CN104098142B - A kind of ε-MnO of hexagonal star-shape2Preparation method and ORR application thereof - Google Patents
A kind of ε-MnO of hexagonal star-shape2Preparation method and ORR application thereof Download PDFInfo
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- CN104098142B CN104098142B CN201410328623.1A CN201410328623A CN104098142B CN 104098142 B CN104098142 B CN 104098142B CN 201410328623 A CN201410328623 A CN 201410328623A CN 104098142 B CN104098142 B CN 104098142B
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- 238000000034 method Methods 0.000 title abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910006343 ε-MnO2 Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Abstract
The present invention relates to the preparation method field of inorganic nano material, be specifically related to a kind of ε-MnO of hexagonal star-shape2Preparation method and ORR application thereof. A kind of ε-MnO of hexagonal star-shape2Preparation method, comprise following steps: 1) by manganese acetate, sodium chlorate is dissolved in distilled water, stir completely dissolve after form solution A; 2) one side agitating solution A, adds acetic acid to form solution B on one side; 3) solution B is placed in to hydro-thermal reaction at 140 ~ 160 DEG C and obtains after 4 ~ 12 hours the ε-MnO of described hexagonal star-shape2. Preparation method's provided by the invention raw material is cheap and easy to get, and cost is low, and synthesis temperature is low, and technique is simple and easy to realize, and constant product quality and process repeatability can be good, easily suitability for industrialized production.
Description
Technical field
The present invention relates to the preparation method field of inorganic nano material, be specifically related to a kind of ε-MnO of hexagonal star-shape2Preparation method and ORR application thereof.
Background technology
Manganese dioxide is a kind of important transition metal oxide that has industrial use, has been widely used at present the fields such as electrode material, molecular sieve, ion sieve, catalysis]. At present the known oxide of manganese or the crystal formation of hydroxide are nearly 30 several, wherein more common crystal formation has α, β, γ, δ etc., different crystal structures must cause it to have different performances, and this will further determine that it has different using values. For example, α type manganese dioxide is widely used in catalysis material, γ type manganese dioxide is considered to a kind of good electrode material, and δ type manganese dioxide is natural layer structure and has larger specific area, makes it be used for ultracapacitor or sorbing material. Although difference is very large on these manganese dioxide crystalline structures, different crystal forms structurally has a common ground, and they are made up of manganese oxygen octahedra, and different crystal formations is consisted of different connected modes manganese oxygen octahedra. Therefore the manganese dioxide of the synthetic different-shape structure of How to choose is present study hotspot always.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of ε-MnO of hexagonal star-shape2Preparation method.
Another object of the present invention is to provide above-mentioned ε-MnO2Application in ORR.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of ε-MnO of hexagonal star-shape2Preparation method, comprise following steps:
1) by manganese acetate, sodium chlorate is dissolved in distilled water, stirs and dissolves the rear solution A that forms completely;
2) one side agitating solution A, adds acetic acid to form solution B on one side;
3) solution B is placed in to hydro-thermal reaction at 140 ~ 160 DEG C and obtains after 4 ~ 12 hours the ε-MnO of described hexagonal star-shape2。
Further, described manganese acetate, the mol ratio of sodium chlorate is 1:1 ~ 1.5.
Further, described manganese acetate, the mol ratio of sodium chlorate is preferably 1:1.25.
Further, the volume ratio of described distilled water and acetic acid is 15:0.5 ~ 1.
Further, the volume ratio of described distilled water and acetic acid is preferably 15:0.8.
A kind of hexagonal star-shape ε-MnO2ε-MnO that preparation method is prepared2Can be used as the application of catalyst in oxygen reduction reaction.
The present invention has following beneficial effect:
(1) preparation method's provided by the invention raw material is cheap and easy to get, and cost is low, and synthesis temperature is low, and technique is simple and easy to realize, and constant product quality and process repeatability can be good, easily suitability for industrialized production.
(2) manganese dioxide that prepared by the present invention is Magen David structure, does not need to use any catalyst, masterplate agent or surfactant etc. in building-up process.
(3) what prepared by the present invention has hexagonal star-shape ε-MnO2During as catalyst, oxygen reduction reaction is had to good catalytic activity.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the prepared manganese dioxide of embodiments of the invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the prepared manganese dioxide of embodiments of the invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the prepared manganese dioxide of embodiments of the invention 1.
Fig. 4 is the performance map of the catalytic oxidation of the prepared manganese dioxide of embodiments of the invention 1 during as catalyst.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1
First 1mmol manganese acetate and 1.25mmol sodium chlorate are dissolved in 15mL distilled water, stir and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side acetic acid is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and acetic acid is 15:1; Described mixed liquid B is placed at 160 DEG C, to react after 12 hours obtains product, product is used respectively to distilled water and absolute ethanol washing for several times, put into 60 DEG C of drying boxes dry, obtain hexagonal star-shape ε-MnO2. Product is accredited as α-MnO through X-ray powder diffraction2; Powder x-ray diffraction result as shown in Figure 1; Material pattern obtains by transmission electron microscope results, as shown in Figure 2, has hexagonal star-shape structure as figure can find out material, and size homogeneous.
Embodiment 2
First 1mmol manganese acetate and 1mmol sodium chlorate are dissolved in 15mL distilled water, stir and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side acetic acid is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and acetic acid is 15:0.8; Described mixed liquid B is placed at 140 DEG C, to react after 6 hours obtains product, product is used respectively to distilled water and absolute ethanol washing for several times, put into 60 DEG C of drying boxes dry, obtain hexagonal star-shape ε-MnO2. Products therefrom is through X-ray powder diffraction (manganese dioxide of preparing with embodiment 1 is similar), ESEM qualification (Fig. 3), and known material has hexagonal star-shape structure, and size homogeneous.
Embodiment 3
First 1mmol manganese acetate and 1.5mmol sodium chlorate are dissolved in 15mL distilled water, stir and dissolve the rear solution A that forms completely; Stir described solution A on one side, on one side acetic acid is joined in solution A, after stirring, form mixed liquid B; The volume ratio of wherein said distilled water and acetic acid is 15:0.9; Described mixed liquid B is placed at 150 DEG C, to react after 10 hours obtains product, product is used respectively to distilled water and absolute ethanol washing for several times, put into 60 DEG C of drying boxes dry, obtain hexagonal star-shape ε-MnO2. Products therefrom is through X-ray powder diffraction, ESEM qualification (manganese dioxide of preparing with embodiment 1 is similar), and known material has hexagonal star-shape structure, and size homogeneous.
Embodiment 4
Manganese dioxide prepared embodiment 1 is made to electrode and in alkaline solution, test electrocatalytic oxidation reducing power (its electrode preparation and experimentation are prior art, are not described in detail at this). As shown in Figure 4, its half wave potential is near-0.1V for the performance map of its catalytic oxidation, and it has good electrocatalytic oxidation reducing power surface.
The above embodiment has only expressed embodiments of the present invention; it describes comparatively concrete and detailed; but can not therefore be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme that adopts the form that is equal to replacement or equivalent transformation to obtain, within all should dropping on protection scope of the present invention.
Claims (4)
1. ε-the MnO of a hexagonal star-shape2Preparation method, it is characterized in that comprising following steps:
1) by manganese acetate, sodium chlorate is dissolved in distilled water, stirs and dissolves the rear solution A that forms completely;
2) one side agitating solution A, adds acetic acid to form solution B on one side;
3) solution B is placed in to hydro-thermal reaction at 140 ~ 160 DEG C and obtains after 4 ~ 12 hours the ε-MnO of described hexagonal star-shape2；
Described manganese acetate, the mol ratio of sodium chlorate is 1:1 ~ 1.5;
The volume ratio of described distilled water and acetic acid is 15:0.5 ~ 1.
2. ε-the MnO of a kind of hexagonal star-shape according to claim 12Preparation method, it is characterized in that: described manganese acetate, the mol ratio of sodium chlorate is preferably 1:1.25.
3. ε-the MnO of a kind of hexagonal star-shape according to claim 12Preparation method, it is characterized in that: the volume ratio of described distilled water and acetic acid is preferably 15:0.8.
4. a kind of hexagonal star-shape ε-MnO as described in claim 1 ~ 3 any one2ε-MnO that preparation method is prepared2Can be used as the application of catalyst in oxygen reduction reaction.
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| CN103193273A (en) * | 2013-05-03 | 2013-07-10 | 广东工业大学 | Preparation method of extra-long manganese dioxide nanowires |
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| CN103193273A (en) * | 2013-05-03 | 2013-07-10 | 广东工业大学 | Preparation method of extra-long manganese dioxide nanowires |
Non-Patent Citations (1)
| Title |
|---|
| Hydrothermal growth of manganese dioxide into three-dimensional hierarchical nanoarchitectures;Yun-Shuang Ding, et al.;《Advanced Functional Materials》;20060103;第16卷;第550页右栏第4行至第13行，第555页左栏第12行至第14行 * |
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