CN105481018B - Adjustable 3D network structures meso-porous titanium dioxide manganese of structure and preparation method thereof - Google Patents
Adjustable 3D network structures meso-porous titanium dioxide manganese of structure and preparation method thereof Download PDFInfo
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- CN105481018B CN105481018B CN201610023322.7A CN201610023322A CN105481018B CN 105481018 B CN105481018 B CN 105481018B CN 201610023322 A CN201610023322 A CN 201610023322A CN 105481018 B CN105481018 B CN 105481018B
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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 adjustable 3D network structures meso-porous titanium dioxide manganese of structure and preparation method thereof.The meso-porous titanium dioxide manganese of gained of the invention is self-assembly of that 3D network structure classes are spongy or cellular porous block by manganese dioxide nano-plates hinge, has specific surface area big（More than 150 m2 g‑1）, pore-size distribution is narrow（I.e. pore size homogeneity is good）And crystalline particles size it is small the features such as, therefore, can be applied in ultracapacitor, battery, catalysis, field of sewage treatment.And provided preparation method the has advantage such as yield is high, with short production cycle and equipment requirement is low, it is a kind of method for preparing meso-porous titanium dioxide manganese that technological process is simple, energy consumption is small, reaction time is short and cost is low, there is huge commercial application to be worth.
Description
Technical field
The present invention relates to a kind of meso-porous titanium dioxide manganese and preparation method thereof, specifically, be related to a kind of multipurpose, aperture and
Adjustable 3D network structures meso-porous titanium dioxide manganese of specific surface area, phase structure and preparation method thereof.
Background technology
In recent decades, the material in the range of nanoscale is because it has many unique light, electricity, acoustic properties, oneself warp
The attention of numerous material supply section scholars is received, turns into the upstart in solid inorganic material field.In this kind of material, mesoporous material has
The pore passage structure being distributed in the range of nanoscale（Aperture 2-50 nm）With huge specific surface area, can provide in the reaction more
More diffusion admittances and reaction site, have broad application prospects in various fields.
Manganese dioxide（MnO2）Resource is extensive, cheap, environment-friendly, has a variety of oxidation states, is a kind of important
New function material.Before good application is shown in fields such as catalysis, bio-sensing, lithium battery, ultracapacitors at present
Scape.And with the development of electronic technology, biotechnology in recent years, meso-porous titanium dioxide manganese is due to the nanopore-channel knot with uniqueness
The features such as structure and Large ratio surface, it is set to have more and more important application demand in New function Material Field.The property of material by
Its architectural characteristic is determined, only controls the structure of meso-porous titanium dioxide manganese to can be only achieved the performance of optimization.
But the preparation of meso-porous titanium dioxide manganese at present relies primarily on template to complete, wherein various surfactants and poly-
Compound template is referred to as soft template, has the template for the meso-hole structure being molded（Such as mesoporous carbon template, mesoporous silicon template）
Referred to as hard template.Either soft mode version method or die version method, its cost is complicated compared with high technology, masterplate removal process complexity and companion
It is not the Perfected process of low-coat scale metaplasia production with there is mesoporous destruction.Meanwhile as other transition metal oxides,
Manganese dioxide has that property is excessively active, heat endurance is poor, under high temperature the problems such as easy-sintering, its structure is difficult to essence in preparation
Really control.
The content of the invention
An object of the present invention is to provide a kind of structure adjustable 3D network structures meso-porous titanium dioxide manganese.
The second object of the present invention is the preparation method for providing the manganese dioxide, to fill up the synthesis of meso-porous titanium dioxide manganese
Method, and the accurate preparation difficulty and synthesis cost of manganese dioxide mesoporous material are reduced, promote its industrialization.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of adjustable 3D network structures meso-porous titanium dioxide manganese of structure, it is characterised in that the meso-porous titanium dioxide manganese is by dioxy
Change manganese nanometer sheet and work out to form that the class with 3D network structures is spongy or cellular porous block by hinge, wherein titanium dioxide
The crystal structure of manganese is α-MnO2、β-MnO2、δ-MnO2、γ-MnO2Or λ-MnO2；Aperture is 2 ~ 50 nm；Specific surface area be 150 ~
320 m2/g。
A kind of method for preparing the adjustable 3D network structures meso-porous titanium dioxide manganese of above-mentioned structure, it is characterised in that including
Following specific steps：
a）Polyatomic alcohol water solution and soluble permanganate water solution is respectively configured；
b）The two kinds of solution prepared in step a are mixed at room temperature；
c）Continue to stir at room temperature, until reaction solution is become colorless by purple, end is reacted；
d）Filtering, filter cake are dried after being washed with deionized water and ethanol solution, produce 3D network structure meso-porous titanium dioxide manganese.
Above-mentioned permanganate is soluble permanganate, such as potassium permanganate, sodium permanganate, barium permanganate or permanganic acid
Ammonium.
Above-mentioned polyalcohol is soluble polyalcohol.
Above-mentioned soluble polyalcohol is chain structure polyalcohol.
Above-mentioned chain structure polyalcohol is Cn, n=3 ~ 9, hydroxy number no less than 2 and termination carbon be connected with hydroxyl it is more
First alcohol.
Above-mentioned chain structure polyalcohol is：Propane diols, glycerine, 1,4- butanediols, butantriol, erythrite, 1,5- penta 2
Alcohol, penta triol, penta tetrol, xylitol, 1,6-HD, hexanetriol, own tetrol, hexanepentol, mannitol, 1,7- heptandiols, heptan
Triol, tetrol in heptan, pentol in heptan, alcohol in heptan six, volemitol, 1,8- ethohexadiols, pungent triol, pungent tetrol, pungent pentol, pungent six alcohol, pungent seven
Alcohol, pungent eight alcohol, 1,9- nonanediols, nonyl triol, nonyl tetrol, nonyl pentol, the alcohol of nonyl six, the alcohol of nonyl seven, the alcohol of nonyl eight or the alcohol of nonyl nine.
Above-mentioned step a）In polyalcohol and the concentration of soluble permanganate water solution be respectively：0.005~
0.15mol/L and 0.1 ~ 0.4 mol/L.
Above-mentioned step b）In the mol ratio of polyalcohol and soluble permanganate be 1：（0.1~1）.
The preparation method of the adjustable 3D network structures meso-porous titanium dioxide manganese of said structure, it is characterised in that step c）In stir
Mode is mixed for magnetic agitation or mechanical agitation or ultrasonic wave to disperse.
The method that the present invention uses is different from conventional template method, its be using soluble manganese salt and soluble chain type polyalcohol as
Raw material, deionized water are solvent and filler（Pore creating material）.The soluble-salt of manganese is dispersed in deionization by polyalcohol connection
In water, then the soluble-salt of manganese generates manganese dioxide with chain type polyol reaction.Using method provided by the present invention, it is not required to
Template or surfactant or heating response are added, by the structure for changing chain type polyalcohol（Species）With molar concentration, and
Regulate and control the molar concentration and species of soluble manganese source, you can phase structure, specific surface area and the accuracy controlling in aperture are realized, so as to close
Into aperture is homogeneous, 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：
1st, the present invention it is raw materials used be easy to get, cost it is low, with short production cycle, yield is high, and preparation technology is simple and technical process
It is pollution-free, it is adapted to industrialized production；
2nd, the reaction that synthetic method of the invention is related to is carried out at ambient temperature, and safe, controllability is strong, is held
Easily accomplish scale production；
3rd, the restricted problem of template is overcome, different pore size and the mesoporous dioxy of specific surface area can be realized interior on a large scale
Change the preparation of manganese；
4th, different phase structures, such as α, β, δ meso-porous titanium dioxide manganese can be obtained by preparation method of the present invention；
5th, meso-porous titanium dioxide manganese has abundant gap structure and big specific surface area, hole obtained by preparation method of the present invention
Footpath is in 2 ~ 50 nm, specific surface area in 150 ~ 320 m2/ g, it is available for metal ion, macromolecular to pass through, lithium can be widely used as
The catalyst for the oxidation reaction that ion battery or electrode material for super capacitor, the zymophore of biology sensor, macromolecular participate in
The theoretical research and application in rank correlation field.
Brief description of the drawings
Fig. 1 is the stereoscan photograph for the meso-porous titanium dioxide manganese that the present invention is prepared by different polyalcohols and permanganate, its
In：A represents embodiment 1, and b represents embodiment 4, and c represents embodiment 6, and d represents embodiment 7；
Fig. 2 is the X-ray diffraction for the meso-porous titanium dioxide manganese that the present invention is prepared by different polyalcohols and potassium permanganate（XRD）
Spectrum, wherein, 1, which represents embodiment 1,2, represents embodiment 4,3 and is represented as embodiment 6, and 1-350 represents the sample air of examples Example 1
Lower 350 DEG C of gained samples of heat treatment；
Fig. 3 is nitrogen adsorption desorption curve of the present invention using meso-porous titanium dioxide manganese obtained by different polyalcohols and potassium permanganate
（a）And pore size distribution curve（b）, wherein, 1 represent embodiment 1,2 represent embodiment 4,3 be represented as embodiment 6,4 represent implement
Example 7；
Fig. 4 is the XRD spectrum for the not jljl phase meso-porous titanium dioxide manganese that the present invention is prepared by different manganese salts with sweet six alcohol, wherein
3, which represent embodiment 6,4, represents embodiment 7,5 and represents embodiment 8.
Embodiment
With reference to embodiment, the present invention is described in further detail and completely, but is not intended to limit present disclosure.
Embodiment 1：At room temperature, 0.4g1,4- butanediols are stirred in 200 mL deionized waters, be configured to dense
Spend the 1,4- butanediol aqueous solution for 0.022mol/L；At room temperature, it is 0.15 mol/L to be slowly added to 50ml concentration while stirring
Potassium permanganate solution；At room temperature, 2h is persistently stirred, solution is become colorless by purple, terminates reaction；After filtering, filter cake is used
Deionized water is washed 2 ~ 3 times, drying, produces black manganese dioxide powder.
Fig. 1 a are the stereoscan photograph of the manganese dioxide sample obtained by the present embodiment, Fig. 2 curves 1 and 1-350 for originally
Manganese dioxide sample and its 350 DEG C of heat treatments obtained by embodiment（Under air atmosphere, 3 h）XRD spectrum.Fig. 3 curves 1 are this
The nitrogen adsorption desorption curve of manganese dioxide sample obtained by embodiment（Fig. 3 a）And pore size distribution curve（Fig. 3 b）.
According to above-mentioned test result, the analysis result that the present embodiment prepares the manganese dioxide of gained is as follows：
Obtained manganese dioxide sample is that nanometer sheet assembles or worked out the three-dimensional network shape loose structure formed, macroscopical chi
It is random to be similar to spongiform porous blocks that degree, which is seen,（See Fig. 1 a and its illustration）；With typical meso-hole structure（See Fig. 3
Curve 1）, it is 169 m to be computed its specific surface area2/ g, average pore size are 22.5 nm.And XRD results are shown, gained sample is prepared
Product to be nanocrystalline（Peak broadening）, phase structure is α-MnO2（1-350 results are consistent with standard card JCPDS#44-0141）.
Embodiment 2：This example difference from Example 1 is：At room temperature, 2.6g 1,7- heptandiols are dissolved in 200
Stirred in mL deionized waters, be configured to 1, the 7- heptandiol aqueous solution that concentration is 0.1mol/L；Remaining content with implementation
It is identical described in example 1.
Test result shows that the pattern and structure of gained manganese dioxide are similar to Example 1：It is the class of nanometer sheet establishment
The spongy or cellular porous α-MnO of 3D network structures2.It is in place of difference, the specific surface area of the present embodiment sample is 158
m2/ g, the nm of average pore size 30.6.
Embodiment 3：This example difference from Example 1 is：At room temperature, 2.4 g triols in 1,2,7- heptan are dissolved in
Stirred in 200 mL deionized waters, be configured to the alcohol solution in 1,2,7- heptan three that concentration is 0.08 mol/L, remaining content
It is consistent with embodiment 1.
Test result shows that the pattern and structure of gained manganese dioxide are similar to Example 1：It is the class of nanometer sheet establishment
Sponge or the cellular porous α-MnO of 3D network structures2.It is in place of difference, the specific surface area of the present embodiment sample and average hole
The size in footpath is respectively 164 m2/ g and 28.7 nm.
Embodiment 4：The present embodiment the difference is that only with embodiment 1：At room temperature, by 0.92 g glycerine（It is sweet
Oil）It is dissolved in 200 mL deionized waters and stirs, is configured to the glycerine water solution that concentration is 0.01mol/L；Remaining content is equal
It is identical with described in embodiment 1.
Fig. 1 b are the stereoscan photograph of the manganese dioxide sample obtained by the present embodiment, and Fig. 2 curves 2 are the present embodiment institute
The XRD spectrum of the manganese dioxide sample obtained.Fig. 3 curves 2 are the nitrogen adsorption desorption of the manganese dioxide sample obtained by the present embodiment
Curve（Fig. 3 a）And pore size distribution curve（Fig. 3 b）.
According to above-mentioned test result, the pattern and structure of the manganese dioxide of the present embodiment preparation gained are similar to Example 1：
It is the spongy porous α-MnO of 3D network structures of class of nanometer sheet establishment2.It is in place of difference, the ratio table of the present embodiment sample
Area is 196.8 m2/ g, the nm of aperture 10.9.
Embodiment 5：The present embodiment the difference is that only with embodiment 1：At room temperature, 0.244g antierythrites are dissolved in
Stirred in 200 mL deionized waters, be configured to the antierythrite aqueous solution that concentration is 0.01mol/L；Remaining content with
It is identical described in embodiment 1.
According to test result, the pattern and structure of the manganese dioxide of the present embodiment preparation gained are similar to Example 1：It is
The spongy porous α-MnO of 3D network structures of class of nanometer sheet establishment2.It is in place of difference, the specific surface area of the present embodiment sample
For 236.8 m2/ g, the nm of average pore size 8.5.
Embodiment 6：The present embodiment the difference is that only with embodiment 1：At room temperature, 0.218 g mannitol is dissolved in
Stirred in 200 mL deionized waters, be configured to the Osmitrol that concentration is 0.06mol/L；Remaining content with reality
Apply identical described in example 1.
Fig. 1 c are the stereoscan photograph of the manganese dioxide sample obtained by the present embodiment, and Fig. 2 curves 3 are the present embodiment institute
The XRD spectrum of the manganese dioxide sample obtained.Fig. 3 curves 3 are the nitrogen adsorption desorption of the manganese dioxide sample obtained by the present embodiment
Curve（Fig. 3 a）And pore size distribution curve（Fig. 3 b）.
According to above-mentioned test result, the pattern and structure of the manganese dioxide of the present embodiment preparation gained are similar to Example 1：
It is the spongy porous α-MnO of 3D network structures of class of nanometer sheet establishment2.It is in place of difference, the ratio table of the present embodiment sample
Area is 301.9 m2/ g, the nm of average pore size 3.9.
Embodiment 7：At room temperature, 0.218 g mannitol is stirred in 200 mL deionized waters, being configured to concentration is
0.006 mol/L Osmitrol；At room temperature, the height that 50ml concentration is 0.15 mol/L is slowly added to while stirring
Mangaic acid aqueous ammonium；At room temperature, continue to stir 2h, solution is become colorless by purple, terminates reaction；Filtering, filter cake deionization
Water washing 2-3 times, drying, produces black manganese dioxide powder.
Fig. 1 d are the stereoscan photograph of the manganese dioxide sample obtained by the present embodiment, and Fig. 3 curves 4 are the present embodiment institute
The nitrogen adsorption desorption curve of obtained manganese dioxide sample（Fig. 3 a）And pore size distribution curve（Fig. 3 b）, Fig. 4 curves 4 are this implementation
The XRD spectrum of the manganese dioxide sample of example gained.
According to above-mentioned test result, the present embodiment prepares the pattern and micro-structural and embodiment 1-6 of the manganese dioxide of gained
It is similar：It is the spongy porous MnO of 3D network structures of class of nanometer sheet establishment2.It is in place of difference, the phase of the present embodiment sample
Structure is β-MnO2, its specific surface area is 268.9 m2/ g, the nm of aperture 5.8.
Embodiment 8：The present embodiment difference from Example 7 is：At room temperature, it is dense that 50ml is slowly added to while stirring
Spend the aqueous sodium permanganate solution for 0.2mol/L；Remaining content is identical with described in embodiment 7.
Fig. 4 curves 5 are the XRD spectrum of the manganese dioxide sample obtained by the present embodiment.
According to test result, the present embodiment prepare the pattern of gained manganese dioxide sample and micro-structural with the phase of embodiment 7
Seemingly：It is the spongy porous MnO of 3D network structures of class of nanometer sheet establishment2It is in place of difference, the mutually knot of the present embodiment sample
Structure is δ-MnO2, its specific surface area is 320.3 m2/ g, the nm of aperture 4.2.
Claims (2)
1. a kind of preparation method of the adjustable 3D network structures meso-porous titanium dioxide manganese of structure, the meso-porous titanium dioxide manganese is by titanium dioxide
Manganese nanometer sheet forms that the class with 3D network structures is spongy or cellular porous block by assembling, wherein the crystalline substance of manganese dioxide
Body structure is α-MnO2、β-MnO2、δ-MnO2、γ-MnO2Or λ-MnO2；Aperture is 2 ~ 50 nm；Specific surface area is 150 ~ 320
m2/g；It is characterized in that this method comprises the following specific steps that：
a）Polyatomic alcohol water solution and soluble permanganate water solution is respectively configured；Chain structure polyalcohol is Cn, n=3 ~ 9, hydroxyl
Radix mesh is no less than 2 and the soluble polyalcohol of chain structure that termination carbon is connected with hydroxyl；Described polyalcohol and solubility
The concentration of permanganate water solution is respectively：0.005 ~ 0.15mol/L and 0.1 ~ 0.4 mol/L；
b）The two kinds of solution prepared in step a are mixed at room temperature, wherein mole of polyalcohol and soluble permanganate
Than for 1：（0.1~1）；
c）Continue to stir at room temperature, until reaction solution is become colorless by purple, end is reacted；
d）Filtering, filter cake are dried after being washed with deionized water and ethanol solution, produce 3D network structure meso-porous titanium dioxide manganese；
The permanganate is sodium permanganate, barium permanganate or ammonium permanganate；
Described chain structure polyalcohol is：1,4- butanediols, butantriol, erythrite, 1,5- pentanediols, penta triol, penta tetrol,
Xylitol, 1,6-HD, hexanetriol, own tetrol, hexanepentol, mannitol, 1,7- heptandiols, triol in heptan, tetrol in heptan, heptan five
Alcohol, alcohol in heptan six, volemitol, 1,8- ethohexadiols, pungent triol, pungent tetrol, pungent pentol, pungent six alcohol, pungent seven alcohol, pungent eight alcohol, 1,9- nonyls
Glycol, nonyl triol, nonyl tetrol, nonyl pentol, the alcohol of nonyl six, the alcohol of nonyl seven, the alcohol of nonyl eight or the alcohol of nonyl nine.
2. the preparation method of the adjustable 3D network structures meso-porous titanium dioxide manganese of structure according to claim 1, it is characterised in that
Step c）In agitating mode disperse for magnetic agitation or mechanical agitation or ultrasonic wave.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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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