thereof |
| CN106082347A (en) * | 2016-06-21 | 2016-11-09 | 苏州帝瀚环保科技股份有限公司 | The preparation method of manganese dioxide |
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| CN105197999A (en) * | 2015-09-10 | 2015-12-30 | 广东工业大学 | Preparation method of sea urchin dendritic gama-MnO2 and electro-catalysis application thereof |
| CN106082347A (en) * | 2016-06-21 | 2016-11-09 | 苏州帝瀚环保科技股份有限公司 | The preparation method of manganese dioxide |
| CN106348346A (en) * | 2016-09-12 | 2017-01-25 | 太原理工大学 | Method for preparing manganese dioxide nanowires with microwave method |
| CN108147465A (en) * | 2018-02-27 | 2018-06-12 | 宝鸡文理学院 | A kind of nano-scale δ-MnO2Thin slice and preparation method thereof |
| CN108550472A (en) * | 2018-05-11 | 2018-09-18 | 西北师范大学 | A kind of preparation method of manganese dioxide electrode material for super capacitor |
| CN110240203A (en) * | 2019-06-04 | 2019-09-17 | 上海大学 | The preparation method and applications for the manganese oxide catalyst that hydrogen peroxide decomposes |
| CN114804209A (en) * | 2022-04-28 | 2022-07-29 | 中山大学 | Burr microspheric MnO 2 Preparation method of material and application of material in sterilization and disinfection |
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