CN108031455B - A kind of preparation method of hollow porous micro sphere adsorbent - Google Patents
A kind of preparation method of hollow porous micro sphere adsorbent Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a kind of preparation methods of hollow porous micro sphere adsorbent, belong to environment-friendly function technical field of material.Using ZIF-8 nanoparticle as the stable particle of Pickering lotion, it is scattered in solution as water phase；Dodecane is as oil phase solvent, and crosslinking agent azodiisobutyronitrile, styrene and divinylbenzene mixing are as oily phase；Water phase, oil form stable Pickering lotion after mixing；Hollow porous micro sphere adsorbent is prepared using thermal booster reaction, and is applied to the adsorbing separation of Amoxicillin in aqueous solution.The product has big specific surface area and good stability, be conducive to the absorption to target molecule, it is attached to the porous ZIF-8 outside hollow microsphere and provides a large amount of adsorption site for material, stablize the ZIF-8 nanoparticle being attached on hollow microsphere and be more convenient for recycling than the ZIF-8 particle of discrete distribution.
Description
Technical field
The present invention relates to a kind of stable using class zeolitic imidazolate framework material ZIF-8 nanoparticle Pickering cream
The method that liquid polymerization prepares hollow porous micro sphere adsorbent belongs to environment-friendly function technical field of material.
Background technique
In recent years, antibiotic is largely used to the disease treatment of humans and animals, meanwhile, it is made an addition to asian treatment doses over long periods
Prevent disease in animal feed and promote growth of animal, plays important work in terms of ensureing human health and promoting animal husbandry development
With.But it is some studies have shown that the antibiotic of 85 % or more enters ecological environment in the form of raw medicine and metabolite, by one
Sequence of transformations is finally most of to be will be present in nature water body, in agricultural land soil, earth's surface and underground water and the ecosystem
Different kind organism generates harm, and induces and propagate drug-resistant bacteria caused by all kinds of antibiotic, generates threat to human health, simultaneously
The huge challenge that antibiotic in water body is reused at water resource.Therefore, in time in detection and processing environment water body
Antibiotic is necessary.
Currently used antibiotic treatment method has the methods of a filtering, biological treatment, electrochemistry, oxidation, but these sides
Method there are treatment effeciencies the disadvantages of low, preparatory culture microorganism is inconvenient, equipment is expensive or selectivity is not strong, it cannot make extensively
With.Pickering lotion is a kind of lotion for replacing surfactant to be formed with amphipathic solid particle.In recent years,
Pickering lotion is applied to numerous areas, and Pickering lotion due to characteristics such as its low cost, environmental protection and stability
Polymerization has been developed as the novel polymerization reaction of one kind to prepare organic/inorganic composite microsphere.Currently, Pickering lotion
In common inorganic particle have silica, clay, carbon nanotube, ferriferrous oxide particles etc., organic granular has lignin, poly-
Phenylethylene micro ball, attapulgite etc..Metal-organic framework materials (MOFs) are the material newly risen in recent years, the high-ratio surface having
The features such as long-pending, flexible structural adjustment and stability, enables it become the hot spot of new material research, class zeolite imidazole ester skeleton
Material (ZIFs) is the MOFs material with similar zeolite topological, the good, specific surface with thermal stability and chemical stability
The advantages that product is big, aperture is adjustable.In H2、CH4、CO2Nuisance separation absorption aspect in equal gas storage and transportations and solution, has good
Performance.But ZIFs nanoparticle receives ZIFs because its too small physical size is difficult to recycle in the solution in actual use
Rice corpuscles is rarely reported as the stable particle of Pickering lotion.As can then can using Pickering emulsion polymerization
The characteristics of giving full play to ZIFs material, and can effectively overcome the shortcomings of its hardly possible recycling.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for preparing hollow porous micro sphere adsorbent, to improve the absorption of product
And separating property.
In order to solve the above technical problems, the present invention prepares hollow porous micro sphere suction using Pickering emulsion polymerization
Attached dose.Wherein using ZIF-8 nano particle as stable particle, it is scattered in solution as water phase.Dodecane as oil phase solvent,
Crosslinking agent azodiisobutyronitrile, styrene and divinylbenzene mixing are as oily phase.Water phase, oil form stable after mixing
Pickering lotion.Hollow porous micro sphere adsorbent is prepared using thermal booster reaction, and is applied to Ah not in aqueous solution
The adsorbing separation in XiLin.The product has big specific surface area and good stability, is conducive to the absorption to target molecule, hollow
Spherical structure has stable physical structure, and external exposed ZIF-8 provides a large amount of adsorption site, and spherical structure
Recycling is easily facilitated compared to discrete nanometer ZIF-8 particle.Specific technical solution is as follows:
The technical solution adopted by the present invention is that:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to
Following step carries out:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to
Following step carries out:
(1) ZIF-8 nanoparticle is prepared, the Zn (NO of 0.59-0.70 g is taken3)2·6H2O is added to the distilled water of 40 ml
In, solution clarification is continued stirring until, solution A is obtained；According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O:2-
Methylimidazole is 1:(65-75) mass ratio take corresponding 2-methylimidazole to be added in distilled water, then continue stirring until 2-
Methylimidazole is fully dissolved in distilled water, obtains solution B；Obtained solution A and B are mixed, at room temperature
1000-3000 rpm stirs 1-3 h, finally obtained solution is centrifuged 15 min under the speed of 8000-10000 rpm, taken
The white crystal that is collected by centrifugation and with being centrifuged again after distilled water oscillation cleaning, is repeated 3 times；Obtained white crystal is in room temperature condition
Lower natural air drying, obtains ZIF-8 nanoparticle.
(2) it prepares ZIF-8 hollow porous micro sphere adsorbent: 0.15-0.25g ZIF-8 nanoparticle being taken to leach using ultrasound
In 10-15 ml distilled water, solution C is obtained, this is as water phase；0.0056-0.0090 g AIBN is dissolved in 0.14-0.18 g
In the mixture of styrene, 0.21-0.25 g divinylbenzene and 0.40-0.48 g dodecane, it is uniformly mixed and obtains solution D,
This is as oily phase；Jiang Shui, oil are mutually mixed, and are placed in a beaker, are utilized high speed homogenization device, under room temperature, 12500-16500
Rpm carries out shear treatment to mixture, and process continues 2-3 min, obtains pickering emulsion；Obtained pickering emulsion is placed in
In neck round bottom flask, it is equipped with condensing unit, leads to N2It is bubbled 15-30 min；338- is heated to the pickering emulsion in flask
348 K, and 16 h is kept to make its polymerization；Solution filtering after reaction, the white solid ethanol washing being obtained by filtration, washing lotion exist
Under 1000-1500 rpm be centrifuged 5-10 min, remove supernatant, the white solid after wash, repeat this operate 3 times with
On；By the white solid finally obtained in natural air drying under room temperature to get arrive hollow porous micro sphere adsorbent.
Technological merit of the invention: the product combination Pickering lotion and metal-organic framework materials have both the two
It is long, there is good absorption and separating property, and have significant adsorption effect to Amoxicillin.ZIF- in resulting product
8 are stabilized in tiny balloon surface, can come into full contact with the external world into water body, give full play to ZIF-8 high-specific surface area
Feature reaches maximum adsorption effect.The micro-sphere structure of formation is good, and performance is stablized, convenient for recycling.
Detailed description of the invention
Fig. 1 is the optical microscope photograph of Pickering lotion；Fig. 2,3 are respectively hollow microsphere in different zoom ratio
Under SEM figure, Fig. 4 is that the Xrd of ZIF-8 particle and hollow porous micro sphere adsorbent schemes.It is seen in fig. 1, that obtain
Pickering lotion is more stable, and drop is micron order (20 microns -100 microns).It can be seen that from Fig. 2, Fig. 3, after thermal polymerization, shape
At micro-sphere structure it is good, and Microsphere Size is consistent substantially with emulsion droplet, shows to be formed in preparation process
Pickering good emulsion stability；The porous microsphere surface of formation is coated with fine and close ZIF-8 nanoparticle, hollow structure sample
Product and expected consistent, experimental result ideal.From fig. 4, it can be seen that ZIF-8 nanoparticle and hollow porous micro sphere adsorbent (ZIF-8@
PS XRD diffraction maximum) is almost the same, but the peak intensity of hollow porous micro sphere adsorbent is relatively weak, this illustrates that adsorbent contains
Other non-crystal ingredients, mainly caused by the microballoon film of crosslinking ZIF-8 particle, result absolutely proves the adsorbent to be formed in figure
In only include ZIF-8 crystal, without other crystal grains.
Specific embodiment
Absorption property analysis test method as described in the above technical scheme specifically:
Adsorption test
Hollow porous micro sphere adsorbent (ZIF-8@PS) is added in the certain density Amoxicillin solution of 10 mL, is placed on
Certain time is vibrated in 298K, 308K constant temperature air bath shaker, investigates the initial concentration of Amoxicillin, different temperatures in test solution
And influence of the adsorption time variation to adsorbent absorption Amoxicillin；After saturation absorption, adsorbent is separated with inorganic filter membrane, is used
Unadsorbed Amoxicillin concentration can be obtained in the concentration of the derivative of Amoxicillin in ultraviolet specrophotometer measurement solution.And root
According to result calculate adsorption capacity (Q t , mmol g-1):
WhereinC 0 (mg L-1) andC t (mg L-1) it is the concentration for adsorbing front and back erythromycin respectively,V It (L) is test liquid
Product,m It (g) is adsorbent amount,MFor the molecular weight of Amoxicillin.
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
A method of preparing hollow porous adsorbent, it is characterised in that follow the steps below:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to
Following step carries out:
(1) ZIF-8 nanoparticle is prepared
Firstly, taking the Zn (NO of 0.59 g3)2·6H2O is added in the distilled water of 40 ml, continues stirring until solution clarification,
Obtain solution A；According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O:2- methylimidazole is the mass ratio of 1:70
It takes corresponding 2-methylimidazole to be added in distilled water, then continues stirring until 2-methylimidazole and be fully dissolved in distilled water,
Obtain solution B；Obtained solution A and B are mixed, 1000 rpm stir 1 h at room temperature, finally molten by what is obtained
Liquid is centrifuged 15 min under the speed of 8000 rpm, obtain the white crystal being centrifuged out and with after distilled water oscillation cleaning again from
The heart, repetitive cycling 3 times；Natural air drying can obtain ZIF-8 nanoparticle to obtained white crystal at room temperature.
(2) the hollow porous adsorbent of ZIF-8 is prepared
Firstly, 0.15 g ZIF-8 nanoparticle is taken to leach in 10 ml distilled water using ultrasound, solution C is obtained, this work
For water phase；0.0056g AIBN is dissolved in 0.14 g styrene, the mixture of 0.21 g divinylbenzene and 0.40 g dodecane
In, it is uniformly mixed and obtains solution D, this is as oily phase；Jiang Shui, oil are mutually mixed, and are placed in a beaker, using high speed homogenization device,
Under room temperature, 12500 rpm carry out shear treatment to mixture, and process continues 2 min, obtains pickering emulsion；It will obtain
Pickering emulsion be placed in neck round bottom flask, be equipped with condensing unit, lead to N2It is bubbled 15 min；To the pik woods cream in flask
Liquid is heated to 338 K, and 16 h is kept to enable its polymerization；The solution obtained after filtering reaction, and the white solid that will be obtained by filtration
It being washed with ethyl alcohol, the cleaning solution containing white solid is placed in a centrifuge, and 1000 rpm are centrifuged 5 min, supernatant is removed,
White solid after being washed repeats this operation 3 times or more；By the white solid finally obtained in natural wind under room temperature
It is dry, obtain hollow porous micro sphere adsorbent.
Embodiment 2:
A method of preparing hollow porous adsorbent, it is characterised in that follow the steps below:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to
Following step carries out:
(1) ZIF-8 nanoparticle is prepared
Firstly, taking the Zn (NO of 0.65 g3)2·6H2O is added in the distilled water of 40 ml, continues stirring until solution clarification,
Obtain solution A；According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O:2- methylimidazole is the mass ratio of 1:65
It takes corresponding 2-methylimidazole to be added in distilled water, then continues stirring until 2-methylimidazole and be fully dissolved in distilled water,
Obtain solution B；Obtained solution A and B are mixed, 2000 rpm stir 2 h at room temperature, finally molten by what is obtained
Liquid is centrifuged 15 min under the speed of 9000 rpm, obtain the white crystal being centrifuged out and with after distilled water oscillation cleaning again from
The heart, repetitive cycling 3 times；Natural air drying can obtain ZIF-8 nanoparticle to obtained white crystal at room temperature.
(2) ZIF-8 hollow porous micro sphere adsorbent is prepared
Firstly, 0.20 g ZIF-8 nanoparticle is taken to leach in 12 ml distilled water using ultrasound, solution C is obtained, this work
For water phase；0.0078 g AIBN is dissolved in 0.16 g styrene, the mixing of 0.23 g divinylbenzene and 0.44 g dodecane
It in object, is uniformly mixed and obtains solution D, this is as oily phase；Jiang Shui, oil are mutually mixed, and are placed in a beaker, are utilized high speed homogenization
Device, under room temperature, 14000 rpm carry out shear treatment to mixture, and process continues 2.5 min, obtains pickering emulsion；It will
Obtained pickering emulsion is placed in neck round bottom flask, is equipped with condensing unit, leads to N2It is bubbled 20 min；To the pik in flask
Woods lotion is heated to 343 K, and 16 h is kept to enable its polymerization；The solution obtained after filtering reaction, and the white that will be obtained by filtration
Solid is washed with ethyl alcohol, and the cleaning solution containing white solid is placed in a centrifuge, and 1200 rpm are centrifuged 8 min, is gone
Clear liquid, the white solid after being washed repeat this operation 3 times or more；By the white solid finally obtained under room temperature
Natural air drying can obtain hollow porous micro sphere adsorbent.
Embodiment 3:
A method of preparing hollow porous adsorbent, it is characterised in that follow the steps below:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to
Following step carries out:
(1) ZIF-8 nanoparticle is prepared
Firstly, taking the Zn (NO of 0.70 g3)2·6H2O is added in the distilled water of 40 ml, continues stirring until solution clarification,
Obtain solution A；According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O:2- methylimidazole is the mass ratio of 1:75
It takes corresponding 2-methylimidazole to be added in distilled water, then continues stirring until 2-methylimidazole and be fully dissolved in distilled water,
Obtain solution B；Obtained solution A and B are mixed, 3000 rpm stir 3 h at room temperature, finally molten by what is obtained
Liquid is centrifuged 15 min under the speed of 10000 rpm, obtain the white crystal being centrifuged out and with after distilled water oscillation cleaning again
Centrifugation, repetitive cycling 3 times；Natural air drying can obtain ZIF-8 nanoparticle to obtained white crystal at room temperature.
(2) it prepares ZIF-8 hollow porous micro sphere adsorbent: 0.25 g ZIF-8 nanoparticle being taken to leach using ultrasound in 15
In ml distilled water, solution C is obtained, this is as water phase；0.0090 g AIBN is dissolved in 0.18 g styrene, 0.25 g divinyl
It in the mixture of base benzene and 0.48 g dodecane, is uniformly mixed and obtains solution D, this is as oily phase；Jiang Shui, oil are mutually mixed,
It is placed in a beaker, using high speed homogenization device, under room temperature, 16500 rpm carry out shear treatment to mixture, and process continues 3
Min obtains pickering emulsion；Obtained pickering emulsion is placed in neck round bottom flask, condensing unit is equipped with, leads to N2It is bubbled
30 min；348 K are heated to the pickering emulsion in flask, and 16 h is kept to enable its polymerization；It is obtained after filtering reaction molten
Liquid, and the white solid being obtained by filtration is washed with ethyl alcohol, the cleaning solution containing white solid is placed in a centrifuge, and 1500
Rpm is centrifuged 10 min, removes supernatant, the white solid after being washed, and repeats this operation 3 times or more；By what is finally obtained
White solid can obtain hollow porous micro sphere adsorbent in natural air drying under room temperature.
Absorption property analysis test
(1) taking 20 mL initial concentrations is respectively 10,20,50,100,150,200,300 mg L-1Amoxicillin solution
It is added in conical flask, is separately added into the hollow porous micro sphere adsorbent that in 10 mg embodiments 1 prepared by the above method, test
Liquid is individually placed to after vibrating 12 h in the gas bath of 298 K, 308 K, with inorganic membrane filtration adsorbent, unadsorbed Amoxicillin
Molecular concentration is measured with ultraviolet-uisible spectrophotometer, and calculates adsorption capacity according to result.
The result shows that: saturated adsorption capacity of the hollow porous micro sphere adsorbent in 298 K is 0.2779 mmol g-1,
Saturated adsorption capacity when 308 K is 0.3268 mmol g-1.It can be seen that adsorbent adsorption effect becomes as temperature increases
It is good.
(2) taking 20 mL initial concentrations is 100 mg L-1Amoxicillin solution be added in conical flask, be separately added into 10
The hollow porous micro sphere adsorbent that in mg embodiment 1 prepared by the above method, test fluid is placed in the gas bath of 308 K oscillation 10,
20, after 30,60,120,180,240,360,480,600,720 min, with inorganic membrane filtration adsorbent, unadsorbed Ah not
XiLin molecular concentration is measured with ultraviolet-uisible spectrophotometer, and calculates adsorption capacity according to result.
The result shows that: magnetic molecularly imprinted and non-trace adsorbent has had reached equilibrium adsorption capacity in 60 min
78.99%, then progressively reach adsorption equilibrium after adsorbing 120-360 min, the balance of hollow porous micro sphere adsorbent when balance
Adsorbance is 0.1405 mmol g-1。
Claims (1)
1. a kind of preparation method of hollow porous micro sphere adsorbent, it is characterised in that follow the steps below:
The method that the stable Pickering emulsion polymerization of ZIF-8 nanoparticle prepares hollow porous micro sphere adsorbent, according to following
Step carries out:
(1) ZIF-8 nanoparticle is prepared, the Zn (NO of 0.59-0.70 g is taken3)2·6H2O is added in the distilled water of 40 ml, is held
Continuous stirring to solution is clarified, and solution A is obtained；According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O:2- methyl
Imidazoles is 1:(65-75) mass ratio take corresponding 2-methylimidazole to be added in distilled water, then continue stirring until 2- methyl
Imidazoles is fully dissolved in distilled water, obtains solution B；Obtained solution A and B are mixed, at room temperature 1000-
3000 rpm stir 1-3 h, and obtained solution is finally centrifuged 15 min under the speed of 8000-10000 rpm, and centrifugation is taken to receive
The white crystal of collection and with being centrifuged again after distilled water oscillation cleaning, is repeated 3 times；Obtained white crystal is natural at room temperature
It air-dries, obtains ZIF-8 nanoparticle；
(2) prepare ZIF-8 hollow porous micro sphere adsorbent: take 0.15-0.25g ZIF-8 nanoparticle using ultrasound leach in
In 10-15 ml distilled water, solution C is obtained, this is as water phase；0.0056-0.0090 g AIBN is dissolved in 0.14-0.18 g benzene
In the mixture of ethylene, 0.21-0.25 g divinylbenzene and 0.40-0.48 g dodecane, it is uniformly mixed and obtains solution D, this
As oily phase；Jiang Shui, oil are mutually mixed, and are placed in a beaker, are utilized high speed homogenization device, under room temperature, 12500-16500
Rpm carries out shear treatment to mixture, and process continues 2-3 min, obtains pickering emulsion；Obtained pickering emulsion is placed in
In neck round bottom flask, it is equipped with condensing unit, leads to N2It is bubbled 15-30 min；338- is heated to the pickering emulsion in flask
348 K, and 16 h is kept to make its polymerization；Solution filtering after reaction, the white solid ethanol washing being obtained by filtration, washing lotion exist
Under 1000-1500 rpm be centrifuged 5-10 min, remove supernatant, the white solid after wash, repeat this operate 3 times with
On；By the white solid finally obtained in natural air drying under room temperature to get arrive hollow porous micro sphere adsorbent.
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| CN109261141B (en) * | 2018-09-06 | 2021-11-02 | 华南协同创新研究院 | ZIF-8 nanocrystal and preparation method and application thereof |
| CN110252264A (en) * | 2019-07-01 | 2019-09-20 | 河南城建学院 | A kind of cocoanut shell biomass carbon microsphere surface imprinted material and its preparation method and application |
| CN110465251B (en) * | 2019-09-11 | 2022-03-01 | 成都工业学院 | Long-acting repairing type double-layer microcapsule |
| CN110776662B (en) * | 2019-11-19 | 2022-02-11 | 常州大学 | Preparation method and application of modified brominated butyl rubber porous material |
| CN112657475B (en) * | 2020-12-02 | 2023-09-26 | 常州大学 | Boron affinity functionalized microsphere adsorbent and preparation method and application thereof |
| CN113337497B (en) * | 2021-05-25 | 2023-04-25 | 天津大学 | Preparation and application of Pickering microcapsule based on metal organic framework material embedded carbonic anhydrase |
| CN114702765B (en) * | 2022-06-07 | 2022-08-26 | 上海科进生物技术有限公司 | Modified nano-microsphere, PC/PET composite material and preparation method thereof |
| CN115920971A (en) * | 2022-12-27 | 2023-04-07 | 辽宁大学 | ZIF-8 pickering emulsion based on metal organic framework and preparation method and application thereof |
| CN116059981B (en) * | 2023-01-13 | 2023-07-14 | 北京理工大学唐山研究院 | Multistage Kong Shuixiang adsorption film and preparation method and application thereof based on template method |
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| CN103788308B (en) * | 2014-01-20 | 2016-01-27 | 江苏大学 | The method of macropore trace sorbent material is prepared in a kind of Pickering letex polymerization |
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