CN109967064A - It is a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst - Google Patents
It is a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst Download PDFInfo
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- CN109967064A CN109967064A CN201910338262.1A CN201910338262A CN109967064A CN 109967064 A CN109967064 A CN 109967064A CN 201910338262 A CN201910338262 A CN 201910338262A CN 109967064 A CN109967064 A CN 109967064A
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000005018 casein Substances 0.000 title claims abstract description 44
- 235000021240 caseins Nutrition 0.000 title claims abstract description 43
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006210 lotion Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- LPOMRUVHKIQEQT-KYJUHHDHSA-N (5S)-5-benzyl-1-[4-[(2S)-5,6-dioxo-1-(2-phenylethyl)piperazin-2-yl]butyl]-4-[2-(4-hydroxyphenyl)ethyl]piperazine-2,3-dione Chemical compound C1=CC(O)=CC=C1CCN1C(=O)C(=O)N(CCCC[C@@H]2N(C(=O)C(=O)NC2)CCC=2C=CC=CC=2)C[C@@H]1CC1=CC=CC=C1 LPOMRUVHKIQEQT-KYJUHHDHSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
Abstract
The present invention relates to a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst.The technical solution of the present invention is as follows: be modified first with caprolactam to casein, obtain that stability is good and the modified Casein lotion of size uniformity, is then slowly added to nano-TiO thereto2Presoma is simultaneously ultrasonically treated gained mixed liquor, injects in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle carry out hydro-thermal reaction later.Using the hydrophobic hole of multistage inside modified Casein micella to nano-TiO2Presoma loaded, thus Situ Hydrothermal growth obtain porous spherical TiO2Nanocatalyst.The present invention, which can be made, has both high photocatalysis efficiency and the catalysis material weaker to substrate degradation, is expected to be used for the photocatalytic degradation of dirty organic pollutants and constructing for automatic cleaning coating.
Description
Technical field
The invention belongs to a kind of preparation methods of photochemical catalyst, and in particular to a kind of using natural casein as the porous ball of template
Shape TiO2The preparation method of nanocatalyst.
Background technique
Environment and the energy are the major issues of 21 century facing mankind.Photocatalysis can directly using solar energy as light source come
Drive catalytic degradation, it has also become a kind of ideal and environmental protection environmental pollution treatment technology.In numerous catalyst, nano-TiO2
Cause the extensive concern of people because its high activity, low cost, stability are good.Up to now, nano-TiO2As photochemical catalyst
It has been widely used in sewage treatment and automatic cleaning coating field.However, nano-TiO2Photochemical catalyst exists in use
The low defect of photocatalysis efficiency, and be applied to easily generate degradation to substrate itself when automatic cleaning coating, to its practical application
Effect has an immense impact on (T. Adachi, S. S. Latthe, S. W. Gosavi, et al. Applied
Surface Science, 2018,458:917-923).Therefore exploitation has high photocatalysis efficiency and can effectively avoid to base
The novel photocatalysis material of the degradation of material is very urgent.
Casein is a kind of native protein extracted from milk.In the solution, casein exists in the form of micella, and micella
There is multistage hydrophobic region in inside, external hydrophilic region can play emulsification (C. G. Kruif, C. Holt. in water
Springer US:Advanced Dairy Chemistry-1 Proteins, 2003:233-276).However, natural junket
Plain micellar structure is complicated and appearance and size is irregular, research shows that: the size through the modified gained casein micella of caprolactam is more
Add uniform and stability preferable, if preparing TiO using it as template2Nanoparticle, then being expected to obtain has multi-stage pore structure
Nano-TiO2, thus increase nano-TiO2Surface area, improve its photocatalysis efficiency.In addition, gained nano-TiO2It is being applied to base
The presence of casein template can slow down TiO to a certain extent when material surface2Degradation of the catalyst to substrate, to be carried out to substrate
Protection.Up to now, porous spherical TiO is prepared by template of natural casein2The research of nanocatalyst is also rarely reported.
Summary of the invention
It is a kind of using natural casein as the porous spherical TiO of template the invention aims to provide2The system of nanocatalyst
Preparation Method obtains having both high photocatalysis efficiency and the catalysis material weaker to substrate degradation, is expected to be used for having in sewage
The photocatalytic degradation of machine pollutant and constructing for automatic cleaning coating.
In order to achieve the above object, a kind of natural casein provided by the invention is the porous spherical TiO of template2Nano-catalytic
The preparation method of agent is modified casein first with caprolactam, obtains that stability is good and the modified Casein of size uniformity
Then lotion is slowly added to nano-TiO thereto2Presoma is simultaneously ultrasonically treated gained mixed liquor, injects poly- four later
Hydro-thermal reaction is carried out in vinyl fluoride hydrothermal reaction kettle.Using the hydrophobic hole of multistage inside modified Casein micella to nano-TiO2's
Presoma is loaded, and thus Situ Hydrothermal growth obtains porous spherical TiO2Nanocatalyst.
Above-mentioned natural casein is the porous spherical TiO of template2The preparation method of nanocatalyst specifically includes following step
It is rapid:
Step 1: the aqueous acetic acid that configuration pH is 2~3 is poured into three-necked flask, casein powder is then added and carries out
The mass volume ratio of dissolution, casein and aqueous acetic acid is (6~19mg): (60~140mL), and solution temperature is 30~40 DEG C,
5~12h of stirring and dissolving is continued using churned mechanically mode, mixing speed is 100~200r/min, is warming up to 82~85 later
DEG C, and caprolactam 2~5h of isothermal reaction is added, the mass ratio of caprolactam and casein is 2~6:1~5, is surpassed after completion of the reaction
15~60min of sonication obtains caprolactam modified Casein lotion；
Step 2: above-mentioned modified Casein lotion being poured into beaker and continues to stir, and mixing speed is 300~600r/min, room
By TiO under temperature2Presoma titanium tetrachloride, butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2
The volume ratio of presoma is 100~300:1~10,30~80min is persistently stirred after being added dropwise, and inject polytetrafluoroethylene (PTFE) water
Hydro-thermal reaction is carried out in thermal response kettle, hydrothermal temperature is 200~300 DEG C, and the reaction time is 5~20h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and washs 3~6 respectively using deionized water and ethyl alcohol
It is secondary, it will be dried, finally obtained using natural casein as the porous ball of template in the baking oven for being deposited in 40~80 DEG C after washing
Shape TiO2Nanocatalyst.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst, is had both
High catalytic efficiency and the catalysis material weaker to the degradation of substrate, and preparation process is simple.Gained porous spherical TiO2
Nanocatalyst can be used for the photocatalytic degradation of dirty organic pollutants and constructing for automatic cleaning coating, in weaving, leather, too
Positive energy device, sewage treatment field have a good application prospect.
Detailed description of the invention
Fig. 1 is porous spherical TiO made from embodiment 12The SEM of nanocatalyst schemes.
Fig. 2 is porous spherical TiO made from embodiment 22Nanocatalyst imitates the degradation of dye, rhodamine B in aqueous solution
Fruit.
Fig. 3 is porous spherical TiO made from embodiment 3 under ultraviolet light2Nanocatalyst treated cotton fabric matter
Amount variation.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but embodiments of the present invention include
But it is not limited to the range of following embodiment expression.
It is according to the present invention a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst,
Specifically realized by following steps:
Step 1: the aqueous acetic acid that configuration pH is 2~3 is poured into three-necked flask, casein powder is then added and carries out
The mass volume ratio of dissolution, casein and aqueous acetic acid is (6~19mg): (60~140mL), and solution temperature is 30~40 DEG C,
5~12h of stirring and dissolving is continued using churned mechanically mode, mixing speed is 100~200r/min, is warming up to 82~85 later
DEG C, and caprolactam 2~5h of isothermal reaction is added, the mass ratio of caprolactam and casein is (2~6): (1~5), end of reaction
It is ultrasonically treated 15~60min afterwards, obtains caprolactam modified Casein lotion；
Step 2: above-mentioned modified Casein lotion being poured into beaker and continues to stir, and mixing speed is 300~600r/min, room
By TiO under temperature2Presoma titanium tetrachloride, butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2
The volume ratio of presoma is (100~300mL): (1~10mL) persistently stirs 30~80min after being added dropwise, and injects poly- four
Hydro-thermal reaction is carried out in vinyl fluoride hydrothermal reaction kettle, hydrothermal temperature is 200~300 DEG C, and the reaction time is 5~20h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and washs 3~6 respectively using deionized water and ethyl alcohol
It is secondary, it will be dried, finally obtained using natural casein as the porous ball of template in the baking oven for being deposited in 40~80 DEG C after washing
Shape TiO2Nanocatalyst.
Gained porous spherical TiO of the invention2The size uniformity and size tunable of nanocatalyst, can be anti-by changing hydro-thermal
Temperature and time is answered to obtain porous spherical TiO of the partial size at 0.5~5 μm2Nanocatalyst.
Embodiment 1
Step 1: the aqueous acetic acid that configuration pH is 2 is poured into three-necked flask, it is molten that the progress of casein powder is then added
The mass volume ratio of solution, casein and aqueous acetic acid is 7mg:80mL, and solution temperature is 40 DEG C, is held using churned mechanically mode
Continuous stirring and dissolving 10h, mixing speed 150r/min is warming up to 90 DEG C later, and caprolactam isothermal reaction 3h is added, in oneself
The mass ratio of amide and casein is 5:3, is ultrasonically treated 30min after completion of the reaction, obtains caprolactam modified Casein lotion；
Step 2: above-mentioned modified Casein lotion being poured into beaker and continues to stir, mixing speed 500r/min, at room temperature will
TiO2Presoma titanium tetrachloride, butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2Presoma
Volume ratio be 200mL:6mL, 60min is persistently stirred after being added dropwise, and inject in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and carry out
Hydro-thermal reaction, hydrothermal temperature are 250 DEG C, reaction time 10h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and is washed respectively 3 times using deionized water and ethyl alcohol,
It will be dried in the baking oven for being deposited in 50 DEG C after washing, finally obtain the porous spherical TiO using natural casein as template2It receives
Rice catalyst.
Fig. 1 is TiO obtained by embodiment 12The SEM photograph of nanocatalyst.It will be seen from figure 1 that utilizing natural junket
Plain micella is the TiO of template preparation2Nanocatalyst glomeration, and there are multi-stage pore structures on surface.
Embodiment 2
Step 1: the aqueous acetic acid that configuration pH is 1.5 is poured into three-necked flask, casein powder is then added and carries out
The mass volume ratio of dissolution, casein and aqueous acetic acid is 19mg:140mL, and solution temperature is 35 DEG C, and use is churned mechanically
Mode continues stirring and dissolving 8h, and mixing speed 200r/min is warming up to 85 DEG C later, and caprolactam isothermal reaction is added
The mass ratio of 5h, caprolactam and casein is 5:2, is ultrasonically treated 60min after completion of the reaction, obtains caprolactam modified Casein cream
Liquid；
Step 2: above-mentioned modified Casein milk solution being poured into beaker and continues to stir, mixing speed 600r/min, at room temperature
By TiO2Presoma titanium tetrachloride, butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2Forerunner
The volume ratio of body be 150mL:7mL, 40min is persistently stirred after being added dropwise, and inject in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle into
Row hydro-thermal reaction, hydrothermal temperature are 300 DEG C, reaction time 15h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and is washed respectively 5 times using deionized water and ethyl alcohol,
It will be dried in the baking oven for being deposited in 80 DEG C after washing, finally obtain the porous spherical TiO using natural casein as template2It receives
Rice catalyst.
Fig. 2 is 2 gained porous spherical TiO of embodiment2Nanocatalyst imitates the degradation of dye, rhodamine B in aqueous solution
Fruit.Figure it is seen that by porous spherical TiO2After rhodamine B solution is added in nanocatalyst, with time of ultraviolet irradiation
Extend, catalyst is gradually increased the degradation efficiency of rhodamine B, and after irradiating 10h, the rhodamine B in solution is almost dropped completely
Solution.
Embodiment 3
Step 1: the aqueous acetic acid that configuration pH is 2.5 is poured into three-necked flask, casein powder is then added and carries out
The mass volume ratio of dissolution, casein and aqueous acetic acid is 12mg:100mL, and solution temperature is 40 DEG C, using churned mechanically side
Formula continues stirring and dissolving 5h, and mixing speed 100r/min is warming up to 85 DEG C later, and caprolactam isothermal reaction 2h is added,
The mass ratio of caprolactam and casein is 2:1, is ultrasonically treated 15min after completion of the reaction, obtains caprolactam modified Casein lotion；
Step 2: above-mentioned modified Casein solution being poured into beaker and continues to stir, mixing speed 350r/min, at room temperature will
TiO2Presoma titanium tetrachloride, butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2Presoma
Volume ratio be 250mL:3mL, 60min is persistently stirred after being added dropwise, and inject in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and carry out
Hydro-thermal reaction, hydrothermal temperature are 210 DEG C, reaction time 8h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and is washed respectively 4 times using deionized water and ethyl alcohol,
It will be dried in the baking oven for being deposited in 65 DEG C after washing, finally obtain the porous spherical TiO using natural casein as template2It receives
Rice catalyst.
Fig. 3 is 3 gained porous spherical TiO of embodiment2Nanocatalyst treated cotton fabric is under ultraviolet light
Mass change.From figure 3, it can be seen that under ultraviolet light irradiation, through porous spherical TiO2Nanocatalyst treated cotton fabric
Mass change is little, this shows gained TiO2Nanocatalyst makees the catalytic degradation of cotton fabric itself after being applied to cotton fabric
With weaker.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (4)
1. a kind of using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst, first with caprolactam
Casein is modified, modified Casein lotion is obtained, is then slowly added to nano-TiO thereto2Presoma simultaneously mixes gained
Liquid is ultrasonically treated, and injects in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle carry out hydro-thermal reaction later.
2. according to claim 1 using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst,
It is characterized in that:
Specifically includes the following steps:
Step 1: the aqueous acetic acid that configuration pH is 2~3 is poured into three-necked flask, casein powder is then added and carries out
The mass volume ratio of dissolution, casein and aqueous acetic acid is 6~19mg:60~140mL, and solution temperature is 30~40 DEG C, is continued
5~12h of stirring and dissolving is warming up to 82~85 DEG C later, and caprolactam 2~5h of isothermal reaction, caprolactam and casein is added
Mass ratio be 2~6:1~5, after completion of the reaction be ultrasonically treated 15~60min, obtain caprolactam modified Casein lotion；
Step 2: above-mentioned modified Casein lotion is poured into beaker and continues to stir, at room temperature by TiO2Presoma titanium tetrachloride,
Butyl titanate or titanium sulfate are added to modified Casein lotion, modified Casein lotion and TiO2The volume ratio of presoma be 100~
30~80min is persistently stirred in 300:1~10 after being added dropwise, and it is anti-to inject progress hydro-thermal in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
It answers, hydrothermal temperature is 200~300 DEG C, and the reaction time is 5~20h；
Step 3: the product that above-mentioned reaction is obtained carries out centrifugal treating, and washs 3~6 respectively using deionized water and ethyl alcohol
It is secondary, it will be dried, finally obtained using natural casein as the porous ball of template in the baking oven for being deposited in 40~80 DEG C after washing
Shape TiO2Nanocatalyst.
3. according to claim 2 using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst,
It is characterized in that:
In the step 1, mixing speed is 100~200r/min, is mechanical stirring.
4. according to claim 3 using natural casein as the porous spherical TiO of template2The preparation method of nanocatalyst,
Be characterized in that: in the step 2, mixing speed is 300~600r/min.
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| CN112206833A (en) * | 2020-10-19 | 2021-01-12 | 陕西科技大学 | Hollow titanium dioxide @ MIL-101 composite nano microsphere and preparation method and application thereof |
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