CN102041553B - Preparation method and application of crystalline-state beta-MnOOH nanowire - Google Patents
Preparation method and application of crystalline-state beta-MnOOH nanowire Download PDFInfo
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- CN102041553B CN102041553B CN2010105982959A CN201010598295A CN102041553B CN 102041553 B CN102041553 B CN 102041553B CN 2010105982959 A CN2010105982959 A CN 2010105982959A CN 201010598295 A CN201010598295 A CN 201010598295A CN 102041553 B CN102041553 B CN 102041553B
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Abstract
The invention discloses a preparation method and application of a crystalline-state beta-MnOOH nanowire. The preparation method of the crystalline-state beta-MnOOH nanowire comprises the following steps of: mixing 0.4-0.6 mM of manganous saline solution with 0.8-1.0 mM of aqueous alkali, which have same volumes, under magnetic stirring at normal temperature; and standing for 1-2 days to generate crystalline-state beta-MnOOH nanowire precipitates, wherein the crystalline-state beta-MnOOH nanowire is used for preparing a mesoporous separation membrane with the thickness of 120-600 nanometers and has a very good beta-MnOOH crystalline structure and a mean diameter of 25 nanometers; easily carrying out ultrasonic dispersion for 5-10 minutes, filtering 2-10 ml of dispersion liquid on a porous substrate to form a mesoporous membrane with the thickness of 120-600 nanometers, wherein the mesoporous membrane can effectively separate granules of 10 nanometers from a water solution, and the flow velocity reaches up to 15,120 L/m<2>hbar; annealing the crystalline-state beta-MnOOH nanowire in the air at 350-450 DEG C for 1 hour, and then converting into a trimanganese tetroxide nanowire with high specific surface area of 70 m<2>/g, which is used for catalyzing and degrading dye molecules.
Description
Technical field
The present invention relates to a kind of Preparation method and use of β-MnOOH nano wire of crystalline state.
Background technology
Mn oxide and nanostructure thereof have been widely used in fields such as catalysis, battery.They normally make through following several method: hydrothermal oxidization reduction method, the sol-gel method in the organic solvent, salt scorification etc.These methods all are power consumptions or are not the methods of very environmental protection.And the specific surface area of the nanostructure that is obtained is all smaller usually.The present invention mainly is the method for β-MnOOH nano wire of introducing a kind of eco-friendly preparation high-specific surface area.Under this normal temperature, simple synthetic method can satisfy the requirement that the industriallization big area is produced in the aqueous solution, and energy saving economy environmental protection again.And this nano wire further expanded be applied to separatory membrane and catalyzing oxidizing degrading organic dye molecule.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of Preparation method and use of β-MnOOH nano wire of crystalline state is provided.
The preparation method of the β of crystalline state-MnOOH nano wire is: under the normal temperature, the 0.4-0.6 mM manganous salt aqueous solution of equal volume is mixed under magnetic agitation with 0.8-1.0 mM alkali aqueous solution, placed 1-2 days, generate the β-MnOOH nano wire throw out of crystalline state.
Described manganous salt is Mn nitrate, manganese sulfate or protochloride manganese.Described alkali is thanomin, sodium hydroxide or Pottasium Hydroxide.
The β of crystalline state-MnOOH nano wire is used to prepare the mesoporous separatory membrane of 120-600 nanometer thickness.
The preparation method of the mesoporous separatory membrane of described 120-600 nanometer thickness is: with the β of crystalline state-MnOOH nano wire flocks ultra-sonic dispersion 5～10 minutes, β-MnOOH nano wire dispersion liquid of getting 2～10 ml crystalline state filtered the mesoporous separatory membrane that in the porous substrate, forms one deck 120～600 nanometer thickness.
The β of crystalline state-MnOOH nano wire is used for the degradation of dye molecule.
The method steps of described degradation of dye molecule is:
1) with the β-MnOOH nano wire of crystalline state in air, 350～450
oC annealing changed into manganic manganous oxide nanometer wire after 1～2 hour;
2) get the manganic manganous oxide nanometer wire powder that makes more than 20 mg and add 100 ml, in the methylene blue solution of 25 mg/L, add the H of 15 ml 30% then
2O
2, can the degradation of dye molecule.
The beneficial effect that the present invention compared with prior art has:
1) preparation of β-MnOOH nano wire is carried out in the aqueous solution at normal temperatures, and it is with low cost, and technology is simple, is easy to industry and goes up volume production.
2) β that makes-MnOOH nano wire not only has good crystal property, also has very high specific surface area 104 m
2/ g.
3) β that makes-MnOOH nano wire can form dispersion liquid preferably, and simple filtering just can obtain mesoporous separatory membrane, can be used for separating the particle of 10 nanometers.
4) β that makes-MnOOH nano wire can change into corresponding Mn oxide nano wire through brief heat treating, can be used for the catalyzed degradation organic dye molecule.
5) β-MnOOH nano wire of making of the present invention can be used for environmental improvement and WWT aspect.
Description of drawings
Fig. 1 is the β-MnOOH nano wire XRD figure that makes.
Fig. 2 is the β-MnOOH nano wire SEM photo that makes.
Fig. 3 is the section SEM photo of the β-mesoporous separatory membrane of MnOOH nano wire of 120 nanometer thickness.
Fig. 4 is that the β-mesoporous separatory membrane of MnOOH nano wire of 120 nanometer thickness separates the Uv-Vis curve of 10 nm gold particless.
Fig. 5 is that β-MnOOH nano wire is in air 400
0C thermal treatment changed into Mn in 1 hour
3O
4The XRD figure of nano wire.
Fig. 6 is that β-MnOOH nano wire is in air 400
0C thermal treatment changed into Mn in 1 hour
3O
4The SEM photo of nano wire.
Fig. 7 is that β-MnOOH nano wire is in air 400
0C thermal treatment changed into Mn in 1 hour
3O
4The change curve in time of the degradation of methylene blue of nano wire and the molecular structure of methylene blue.。
Embodiment
Further specify the present invention below in conjunction with instance.
The preparation and the sign of β-MnOOH nano wire: under the normal temperature, under magnetic agitation, with 10 ml, 0.8 mM thanomin (NH
2CH
2CH
2OH) aqueous solution adds 0.4 mM Mn nitrate (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow stirring velocity, and reaction vessel is sealed.After one day, can obtain the brown flocks, this deposition of XRD proof has β-MnOOH crystalline structure (see figure 1).The SEM morphology analysis shows that these depositions are that mean diameter is 25 nanometers, and length is the nano wire about 1 micron, and high power SEM shows that these nano wires are fascircular texture (see figure 1)s that the nano wire by thinner 3-5 nanometer is arranged in parallel and forms.The specific surface area that the BET test shows these nano wires is up to 104 m
2/ g.
Embodiment 2
The preparation and the sign of β-MnOOH nano wire: normal temperature, under magnetic agitation, with 10 ml, the 0.8 mM NaOH aqueous solution adds 0.4 mM Mn nitrate (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow stirring velocity, and reaction vessel is sealed.After one day, can obtain the brown flocks, this deposition of XRD proof has β-MnOOH crystalline structure.The SEM morphology analysis shows that these depositions are that mean diameter is 25 nanometers, and length is the nano wire about 1 micron, and high power SEM shows that these nano wires are fascircular textures that the nano wire by thinner 3-5 nanometer is arranged in parallel and forms.
Embodiment 3
The preparation and the sign of β-MnOOH nano wire: normal temperature, under magnetic agitation, with 10 ml, the 1.0 mM NaOH aqueous solution add 0.6 mM protochloride manganese (Mn (NO) fast
3) in the aqueous solution, after 1 minute, transfer slow stirring velocity, and reaction vessel is sealed.After two days, can obtain the brown flocks, this deposition of XRD proof has β-MnOOH crystalline structure.The SEM morphology analysis shows that these depositions are that mean diameter is 25 nanometers, and length is the nano wire about 1 micron, and high power SEM shows that these nano wires are fascircular textures that the nano wire by thinner 3-5 nanometer is arranged in parallel and forms.
Embodiment 4
The preparation and the sign of β-MnOOH nano wire: normal temperature, under magnetic agitation, with 10 ml, the 1.0 mM KOH aqueous solution add 0.6 mM fast and vulcanize inferior manganese (Mn (NO)
3) in the aqueous solution, after 1 minute, transfer slow stirring velocity, and reaction vessel is sealed.After two days, can obtain the brown flocks, this deposition of XRD proof has β-MnOOH crystalline structure.The SEM morphology analysis shows that these depositions are that mean diameter is 25 nanometers, and length is the nano wire about 1 micron, and high power SEM shows that these nano wires are fascircular textures that the nano wire by thinner 3-5 nanometer is arranged in parallel and forms.
Embodiment 5
Meso-porous nano line separatory membrane: more than the β-MnOOH nano wire deposition that makes through ultra-sonic dispersion 10 minutes; Get this dispersion liquid of 2 ml, through filtering method, at porous polycarbonate film (2.5 cm; Aperture 200 nm, voidage 10%) the last one deck β-MnOOH nano wire filtering layer that forms.SEM shows that filtering layer is a successive, and thickness is about 120 nanometers, overlaps each other between the nano wire to form very the porous separating layer shown in Fig. 2 a-2 c.This tunic can effectively separate the gold grain of 10 nanometers from the aqueous solution, rejection is 93% (see figure 2), and flow velocity is 15120 L/m
2Hbar.
Embodiment 6
Meso-porous nano line separatory membrane: more than the β-MnOOH nano wire deposition that makes through ultra-sonic dispersion 10 minutes; Get this dispersion liquid of 10 ml, through filtering method, at porous polycarbonate film (2.5 cm; Aperture 200 nm, voidage 10%) the last one deck β-MnOOH nano wire filtering layer that forms.SEM shows that filtering layer is a successive, and thickness is 600 nanometers, overlaps each other between the nano wire to form very that this tunic of porous separating layer can effectively separate the gold grain of 10 nanometers from the aqueous solution.
Embodiment 7
The above β that makes-MnOOH nano wire is collected through spinning dry, again in air 350
oAfter the C thermal treatment 1 hour, (temperature rise rate is 10
oC/ minute), it is as shown in Figure 3 just to obtain manganic manganous oxide nanometer wire, and the shape of nano wire remains intact basically.Its specific surface area is 71 m
2/ g.Get the manganic manganous oxide nanometer wire powder that makes more than 20 mg and add 100 ml, in the methylene blue of 25 mg/L (Fig. 3 molecular structure) solution, add the H of 15 ml 30% then
2O
2Whole catalytic process detects the methylene blue concentration in the solution by the Uv-Vis spectrograph.The result finds to have only manganic manganous oxide nanometer wire or having only H
2O
2The time, do not observe the degraded of tangible methylene blue basically.But two when adding together, reach 93% after the degraded of methylene blue just reaches 81%, one hour within 5 minutes.It mainly is the manganic manganous oxide nanometer wire catalyzing and decomposing H
2O
2Form very highly active HO
, HOO
, or O
2-Group.These groups could degradation of methylene blue.Because the high-specific surface area of manganic manganous oxide nanometer wire has caused its high catalytic activity.
Embodiment 8
The above β that makes-MnOOH nano wire is collected through spinning dry, again in air 450
oAfter the C thermal treatment 2 hours, (temperature rise rate is 10
oC/ minute), it is as shown in Figure 3 just to obtain manganic manganous oxide nanometer wire, and the shape of nano wire remains intact basically.Get the manganic manganous oxide nanometer wire powder that makes more than 20 mg and add 100 ml, in the methylene blue of 25 mg/L (Fig. 3 molecular structure) solution, add the H of 15 ml 30% then
2O
2Whole catalytic process detects the methylene blue concentration in the solution by the Uv-Vis spectrograph.The result finds to have only manganic manganous oxide nanometer wire or having only H
2O
2The time, do not observe the degraded of tangible methylene blue basically.But two when adding together, reach 95% after the degraded of methylene blue just reaches 82%, one hour within 5 minutes.It mainly is the manganic manganous oxide nanometer wire catalyzing and decomposing H
2O
2Form very highly active HO
, HOO
, or O
2-Group.These groups could degradation of methylene blue.Because the high-specific surface area of manganic manganous oxide nanometer wire has caused its high catalytic activity.
Claims (5)
1. the preparation method of the β of a crystalline state-MnOOH nano wire; It is characterized in that: under the normal temperature; The 0.4-0.6mM manganous salt aqueous solution of equal volume is mixed under magnetic agitation with the 0.8-1.0mM alkali aqueous solution, placed 1-2 days, generate the β-MnOOH nano wire throw out of crystalline state; Described alkali is thanomin, sodium hydroxide or Pottasium Hydroxide.
2. the preparation method of the β of a kind of crystalline state according to claim 1-MnOOH nano wire is characterized in that described manganous salt is Mn nitrate, manganese sulfate or protochloride manganese.
3. the purposes of the β-MnOOH nano wire of the crystalline state of method preparation according to claim 1 is characterized in that: the mesoporous separatory membrane that is used to prepare the 120-600 nanometer thickness.
4. the purposes of the β of a kind of crystalline state according to claim 3-MnOOH nano wire; The preparation method who it is characterized in that the mesoporous separatory membrane of described 120-600 nanometer thickness is: with the β of crystalline state-MnOOH nano wire flocks ultra-sonic dispersion 5～10 minutes, β-MnOOH nano wire dispersion liquid of getting 2～10ml crystalline state filtered the mesoporous separatory membrane that in the porous substrate, forms one deck 120～600 nanometer thickness.
5. the purposes of the β-MnOOH nano wire of the crystalline state of method preparation according to claim 1 is characterized in that: be used for the degradation of dye molecule; The method steps of described degradation of dye molecule is:
1) with the β-MnOOH nano wire of crystalline state in air, 350～450 ℃ of annealing changed into manganic manganous oxide nanometer wire after 1～2 hour;
2) get the manganic manganous oxide nanometer wire powder that makes more than the 20mg and add 100ml, in the methylene blue solution of 25mg/L, add the H of 15ml 30% then
2O
2, can the degradation of dye molecule.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012167010A2 (en) * | 2011-06-02 | 2012-12-06 | Cornell University | Manganese oxide nanoparticles, methods and applications |
| CN102502848A (en) * | 2011-10-27 | 2012-06-20 | 湖南科技大学 | Solvothermal preparation method for alkali manganese oxide nanowires |
| CN103606654B (en) * | 2012-12-21 | 2016-01-06 | 燕山大学 | The preparation method of the coated manganese oxide composite material of a kind of carbon |
| CN108059191A (en) * | 2018-01-24 | 2018-05-22 | 安徽大学 | A kind of alkali formula manganese oxide of nano wire pattern and preparation method thereof |
| CN109264786A (en) * | 2018-10-17 | 2019-01-25 | 国电环境保护研究院有限公司 | A kind of γ-MnOOH, preparation method and its application |
| CN110540242A (en) * | 2019-09-06 | 2019-12-06 | 辽宁星空新能源发展有限公司 | method for preparing two-dimensional basic manganese oxide nanosheet through rapid precipitation |
| CN110482611A (en) * | 2019-09-06 | 2019-11-22 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares alkaline oxygenated manganese nanometer sheet self assembled three-dimensional ball |
| CN115106079A (en) * | 2021-03-18 | 2022-09-27 | 中国科学院上海硅酸盐研究所苏州研究院 | Catalyst capable of promoting generation of singlet oxygen and preparation method and application thereof |
| CN114853073A (en) * | 2022-05-30 | 2022-08-05 | 荆门市格林美新材料有限公司 | Preparation method of linear MnOOH, negative electrode material and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4450148A (en) * | 1982-09-30 | 1984-05-22 | Chemetals Incorporated | Preparation of manganite, MnOOH |
| US6773851B1 (en) * | 2002-07-01 | 2004-08-10 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of Li2Mn4O9 using lithium permanganate precursor |
| CN101851008A (en) * | 2010-07-06 | 2010-10-06 | 江苏技术师范学院 | Method for preparing MnOOH nano rods |
-
2010
- 2010-12-21 CN CN2010105982959A patent/CN102041553B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4450148A (en) * | 1982-09-30 | 1984-05-22 | Chemetals Incorporated | Preparation of manganite, MnOOH |
| US6773851B1 (en) * | 2002-07-01 | 2004-08-10 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of Li2Mn4O9 using lithium permanganate precursor |
| 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 |
|---|
| Xiaodan Sun et.al..Preparation and characterization of MnOOH and β-MnO2 whiskers.《Inorganic Chemistry Communications》.2002,第5卷747-750. * |
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