CN102092789B - Preparation method of beta-MnOOH hexagonal nanosheet - Google Patents
Preparation method of beta-MnOOH hexagonal nanosheet Download PDFInfo
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- CN102092789B CN102092789B CN2011100866867A CN201110086686A CN102092789B CN 102092789 B CN102092789 B CN 102092789B CN 2011100866867 A CN2011100866867 A CN 2011100866867A CN 201110086686 A CN201110086686 A CN 201110086686A CN 102092789 B CN102092789 B CN 102092789B
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- mnooh
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- flake
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- 229910003174 MnOOH Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002135 nanosheet Substances 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000002060 nanoflake Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 13
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002524 electron diffraction data Methods 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of a beta-MnOOH hexagonal nanosheet. The method is as follows: water is used as reaction medium, MnSO4 and ethylenediamine are dissolved in a mixed solvent, NaOH is used as precipitant, the solution contains a small amount of dissolved oxygen, and reaction is performed under a certain condition; and after the reaction, centrifugal washing is performed to the obtained product, and then drying is performed to obtain the beta-MnOOH hexagonal nanosheet. The preparation method of the invention is simple, and the size, structure and morphology of the product beta-MnOOH hexagonal nanosheet are easy to control. The problem of the prior art that the phase and structure of the beta-MnOOH are difficult to control can be solved.
Description
Technical field
The present invention relates to the preparation method of a kind of β phase MnOOH, specifically, relate to a kind of preparation method of β phase MnOOH hexagonal nano-flake.
Background technology
The manganese oxide of various structures and manganous hydroxide are widely used in fields such as electrochemistry, battery, electrochromism owing to having unique physicochemical property.It is reported that the distinctive character of manganese oxide (manganous hydroxide) depends on its crystal morphology, crystalline structure and density thereof.Therefore, people are devoted to the manganese oxide of various patterns and synthesizing of manganous hydroxide.There is multiple crystal formation (for example α, β and γ phase) in MnOOH, mainly is octahedra unit [Mn basic in its crystalline structure
3+(O, OH)
6] on-link mode (OLM) be different.Wherein, γ-MnOOH receives much concern, and a lot of reported in literature utilize MnO
2Or KMnO
4With the reductive agent reaction, perhaps in the presence of different organic solvents, with Mn
2+With the synthetic γ of oxidant reaction-MnOOH nano wire and nanometer rod, the long route that clusters is rolled into a ball in utilization also can prepare γ-MnOOH nanometer rod.Chinese patent document CN101851008A discloses a kind of with potassium permanganate and N, and dinethylformamide carries out the method that solvent reaction prepares γ-MnOOH nanometer rod, and patent documentation CN101428860A discloses a kind of MnO of using
2With Mn
3O
4Hydro-thermal reaction prepares the method for γ-MnOOH nanometer rod.In the used raw material of these methods, MnO
2Be insoluble in water, solid state reaction is not too even, is prone to sneak into impurity in the product, and KMnO
4Price is higher.Product is γ-MnOOH.
β-MnOOH is considered to the steady phase of Jie of manganese oxide forming process usually, and its phase transition process is studied fully.Although the γ-MnOOH's of stable phase is synthetic by wide coverage, not synthetic not the appearing in the newspapers that the steady phase β-MnOOH that is situated between is nanocrystalline.
For these reasons, how finding that a kind of technology is simple relatively, reaction conditions is gentle, and can prepare the size Jie steady mutually β-MnOOH hexagonal nano-flake controlled with pattern, then is subject matter to be solved by this invention.
Summary of the invention
The present invention is directed in the prior art the nanocrystalline preparation feedback condition of β-MnOOH harsh, be difficult to obtain pure thing and equate problem; A kind of preparation method of β phase MnOOH hexagonal nano-flake has been proposed; This method technology is simple, and reaction conditions is gentle, can obtain the MnOOH of pure β phase; Prepared go out the size and the pattern of β-MnOOH nanometer sheet control easily, have the batch process feasibility.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to be achieved:
A kind of preparation method of MnOOH hexagonal nano-flake of β phase is characterized in that said method comprises the steps:
(1) a certain amount of MnSO
4Be dissolved in the water with quadrol, obtain Mn
2+With quadrol coordinate mixed solution;
(2) a certain amount of NaOH is dissolved in the water, obtains certain density NaOH solution;
(3) with above-mentioned two kinds of solution short mix, obtain containing yellowish pink sedimentary mixed solution;
(4) contain yellowish pink sedimentary mixed solution and transfer in the reaction kettle above-mentioned, react for some time at a certain temperature, obtain containing the mixed solution of β-MnOOH;
(5) with after the above-mentioned mixed solution cooling that contains β-MnOOH, centrifugal under certain rotating speed, outwell supernatant liquid, and water and ethanol repeated washing, obtain brown β-MnOOH throw out,
(6) it is dry β-MnOOH the throw out that obtains in the step (5) to be put into loft drier, obtains β-MnOOH hexagonal nano-flake.
Wherein, in the mixed solution of step (1), Mn
2+With the mol ratio of quadrol be 1:1-1:8.
Further, in step (2), the concentration of NaOH is 3.0-7.0 molL
-1
Further, in step (3), the temperature of short mix is 25 ℃.
Further again, in step (4), the temperature of reaction is 150-200 ℃, and the time of reaction is 0.5h-2 h.
Further again, in step (5), said centrifugal rotational speed is 3000-4000 r/min, and centrifugation time is 2-5min.
Further again, in step (6), the exsiccant temperature is 40-80 ℃, and the exsiccant time is 12-24 h.
Description of drawings
Fig. 1 is X ray diffracting spectrum and the standard spectrogram of β-MnOOH that utilizes the β-MnOOH hexagonal nano-flake of the method for the invention preparation.
Fig. 2 is sem (SEM) photo, transmission electron microscope (TEM) photo and the electron diffraction pattern (ED) that utilizes the β-MnOOH hexagonal nano-flake of the method for the invention preparation.
Fig. 3 is the SEM photo of the prepared β-MnOOH nanometer sheet of NaOH concentration for a change.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further detailed explanation.
Embodiment one:
(1) pipettes 2.2 ml, 0.36 molL with transfer pipet earlier
-1MnSO
4Solution adds in the 50 ml beakers, pipettes 0.6 ml quadrol with 1 ml transfer pipet again and adds in the beaker, obtains Mn
2+With quadrol coordinate mixed solution;
(2) pipette 19.2 ml, 7.0 molL with transfer pipet
-1NaOH;
(3) with above-mentioned two kinds of solution short mix, obtain containing yellowish pink sedimentary mixed solution;
(4) mixing solutions is transferred in the reaction kettle,, obtained containing the mixed solution of β-MnOOH at 170 ℃ of reaction 0.5 h;
(5) with after the above-mentioned mixed solution cooling that contains β-MnOOH, centrifugal under the 3000r/min rotating speed, outwell supernatant liquid, and water and ethanol repeated washing three times respectively, acquisition β-MnOOH throw out.
(6) β-MnOOH throw out that obtains in the step (3) is put into 80 ℃ of dry 12 h of loft drier, obtain β-MnOOH hexagonal nano-flake.
Fig. 1 is the X ray diffracting spectrum of the prepared β-MnOOH hexagonal nano-flake of embodiment one.The peak position of the diffraction peak of indexing is all consistent with the standard spectrogram in the spectrogram, but the relative intensity at (002) peak is compared obvious enhancing with the standard spectrogram, shows that the product of embodiment one preparation is the hexagonal water manganese ore structure MnOOH of β phase, and spacer is P-3
m1, orientation growth of crystals is obvious.Fig. 2 is the SEM photo of the prepared β phase MnOOH hexagonal nano-flake of embodiment one, and wherein, Fig. 2 a is the SEM picture of low power, as can be seen from the figure gained nanometer sheet size evenly, pattern is regular.Fig. 2 b is that the prepared β of embodiment one-MnOOH hexagonal nano-flake amplifies the SEM photo, can clearly be seen that therefrom sample has hexagonal structure, the thickness of six side's sheets about 40 nanometers, about 200 nanometers of the length of side.Fig. 2 c is transmission electron microscope (TEM) photo of the prepared β-MnOOH hexagonal nano-flake of embodiment one, can find out β-MnOOH nanometer sheet good dispersivity, even structure.Illustration among Fig. 2 c is the electron diffraction pattern of sample, can find out the β-MnOOH nanometer sheet well-crystallized with hexagonal structure.
Embodiment two:
(1) pipettes 2.2 ml, 0.36 molL with transfer pipet earlier
-1MnSO
4Solution adds in the 50 ml beakers, pipettes 0.6 ml quadrol with 1 ml transfer pipet again and adds in the beaker, obtains Mn
2+With quadrol coordinate mixed solution;
(2) pipette 19.2ml 5 molL with transfer pipet
-1NaOH;
(3) with above-mentioned two kinds of solution short mix, obtain containing yellowish pink sedimentary mixed solution;
(4) mixing solutions is transferred in the reaction kettle,, obtained containing the mixed solution of the MnOOH of β phase at 170 ℃ of reaction 0.5 h;
(5) with after the above-mentioned mixed solution cooling that contains β-MnOOH, centrifugal under the 3000r/min rotating speed, outwell supernatant liquid, and water and ethanol repeated washing three times respectively, acquisition β-MnOOH throw out.
(6) β-MnOOH throw out that obtains in the step (3) is put into 80 ℃ of dry 12 h of loft drier, obtain the MnOOH hexagonal nano-flake of β phase.
Embodiment three:
(1) pipettes 2.2 ml, 0.36 molL with transfer pipet earlier
-1MnSO
4Solution adds in the 50 ml beakers, pipettes 0.6 ml quadrol with 1 ml transfer pipet again and adds in the beaker, obtains Mn
2+With quadrol coordinate mixed solution;
(2) pipette 19.2ml 3.0 molL with transfer pipet
-1NaOH;
(3) with above-mentioned two kinds of solution short mix, obtain containing yellowish pink sedimentary mixed solution;
(4) mixing solutions is transferred in the reaction kettle,, obtained containing the mixed solution of the MnOOH of β phase at 170 ℃ of reaction 2 h;
(5) after the mixed solution cooling with the above-mentioned MnOOH that contains the β phase, centrifugal under the 3000r/min rotating speed, outwell supernatant liquid, and water and ethanol repeated washing three times respectively, the MnOOH throw out of acquisition β phase.
(6) the MnOOH throw out of the β phase that obtains in the step (3) is put into 80 ℃ of dry 12 h of loft drier, obtain the MnOOH hexagonal nano-flake of β phase.
Claims (6)
1. the preparation method of a β phase MnOOH hexagonal nano-flake is characterized in that prepared MnOOH has the crystalline structure of β phase, and said method comprises the steps:
(1) with a certain amount of MnSO
4Be dissolved in the water with quadrol, obtain Mn
2+With quadrol coordinate mixed solution;
(2) NaOH is dissolved in the water, obtains certain density NaOH solution;
(3) with above-mentioned two kinds of solution short mix, obtain containing yellowish pink sedimentary mixed solution;
(4) contain yellowish pink sedimentary mixed solution and transfer in the reaction kettle above-mentioned, reaction 0.5h-2 h under 150-200 ℃ of temperature obtains containing the mixed solution of β-MnOOH;
(5) with after the above-mentioned mixed solution cooling that contains β-MnOOH, centrifugal under certain rotating speed, outwell supernatant liquid, and water and ethanol repeated washing, obtain brown β-MnOOH throw out,
(6) it is dry β-MnOOH the throw out that obtains in the step (5) to be put into loft drier, obtains β-MnOOH hexagonal nano-flake.
2. the preparation method of β phase MnOOH hexagonal nano-flake according to claim 1 is characterized in that, in the mixed solution of step (1), and Mn
2+With the mol ratio of quadrol be 1:1-1:8.
3. the preparation method of β phase MnOOH hexagonal nano-flake according to claim 2 is characterized in that the concentration of NaOH is 3.0-7.0 molL
-1
4. the preparation method of β phase MnOOH hexagonal nano-flake according to claim 3 is characterized in that, in step (3), the temperature of short mix is 25 ℃.
5. the preparation method of β phase MnOOH hexagonal nano-flake according to claim 1 is characterized in that, in step (5), said centrifugal rotational speed is 3000-4000 r/min, and centrifugation time is 2-5min.
6. the preparation method of β phase MnOOH hexagonal nano-flake according to claim 1 is characterized in that, in step (6), the exsiccant temperature is 40-80 ℃, and the exsiccant time is 12-24 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428860A (en) * | 2008-12-08 | 2009-05-13 | 北京科技大学 | Method for producing high purity MnOOH |
| CN101851008A (en) * | 2010-07-06 | 2010-10-06 | 江苏技术师范学院 | Method for preparing MnOOH nano rods |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428860A (en) * | 2008-12-08 | 2009-05-13 | 北京科技大学 | Method for producing high purity MnOOH |
| CN101851008A (en) * | 2010-07-06 | 2010-10-06 | 江苏技术师范学院 | Method for preparing MnOOH nano rods |
Non-Patent Citations (1)
| Title |
|---|
| J. K. KLEWICKI et al.Dissolution of β-MnOOH particles by ligands: Pyrophosphate, ethylenediaminetetraacetate, and citrate.《Geochimica et Cosmochimica Acta》.1999,第63卷(第19/20期),3017-3024. * |
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