CN108031455A - 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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- CN108031455A CN108031455A CN201711396117.6A CN201711396117A CN108031455A CN 108031455 A CN108031455 A CN 108031455A CN 201711396117 A CN201711396117 A CN 201711396117A CN 108031455 A CN108031455 A CN 108031455A
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- 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
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract
The invention discloses a kind of preparation method of hollow porous micro sphere adsorbent, belongs to environment-friendly function technical field of material.By the use of 8 nano-particles of ZIF as the stable particle of Pickering lotions, it is scattered in solution and is used as water phase.Dodecane is used as oil phase as oil phase solvent, crosslinking agent azodiisobutyronitrile, styrene and vinyl benzene mixing.Stable Pickering lotions are formed after water phase, oil phase 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 substantial amounts of adsorption site for material, stablizes 8 nano-particles of ZIF being attached on hollow microsphere and be more convenient for recycling than 8 particles of ZIF of discrete distribution.
Description
Technical field
The present invention relates to a kind of Pickering breasts stablized using class zeolitic imidazolate framework material ZIF-8 nano-particles
The method that liquid polymerization prepares hollow porous micro sphere adsorbent, belongs to environment-friendly function technical field of material.
Background technology
In recent years, antibiotic is largely used to the disease treatment of humans and animals, meanwhile, made an addition to asian treatment doses over long periods
Prevention disease and promotion growth of animal in animal feed, important work has been played in terms of ensureing human health and promoting animal husbandry development
With.But some researchs show, more than 85% antibiotic enters ecological environment in the form of active compound 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 produces harm, and induces and propagate drug-resistant bacteria caused by all kinds of antibiotic, produces threat to human health, at the same time
The huge challenge that antibiotic in water body is reused into water resource.Therefore, in time in detection and processing environment water body
Antibiotic is necessary.
Currently used antibiotic treatment method has the methods of filtering, biological treatment, electrochemistry, oxidation, but these sides
Method cannot make extensively there are the shortcomings for the treatment of effeciency is low, advance culture microorganism is inconvenient, equipment is expensive or selectivity is not strong
With.Pickering lotions are a kind of lotions for replacing surfactant to be formed with amphipathic solid particle.In recent years,
Pickering lotions are applied to numerous areas, and Pickering lotions due to characteristics such as its low cost, environmental protection and stability
Polymerization has been developed as a kind of new polymerisation to prepare organic/inorganic complex microsphere.At present, Pickering lotions
In common inorganic particle have silica, clay, carbon nanotubes, ferriferrous oxide particles etc., organic granular has lignin, poly-
Phenylethylene micro ball, attapulgite etc..Metal-organic framework materials (MOFs) are the materials newly risen in recent years, the high-ratio surface having
The features such as long-pending, flexible structural adjustment and stability, makes it become the hot spot of new material research, class zeolite imidazole ester skeleton
Material (ZIFs) is the MOFs materials with similar zeolite topological, with heat endurance and chemical stability are good, compare surface
The advantages that product is big, aperture is adjustable.In H2、CH4、CO2In terms of Deng the nuisance separation absorption in gas storage and transportation and solution, have good
Performance.But ZIFs nano-particles receive 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 lotions.As can using Pickering emulsion polymerizations, then can
The characteristics of giving full play to ZIFs materials, and can effectively overcome the shortcomings of its hardly possible recycling.
The content of the invention
It is an object of the invention to provide a kind of method for preparing hollow porous micro sphere adsorbent, to improve the absorption of product
And separating property.
Inhaled in order to solve the above technical problems, the present invention prepares hollow porous micro sphere using Pickering emulsion polymerizations
Attached dose.Wherein using ZIF-8 nano particles as stable particle, it is scattered in solution and is used as water phase.Dodecane as oil phase solvent,
Crosslinking agent azodiisobutyronitrile, styrene and vinyl benzene mixing are used as oil phase.Stabilization is formed after water phase, oil phase mixing
Pickering lotions.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 arrangement, and exterior exposed ZIF-8 provides substantial amounts of adsorption site, and spherical structure
Recycling is easily facilitated compared to discrete nanometer ZIF-8 particles.Concrete technical scheme is as follows：
The technical solution adopted by the present invention is：
The method that the Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to
Following step carries out：
The method that the Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to
Following step carries out：
(1) ZIF-8 nano-particles are prepared, take the Zn (NO of 0.59-0.70g3)2·6H2O is added in the distilled water of 40ml,
Solution clarification is continued stirring until, obtains solution A.According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O：2- first
Base imidazoles is 1：The mass ratio of (65-75) takes corresponding 2-methylimidazole to be added in distilled water, then continues stirring until 2- first
Base imidazoles is fully dissolved in distilled water, obtains solution B.Obtained solution A and B are mixed, at ambient temperature 1000-
3000rpm stirs 1-3h, and obtained solution finally is centrifuged 15min under the speed of 8000-10000rpm, takes what is be collected by centrifugation
White crystal and with being centrifuged again after distilled water oscillation cleaning, is repeated 3 times.Obtained white crystal natural wind at ambient temperature
It is dry, obtain ZIF-8 nano-particles.
(2) ZIF-8 hollow porous micro sphere adsorbents are prepared：0.15-0.25g ZIF-8 nano-particles are taken to be leached using ultrasound
In 10-15ml distilled water, solution C is obtained, this is as water phase.0.0056-0.0090g AIBN are dissolved in 0.14-0.18g benzene
In the mixture of ethene, 0.21-0.25g vinyl benzenes and 0.40-0.48g dodecanes, it is uniformly mixed and obtains solution D, this conduct
Oil phase.Water, oil phase are mixed, are placed in beaker.Utilize high speed homogenization device, under room temperature, 12500-16500rpm pairs
Mixture carries out shear treatment, and process continues 2-3min.Obtain pickering emulsion.Obtained pickering emulsion is placed in double neck circles
In the flask of bottom, condensing unit is equipped with, leads to N2Bubbling 15-30min.338-348K is heated to the pickering emulsion in flask, and
16h is kept to make its polymerization.Solution filtering after reaction, the white solid being obtained by filtration are washed with ethanol, and washing lotion is in 1000-
5-10min is centrifuged under 1500rpm, removes supernatant, the white solid after being washed, repeats this operation more than 3 times.Will be last
Obtained white solid obtains hollow porous micro sphere adsorbent in natural air drying under room temperature.
The technological merit of the present invention：The product combination Pickering lotions and metal-organic framework materials, have both concurrently it
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 be come into full contact with into water body with the external world, give full play to ZIF-8 high-specific surface areas
Feature, reaches maximum adsorption effect.The micro-sphere structure of formation is good, and performance is stablized, easy to recycle.
Brief description of the drawings
Fig. 1 is the optical microscope photograph of Pickering lotions；Fig. 2,3 respectively hollow microspheres are in different zoom ratio
Under SEM figures, Fig. 4 is that the Xrd of ZIF-8 particles and hollow porous micro sphere adsorbent schemes.It is seen in fig. 1, that obtain
Pickering lotions are relatively stablized, and drop is micron order (20 microns -100 microns).It can be seen that from Fig. 2, Fig. 3, after thermal polymerization, shape
Into micro-sphere structure it is good, and Microsphere Size is consistent substantially with emulsion droplet, shows what is formed in preparation process
Pickering good emulsion stabilities；The porous microsphere surface of formation is coated with the ZIF-8 nano-particles of densification, hollow structure sample
For product with expected consistent, experimental result is preferable.From fig. 4, it can be seen that ZIF-8 nano-particles and hollow porous micro sphere adsorbent (ZIF-8@
PS XRD diffraction maximums) are basically identical, but the peak intensity of hollow porous micro sphere adsorbent is relatively weak, this explanation adsorbent contains
Other non-crystal components, are mainly crosslinked caused by the microballoon film of ZIF-8 particles, result absolutely proves the adsorbent to be formed in figure
In only include ZIF-8 crystal, without other crystal grains.
Embodiment
Absorption property analysis test method described in above-mentioned technical proposal is specially：
Adsorption test
Hollow porous micro sphere adsorbent (ZIF-8@PS) is added in the certain density Amoxicillin solution of 10mL, is placed on
Certain time is vibrated in 298K, 308K constant temperature gas bath shaking table, investigates the initial concentration of Amoxicillin, different temperatures in test solution
And influence of the adsorption time change to adsorbent absorption Amoxicillin；After saturation absorption, adsorbent is separated with inorganic filter membrane, is used
The concentration of the derivative of Amoxicillin can obtain unadsorbed Amoxicillin concentration in ultraviolet specrophotometer measurement solution.And root
Adsorption capacity (Q is calculated according to resultt, mmol g-1)：
Wherein C0(mg L-1) and Ct(mg L-1) be respectively erythromycin before and after absorption concentration, V (L) is test fluid volume, m
(g) it is adsorbent amount, M is the molecular weight of Amoxicillin.
With reference to specific implementation example, the present invention will be further described.
Embodiment 1：
A kind of method for preparing hollow porous adsorbent, it is characterised in that follow the steps below：
The method that the Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to
Following step carries out：
(1) ZIF-8 nano-particles are prepared
First, the Zn (NO of 0.59g are taken3)2·6H2O is added in the distilled water of 40ml, is continued stirring until solution clarification, is obtained
To solution A.According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O：2-methylimidazole is 1：70 mass ratio takes
Corresponding 2-methylimidazole is added in distilled water, is then continued stirring until 2-methylimidazole and is fully dissolved in distilled water, obtains
To solution B.Obtained solution A and B are mixed, 1000rpm stirs 1h at ambient temperature, and finally obtained solution exists
15min is centrifuged under the speed of 8000rpm, obtains the white crystal that is centrifuged out and with being centrifuged again after distilled water oscillation cleaning, weight
Circulate 3 times again.Natural air drying can obtain ZIF-8 nano-particles to obtained white crystal at ambient temperature.
(2) the hollow porous adsorbents of ZIF-8 are prepared
First, take 0.15g ZIF-8 nano-particles to be leached using ultrasound in 10ml distilled water, obtain solution C, this conduct
Water phase.0.0056g AIBN are dissolved in 0.14g styrene, in the mixture of 0.21g vinyl benzenes and 0.40g dodecanes, mixing
Solution D uniformly is obtained, this is as oil phase.Water, oil phase are mixed, are placed in beaker.Utilize high speed homogenization device, room temperature condition
Under, 12500rpm carries out shear treatment to mixture, and process continues 2min.Obtain pickering emulsion.By obtained pik woods breast
Liquid is placed in neck round bottom flask, is equipped with condensing unit, leads to N2Bubbling 15min.Pickering emulsion in flask is heated to
338K, and keep 16h to make its polymerization.The solution obtained after filtering reaction, and the white solid being obtained by filtration is carried out with ethanol
Washing, the cleaning solution containing white solid are placed in a centrifuge, and 1000rpm centrifugation 5min, remove supernatant, after being washed
White solid, repeats this operation more than 3 times.By the white solid finally obtained in natural air drying under room temperature, obtain hollow
Porous microsphere sorbent.
Embodiment 2：
A kind of method for preparing hollow porous adsorbent, it is characterised in that follow the steps below：
The method that the Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to
Following step carries out：
(1) ZIF-8 nano-particles are prepared
First, the Zn (NO of 0.65g are taken3)2·6H2O is added in the distilled water of 40ml, is continued stirring until solution clarification, is obtained
To solution A.According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O：2-methylimidazole is 1：65 mass ratio takes
Corresponding 2-methylimidazole is added in distilled water, is then continued stirring until 2-methylimidazole and is fully dissolved in distilled water, obtains
To solution B.Obtained solution A and B are mixed, 2000rpm stirs 2h at ambient temperature, and finally obtained solution exists
15min is centrifuged under the speed of 9000rpm, obtains the white crystal that is centrifuged out and with being centrifuged again after distilled water oscillation cleaning, weight
Circulate 3 times again.Natural air drying can obtain ZIF-8 nano-particles to obtained white crystal at ambient temperature.
(2) ZIF-8 hollow porous micro sphere adsorbents are prepared
First, take 0.20g ZIF-8 nano-particles to be leached using ultrasound in 12ml distilled water, obtain solution C, this conduct
Water phase.0.0078g AIBN are dissolved in 0.16g styrene, in the mixture of 0.23g vinyl benzenes and 0.44g dodecanes, mixing
Solution D uniformly is obtained, this is as oil phase.Water, oil phase are mixed, are placed in beaker.Utilize high speed homogenization device, room temperature condition
Under, 14000rpm carries out shear treatment to mixture, and process continues 2.5min.Obtain pickering emulsion.The pik woods that will be obtained
Lotion is placed in neck round bottom flask, is equipped with condensing unit, leads to N2Bubbling 20min.Pickering emulsion in flask is heated to
343K, and keep 16h to make its polymerization.The solution obtained after filtering reaction, and the white solid being obtained by filtration is carried out with ethanol
Washing, the cleaning solution containing white solid are placed in a centrifuge, and 1200rpm centrifugation 8min, remove supernatant, after being washed
White solid, repeats this operation more than 3 times.By the white solid finally obtained in natural air drying under room temperature, can obtain
Hollow porous micro sphere adsorbent.
Embodiment 3：
A kind of method for preparing hollow porous adsorbent, it is characterised in that follow the steps below：
The method that the Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to
Following step carries out：
(1) ZIF-8 nano-particles are prepared
First, the Zn (NO of 0.70g are taken3)2·6H2O is added in the distilled water of 40ml, is continued stirring until solution clarification, is obtained
To solution A.According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O：2-methylimidazole is 1：75 mass ratio takes
Corresponding 2-methylimidazole is added in distilled water, is then continued stirring until 2-methylimidazole and is fully dissolved in distilled water, obtains
To solution B.Obtained solution A and B are mixed, 3000rpm stirs 3h at ambient temperature, and finally obtained solution exists
15min is centrifuged under the speed of 10000rpm, obtains the white crystal that is centrifuged out and with being centrifuged again after distilled water oscillation cleaning, weight
Circulate 3 times again.Natural air drying can obtain ZIF-8 nano-particles to obtained white crystal at ambient temperature.
(2) ZIF-8 hollow porous micro sphere adsorbents are prepared：Take 0.25g ZIF-8 nano-particles using ultrasound leach in
In 15ml distilled water, solution C is obtained, this is as water phase.0.0090g AIBN are dissolved in 0.18g styrene, 0.25g vinyl benzenes
In the mixture of 0.48g dodecanes, it is uniformly mixed and obtains solution D, this is as oil phase.Water, oil phase are mixed, are placed in burning
In cup.Using high speed homogenization device, under room temperature, 16500rpm carries out shear treatment to mixture, and process continues 3min.Obtain
Pickering emulsion.Obtained pickering emulsion is placed in neck round bottom flask, is equipped with condensing unit, leads to N2Bubbling 30min.It is right
Pickering emulsion in flask is heated to 348K, and keeps 16h to make its polymerization.The solution obtained after filtering reaction, and will filtering
Obtained white solid is washed with ethanol, and the cleaning solution containing white solid is placed in a centrifuge, 1500rpm centrifugations
10min, removes supernatant, the white solid after being washed, and repeats this operation more than 3 times.The white solid that will be finally obtained
In natural air drying under room temperature, hollow porous micro sphere adsorbent can be obtained.
Absorption property analysis test
(1) to take 20mL initial concentrations be respectively 10,20,50,100,150,200,300mg L-1Amoxicillin solution add
Enter into conical flask, be separately added into the hollow porous micro sphere adsorbent that in 10mg embodiments 1 prepared by the above method, test fluid point
It is not placed on after vibrating 12h in the gas bath of 298K, 308K, it is dense with inorganic membrane filtration adsorbent, unadsorbed Amoxicillin molecule
Degree 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 298K is 0.2779mmol g-1,308K
When saturated adsorption capacity be 0.3268mmol g-1.As can be seen here as temperature raises, adsorbent adsorption effect improves.
(2) it is 100mg L to take 20mL initial concentrations-1Amoxicillin solution be added in conical flask, be separately added into 10mg
The hollow porous micro sphere adsorbent that in embodiment 1 prepared by the above method, test fluid is placed in the gas bath of 308K vibration 10,20,
30th, 60,120,180,240,360,480,600, after 720min, 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：Magnetic molecularly imprinted and non-trace adsorbent has had reached equilibrium adsorption capacity in 60min
78.99%, then progressively reach adsorption equilibrium after 120-360min is adsorbed, the balance of hollow porous micro sphere adsorbent during balance
Adsorbance is 0.1405mmol 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 Pickering emulsion polymerizations that ZIF-8 nano-particles are stablized prepare hollow porous micro sphere adsorbent, according to following
Step carries out：
(1) ZIF-8 nano-particles are prepared, take the Zn (NO of 0.59-0.70g3)2·6H2O is added in the distilled water of 40ml, is continued
Stirring to solution is clarified, and obtains solution A.According to the Zn (NO taken3)2·6H2The amount of O presses Zn (NO3)2·6H2O：2- methyl miaows
Azoles is 1：The mass ratio of (65-75) takes corresponding 2-methylimidazole to be added in distilled water, then continues stirring until 2- methyl miaows
Azoles is fully dissolved in distilled water, obtains solution B.Obtained solution A and B are mixed, at ambient temperature 1000-
3000rpm stirs 1-3h, and obtained solution finally is centrifuged 15min under the speed of 8000-10000rpm, takes what is be collected by centrifugation
White crystal and with being centrifuged again after distilled water oscillation cleaning, is repeated 3 times.Obtained white crystal natural wind at ambient temperature
It is dry, obtain ZIF-8 nano-particles.
(2) ZIF-8 hollow porous micro sphere adsorbents are prepared：Take 0.15-0.25g ZIF-8 nano-particles using ultrasound leach in
In 10-15ml distilled water, solution C is obtained, this is as water phase.0.0056-0.0090g AIBN are dissolved in 0.14-0.18g benzene second
In the mixture of alkene, 0.21-0.25g vinyl benzenes and 0.40-0.48g dodecanes, it is uniformly mixed and obtains solution D, this is as oil
Phase.Water, oil phase are mixed, are placed in beaker.Using high speed homogenization device, under room temperature, 12500-16500rpm is to mixed
Compound carries out shear treatment, and process continues 2-3min.Obtain pickering emulsion.Obtained pickering emulsion is placed in double-necked round bottom
In flask, condensing unit is equipped with, leads to N2Bubbling 15-30min.338-348K is heated to the pickering emulsion in flask, and is protected
Holding 16h makes its polymerization.Solution filtering after reaction, the white solid being obtained by filtration are washed with ethanol, and washing lotion is in 1000-
5-10min is centrifuged under 1500rpm, removes supernatant, the white solid after being washed, repeats this operation more than 3 times.Will be last
Obtained white solid obtains hollow porous micro sphere adsorbent in natural air drying under room temperature.
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| CN109261141A (en) * | 2018-09-06 | 2019-01-25 | 华南协同创新研究院 | A kind of ZIF-8 is nanocrystalline and its preparation method and application |
| 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 |
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| CN112657475A (en) * | 2020-12-02 | 2021-04-16 | 常州大学 | Boron affinity functionalized microsphere adsorbent and preparation method and application thereof |
| CN113337497A (en) * | 2021-05-25 | 2021-09-03 | 天津大学 | Preparation and application of Pickering microcapsule based on carbonic anhydrase embedded in metal organic framework material |
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| 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 |
| CN116059981A (en) * | 2023-01-13 | 2023-05-05 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805361A (en) * | 2010-03-19 | 2010-08-18 | 上海师范大学 | Double-shell hollow spherical organic metal framework material and preparation method thereof |
| CN103788308A (en) * | 2014-01-20 | 2014-05-14 | 江苏大学 | Method for preparing macromolecular imprinting adsorbent by polymerization of Pickering emulsion |
| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
| CN106188437A (en) * | 2016-07-12 | 2016-12-07 | 江苏大学 | A kind of method that metal organic frame particle trace adsorbent is prepared in Pickering emulsion polymerization |
-
2017
- 2017-12-21 CN CN201711396117.6A patent/CN108031455B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805361A (en) * | 2010-03-19 | 2010-08-18 | 上海师范大学 | Double-shell hollow spherical organic metal framework material and preparation method thereof |
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