CN100361900C - Porous manganese oxide sheet material and method for preparing the same - Google Patents
Porous manganese oxide sheet material and method for preparing the same Download PDFInfo
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- CN100361900C CN100361900C CNB031133886A CN03113388A CN100361900C CN 100361900 C CN100361900 C CN 100361900C CN B031133886 A CNB031133886 A CN B031133886A CN 03113388 A CN03113388 A CN 03113388A CN 100361900 C CN100361900 C CN 100361900C
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Abstract
The present invention relates to a porous nanometer sheet material of manganese oxide and a preparation method thereof, particularly to a porous material of nanometer sheets and a preparation method thereof. Permanganic acid hyamine is used as a precursor by the material. The thickness of porous manganese oxide of a nanometer sheet of binary manganese oxide obtained after reaction is 11-80 nanometer, an average pore diameter is 4.0-50.0 nanometer, phase structures are Mn#-[3]O#-[4] or Mn#-[3]O#-[4] and Mn#-[5]O#-[8] or Mn#-[2]O#-[3]. The hyamine can be from octal trimethyl ammonium bromide to octadecy l trimethyl ammonium bromide, particularly cetyl trimethyl ammonium bromide. The preparation method comprises: potassium permanganate KMnO#-[4] and hyamine with equal molar weight are respectively dissolved by solution, and then the two solutions are mixed so as to generate mauve gels; the mauve gels are filtered, washed and dried at a room temperature so as to obtain the permanganic acid hyamine with a layered structure; the material is processed by heat so as to obtain sheet-shaped porous manganese oxide of a nanometer level. The present invention has the advantages of simple preparation method and means, strong operability and easy popularization. The obtained material is a two-dimensional porous nanometer sheet material, the degree of crystallization is adjustable and the dimension of a pore canal is adjustable.
Description
One, technical field:
The present invention is a kind of nano flake material and preparation method thereof, especially a kind of porous manganese oxide nano flake material and preparation method thereof.
Two, background technology
The porous manganese oxide is divided into micropore manganese oxide (aperture≤2 nanometers), mesoporous manganese oxide (aperture is in 2～50 nanometers) and macropore manganese oxide (aperture 〉=50 nanometers) by the size in aperture.Synthetic method is mainly template.Kind by template is divided into: (1) ion template, be used for synthetic microporous manganese oxide [Y.Chabre and J.Pannetier, Prog.Solid State Chem., 1995,23,1.].Be that the manganese oxygen octahedra centers on the duct that template ion is built into certain scale size, the structure and the size in duct depend on template ion.Template ion becomes the component of micropore manganese oxide again and is retained in the duct.The synthetic hydrothermal method that passes through of product.(2) surfactant templates is used for synthesising mesoporous manganese oxide [Z.Tian, W.Tong, J.Wang, N.Duan, V.V.Krishnan, S.L.Suib, Science, 1997,276,926.; J.Luo, S.L.Suib, Chem.Commun., 1997,1031.].The oxide fine particle of manganese is constructed by the formed micelle shape of tensio-active agent.After the constructed Stability Analysis of Structures of manganese oxide particle, remove tensio-active agent, obtain mesoporous manganese oxide.The synthetic hydrothermal method or the ethanol reduction method passed through of product.(3) colloidal crystal template is used for synthetic macropore manganese oxide [H.Yan, C.F.Blanford, B.T.Holland, W.H.Smyrl, A.Stein, Chem.Mater., 2000,12,1134.].The soluble manganese salts solution is filled in the space of colloidal crystal, and evaporating solvent is stayed in the space manganese salt, and proper temperature is handled and made manganese salt change oxide compound in colloidal crystal template.After the constructed Stability Analysis of Structures of manganese oxide particle, remove colloidal crystal, obtain the macropore manganese oxide.The synthetic colloidal sol that passes through---the gel method of product.The method of another kind of synthesising mesoporous manganese oxide is hydrolysis method [A.D.Zarlaha, P.G.Routsoukos, C.Skordilis, P.J.Pomonis, J.Colloid Interface Sci., 1998,202,301; C.E.Salmas, V.N.Stathopoulos, P.J.Pomonis, G.P.Androutsopoulos, Langmuir, 2002,18,423.], i.e. hydrolysis [Mn under certain condition
3(CH
3COO)
6(Pyr)
3] ClO
4Compound forms the mesoporous manganese oxide that is formed by particle packing.
Wherein, the duct of micropore manganese oxide is less, is subjected to certain restriction on using.Difficulty is bigger technically for mesoporous manganese oxide synthetic.The preparation process complexity of colloidal crystal template, technical difficulty is higher, has limited the synthetic of macropore manganese oxide.Concerning mesoporous and macropore manganese oxide, need on synthetic method and means, have breakthrough, could obtain the sample of appreciable amount.And described mesoporous and macropore manganese oxide is respectively powdery and bulk, is difficult to further be processed into the nano flake material, and its range of application is restricted.
Three, summary of the invention
1, technical problem
Purpose of the present invention aims to provide porous manganese oxide nano flake material that a kind of preparation method is simple, crystallization degree is high, the duct scale size is adjustable and preparation method thereof.
2, technical scheme
Potassium permanganate KMnO with equimolar amount
4Dissolve with solution respectively with quaternary ammonium salt, again two solution are mixed, generate mauve gel; Filter, washing, drying at room temperature obtains laminate structure permanganic acid quaternary ammonium salt; This material is heat-treated, obtain the laminar porous manganese oxide of nano level.Wherein, treatment of different temperature can obtain the nano flake porous manganese oxide of different structure.300～400 ℃ of processing, obtaining thickness is the porous manganese oxide nano flake of 13 ± 2 nanometers, mean pore size 4.0～7.0 nanometers, and phase structure is respectively Mn
3O
4(300 ℃ of processing), Mn
3O
4And Mn
5O
8(400 ℃ of processing).When treatment temp is 550～800 ℃, obtain thickness and be about the porous manganese oxide nano flake that 70 ± 10 nanometers, mean pore size are about 20～50 nanometers, phase structure is Mn
2O
3
Wherein, quaternary ammonium salt can use eight～octadecyl trimethylammonium bromide, cetyl trimethylammonium bromide especially, and its source is wide, cost is low; The solution of potassium permanganate and quaternary ammonium salt can be the aqueous solution of using always, also can be that (both can be same solvent by employed solvent to other solution, or mutual mutual solvents, or partial miscibility solvent, these solvents can only the solubilizing reaction thing, can not react with reactant and product), concentration is not limit.The drying at room temperature process can be air-dry under state of nature, also can be dry under vacuum condition.Vacuum drying purpose is to accelerate rate of drying.Heat treatment process can be used common process furnace (box-type furnace, tube furnace etc.).
3, beneficial effect
Advantage of the present invention be simple on (1) preparation method and the means, workable, be easy to promote.(2) the gained material is two-dimentional porous nano sheeting.(3) crystallization degree is adjustable.(4) the duct scale size is adjustable.
Four, description of drawings
300 ℃ of sample stereoscan photographs of handling 5 hours of Fig. 1, sheet thickness is 13 nanometers.
300 ℃ of sample transmission electron microscope photos of handling 5 hours of Fig. 2, mean pore size is 4.0 nanometers.
400 ℃ of sample transmission electron microscope photos of handling 5 hours of Fig. 3, mean pore size is 6.5 nanometers.
550 ℃ of sample stereoscan photographs of handling 5 hours of Fig. 4, mean pore size is 21.1 nanometers.
800 ℃ of sample stereoscan photographs of handling 5 hours of Fig. 5, mean pore size is 50.7 nanometers.
The x-ray diffraction pattern of sample after Fig. 6 treatment of different temperature (digital alignment processing temperature among the figure).
Five, embodiment
Embodiment 1
The potassium permanganate of equimolar amount and cetyl trimethylammonium bromide (in the quaternary ammonium salt a kind of) are mixed with the aqueous solution of 0.4 mol respectively, again both mixing are made its reaction, obtain the cetyl trimethyl ammonium permanganate.This material is a laminate structure, and interlamellar spacing is 23.86 nanometers.Its stoichiometric equation of ultimate analysis is C
19H
41NMnO
4, theoretical value is C
19H
42NMnO
4
Gained cetyl trimethyl ammonium permanganate was handled 5 hours at 300 ℃, and it is expanded that its spontaneous reaction is taken place, and obtaining mean pore size is 4.0 nanometers, and thickness is the porous manganese oxide sheeting of 13 ± 2 nanometers.Specific surface area is 45.93m
2/ g.The average Oxidation Number of manganese is 2.69.Phase structure is Mn
3O
4
Embodiment 2
The specimen preparation process is with embodiment 1.
Gained cetyl trimethyl ammonium permanganate was handled 5 hours at 400 ℃, and it is expanded that its spontaneous reaction is taken place, and obtaining mean pore size is 6.5 nanometers, and thickness is the porous manganese oxide sheeting of 13 ± 2 nanometers.Specific surface area is 21.11m
2/ g.The average Oxidation Number of manganese is 2.85.Phase structure is Mn
3O
4(principal goods phase) and Mn
5O
8(inferior thing phase).
Embodiment 3
The specimen preparation process is with embodiment 1.
Gained cetyl trimethyl ammonium permanganate was handled 5 hours at 550 ℃, and it is expanded that its spontaneous reaction is taken place, and obtaining mean pore size is 21.1 nanometers, and thickness is the porous manganese oxide sheeting of 70 ± 10 nanometers.Specific surface area is 8.31m
2/ g.The average Oxidation Number of manganese is 3.00.Phase structure is Mn
2O
3
Embodiment 4
The specimen preparation process is with embodiment 1.
Gained cetyl trimethyl ammonium permanganate was handled 5 hours at 800 ℃, and it is expanded that its spontaneous reaction is taken place, and obtaining mean pore size is 50.7 nanometers, and thickness is the porous manganese oxide sheeting of 70 ± 10 nanometers.Specific surface area is 4.56m
2/ g.The average Oxidation Number of manganese is 3.00.Phase structure is Mn
2O
3
Claims (4)
1. porous manganese oxide nano flake material, it is characterized in that this material is a persursor material with the potassium permanganate of equimolar amount and the permanganic acid quaternary ammonium salt of quaternary ammonium salt reaction gained, obtaining mean pore size after reaction is 4.0～7.0 nanometers, and thickness is 13 ± 2 nanometers, and phase structure is Mn
3O
4, or Mn
3O
4And Mn
5O
8The nano flake porous manganese oxide of mixture; Perhaps, obtaining mean pore size is 20～50 nanometers, and thickness is 70 ± 10 nanometers, and phase structure is Mn
2O
3Nano flake porous manganese oxide.
2. porous manganese oxide nano flake material according to claim 1 is characterized in that quaternary ammonium salt is eight～octadecyl trimethylammonium bromide.
3. the preparation method of a porous manganese oxide nano flake is characterized in that the method for preparing is: with the potassium permanganate KMnO of equimolar amount
4Be dissolved into solution respectively with quaternary ammonium salt, again two solution mixed, generate mauve gel; Filter, washing, drying at room temperature obtains laminate structure permanganic acid quaternary ammonium salt; This material is heat-treated at 300 ℃～400 ℃, and obtaining mean pore size is 4.0～7.0 nanometers, and thickness is 13 ± 2 nanometers, and phase structure is Mn
3O
4, or Mn
3O
4And Mn
5O
8The nano flake porous manganese oxide of mixture; Perhaps, heat-treat at 550 ℃～800 ℃, obtaining mean pore size is 20～50 nanometers, and thickness is 70 ± 10 nanometers, and phase structure is Mn
2O
3Nano flake porous manganese oxide.
4. porous manganese oxide nano flake preparation method according to claim 3, the solvent that it is characterized in that dissolving potassium permanganate and quaternary ammonium salt for can not with the solvent of the product generation chemical reaction of potassium permanganate or quaternary ammonium salt and this reactant.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101310883B1 (en) | 2006-03-29 | 2013-09-25 | 삼성에스디아이 주식회사 | Porous metal oxide and process for preparing the same |
| KR100818257B1 (en) | 2006-09-07 | 2008-04-01 | 삼성에스디아이 주식회사 | Porous carbon material and process for preparing the same |
| CN100558644C (en) * | 2006-09-27 | 2009-11-11 | 中国科学院理化技术研究所 | Layered mesoporous birnessite type manganese dioxide honeycomb nanospheres and preparation method and application thereof |
| CN102092791B (en) * | 2011-03-16 | 2013-04-17 | 陕西师范大学 | Method for preparing demixed manganese oxide flower spheres with large specific surface areas |
| CN105858732B (en) * | 2016-06-01 | 2017-06-06 | 中国工程物理研究院化工材料研究所 | The regulation and control method and manganese sesquioxide managnic oxide powder of manganese sesquioxide managnic oxide nanostructured |
| CN113690453B (en) * | 2020-05-18 | 2022-08-09 | 中国科学院上海硅酸盐研究所 | Mn (manganese) 5 O 8 Nano cage-shaped oxygen reduction electrocatalyst and preparation method thereof |
| CN114105207B (en) * | 2021-12-01 | 2022-07-26 | 西安交通大学 | High-voltage two-dimensional lithium nickel manganese oxide positive electrode material prepared from porous nano flaky manganese sesquioxide intermediate and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627694A (en) * | 1963-09-27 | 1971-12-14 | Gen Aniline & Film Corp | Production of aqueous suspension of manganese dioxide |
| FR2659075A1 (en) * | 1990-03-01 | 1991-09-06 | France Etat Armement | Process for the preparation of manganese oxides via the sol/gel route |
| EP0710624A1 (en) * | 1994-11-07 | 1996-05-08 | Texaco Development Corporation | Sol-gel synthesis of manganese oxide material possessing octahedral structure |
| US6503476B1 (en) * | 1999-07-23 | 2003-01-07 | The University Of Connecticut | Manganese oxide helices, rings, strands, and films, and methods for their preparation |
-
2003
- 2003-05-01 CN CNB031133886A patent/CN100361900C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627694A (en) * | 1963-09-27 | 1971-12-14 | Gen Aniline & Film Corp | Production of aqueous suspension of manganese dioxide |
| FR2659075A1 (en) * | 1990-03-01 | 1991-09-06 | France Etat Armement | Process for the preparation of manganese oxides via the sol/gel route |
| EP0710624A1 (en) * | 1994-11-07 | 1996-05-08 | Texaco Development Corporation | Sol-gel synthesis of manganese oxide material possessing octahedral structure |
| US6503476B1 (en) * | 1999-07-23 | 2003-01-07 | The University Of Connecticut | Manganese oxide helices, rings, strands, and films, and methods for their preparation |
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