CN105481018A - Structurally-adjustable 3D network-structured mesoporous manganese dioxide and preparation method thereof - Google Patents
Structurally-adjustable 3D network-structured mesoporous manganese dioxide and preparation method thereof Download PDFInfo
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- CN105481018A CN105481018A CN201610023322.7A CN201610023322A CN105481018A CN 105481018 A CN105481018 A CN 105481018A CN 201610023322 A CN201610023322 A CN 201610023322A CN 105481018 A CN105481018 A CN 105481018A
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses structurally-adjustable 3D network-structured mesoporous manganese dioxide and a preparation method thereof. The structurally-adjustable 3D network-structured mesoporous manganese dioxide is characterized in that manganese dioxide nanosheet hinges are self-assembled to form 3D network-structured spongy or cellular porous block bodies, has the characteristics of large specific surface area (larger than 150 m<2>g<-1>), narrow pore size distribution (good aperture uniformity), small crystallization particle size and the like, and then can be applied to the super capacitor, battery, catalysis and sewage control fields. The provided preparation method has the advantages of being high in productivity, short in production period , low in equipment requirement and the like, is a mesoporous manganese dioxide preparation method which is simple in technological process, low in energy consumption, short in reaction period and low in cost, and has a huge industrial application value.
Description
Technical field
The present invention relates to a kind of meso-porous titanium dioxide manganese and preparation method thereof, specifically, relate to a kind of multi-usage, aperture and specific surface area, 3D network structure meso-porous titanium dioxide manganese that phase structure is adjustable and preparation method thereof.
Background technology
In recent decades, the material within the scope of nanoscale has optical, electrical, the acoustic properties of many uniquenesses because of it, and oneself has been subjected to the attention of numerous material supply section scholar, becomes the upstart in solid inorganic material field.In this kind of material, mesoporous material has and is distributed in pore passage structure (aperture 2-50nm) within the scope of nanoscale and huge specific surface area, can provide more diffusion admittances and reaction site in the reaction, have broad application prospects in various fields.
Manganse Dioxide (MnO
2) resource is extensive, cheap, environmental friendliness, has multiple oxidation state, is a kind of important New function material.Show good application prospect in fields such as catalysis, bio-sensing, lithium cell, ultracapacitors at present.And along with the development of electronic technology, biotechnology in recent years, meso-porous titanium dioxide manganese, owing to having the features such as unique nanopore-channel structure and large specific surface, makes it have more and more important application demand at New function Material Field.The character of material determined by its structural performance, only has the structure controlling meso-porous titanium dioxide manganese just can reach the performance of optimization.
But the preparation of current meso-porous titanium dioxide manganese mainly relies on template, and wherein various surfactants and polymer template are called as soft template, the template (as mesoporous carbon template, mesoporous silicon template etc.) with shaping meso-hole structure is called hard template.No matter be soft mode version method or die version method, its cost comparatively high technology is complicated, and masterplate is removed process complexity and is attended by mesoporous destruction, is not the Perfected process that low-coat scaleization is produced.Meanwhile, the same with other transition metal oxide, Manganse Dioxide exists that character is too active, the problem such as easy-sintering under poor heat stability, high temperature, makes its structure in preparation, be difficult to accurate control.
Summary of the invention
An object of the present invention is the 3D network structure meso-porous titanium dioxide manganese providing a kind of structure adjustable.
Two of object of the present invention is the preparation method providing this Manganse Dioxide, to fill up the synthetic method of meso-porous titanium dioxide manganese, and reduces accurate preparation difficulty and the synthesis cost of manganese dioxide mesoporous material, promotes its industrialization.
The technical solution adopted for the present invention to solve the technical problems is:
The 3D network structure meso-porous titanium dioxide manganese that a kind of structure is adjustable, it is characterized in that this meso-porous titanium dioxide manganese to be worked out by hinge by manganese dioxide nano-plates to form the spongy or cellular porous block of the class with 3D network structure, wherein the crystalline structure of Manganse Dioxide is α-MnO
2, β-MnO
2, δ-MnO
2, γ-MnO
2or λ-MnO
2; Aperture is 2 ~ 50nm; Specific surface area is 150 ~ 320m
2/ g.
Prepare a method for the adjustable 3D network structure meso-porous titanium dioxide manganese of above-mentioned structure, it is characterized in that, comprise following concrete steps:
A) polyatomic alcohol water solution and solubility permanganate water solution is configured respectively;
B) the two kinds of solution mixing at room temperature will prepared in step a;
C) continue under room temperature to stir, until reaction soln is become colorless by purple, terminate reaction;
D) filter, filter cake deionized water and ethanolic soln washing post-drying, obtain 3D network structure meso-porous titanium dioxide manganese.
Above-mentioned permanganate is solubility permanganate, as potassium permanganate, sodium permanganate, barium permanganate or ammonium permanganate.
Above-mentioned polyvalent alcohol is solubility polyvalent alcohol.
Above-mentioned solubility polyvalent alcohol is chain structure polyvalent alcohol.
Above-mentioned chain structure polyvalent alcohol is C
n, n=3 ~ 9, hydroxy number is no less than 2 and the polyvalent alcohol that is connected with hydroxyl of termination carbon.
Above-mentioned chain structure polyvalent alcohol is: propylene glycol, glycerine, 1,4-butyleneglycol, trihydroxybutane, tetrahydroxybutane, 1,5-pentanediol, penta triol, penta tetrol, Xylitol, 1,6-hexylene glycol, hexanetriol, own tetrol, hexanepentol, N.F,USP MANNITOL, 1,7-heptanediol, heptan triol, heptan tetrol, heptan pentol, heptan six alcohol, volemitol, 1,8-ethohexadiol, pungent triol, pungent tetrol, pungent pentol, pungent six alcohol, pungent seven alcohol, pungent eight alcohol, 1,9-nonanediol, the ninth of the ten Heavenly Stems triol, the ninth of the ten Heavenly Stems tetrol, the ninth of the ten Heavenly Stems pentol, the ninth of the ten Heavenly Stems six alcohol, the ninth of the ten Heavenly Stems seven alcohol, the ninth of the ten Heavenly Stems eight alcohol or the ninth of the ten Heavenly Stems nine alcohol.
The concentration of the polyvalent alcohol in above-mentioned step a) and solubility permanganate water solution is respectively: 0.005 ~ 0.15mol/L and 0.1 ~ 0.4mol/L.
The mol ratio of the polyvalent alcohol in above-mentioned step b) and solubility permanganate is 1:(0.1 ~ 1).
The preparation method of the 3D network structure meso-porous titanium dioxide manganese that said structure is adjustable, the alr mode that it is characterized in that in step c) is magnetic agitation or mechanical stirring or ultrasonic wave dispersion.
The method that the present invention adopts is different from conventional template method, and it is that deionized water is solvent and weighting agent (pore-forming material) with soluble manganese salt and solubility chain type polyvalent alcohol for raw material.The soluble salt of manganese is connected by polyvalent alcohol and is dispersed in deionized water, and then the soluble salt of manganese and chain type polyol reaction generate Manganse Dioxide.Adopt method provided by the present invention, do not need to add template or tensio-active agent or reacting by heating, by changing structure (kind) and the volumetric molar concentration of chain type polyvalent alcohol, with volumetric molar concentration and the kind in regulation and control soluble manganese source, the accuracy controlling in phase structure, specific surface area and aperture can be realized, thus synthetic aperture homogeneous, the different phase structure meso-porous titanium dioxide manganese of high-specific surface area.
Compared with prior art, the present invention has following remarkable advantage or beneficial effect:
1, the present invention is raw materials usedly easy to get, cost is low, with short production cycle, and productive rate is high, and preparation technology is simple and technological process is pollution-free, is applicable to suitability for industrialized production;
2, the reaction that synthetic method of the present invention relates to is carried out all at ambient temperature, and security is high, can be by force handling, easily accomplishes scale production;
3, overcome the restricted problem of template, can on a large scale in realize the preparation of different pore size and specific surface area meso-porous titanium dioxide manganese;
4, different phase structure can be obtained, as meso-porous titanium dioxide manganese such as α, β, δ by preparation method of the present invention;
5, by preparation method's gained meso-porous titanium dioxide manganese of the present invention, there is abundant gap structure and large specific surface area, aperture in 2 ~ 50nm, specific surface area at 150 ~ 320m
2/ g, can supply metal ion, macromole passes through smoothly, can be widely used as lithium ion battery or electrode material for super capacitor, the theoretical investigation of the catalyst grade association area of oxidizing reaction that the enzyme carrier of biosensor, macromole participate in and application.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the meso-porous titanium dioxide manganese that the present invention is prepared by different polyvalent alcohol and permanganate, wherein: a represents embodiment 1, b and represents embodiment 4, c and represent embodiment 6, d and represent embodiment 7;
Fig. 2 is that the X-ray diffraction (XRD) of the meso-porous titanium dioxide manganese that the present invention is prepared by different polyvalent alcohol and potassium permanganate is composed, wherein, 1 represents embodiment 1, and 2 represent embodiment 4,3 are represented as embodiment 6,1-350 represents thermal treatment 350 DEG C of gained samples under examples Example 1 sample air;
Fig. 3 is nitrogen adsorption desorption curve (a) and the pore size distribution curve (b) that the present invention uses different polyvalent alcohol and potassium permanganate gained meso-porous titanium dioxide manganese, and wherein, 1 represents embodiment 1, and 2 represent embodiment 4, and 3 are represented as embodiment 6, and 4 represent embodiment 7;
Fig. 4 is that the XRD figure of the not jljl phase meso-porous titanium dioxide manganese that the present invention is prepared by different manganese salt and sweet six alcohol is composed, and wherein 3 represent embodiment 6,4 represent embodiment 7, and 5 represent embodiment 8.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail and completely, but do not limit content of the present invention.
Embodiment 1: under room temperature, 0.4g1,4-butanediol is even in 200mL deionized water for stirring, be mixed with the BDO aqueous solution that concentration is 0.022mol/L; Under room temperature, slowly add the potassium permanganate solution that 50ml concentration is 0.15mol/L while stirring; Under room temperature, Keep agitation 2h, solution is become colorless by purple, terminates reaction; After filtration, filter cake deionized water wash 2 ~ 3 times, dries, obtains black manganese dioxide powder.
The stereoscan photograph of the Manganse Dioxide sample of Fig. 1 a obtained by the present embodiment, Fig. 2 curve 1 and 1-350 are the Manganse Dioxide sample of the present embodiment gained and the XRD figure spectrum of 350 DEG C of thermal treatments (under air atmosphere, 3h) thereof.(Fig. 3 a) and pore size distribution curve (Fig. 3 b) for the nitrogen adsorption desorption curve of the Manganse Dioxide sample of Fig. 3 curve 1 obtained by the present embodiment.
According to above-mentioned test result, the analytical results that the present embodiment prepares the Manganse Dioxide of gained is as follows:
Obtained Manganse Dioxide sample is the three-dimensional network shape vesicular structure that nanometer sheet assembling or establishment are formed, and macro-scale sees it is randomly be similar to spongiform porous blocks (see Fig. 1 a and illustration thereof); Have typical meso-hole structure (see Fig. 3 curve 1), its specific surface area is 169m as calculated
2/ g, mean pore size is 22.5nm.And the display of XRD result, what prepare gained sample is nanocrystalline (peak broadening), and phase structure is α-MnO
2(1-350 result is consistent with standard card JCPDS#44-0141).
Embodiment 2: this example difference from Example 1 is: under room temperature, is dissolved in 200mL deionized water for stirring even, is mixed with 1, the 7-heptanediol aqueous solution that concentration is 0.1mol/L by 2.6g1,7-heptanediol; All the other contents are all identical with described in embodiment 1.
Test result shows, the morphology of gained Manganse Dioxide is similar to embodiment 1: be the spongy or cellular 3D network structure porous α-MnO of class that nanometer sheet works out
2.Difference part is, the specific surface area of the present embodiment sample is 158m
2/ g, mean pore size 30.6nm.
Embodiment 3: this example difference from Example 1 is: under room temperature, by 2.4g1, it is even that 2,7-triol in heptan is dissolved in 200mL deionized water for stirring, be mixed with concentration be 0.08mol/L 1,2,7-heptan three alcohol solution, all the other contents are consistent with embodiment 1.
Test result shows, the morphology of gained Manganse Dioxide is similar to embodiment 1: be class sponge or cellular 3D network structure porous α-MnO that nanometer sheet works out
2.Difference part is, the specific surface area of the present embodiment sample and the size of mean pore size are respectively 164m
2/ g and 28.7nm.
Embodiment 4: the difference of the present embodiment and embodiment 1 is only: under room temperature, is dissolved in 200mL deionized water for stirring even, is mixed with the aqueous glycerin solution that concentration is 0.01mol/L by 0.92g glycerol (glycerine); All the other contents are all identical with described in embodiment 1.
The stereoscan photograph of the Manganse Dioxide sample of Fig. 1 b obtained by the present embodiment, Fig. 2 curve 2 is the XRD figure spectrum of the Manganse Dioxide sample of the present embodiment gained.(Fig. 3 a) and pore size distribution curve (Fig. 3 b) for the nitrogen adsorption desorption curve of the Manganse Dioxide sample of Fig. 3 curve 2 obtained by the present embodiment.
According to above-mentioned test result, the pattern that the present embodiment prepares the Manganse Dioxide of gained is similar to embodiment 1 with structure: be the class spongy 3D network structure porous α-MnO that nanometer sheet is worked out
2.Difference part is, the specific surface area of the present embodiment sample is 196.8m
2/ g, aperture 10.9nm.
Embodiment 5: the difference of the present embodiment and embodiment 1 is only: under room temperature, is dissolved in 200mL deionized water for stirring even, is mixed with the erythritol aqueous solution that concentration is 0.01mol/L by 0.244g erythritol; All the other contents are all identical with described in embodiment 1.
According to test result, the pattern that the present embodiment prepares the Manganse Dioxide of gained is similar to embodiment 1 with structure: be the class spongy 3D network structure porous α-MnO that nanometer sheet is worked out
2.Difference part is, the specific surface area of the present embodiment sample is 236.8m
2/ g, mean pore size 8.5nm.
Embodiment 6: the difference of the present embodiment and embodiment 1 is only: under room temperature, is dissolved in 200mL deionized water for stirring even, is mixed with the Osmitrol that concentration is 0.06mol/L by 0.218g N.F,USP MANNITOL; All the other contents are all identical with described in embodiment 1.
The stereoscan photograph of the Manganse Dioxide sample of Fig. 1 c obtained by the present embodiment, Fig. 2 curve 3 is the XRD figure spectrum of the Manganse Dioxide sample of the present embodiment gained.(Fig. 3 a) and pore size distribution curve (Fig. 3 b) for the nitrogen adsorption desorption curve of the Manganse Dioxide sample of Fig. 3 curve 3 obtained by the present embodiment.
According to above-mentioned test result, the pattern that the present embodiment prepares the Manganse Dioxide of gained is similar to embodiment 1 with structure: be the class spongy 3D network structure porous α-MnO that nanometer sheet is worked out
2.Difference part is, the specific surface area of the present embodiment sample is 301.9m
2/ g, mean pore size 3.9nm.
Embodiment 7: under room temperature, 0.218g N.F,USP MANNITOL is even in 200mL deionized water for stirring, be mixed with the Osmitrol that concentration is 0.006mol/L; Under room temperature, slowly add the ammonium permanganate aqueous solution that 50ml concentration is 0.15mol/L while stirring; Under room temperature, continue to stir 2h, solution is become colorless by purple, terminates reaction; Filter, filter cake deionized water wash 2-3 time, oven dry, obtains black manganese dioxide powder.
The stereoscan photograph of the Manganse Dioxide sample of Fig. 1 d obtained by the present embodiment, (a) and pore size distribution curve (Fig. 3 b), Fig. 4 curve 4 be that the XRD figure of the Manganse Dioxide sample of the present embodiment gained is composed to Fig. 3 for the nitrogen adsorption desorption curve of the Manganse Dioxide sample of Fig. 3 curve 4 obtained by the present embodiment.
According to above-mentioned test result, the pattern that the present embodiment prepares the Manganse Dioxide of gained is similar to embodiment 1-6 with microstructure: the class spongy 3D network structure porous MnO being nanometer sheet establishment
2.Difference part is, the phase structure of the present embodiment sample is β-MnO
2, its specific surface area is 268.9m
2/ g, aperture 5.8nm.
Embodiment 8: the present embodiment difference from Example 7 is: under room temperature, slowly adds the aqueous sodium permanganate solution that 50ml concentration is 0.2mol/L while stirring; All the other contents are all identical with described in embodiment 7.
Fig. 4 curve 5 is the XRD figure spectrum of the Manganse Dioxide sample of the present embodiment gained.
According to test result, the pattern that the present embodiment prepares gained Manganse Dioxide sample is all similar to embodiment 7 to microstructure: be the class spongy 3D network structure porous MnO that nanometer sheet is worked out
2difference part is, the phase structure of the present embodiment sample is δ-MnO
2, its specific surface area is 320.3m
2/ g, aperture 4.2nm.
Claims (10)
1. the 3D network structure meso-porous titanium dioxide manganese that a structure is adjustable, it is characterized in that this meso-porous titanium dioxide manganese to be worked out by hinge by manganese dioxide nano-plates to form the spongy or cellular porous block of the class with 3D network structure, wherein the crystalline structure of Manganse Dioxide is α-MnO
2, β-MnO
2, δ-MnO
2, γ-MnO
2or λ-MnO
2; Aperture is 2 ~ 50nm; Specific surface area is 150 ~ 320m
2/ g.
2. prepare a method for the adjustable 3D network structure meso-porous titanium dioxide manganese of structure according to claim 1, it is characterized in that, comprise following concrete steps:
A) polyatomic alcohol water solution and solubility permanganate water solution is configured respectively;
B) the two kinds of solution mixing at room temperature will prepared in step a;
C) continue under room temperature to stir, until reaction soln is become colorless by purple, terminate reaction;
D) filter, filter cake deionized water and ethanolic soln washing post-drying, obtain 3D network structure meso-porous titanium dioxide manganese.
3. method according to claim 2, is characterized in that described permanganate is solubility permanganate, as potassium permanganate, sodium permanganate, barium permanganate or ammonium permanganate.
4. method according to claim 2, is characterized in that described polyvalent alcohol is solubility polyvalent alcohol.
5. method according to claim 4, is characterized in that described solubility polyvalent alcohol is chain structure polyvalent alcohol.
6. method according to claim 5, is characterized in that described chain structure polyvalent alcohol is C
n, n=3 ~ 9, hydroxy number is no less than 2 and the polyvalent alcohol that is connected with hydroxyl of termination carbon.
7. method according to claim 6, it is characterized in that described chain structure polyvalent alcohol is: propylene glycol, glycerine, 1, 4-butyleneglycol, trihydroxybutane, tetrahydroxybutane, 1, 5-pentanediol, penta triol, penta tetrol, Xylitol, 1, 6-hexylene glycol, hexanetriol, own tetrol, hexanepentol, N.F,USP MANNITOL, 1, 7-heptanediol, heptan triol, heptan tetrol, heptan pentol, heptan six alcohol, volemitol, 1, 8-ethohexadiol, pungent triol, pungent tetrol, pungent pentol, pungent six alcohol, pungent seven alcohol, pungent eight alcohol, 1, 9-nonanediol, the ninth of the ten Heavenly Stems triol, the ninth of the ten Heavenly Stems tetrol, the ninth of the ten Heavenly Stems pentol, the ninth of the ten Heavenly Stems six alcohol, the ninth of the ten Heavenly Stems seven alcohol, the ninth of the ten Heavenly Stems eight alcohol or the ninth of the ten Heavenly Stems nine alcohol.
8. method according to claim 2, is characterized in that the concentration of polyvalent alcohol in described step a) and solubility permanganate water solution is respectively: 0.005 ~ 0.15mol/L and 0.1 ~ 0.4mol/L.
9. method according to claim 2, is characterized in that the mol ratio of polyvalent alcohol in described step b) and solubility permanganate is 1:(0.1 ~ 1).
10. the preparation method of the 3D network structure meso-porous titanium dioxide manganese that structure is adjustable according to claim 2, the alr mode that it is characterized in that in step c) is magnetic agitation or mechanical stirring or ultrasonic wave dispersion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939087A (en) * | 2021-04-07 | 2021-06-11 | 上海大学 | Nanowire structure porous manganese dioxide and preparation method thereof |
| EP3889322A4 (en) * | 2018-11-29 | 2022-11-09 | Tosoh Corporation | Electrolytic manganese dioxide, method for manufacturing same, and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107909A (en) * | 2011-01-11 | 2011-06-29 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous nano manganese dioxide |
| CN103754936A (en) * | 2014-01-23 | 2014-04-30 | 山东科技大学 | Method for synthesizing mesoporous manganese oxide |
| CN104671287A (en) * | 2015-01-27 | 2015-06-03 | 北京航空航天大学 | Environment-friendly preparation method of nano manganese oxide composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107909A (en) * | 2011-01-11 | 2011-06-29 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous nano manganese dioxide |
| CN103754936A (en) * | 2014-01-23 | 2014-04-30 | 山东科技大学 | Method for synthesizing mesoporous manganese oxide |
| CN104671287A (en) * | 2015-01-27 | 2015-06-03 | 北京航空航天大学 | Environment-friendly preparation method of nano manganese oxide composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3889322A4 (en) * | 2018-11-29 | 2022-11-09 | Tosoh Corporation | Electrolytic manganese dioxide, method for manufacturing same, and use thereof |
| CN112939087A (en) * | 2021-04-07 | 2021-06-11 | 上海大学 | Nanowire structure porous manganese dioxide and preparation method thereof |
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