CN110171851B - One-dimensional manganese dioxide material and preparation method and application thereof - Google Patents
One-dimensional manganese dioxide material and preparation method and application thereof Download PDFInfo
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Abstract
A one-dimensional manganese dioxide material and a preparation method and application thereof are provided, wherein the preparation method comprises the following steps: mixing manganese dioxide with the neutral solution and carrying out hydrothermal reaction; and separating the mixed solution after the hydrothermal reaction to obtain solid, namely the one-dimensional manganese dioxide material. According to the invention, manganese dioxide with low cost, environmental friendliness and stable physical and chemical properties is selected as a manganese source, a neutral solution is used as a material synthesis environment, the one-dimensional manganese dioxide material is directly synthesized by one-step hydrothermal synthesis, the process flow is simple, the conditions are controllable, the production cost is low, the environment is friendly, the safety is realized, the large-scale preparation is easy, and the industrial application prospect is good.
Description
Technical Field
The invention belongs to the field of preparation of manganese dioxide materials, and particularly relates to a one-dimensional manganese dioxide material, and a preparation method and application thereof.
Background
Manganese dioxide has excellent physicochemical properties and is inexpensive, and therefore, manganese dioxide is widely used in the fields of industrial catalysis, heavy metal adsorption, batteries, supercapacitors, biosensors and the like. The microstructure of manganese dioxide is [ MnO ]6]Octahedron is formed by different corner connection modes of different basic units [ MnO ]6]The octahedron combination mode can form manganese dioxide with different crystal forms, and alpha-MnO is common2、β-MnO2、γ-MnO2、δ-MnO2And the like. Meanwhile, the manganese dioxide formed under different synthesis conditions has different microstructures, such as lamellar, flower-shaped, rod-shaped, and linear shapes. The diversification of the crystal form and the appearance of the manganese dioxide determines the diversification of the application of the manganese dioxide. Among them, the one-dimensional manganese dioxide has strong catalytic ability and good electrochemical performance, and thus has attracted extensive attention in various industrial applications and scientific research. At present, the method for synthesizing the one-dimensional manganese dioxide material mainly comprises the following steps: sol-gel template method, reflux method, pyrolysis method, acid treatment method, hydrothermal method, and the like. Hydrothermal method compared with other methodsIn other words, the method has the advantages of energy conservation, environmental protection, short production period, uniform product phase and the like.
The existing material preparation technology mainly comprises a reduction method and an oxidation method. The reduction method is characterized in that potassium permanganate is used as a raw material, other reducing substances are used as reducing agents, the mixed solution is placed in a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction, after natural cooling, reaction products are centrifuged, washed and dried to obtain the one-dimensional manganese dioxide material. The method has the advantages of low cost, mild reaction conditions and high product quality, but has the problem of easy generation of manganese-containing wastewater, thereby causing environmental pollution. The oxidation method is characterized in that divalent manganese salt is used as a raw material, other oxidizing substances are used as oxidants, the mixed solution is stirred uniformly and then transferred into a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction, after natural cooling, the reaction product is centrifuged, washed and dried to obtain the one-dimensional manganese dioxide material. The method has the advantages of low cost, mild reaction conditions and convenient control, but also has the problem of easy generation of manganese-containing wastewater, thereby causing environmental pollution. The preparation process of the one-dimensional manganese dioxide material does not describe the treatment mode of wastewater generated in the preparation process of the material, which limits the industrial production of the one-dimensional manganese dioxide.
Disclosure of Invention
In view of the above, one of the main objects of the present invention is to provide a one-dimensional manganese dioxide material, and a preparation method and applications thereof, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, as an aspect of the present invention, there is provided a method for preparing a one-dimensional manganese dioxide material, comprising the steps of:
(1) mixing manganese dioxide with the neutral solution and carrying out hydrothermal reaction;
(2) and (2) separating the mixed solution after the hydrothermal reaction in the step (1) to obtain solid, namely the one-dimensional manganese dioxide material.
As another aspect of the present invention, there is also provided a one-dimensional manganese dioxide material obtained by the preparation method as described above.
As a further aspect of the invention, the application of the one-dimensional manganese dioxide material in the fields of industrial catalysis, heavy metal adsorption, batteries, supercapacitors and biosensors is also provided.
Based on the technical scheme, compared with the prior art, the one-dimensional manganese dioxide material and the preparation method and application thereof have at least one of the following advantages:
1. according to the invention, manganese dioxide with low cost, environmental friendliness and stable physical and chemical properties is selected as a manganese source, a neutral solution is used as a material synthesis environment, the one-dimensional manganese dioxide material is directly synthesized by one-step hydrothermal synthesis, the process flow is simple, the conditions are controllable, the production cost is low, the environment is friendly, the safety is realized, the large-scale preparation is easy, and the industrial application prospect is good;
2. the waste water generated by the synthetic material can be recycled, so the invention can realize zero discharge of waste;
3. the material prepared by the invention can be used as electrode materials of super capacitors and lithium ion batteries, catalyst materials and heavy metal adsorption materials in environmental protection, and has good industrial application prospect;
4. the pure-phase one-dimensional manganese dioxide material can be obtained by the method.
Drawings
FIG. 1 is a flow chart of a process for preparing a one-dimensional manganese dioxide material according to the present invention;
FIG. 2 is a powder XRD pattern of one-dimensional manganese dioxide material of example 1 in accordance with the present invention;
FIG. 3 is a powder SEM photograph of one-dimensional manganese dioxide material of example 1 of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses a preparation method of a one-dimensional manganese dioxide material, which comprises the following steps:
(1) mixing manganese dioxide with the neutral solution and carrying out hydrothermal reaction;
(2) and (2) separating the mixed solution after the hydrothermal reaction in the step (1) to obtain solid, namely the one-dimensional manganese dioxide material.
Wherein, after the step (2) is finished, the method also comprises the step (3): and (3) washing and drying the solid obtained in the step (2).
Wherein the liquid-solid ratio of the neutral solution to manganese dioxide in the step (1) is 5-1000mL/g, for example 300 mL/g.
Wherein the concentration of the neutral solution in the step (1) is 0.1-10mol/L, for example, 5 mol/L.
Wherein the pH of the neutral solution in step (1) is 6-8, for example 7.
Wherein the neutral solution in the step (1) is LiCl, LiBr, LiI or LiNO3、Li2SO4、NaCl、NaBr、NaI、NaNO3、Na2SO4、KCl、KBr、KI、KNO3、K2SO4、MgCl2、MgBr2、MgI2、Mg(NO3)2、MgSO4、CaCl2、CaBr2、CaI2、Ca(NO3)2Any one or more aqueous solutions of (a).
Wherein, the manganese dioxide in the step (1) is gamma-MnO2、λ-MnO2、ε-MnO2Any one or more of.
Wherein the temperature of the hydrothermal reaction in the step (1) is 40 to 400 ℃, for example, 150 ℃.
Wherein the hydrothermal reaction time in the step (1) is 2-120h, for example 100 h.
Wherein, the liquid separated in the step (2) is recycled for preparing the neutral solution in the step (1).
Wherein the solid in the step (2) comprises powder.
The invention also discloses a one-dimensional manganese dioxide material obtained by the preparation method.
Wherein, the diameter of the one-dimensional manganese dioxide material is 100-1000nm, such as 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 nm.
Wherein the aspect ratio of the one-dimensional manganese dioxide material is 2-1000, such as 2, 5, 10, 20, 30, 50, 100, 200, 300, 500, 600, 700, 800, 900, 1000.
The invention also discloses application of the one-dimensional manganese dioxide material in the fields of industrial catalysis, heavy metal adsorption, batteries, supercapacitors or biosensors.
In one embodiment of the present invention, the present invention adopts, for example, the following technical solutions:
the preparation method of the one-dimensional manganese dioxide material mainly comprises the following steps: mixing manganese dioxide with the neutral solution, carrying out hydrothermal reaction for 2-120h at 40-400 ℃, washing and drying the obtained solid, and obtaining the one-dimensional manganese dioxide material. Different preparation conditions can obtain materials with different diameters and/or aspect ratios of 100-1000nm in diameter and 2-1000 in aspect ratio.
In a preferred embodiment, the present invention adopts the following technical solutions, for example:
a preparation method of a one-dimensional manganese dioxide material comprises the following steps:
(1) hydrothermal synthesis: mixing manganese dioxide with a neutral solution and carrying out hydrothermal reaction at a certain temperature and pressure;
(2) washing and drying: and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain dry powder, wherein the powder is a one-dimensional manganese dioxide material, and the obtained liquid can be recycled for preparing a neutral solution.
Wherein manganese dioxide in the step (1) is gamma-MnO2、λ-MnO2、ε-MnO2And the like.
Wherein the neutral solution in the step (1) is LiCl, LiBr, LiI or LiNO3、Li2SO4、NaCl、NaBr、NaI、NaNO3、Na2SO4、KCl、KBr、KI、KNO3、K2SO4、MgCl2、MgBr2、MgI2、Mg(NO3)2、MgSO4、CaCl2、CaBr2、Cai2、Ca(NO3)2One of theOne or more solutions mixed with water.
Wherein the liquid-solid ratio of the solution in the step (1) to the manganese dioxide is 5-1000 mL/g.
Wherein the concentration of the neutral solution in the step (1) is 0.1-10 mol/L.
Wherein the temperature of the hydrothermal reaction in the step (1) is 40-400 ℃.
Wherein the hydrothermal reaction time in the step (1) is 2-120 h.
Wherein, the liquid obtained after the solid-liquid separation in the step (2) and the compound in the step (1) can be prepared into a neutral solution again and recycled in the step (1).
In another preferred embodiment, the present invention adopts, for example, the following technical solutions:
a preparation method of one-dimensional manganese dioxide comprises the following steps:
(1) hydrothermal synthesis: mixing manganese dioxide with a neutral solution and carrying out hydrothermal reaction at a certain temperature and pressure;
(2) washing and drying: and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain dry powder, wherein the powder is a one-dimensional manganese dioxide material, and the obtained liquid can be recycled for preparing a neutral solution.
Wherein, manganese dioxide in the step (1) can be gamma-MnO2、λ-MnO2、ε-MnO2One or more of the following;
wherein the neutral solution in step (1) can be LiCl, LiBr, LiI or LiNO3、Li2SO4、NaCl、NaBr、NaI、NaNO3、Na2SO4、KCl、KBr、KI、KNO3、K2SO4、MgCl2、MgBr2、MgI2、Mg(NO3)2、MgSO4、CaCl2、CaBr2、CaI2、Ca(NO3)2Etc. mixed with water;
wherein, the liquid-solid ratio of the solution and manganese dioxide in the step (1) is 5-1000mL/g, for example, 5, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000mL/g, etc.;
wherein, the concentration of the neutral solution in the step (1) is 0.1-10mol/L, for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10mol/L and the like;
wherein, the temperature of the hydrothermal reaction in the step (1) is 40-400 ℃, for example, 40, 80, 120, 160, 200, 240, 280, 320, 360, 400 ℃ and the like;
wherein, the hydrothermal reaction time in the step (1) is 2-120h, for example, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120h, etc.;
wherein, the liquid obtained after the solid-liquid separation in the step (2) and the compound in the step (1) can be prepared into a neutral solution again and recycled in the step (1).
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Example 1
(1) Weighing 10g of gamma-MnO26g LiCl and 6g NaCl are mixed in 100mL deionized water, and then hydrothermal reaction is carried out at 150 ℃ for 30h by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
The XRD pattern of the material obtained in this example is shown in FIG. 2, which shows β -MnO2Phase, no miscellaneous peaks; the SEM atlas is shown in FIG. 3, which shows that the material is in a uniform one-dimensional rod-like shape, the length is 5-10 μm, and the diameter is 0.5-1 μm. In summary, the above-mentionedThe pure-phase one-dimensional manganese dioxide material can be obtained by the method. When manganese dioxide raw material is in hydrothermal environment, manganese dioxide raw material can be decomposed into [ MnO ]6]Matrix, neutral environment and different anions and cations will induce [ MnO ]6]The matrix grows along the high-energy surface, and finally the one-dimensional material with good crystallinity (shown in figure 2) and uniform appearance (shown in figure 3) is generated.
Example 2
(1) Weighing 4g of lambda-MnO2、10g NaNO3、4g K2SO4With 0.5g MgI2Mixing the mixture in 50mL of deionized water, and then carrying out hydrothermal reaction at 300 ℃ for 20 hours by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out liquid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
Example 3
(1) Weighing 0.5g of epsilon-MnO2、5g Li2SO44g of KBr and 0.5g of NaI are mixed in 80mL of recycled neutral solution, and then hydrothermal reaction is carried out at 80 ℃ for 6 hours by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
Example 4
(1) Weighing 5g of gamma-MnO2、10gε-MnO2、25g NaNO3With 25g of CaCl2Mixing the mixture in 100mL of recycled neutral solution, and then performing hydrothermal reaction at 100 ℃ for 100 hours by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
Example 5
(1) Weighing 4g of epsilon-MnO2、4g λ-MnO20.5g LiI and 4g MgSO4Mixing the mixture in 40mL of recycled neutral solution, and then carrying out hydrothermal reaction at 350 ℃ for 60h by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
Example 6
(1) Weighing 12g of gamma-MnO2、4g λ-MnO2、0.67g Ca(NO3)2With 1g of MgCl2Mixing the mixture in 100mL of recycled neutral solution, and then carrying out hydrothermal reaction at 370 ℃ for 110h by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
Example 7
(1) Weighing 6g of gamma-MnO2、3g λ-MnO2、4g ε-MnO210g LiBr, 10g K1 and 6g Na2SO4Mixing the mixture in 90mL of recycled neutral solution, and then carrying out hydrothermal reaction at 170 ℃ for 70h by adopting a hydrothermal synthesis method;
(2) and (2) washing and drying powder obtained by carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a one-dimensional manganese dioxide material, and keeping the obtained liquid for preparing a neutral solution.
Pure phase one-dimensional manganese dioxide material can be obtained by the embodiment.
In conclusion, the preparation method of the one-dimensional manganese dioxide material can be used for synthesizing the one-dimensional manganese dioxide material simply, controllably, in batches, safely and environmentally.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the one-dimensional manganese dioxide material is characterized by comprising the following steps of:
(1) mixing manganese dioxide with neutral solution and carrying out hydrothermal reaction, wherein the manganese dioxide is gamma-MnO2、λ-MnO2、ε-MnO2Any one or more combinations of; the neutral solution is LiCl, LiBr, LiI or LiNO3、NaCl、NaBr、NaI、NaNO3、KCl、KBr、KI、KNO3、MgCl2、MgBr2、MgI2、Mg(NO3)2、CaCl2、CaBr2、CaI2、Ca(NO3)2An aqueous solution of any one or more of;
(2) separating the mixed solution after the hydrothermal reaction in the step (1) to obtain solid, namely the one-dimensional manganese dioxide material;
wherein, the liquid separated in the step (2) is recycled for preparing the neutral solution in the step (1).
2. The production method according to claim 1,
and (3) after the step (2) is finished: and (3) washing and drying the solid obtained in the step (2).
3. The production method according to claim 1,
the liquid-solid ratio of the neutral solution to the manganese dioxide in the step (1) is 5-1000 mL/g.
4. The production method according to claim 3,
the liquid-solid ratio of the neutral solution to the manganese dioxide in the step (1) is 300 mL/g.
5. The production method according to claim 1,
the concentration of the neutral solution in the step (1) is 0.1-10 mol/L;
the pH value of the neutral solution in the step (1) is 6-8.
6. The production method according to claim 5,
the concentration of the neutral solution in the step (1) is 5 mol/L;
the pH of the neutral solution in the step (1) is 7.
7. The production method according to claim 1,
the temperature of the hydrothermal reaction in the step (1) is 40-400 ℃;
the time of the hydrothermal reaction in the step (1) is 2-120 h.
8. The production method according to claim 7,
the temperature of the hydrothermal reaction in the step (1) is 150 ℃;
the time of the hydrothermal reaction in the step (1) is 100 h.
9. The production method according to claim 1,
the solid in the step (2) comprises powder.
10. A one-dimensional manganese dioxide material produced by the production method according to any one of claims 1 to 9.
11. One-dimensional manganese dioxide material according to claim 10,
the diameter of the one-dimensional manganese dioxide material is 100-1000 nm;
the length-diameter ratio of the one-dimensional manganese dioxide material is 2-1000.
12. The use of one-dimensional manganese dioxide material according to claim 10 or 11 in the fields of industrial catalysis, heavy metal adsorption, batteries, supercapacitors and biosensors.
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