CN103880088B - Preparation method and catalytic application of hollow dual-cone beta-MnO2 - Google Patents
Preparation method and catalytic application of hollow dual-cone beta-MnO2 Download PDFInfo
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- CN103880088B CN103880088B CN201410069792.8A CN201410069792A CN103880088B CN 103880088 B CN103880088 B CN 103880088B CN 201410069792 A CN201410069792 A CN 201410069792A CN 103880088 B CN103880088 B CN 103880088B
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- bipyramid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- 229910006648 β-MnO2 Inorganic materials 0.000 title abstract 4
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical group O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention relates to the fields of preparation and application of inorganic nanometer materials and in particular relates to a preparation method and catalytic application of hollow dual-cone beta-MnO2. The method for preparing the hollow dual-cone beta-MnO2 comprises the following steps: (1) dissolving a soluble manganese salt and potassium chlorate in distilled water, completely stirring, and dissolving to form a solution A; (2) adding concentrated nitric acid to form a solution B while stirring the solution A; (3) putting the solution B into a high-pressure reaction kettle, wherein the filling degree of the high-pressure reaction kettle is 60-80 percent, and reacting the high-pressure reaction kettle in a temperature environment at the temperature of 170-180 DEG C for 9-12 hours to obtain the product. Compared with a conventional synthetic technology, the method has the obvious characteristics that a simple hydrothermal synthesis method is adopted, the hollow dual-cone beta-MnO2 is prepared, and the method has the advantages that high-temperature roasting is not needed, the yield is high, the repeatability is high, and the obtained material catalyst has excellent dye degradation capability under the hydrogen peroxide condition.
Description
Technical field
The present invention relates to inorganic nano material preparation and Application Areas, be specifically related to a kind of hollow bipyramid β-MnO
2preparation method and catalytic applications.
Background technology
Manganse Dioxide is a kind of important functional materials, has much special physics and chemistry character, has been widely used in the field such as catalysis, electrochemistry.The basic structural unit constructing manganese bioxide material is manganese oxygen octahedra, and the mode by being total to rib or corner-sharing between manganese oxygen octahedra forms the Manganse Dioxide of tunnel-like or stratiform.Manganse Dioxide has multiple crystal formation, as α-MnO
2, γ-MnO
2, β-MnO
2with δ-MnO
2deng.Because these crystal formations have different pore sizes and pattern, cause the Manganse Dioxide of different crystal forms on process based prediction model, have larger difference.
β-MnO
2have the pore passage structure in 1 dimension tunnel (1 × 1), it is a kind of crystal formation that in numerous Manganse Dioxide crystal formation, thermodynamics is the most stable.β-the MnO of different-shape
2have different physics or chemical property, three-dimensional structure nano material has more Adsorption than the nano material of two dimension or one-dimentional structure usually, therefore shows the performance of some excellences.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hollow bipyramid β-MnO without template, tensio-active agent or catalyzer
2preparation method.
Another object of the present invention is to provide the β-MnO prepared by this preparation method
2can be used as the application of catalyzer in catalysis.
Technical problem to be solved by this invention is achieved by the following technical programs:
1. a hollow bipyramid β-MnO
2preparation method, comprise the following steps:
1) by soluble manganese salt, Potcrate is dissolved in distilled water, stirs after dissolving completely and forms solution A;
2) one side stirred solution A, adds concentrated nitric acid and forms solution B;
3) solution B is put into autoclave, the compactedness of autoclave is 60 ~ 80 %, and under described autoclave being placed in the temperature environment of 170 ~ 180 DEG C, reaction obtained product after 9 ~ 12 hours.
Further, described soluble manganese salt is Manganous chloride tetrahydrate.
Further, the mol ratio of described soluble manganese salt and Potcrate is 1:1.25 ~ 1.75.
Further, the mol ratio of described soluble manganese salt and Potcrate is preferably 1:1.5.
Further, the volume ratio of described concentrated nitric acid and distilled water is 15:1.5 ~ 2.
β-MnO prepared by this preparation method
2can be used as the application of catalyzer in catalysis.
Further, degraded Methylene blue is applied as described in.
In the present invention, utilize the oxidisability of Potcrate in hydrothermal system, form the β-MnO of thermodynamically stable phase
2; And the concentrated nitric acid added in system, utilize the weak coordination protectiveness of nitrate radical and Mn, make to generate β-MnO
2not dissolved, as utilized concentrated hydrochloric acid to replace concentrated nitric acid, due to the coordinating difference of chlorion, easily making product dissolve completely.
The present invention has following beneficial effect:
Compared with existing synthetic technology, the present invention has following outstanding feature: the present invention adopts simple hydrothermal synthesis method, has prepared hollow bipyramid β-MnO
2, this method is without the need to high-temperature roasting, and productive rate is high, reproducible, and the material catalyst obtained uses, and has good dye degrades ability under the condition of hydrogen peroxide.
Accompanying drawing explanation
The X x ray diffration pattern x of the Manganse Dioxide of Fig. 1 prepared by embodiments of the invention 1.
The scanning electron microscope (SEM) photograph of the Manganse Dioxide of Fig. 2 prepared by embodiments of the invention 1.
The scanning electron microscope (SEM) photograph of the Manganse Dioxide of Fig. 3 prepared by embodiments of the invention 2.
The Manganse Dioxide of Fig. 4 prepared by embodiments of the invention 1 is as the performance map of degraded Methylene blue during catalyzer.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
First 1mmol Manganous chloride tetrahydrate, 1.5mmol Potcrate are dissolved in 15mL distilled water, stir after dissolving completely and form solution A; While stir described solution A, concentrated nitric acid is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and concentrated nitric acid is 15:2; React at described mixed liquid B is placed in 180 DEG C after 12 hours and obtain product, product is used respectively distilled water and absolute ethanol washing for several times, put into 60 DEG C of loft drier dry, obtain the β-MnO of described hollow bipyramid
2.Product is accredited as β-MnO through X ray powder diffraction
2; Powder x-ray diffraction result is as shown in Fig. 1; Material morphology is obtained by transmission electron microscope results, as shown in Figure 2, as figure can find out that material has hollow bipyramid structure, and size uniformity.
embodiment 2
First 1mmol Manganous chloride tetrahydrate, 1.25mmol Potcrate are dissolved in 15mL distilled water, stir after dissolving completely and form solution A; While stir described solution A, concentrated nitric acid is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and concentrated nitric acid is 15:1.5; React at described mixed liquid B is placed in 180 DEG C after 12 hours and obtain product, product is used respectively distilled water and absolute ethanol washing for several times, put into 60 DEG C of loft drier dry, obtain the β-MnO of described hollow bipyramid
2.Products therefrom is through X-ray powder diffraction (Manganse Dioxide of the three-dimensional structure prepared with embodiment 1 is similar), scanning electron microscope qualification (Fig. 3), and known material has hollow bipyramid structure, and size uniformity.
embodiment 3:
Carry out the experiment of degraded Methylene blue
Get the methylene blue solution of the 20mg/L of 75mL, and with the distilled water diluting of 72.5mL it, then add the catalyzer of 10mg embodiment 1, be at room temperature uniformly mixed; Then the hydrogen peroxide adding 2.5mL starts reaction, at the uniform velocity stirs 2 hours; In the process of reaction, take out the mixture of 2mL at the time point determined and use the distilled water diluting of 8mL to be determined to 10mL immediately; The solution diluted is removed rigid granules with whizzer centrifugal 3min under the rotating speed of 10,000 immediately; Then carry out the detection of methylene blue concentration with the ultraviolet spectrophotometer of Shimadzu UV-2450, test design sketch as shown in Figure 4.As can be seen from figure we, the β-MnO of hollow bipyramid structure
2there is good degradation property, and the β-MnO of the same crystal formation of commercialization
2activity is very low.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (7)
1. a hollow bipyramid β-MnO
2preparation method, it is characterized in that, comprise the following steps:
1) by soluble manganese salt, Potcrate is dissolved in distilled water, stirs after dissolving completely and forms solution A;
2) one side stirred solution A, adds concentrated nitric acid and forms solution B;
3) solution B is put into autoclave, the compactedness of autoclave is 60 ~ 80 %, and under described autoclave being placed in the temperature environment of 170 ~ 180 DEG C, reaction obtained product after 9 ~ 12 hours.
2. the hollow bipyramid β of one according to claim 1-MnO
2preparation method, it is characterized in that, described soluble manganese salt is Manganous chloride tetrahydrate.
3. the hollow bipyramid β of one according to claim 1-MnO
2preparation method, it is characterized in that, the mol ratio of described soluble manganese salt and Potcrate is 1:1.25 ~ 1.75.
4. the hollow bipyramid β of one according to claim 3-MnO
2preparation method, it is characterized in that, the mol ratio of described soluble manganese salt and Potcrate is preferably 1:1.5.
5. the hollow bipyramid β of one according to claim 1-MnO
2preparation method, it is characterized in that, the volume ratio of described concentrated nitric acid and distilled water is 15:1.5 ~ 2.
6. the hollow bipyramid β-MnO as described in claim 1 ~ 5 any one
2the β-MnO prepared by preparation method
2can be used as the application of catalyzer in catalysis.
7. the application in catalysis according to claim 6, is characterized in that, described in be applied as degraded Methylene blue.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761000A (en) * | 2015-03-19 | 2015-07-08 | 大连理工大学 | Manganese dioxide micrometer cube, and preparation method and application thereof |
| CN106299336B (en) * | 2015-07-07 | 2019-02-01 | 湖北文理学院 | The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode |
| CN105197999B (en) * | 2015-09-10 | 2016-09-28 | 广东工业大学 | A kind of Hemicentrotus seu Strongylocentrotus dendroid γ-MnO2preparation method and electro-catalysis application |
| CN109650456B (en) * | 2019-01-25 | 2021-08-20 | 安徽益佳通电池有限公司 | Shape-controllable MnO2Preparation method and application of nano material |
| CN115092966B (en) * | 2022-07-04 | 2023-06-20 | 嘉应学院 | Mixed phase MnO of three-dimensional lamellar structure for toluene catalytic combustion 2 Is prepared by the preparation method of (2) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012167010A2 (en) * | 2011-06-02 | 2012-12-06 | Cornell University | Manganese oxide nanoparticles, methods and applications |
| CN103332749A (en) * | 2013-06-09 | 2013-10-02 | 燕山大学 | Method for preparing manganese dioxide with multistage pore structure |
| CN103553136A (en) * | 2013-11-01 | 2014-02-05 | 广东工业大学 | Preparation method of pliers-shaped beta-MnO2 |
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2014
- 2014-02-28 CN CN201410069792.8A patent/CN103880088B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012167010A2 (en) * | 2011-06-02 | 2012-12-06 | Cornell University | Manganese oxide nanoparticles, methods and applications |
| CN103332749A (en) * | 2013-06-09 | 2013-10-02 | 燕山大学 | Method for preparing manganese dioxide with multistage pore structure |
| CN103553136A (en) * | 2013-11-01 | 2014-02-05 | 广东工业大学 | Preparation method of pliers-shaped beta-MnO2 |
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