CN102836745B - Preparation method for photo-catalysis material with aerogel substrate - Google Patents
Preparation method for photo-catalysis material with aerogel substrate Download PDFInfo
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Abstract
The invention provides a preparation method for a photo-catalysis material with an aerogel substrate and relates to the preparation method for the photo-catalysis material. The preparation method is mainly used for solving the technical problem of low photo-catalysis effect caused by the difficulty in utilizing the functionality of the embedded nanometer material of the present nanometer material loading substrate. The preparation method comprises the following steps: 1) weighting nanometer materials with photo-catalysis activity, ionic liquid and celluloses in proportion; 2) uniformly dispersing the nanometer materials in the ionic liquid, and then adding the celluloses, thereby obtaining blended liquid; 3) pouring the blended liquid obtained in the step 2) into a mould, cooling, and then pouring into a regenerating solution, and depositing and regenerating, thereby obtaining a compound gel; and 4) drying the compound gel prepared in the step 3), thereby obtaining the photo-catalysis material with the aerogel substrate. The photo-catalysis material provided by the invention can be used for catalytically degrading the organic pollutants or harmful strains, such as escherichia coli, and the like.
Description
Technical field
The present invention relates to the preparation method of catalysis material.
Background technology
The research of inorganic nanoparticles/polymer composites is the present field of enlivening.Composite organic-inorganic material combines organic and performance inorganic material, has remarkable performance.Nano level metal and metal oxide (semiconductor) particle, gold for example, titanium dioxide, zinc oxide, and iron oxide etc. is because have distinctive size physical chemistry effect and photoelectric effect, is advanced functional material.Metal oxide nanoparticles has a lot of purposes at photoelectrocatalysis, photocatalysis and biomedicine field.Particularly titanium dioxide nano material, due to the extensive application in air cleaning, water purify of its potential photoelectric activity, solar energy conversion performance, self-cleaning surface and photocatalytic activity, has obtained more concern.Some organic pollutions, for example ethanol, phenol, organic dyestuff and carboxylic acid, can be by titanium dioxide nano material light degradation under ultraviolet/visible light is irradiated.Efficiently, the development of green and low consumed removal organic pollution material preparation method is necessary to protection of the environment.Glass, pottery and cellulose are considered to the desirable load matrix of nano material because their stability is high, pattern special controlled, and can control the growth of nano particle.But because glass, ceramic internal structure are closely knit, the functional of nano material that is difficult to embedding brought into play, thereby causes photocatalytic activity low.And in cellulosic matrix, inorganic nano material is fixed, and its electricity, magnetic, light characteristic are retained.Therefore, inorganic nano material/cellulose composite material can be considered to portable catalyst, but its specific area little be 15～80m
2/ g.If the cellulose base body structure of loaded with nano material and nano material self character can be worked in coordination with to transformation, the effective catalyst that just can make Novel portable, easily reclaims.
Summary of the invention
The present invention will solve very difficult the functional of nano material that embedding of existing nano material load matrix to bring the technical problem that causes photocatalysis effect low into play, and a kind of preparation method with the catalysis material of aeroge matrix is provided.
A kind of preparation method with the catalysis material of aeroge matrix of the present invention carries out according to the following steps:
One, by nano material, ionic liquid and the cellulosic mass ratio with photocatalytic activity, be (0.01～1): 100: (1～20) takes nano material, ionic liquid and the cellulose with photocatalytic activity;
Two, at room temperature the nano material with photocatalytic activity is joined in ionic liquid, dispersed after, then add cellulose, under the condition stirring, be warming up to 65～130 ℃ and keep 0.5～4h, obtain blend solution;
Three, it is in the mould of-30 ℃～25 ℃ that blend solution step 2 being obtained is poured temperature into, and after cooling 0.5h～20h, then to join mass fraction be precipitation regeneration in 10%～100% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained is dry, obtains having the catalysis material of aeroge matrix.
The present invention has the following advantages:
The invention provides a kind of ionic liquid that utilizes for working media, dispersed nano material high-efficiency dissolution cellulose, simple, to prepare the fast enhancing photocatalysis effect catalysis material with aeroge matrix.The cellulose gel of regenerating from mixed liquor in preparation process has good structure and character, and its surface and inside are all full of pore space structure and hydroxyl, can very effective fixedly nano material, and formation inorganic nano material/natural polymer catalyst.
The present invention has prepared portable catalyst and has been applied to the photocatalysis under UV-irradiation, this is a kind of new method that generates titanium dioxide/cellulose, titanate/cellulose composite aerogel, is also a kind of environment-friendly preparation method thereof of processing organic pollution catalysis material.
Preparation process of the present invention is simple, does not need expensive device, and products obtained therefrom quality high-performance is good, aspect organic pollution catalytic degradation, can extensively utilize, and efficient, functionalization has been utilized biomass cellulose resource simultaneously.
The matrix material that the present invention uses is living beings cellulosic material, and wide material sources are safe, can not bring pollution to environment, and preparation technology is simple, effect is remarkable, and the ionic liquid of use can reclaim and reuse, and is the preparation method of environment-friendly and green.
Composite aerogel material specific area prepared by the present invention is 150～500m greatly
2/ g, duct connect, surface hydroxyl is many, can have with inorganic nano material strong bonded the photocatalysis effect of enhancing simultaneously.
The present invention can the multiple nano material with photocatalysis characteristic of load, has applicability widely.
The present invention can be solidificated in pulverous nano material on block matrix, is convenient to recycling, and the material of preparing is not only the well loaded body of nano material, while or the new catalyst of good mechanical property.Can be used for harmful bacterial classifications such as photocatalysis degradation organic contaminant or Escherichia coli.
The present invention can obtain having porous or the cancellated nano-TiO of the photocatalysis performance of enhancing
2/ cellulose, titanate/cellulose plural gel, film are a kind of new catalysis materials.The catalytic capability of institute's carrying inorganic nano material can be improved to nearly 10%～40%.The method is utilized solution blending, is prepared and take cellulose as matrix, has the TiO of photocatalytic activity
2/ cellulose, titanate/cellulose composite material.
Accompanying drawing explanation
Fig. 1 is the TEM photo of titanate nanotube in embodiment 1;
Fig. 2 is the electronic diffraction photo of titanate nanotube used in embodiment 1;
Fig. 3 is the photomacrograph of resulting alcogel in embodiment 2 step 3;
Fig. 4 is the plural gel SEM photo obtaining in embodiment 2 step 4;
Fig. 5 has disperseed approximately 0.35% TiO in embodiment 3 step 1
2the SEM photo of the ionic liquid of particle.
The specific embodiment
The specific embodiment one: a kind of preparation method with the catalysis material of aeroge matrix of this specific embodiment carries out according to the following steps:
One, by nano material, ionic liquid and the cellulosic mass ratio with photocatalytic activity, be (0.01～1): 100: (1～20) takes nano material, ionic liquid and the cellulose with photocatalytic activity;
Two, at room temperature the nano material with photocatalytic activity is joined in ionic liquid, dispersed after, then add cellulose, under the condition stirring, be warming up to 65～130 ℃ and keep 0.5～4h, obtain blend solution;
Three, it is in the mould of-30 ℃～25 ℃ that blend solution step 2 being obtained is poured temperature into, and after cooling 0.5h～20h, then to join mass fraction be precipitation regeneration in 10%～100% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained is dry, obtains having the catalysis material of aeroge matrix.
Present embodiment provides a kind of ionic liquid that utilizes for working media, dispersed nano material high-efficiency dissolution cellulose, simple, to prepare fast the nano material cellulose load matrix that strengthens photocatalysis effect method.And the cellulose gel of regenerating from mixed liquor has good structure and character.Surface and inside are all full of pore space structure and hydroxyl, can very effective fixedly nano material, and formation inorganic nano material/natural polymer catalyst.
Present embodiment has been prepared portable catalyst and has been applied to the photocatalysis under UV-irradiation.This is the new method that a step generates titanium dioxide/cellulose, titanate/cellulose composite aerogel, is also a kind of environment-friendly preparation method thereof of processing organic pollution catalysis material.
Present embodiment preparation process is simple, does not need expensive device, and products obtained therefrom quality high-performance is good, aspect organic pollution catalytic degradation, can extensively utilize.Efficient, functionalization has been utilized biomass cellulose resource simultaneously.The matrix material that present embodiment is used is living beings cellulosic material, and wide material sources are safe, can not bring pollution to environment, and preparation technology is simple, effect is remarkable, and the ionic liquid of use can reclaim and reuse, and is the preparation method of environment-friendly and green.
Composite aerogel material specific area prepared by present embodiment is 150～500m greatly
2/ g, duct connect, surface hydroxyl is many, can have with inorganic nano material strong bonded the photocatalysis effect of enhancing simultaneously.
Present embodiment method can the multiple nano material with photocatalysis characteristic of load, has applicability widely.
Present embodiment can be solidificated in pulverous nano material on block matrix, is convenient to recycling, and the material of preparing is not only the well loaded body of nano material, while or the new catalyst of good mechanical property.Can be used for harmful bacterial classifications such as photocatalysis degradation organic contaminant or Escherichia coli.
Present embodiment can obtain having porous or the cancellated nano-TiO of the photocatalysis performance of enhancing
2/ cellulose, titanate/cellulose plural gel, film are a kind of new catalysis materials.The catalytic capability of institute's carrying inorganic nano material can be improved to nearly 10～40%.It is characterized in that the method utilizes solution blending, prepares and take cellulose as matrix, there is the TiO of photocatalytic activity
2/ cellulose, titanate/cellulose composite material.
The specific embodiment two: what present embodiment was different from the specific embodiment one is that the nano material with photocatalytic activity described in step 1 is nano-TiO
2, Sodium Titanate or metatitanic acid hydrogen salt, other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is that the nano material with photocatalytic activity used in step 1 is nanotube, nano wire, nano flower, nanometer sheet, nano particle or the mixed crystal material that is mixed with assorted element, and other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three is that ionic liquid in step 1 is chloro salt, carboxylic acids ionic liquid or the alkyl phosphate salt of dialkylimidazolium class ionic liquid, N-alkyl pyridine class ionic liquid, quaternary amines, and other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that in step 1, homodisperse method is by the method that cooking machine is sheared or mortar grinds, nano material to be dispersed in ionic liquid, jitter time is no more than 10min, and other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is that in step 2, cellulose is holocellulose, wood-fibred, stalk fibre or coir fibre, and other is identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment one to six is that nano material in step 1, ionic liquid and cellulosic mass ratio are 0.1: 100: 10, one of other and specific embodiment one to six with.
The specific embodiment eight: present embodiment is different from one of specific embodiment one to seven is that in step 3, regenerated liquid is any or the two kinds of mixed liquors in any proportion wherein in deionized water, acetone, dimethyl sulfoxide (DMSO), ethanol and cyclohexane, and other is identical with one of specific embodiment one to seven.
The specific embodiment nine: present embodiment is different from one of specific embodiment one to eight is the critical point drying that is carbon dioxide of the drying mode in step 4, supercritical drying or the freeze drying of carbon dioxide, and other is identical with one of specific embodiment one to eight.
The specific embodiment ten: what present embodiment was different from one of specific embodiment one to nine is that in step 4, the feature of drying mode is: the baking temperature temperature of the critical point drying mode of 1600psi carbon dioxide is 35 ℃～40 ℃, and be 30min～60min drying time; The baking temperature of the supercritical drying mode of 1900psi carbon dioxide is 35 ℃～100 ℃, and be 2h～4h drying time; The baking temperature of freeze drying mode is-30 ℃～-100 ℃, and be 5h～72h drying time, and other is identical with one of specific embodiment one to nine.
By following verification experimental verification beneficial effect of the present invention:
Embodiment 1: a kind of preparation method with the catalysis material of aeroge matrix of the present embodiment carries out according to the following steps: by the titanate nanotube with photocatalytic activity, (be one, H
2ti
3o
7, H
2ti
2o
5h
2o and Na
0.8h
1.2ti
3o
7mixed crystal), AMImCl (1-pi-allyl-3-methylimidazole villaumite) and absorbent cotton mass ratio be 0.075: 10: 1.5, taking the titanate nanotube with photocatalytic activity (is H
2ti
3o
7, H
2ti
2o
5h
2o and Na
0.8h
1.2ti
3o
7mixed crystal), AMImCl (1-pi-allyl-3-methylimidazole villaumite) and absorbent cotton;
Two, by the titanate nanotube with photocatalytic activity, (be at room temperature H
2ti
3o
7, H
2ti
2o
5h
2o and Na
0.8h
1.2ti
3o
7mixed crystal) join in AMImCl (1-pi-allyl-3-methylimidazole villaumite), dispersed after, then add absorbent cotton, under the condition stirring, be warming up to 80 ℃ and keep 0.5h, obtain blend solution;
Three, it is in the mould of 25 ℃ that blend solution step 2 being obtained is poured temperature into, and after cooling 2h, then to join mass fraction be precipitation regeneration 10h in 50% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained carries out freeze drying 8h at-30 ℃, obtains having the catalysis material of aeroge matrix.
Shown in TEM photo Fig. 1 of the titanate nanotube that this test makes through step 1; Fig. 2 is the titanate nanotube electronic diffraction photo of the present embodiment, shows that titanate nanotube used is mixed crystal.
The composite aerogel forming after dry has the photocatalysis effect strengthening than ortho-titanate nanotube, and under ultraviolet light, the efficiency of rhodamine B degradation has improved approximately 20%.
Embodiment 2: a kind of preparation method with the catalysis material of aeroge matrix of the present embodiment carries out according to the following steps: one, by the P25 nano particle (golden red and anatase mixture) with photocatalytic activity, ionic liquid BMImCl (1-butyl-3-methylimidazole villaumite) is to take the P25 nano particle (golden red and anatase mixture) with photocatalytic activity at 0.15: 100: 15 with the mass ratio of microcrystalline cellulose, ionic liquid BMImCl (1-butyl-3-methylimidazole villaumite) and microcrystalline cellulose,
Two, at room temperature the P25 nano particle (golden red and anatase mixture) with photocatalytic activity is joined in ionic liquid BMImCl (1-butyl-3-methylimidazole villaumite), after dispersed, add again microcrystalline cellulose, under the condition stirring, be warming up to 130 ℃ and keep 1h, obtain blend solution;
Three, it is in the mould of 25 ℃ that blend solution step 2 being obtained is poured temperature into, and after cooling 2h, then to join mass fraction be precipitation regeneration 10h in 10%～100% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained, at 45 ℃, carries out supercritical CO under 1900psi
2be dried 3h, obtain having the catalysis material of aeroge matrix
Shown in photomacrograph Fig. 3 of the alcogel that this test makes through step 3; Fig. 4 is the plural gel SEM photo that the present embodiment step 4 makes, and visible matrix is loose structure;
The composite aerogel forming after dry has the photocatalysis effect strengthening than former P25, and under ultraviolet light, the efficiency of degradation of phenol has improved approximately 10%.
Embodiment 3: a kind of preparation method with the catalysis material of aeroge matrix of the present embodiment carries out according to the following steps: by the mass ratio with 325 order anatase nano particles, EMImAc and the wood powder of photocatalytic activity, be one, to take nano material, ionic liquid and the cellulose with photocatalytic activity at 0.0105: 10: 1.5;
Two, at room temperature the 325 order anatase nano particles with photocatalytic activity are joined in MImAc, dispersed after, then add wood powder, under the condition stirring, be warming up to 65 ℃ and keep 2h, obtain blend solution;
Three, blend solution step 2 being obtained is poured temperature into in the mould of-20 ℃, and after cooling 20h, then to join mass fraction be precipitation regeneration 10h in 10%～100% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained, at 38 ℃, carries out critical point CO under 1600psi
2be dried 50min, obtain having the catalysis material of aeroge matrix.
The dispersion that this test makes through step 1 approximately 0.35% TiO
2shown in SEM Fig. 5 of the ionic liquid of particle, visible particle is reunited mostly, is difficult for disperseing.
The composite aerogel forming after dry has the photocatalysis effect strengthening than former sharp titanium titanium dioxide, and under ultraviolet light, the efficiency of degradation of methylene blue has improved approximately 5%.
Claims (10)
1. a preparation method with the catalysis material of aeroge matrix, the preparation method who it is characterized in that having the catalysis material of aeroge matrix carries out according to the following steps:
One, by nano material, ionic liquid and the cellulosic mass ratio with photocatalytic activity, be (0.01～1): 100: (1～20) takes nano material, ionic liquid and the cellulose with photocatalytic activity;
Two, at room temperature the nano material with photocatalytic activity is joined in ionic liquid, dispersed after, then add cellulose, under the condition stirring, be warming up to 65～130 ℃ and keep 0.5～4h, obtain blend solution;
Three, it is in the mould of-30 ℃～25 ℃ that blend solution step 2 being obtained is poured temperature into, and after cooling 0.5h～20h, then to join mass fraction be precipitation regeneration in 10%～100% regenerated liquid, obtains plural gel;
Four, plural gel step 3 being obtained is dry, obtains having the catalysis material of aeroge matrix.
2. a kind of preparation method with the catalysis material of aeroge matrix according to claim 1, is characterized in that the nano material with photocatalytic activity in step 1 is nano-TiO
2, Sodium Titanate or metatitanic acid hydrogen salt.
3. a kind of preparation method with the catalysis material of aeroge matrix according to claim 1, is characterized in that the nano material with photocatalytic activity in step 1 is nanotube, nano wire, nano flower, nanometer sheet, nano particle or the mixed crystal material that is mixed with assorted element.
4. a kind of preparation method with the catalysis material of aeroge matrix according to claim 1, is characterized in that the ionic liquid in step 1 is chloro salt, carboxylic acids ionic liquid or the alkyl phosphate salt of dialkylimidazolium class ionic liquid, N-alkyl pyridine class ionic liquid, quaternary amines.
5. according to a kind of preparation method with the catalysis material of aeroge matrix described in claim 1,3 or 4, it is characterized in that in step 2, homodisperse method is for being dispersed in nano material in ionic liquid by the method that cooking machine is sheared or mortar grinds, jitter time is no more than 10min.
6. according to a kind of preparation method with the catalysis material of aeroge matrix described in claim 1,3 or 4, it is characterized in that in step 1, cellulose is holocellulose, wood-fibred, stalk fibre or coir fibre.
7. according to a kind of preparation method with the catalysis material of aeroge matrix described in claim 1,3 or 4, it is characterized in that nano material in step 1, ionic liquid and cellulosic mass ratio are 0.1: 100: 10.
8. according to a kind of preparation method with the catalysis material of aeroge matrix described in claim 1,3 or 4, it is characterized in that regenerated liquid in step 3 is any or the two kinds of mixed liquors in any proportion wherein in deionized water, acetone, dimethyl sulfoxide (DMSO), ethanol and cyclohexane.
9. according to a kind of preparation method with the catalysis material of aeroge matrix described in claim 1,3 or 4, it is characterized in that the critical point drying that the drying mode in step 4 is carbon dioxide, supercritical drying or the freeze drying of carbon dioxide.
10. a kind of preparation method with the catalysis material of aeroge matrix according to claim 9, the baking temperature that it is characterized in that the critical point drying mode of carbon dioxide is 35 ℃～40 ℃, be 30min～60min drying time; The baking temperature of the supercritical drying mode of carbon dioxide is 35 ℃～100 ℃, and be 2h～4h drying time; Cryodesiccated baking temperature is-30 ℃～-100 ℃, and be 5h～72h drying time.
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| CN107349965A (en) * | 2017-06-16 | 2017-11-17 | 中国科学院上海硅酸盐研究所 | A kind of adsorption photochemical catalysis hydrogel material and its application in the cooperative photocatalysis sewage production hydrogen of heavy metallic poison is reversed |
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