CN105480950B - A kind of preparation method of oxide porous material - Google Patents
A kind of preparation method of oxide porous material Download PDFInfo
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- CN105480950B CN105480950B CN201610066557.4A CN201610066557A CN105480950B CN 105480950 B CN105480950 B CN 105480950B CN 201610066557 A CN201610066557 A CN 201610066557A CN 105480950 B CN105480950 B CN 105480950B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G23/005—Alkali titanates
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/16—Pore diameter
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Abstract
The present invention relates to a kind of preparation method of oxide porous material.Its technical scheme is：It is 5 ~ 10mol/L by concentration, oxide precursor salt is dissolved in organic solvent, stirs, obtain solution I；Mass ratio according to oxide precursor salt and binding agent is 1: (0.01 ~ 0.1), binding agent is added in solution I, stirring obtains solution II；Mass ratio according to oxide precursor salt and template is 1: (0.1 ~ 0.35), template is added in solution II, stirring obtains solution III；Solution III is subjected to liquid nitrogen frozen processing again, is then dried in vacuum freeze drier, obtains dried product；The product is placed in tube furnace, 300 ~ 800 DEG C are warming up to 4 ~ 5 DEG C/min speed in argon gas atmosphere or air atmosphere, 4 ~ 12h is incubated, with stove natural cooling, template is removed, obtains oxide porous material.The present invention is easy to operate and suitable for industrialized production, and hole size, porosity and the wall thickness of its product can be in interior regulation and control in a big way.
Description
Technical field
The invention belongs to porous material preparing technical field.Specifically related to a kind of preparation method of oxide porous material.
Background technology
Porous material has specific surface area height, low relative density, good penetrability, lightweight, pore structure unique and adsorptivity
Can be excellent the features such as, energy stores and conversion, catalytic reaction, adsorb, separate, filter, noise reduction and it is heat-insulated etc. it is all it is many-sided must
To extensive use.Therefore, develop a kind of simple and effective preparation method to control the pore structure of porous material, be to realize it
These fields apply key point.
At present, porous material is mainly prepared by colloid crystal templating, including hard template method and soft template method.It is brilliant using glue
During template, it usually needs previously prepared plastic emitting crystal template, and the technics comparing for preparing glue crystal template is complicated, it is more difficult to extensive
Production, meanwhile, glue crystal template is formed by template particles are tightly packed, causes hole size, porosity and wall thickness of target material etc.
Property is difficult in a wide range of interior control.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide oxygen a kind of easy to operate and suitable for industrialized production
The preparation method of compound porous material, the oxide porous material prepared with this method possesses 3 d-dem pore structure, the oxygen
Hole size, porosity and the wall thickness of compound porous material can be in interior regulation and control in a big way.
To achieve the above object, the technical solution adopted by the present invention is：It is characterized in that the preparation method is：
1）It is 5 ~ 10mol/L by concentration, oxide precursor salt is dissolved in organic solvent, stirs 3 ~ 5 hours, obtain solution I.
2）Mass ratio according to oxide precursor salt and binding agent is 1: (0.01 ~ 0.1), binding agent is added into solution I
In, stir 1 ~ 2 hour, obtain solution II.
3）Mass ratio according to oxide precursor salt and template is 1: (0.1 ~ 0.35), template is added into solution II
In, stir 3 ~ 5 hours, obtain solution III.
4）Solution III is subjected to liquid nitrogen frozen processing again, then dries 48 ~ 72 hours, obtains in vacuum freeze drier
Dried product.
5）Dried product is placed in tube furnace, with 4 ~ 5 DEG C/min speed liters in argon gas atmosphere or air atmosphere
Temperature is incubated 4 ~ 12h to 300 ~ 800 DEG C, with stove natural cooling, removes template, obtains oxide porous material.
The oxide precursor salt is salt-mixture, four water manganese nitrates, the titanium sulfate of butyl titanate and two water lithium acetates
In one kind.
The organic solvent is the tert-butyl alcohol or is the mixed solvent of ethanol and glacial acetic acid, the ethanol and ice of in the mixed solvent
The volume ratio of acetic acid is 1 ︰ 1.
The binding agent is ethyl cellulose or is polyvinylpyrrolidone.
The template is one kind in polymethyl methacrylate, polystyrene, silica.
Due to using above-mentioned technical proposal, the present invention has following good effect compared with prior art：
（1）Oxide porous material obtained by the present invention has suitable nanoaperture, can improve the stability of material
And feature, it is to avoid aperture is excessive to cause material overall structure unstable, while can also prevent aperture too small and can not play good
The effect of good buffer volumes expansion.
（2）The template particles for the glue crystal template that traditional colloid crystal templating is used are close packed array, and gained is porous
The pore size and hole wall thickness of material are totally dependent on glue crystal template, and hole size, porosity and the wall thickness of material are difficult in big model
Interior control is enclosed, gained pore structure is usually insertion pore passage structure；And the addition and species of the invention by changing template, energy
Efficiently control hole size, porosity and the wall thickness of obtained oxide porous material, prepared oxide porous material
Possess 3 d-dem pore structure；After tested：The specific surface area of oxide porous material is 30 ~ 80m2/ g, porosity be 0.13 ~
0.28cm3/ g, aperture is 50 ~ 500nm, and wall thickness is 50 ~ 1000nm, so that the hole knot of obtained oxide porous material
Structure can be in a wide range of interior regulation and control.
（3）Traditional colloid crystal templating needs that the glue crystal template of template particles close packed array is first made, it is more difficult to advise
Modelling is produced；And the template in the present invention can be mass produced, it is easy to the oxide porous material of preparation of industrialization.
Therefore, the present invention has easy to operate and the characteristics of suitable for industrialized production, prepared oxide porous material
Possess 3 d-dem pore structure, hole size, porosity and the wall thickness of the oxide porous material can be in interior regulation and control in a big way.
Brief description of the drawings
Fig. 1 is a kind of XRD of manganese dioxide porous material prepared by the present invention；
Fig. 2 is the SEM figures of manganese dioxide porous material shown in Fig. 1；
Fig. 3 is a kind of XRD of TiO 2 porous material prepared by the present invention；
Fig. 4 is the SEM figures of TiO 2 porous material shown in Fig. 3.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
Embodiment 1
A kind of preparation method of manganese dioxide porous material.The preparation method is：
1）It is 5 ~ 6.5mol/L by concentration, four water manganese nitrates is dissolved in the tert-butyl alcohol, stirs 3 ~ 5 hours, obtain solution I.
2）Mass ratio according to four water manganese nitrates and ethyl cellulose is 1: (0.01 ~ 0.04), ethyl cellulose is added
In solution I, stir 1 ~ 2 hour, obtain solution II.
3）Mass ratio according to four water manganese nitrates and silica is 1: (0.25 ~ 0.35), silica is added into solution
In II, stir 3 ~ 5 hours, obtain solution III.
4）Solution III is subjected to liquid nitrogen frozen processing again, then dries 48 ~ 72 hours, obtains in vacuum freeze drier
Dried product.
5）Dried product is placed in tube furnace, with 4 ~ 5 DEG C/min speed liters in argon gas atmosphere or air atmosphere
Temperature is incubated 4 ~ 7h, with stove natural cooling, obtains manganese bioxide material to 300 ~ 500 DEG C；The manganese bioxide material is used
10vol% hydrofluoric acid dips 0.5-1h, then be washed with deionized 3-5 times, dry, obtain manganese dioxide porous material.
Fig. 1 is a kind of XRD of manganese dioxide porous material prepared by embodiment 1, and Fig. 2 is porous silica shown in Fig. 1
The SEM figures of manganese material.As seen from Figure 1, its product is the MnO of pure phase2Material；As seen from Figure 2, its product hole point
Cloth is than more uniform, and aperture is 300 ~ 500nm, and wall thickness is 50 ~ 400nm；Its product is tested through BET, and specific surface area is 60 ~ 80m2/
G, porosity is 0.20 ~ 0.28cm3/ g, it was demonstrated that gained manganese dioxide porous material possesses 3 d-dem pore structure.
Embodiment 2
A kind of preparation method of TiO 2 porous material.The preparation method is：
1）It is 6.5 ~ 8.0mol/L by concentration, titanium sulfate is dissolved in the tert-butyl alcohol, stirs 3 ~ 5 hours, obtain solution I.
2）Mass ratio according to titanium sulfate and polyvinylpyrrolidone is 1: (0.04 ~ 0.07), by polyvinylpyrrolidone
Add in solution I, stir 1 ~ 2 hour, obtain solution II.
3）Mass ratio according to titanium sulfate and polymethyl methacrylate is 1: (0.15 ~ 0.25), by polymethylacrylic acid
Methyl esters is added in solution II, is stirred 3 ~ 5 hours, is obtained solution III.
4）Solution III is subjected to liquid nitrogen frozen processing again, then dries 48 ~ 72 hours, obtains in vacuum freeze drier
Dried product；
5）Dried product is placed in tube furnace, with 4 ~ 5 DEG C/min speed liters in argon gas atmosphere or air atmosphere
Temperature is incubated 7 ~ 10h to 500 ~ 700 DEG C, with stove natural cooling, removes template, obtains oxide porous material.
Fig. 3 is a kind of XRD of TiO 2 porous material prepared by embodiment 2；Fig. 4 is titanium dioxide titanium shown in Fig. 3
The SEM figures of material.As seen from Figure 3, its product is pure phase TiO2Material；As seen from Figure 4, its product distribution of pores compares
Uniformly, aperture is 150 ~ 350nm, and wall thickness is 300 ~ 700nm；Its product is tested through BET, and specific surface area is 45 ~ 65m2/ g, hole
Rate is 0.18 ~ 0.25cm3/ g, it was demonstrated that the TiO 2 porous material of gained possesses 3 d-dem pore structure.
Embodiment 3
A kind of preparation method of lithium titanate porous material.The preparation method is：
1）It is 8.0 ~ 10.0mol/L by the concentration of every kind of material, butyl titanate is successively dissolved in two water lithium acetates to be had
Machine solvent, stirs 3 ~ 5 hours, obtains solution I.
The organic solvent is the mixed solvent of ethanol and glacial acetic acid, the ethanol of in the mixed solvent and the volume ratio of glacial acetic acid
For 1 ︰ 1.
2）Mass ratio according to the salt-mixture and ethyl cellulose of butyl titanate and two water lithium acetates is 1: (0.07 ~
0.10), ethyl cellulose is added in solution I, stirs 1 ~ 2 hour, obtains solution II.
3）Mass ratio according to the salt-mixture and polystyrene of butyl titanate and two water lithium acetates is 1: (0.10 ~
0.15), polystyrene is added in solution II, stirs 3 ~ 5 hours, obtains solution III.
4）Solution III is subjected to liquid nitrogen frozen processing again, then dries 48 ~ 72 hours, obtains in vacuum freeze drier
Dried product.
5）Dried product is placed in tube furnace, with 4 ~ 5 DEG C/min speed liters in argon gas atmosphere or air atmosphere
Temperature is incubated 10 ~ 12h to 700 ~ 800 DEG C, with stove natural cooling, removes template, obtains oxide porous material.
Lithium titanate porous material manufactured in the present embodiment, distribution of pores is than more uniform, and aperture is 50 ~ 260nm, and wall thickness is
600~1000nm；Its product is tested through BET, and specific surface area is 30 ~ 50m2/ g, porosity is 0.13 ~ 0.20cm3/ g, it was demonstrated that gained
Lithium titanate porous material possesses 3 d-dem pore structure.
Present embodiment has following good effect compared with prior art：
（1）Oxide porous material obtained by present embodiment has suitable nanoaperture, can improve material
Stability and feature, it is to avoid aperture is excessive to cause material overall structure unstable, while can also prevent aperture too small and nothing
Method plays the effect of good buffer volumes expansion.
（2）The template particles for the glue crystal template that traditional colloid crystal templating is used are close packed array, and gained is porous
The pore size and hole wall thickness of material are totally dependent on glue crystal template, and hole size, porosity and the wall thickness of material are difficult in big model
Interior control is enclosed, gained pore structure is usually insertion pore passage structure；And present embodiment is by changing the addition of template
And species, hole size, porosity and the wall thickness of obtained oxide porous material, prepared oxide can be efficiently controlled
Porous material possesses 3 d-dem pore structure；After tested：The specific surface area of oxide porous material is 30 ~ 80m2/ g, porosity
For 0.13 ~ 0.28cm3/ g, aperture is 50 ~ 500nm, and wall thickness is 50 ~ 1000nm, so that obtained oxide porous material
Pore structure can regulate and control in a wide range of.
（3）Traditional colloid crystal templating needs that the glue crystal template of template particles close packed array is first made, it is more difficult to advise
Modelling is produced；And the template in present embodiment can be mass produced, it is easy to the oxide porous material of preparation of industrialization.
Therefore, present embodiment has easy to operate and the characteristics of suitable for industrialized production, prepared oxide
Porous material possesses 3 d-dem pore structure, and hole size, porosity and the wall thickness of the oxide porous material can be in larger models
Enclose interior regulation and control.
Claims (2)
1. a kind of preparation method of the oxide porous material with 3 d-dem pore structure, it is characterised in that the preparation method
It is：
1）It is 5 ~ 10mol/L by concentration, oxide precursor salt is dissolved in organic solvent, stirs 3 ~ 5 hours, obtain solution I；
2）Mass ratio according to oxide precursor salt and binding agent is 1: (0.01 ~ 0.1), binding agent is added in solution I, stirred
Mix 1 ~ 2 hour, obtain solution II；
3）Mass ratio according to oxide precursor salt and template is 1: (0.1 ~ 0.35), template is added in solution II,
Stirring 3 ~ 5 hours, obtains solution III；
4）Solution III is subjected to liquid nitrogen frozen processing again, is then dried 48 ~ 72 hours in vacuum freeze drier, obtains drying
Product afterwards；
5）Dried product is placed in tube furnace, is warming up in argon gas atmosphere or air atmosphere with 4 ~ 5 DEG C/min speed
300 ~ 800 DEG C, 4 ~ 12h is incubated, with stove natural cooling, template is removed, obtains oxide porous material；
The oxide precursor salt is in the salt-mixture, four water manganese nitrates, titanium sulfate of butyl titanate and two water lithium acetates
It is a kind of；
The organic solvent is the tert-butyl alcohol or is the mixed solvent of ethanol and glacial acetic acid, the ethanol and glacial acetic acid of in the mixed solvent
Volume ratio be 1 ︰ 1；
The binding agent is ethyl cellulose or is polyvinylpyrrolidone.
2. the method according to claim 1 for preparing oxide porous material, it is characterised in that the template is poly- first
One kind in base methyl acrylate, polystyrene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106395895B (en) * | 2016-09-30 | 2019-02-19 | 温州生物材料与工程研究所 | A method of poriferous titanium dioxide nano material is prepared using freeze-drying |
| CN107986811B (en) * | 2017-11-21 | 2020-12-18 | 西安理工大学 | Porous material obtained by combination of low-temperature solidification and directional annealing and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391811A (en) * | 2008-11-05 | 2009-03-25 | 北京科技大学 | Method for preparing high specific surface area titanic oxide |
| CN104150525A (en) * | 2014-08-21 | 2014-11-19 | 安徽理工大学 | Oxide porous materials and universal preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391811A (en) * | 2008-11-05 | 2009-03-25 | 北京科技大学 | Method for preparing high specific surface area titanic oxide |
| CN104150525A (en) * | 2014-08-21 | 2014-11-19 | 安徽理工大学 | Oxide porous materials and universal preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Construction of hierarchical titanium dioxide nanomaterials by tuning the structure of polyvinylpyrrolidone–titanium butoxide complexes from 2- to 3-dimensional;Baoshun Liu et al.;《Journal of Materials Chemistry A》;20131231;第1卷;第4993-5000页 * |
| Influence of PVP template on the formation of porous TiO2 nanofibers by electrospinning technique for dye-sensitized solar cell;V. Elayappan et al.;《Appl. Phys. A》;20150710;第120卷;第1211-1218页 * |
| 多级孔锰氧化物的制备及其催化氧化性能研究;张志华等;《安徽工程大学学报》;20140930;第29卷(第3期);第37-40页 * |
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