CN106902747A - A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof - Google Patents
A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof Download PDFInfo
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- CN106902747A CN106902747A CN201710194885.7A CN201710194885A CN106902747A CN 106902747 A CN106902747 A CN 106902747A CN 201710194885 A CN201710194885 A CN 201710194885A CN 106902747 A CN106902747 A CN 106902747A
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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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/28—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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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
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- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent, with sodium metasilicate as primary raw material, is synthesized using microwave-hydrothermal method, because sodium metasilicate cost of material is far below tetraethyl orthosilicate, can effectively reduce production cost；And can significantly shorten the reaction time to 12~18h using microwave attenuation materials, improve production efficiency, and microwave attenuation materials can promote spontaneous nucleation, make nucleation evenly, and while microwave-hydrothermal method synthesizing mesoporous silicon dioxide microsphere adsorbent, functional group (amidoxime group) is introduced further with copolycondensation method to be modified adsorbent, gained amidoxim mesoporous silicon dioxide micro-sphere adsorbent has flourishing ordered mesopore structure, good mechanical strength and chemical stability, it is easy to uranium to rapidly enter in duct to adsorb, the separation and recovery of uranium suitable for uranium-containing waste water.
Description
Technical field
Inhaled the present invention relates to inorganic functional material technical field, more particularly to a kind of amidoxim mesoporous silicon dioxide micro-sphere
Attached dose and preparation method thereof.
Background technology
Uranium concentration reaches mg/L magnitudes in the uranium-containing waste water that uranium is produced in process of production, using novel absorption material from uranium-bearing
Separating enriched uranium both can effectively reclaim the uranium resource in waste water in waste water, and the environment dirt that uranium-containing waste water discharge brings can be reduced again
Dye；Mesoporous silicon dioxide micro-sphere not only has good chemical stability and radiation resistance, and high mechanical strength, specific surface area
Greatly, its highly developed orderly pore structure is easy to uranyl ion quick adsorption, therefore is preferable uranium absorption material.Mesoporous dioxy
The production of SiClx microballoon is generally with tetraethyl orthosilicate as raw material, but its production cost is higher, and needs the reaction time grown very much
(24~120h), and then cause low production efficiency, while mesoporous silicon dioxide micro-sphere is generally relatively low to the adsorption capacity of uranium；Cause
How this, effectively reduce mesoporous silicon dioxide micro-sphere adsorbent production cost, improve production efficiency, and improve meso-porous titanium dioxide
Silicon microballoon, to the adsorption capacity of uranium, must be solved using mesoporous silicon dioxide micro-sphere absorption separating enriched uranium from uranium-containing waste water
Major issue.
The content of the invention
Technical problem solved by the invention be provide a kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and its
Preparation method, to solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention is realized using following technical scheme：
A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent, its general formula of molecular structure is：SiO2[O3SiCH2CH2C
(NH2)NOH]x(x=0.06~0.13), molecular structure is schematically as follows：
A kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method, comprises the following steps that：
(1) amidoxim organosilan functionalized reagent is synthesized
In 20mL alcohol-water mixture (ethanol：Water=1.6:120mg (3- cyanogen propyl group) triethoxysilane is added in 5v/v)
(abbreviation CP-TES), 387.2mg azanols (abbreviation AO) and 275mg Na2CO3, reaction 12h is heated at reflux under the conditions of 70 DEG C,
Purified through soxhlet extraction, obtain amidoxim organosilan functionalized reagent ((3- amidoxime groups propyl group) triethoxysilane, abbreviation
AOES), reaction equation is as follows：
(2) amidoxim mesoporous silicon dioxide micro-sphere adsorbent is prepared
60mL absolute ethyl alcohols, 80mL deionized waters, 30mL acetums (25wt.%) and 2.0mL pore templates is taken to put
The quick stirring mixing in container, side stirring, while to added in the container 50mL sodium silicate solutions and (1.0~3.0g) together with amine
Oximate organosilan functionalized reagent fully mixes to obtain mixture；Gained mixture is placed in reactor again, in 40 DEG C of conditions
2~3h of lower stirring, then microwave hydrothermal treatment 10h is carried out under the conditions of being warming up to 90 DEG C obtain intermediate compound I；Then this intermediate compound I is passed through
Cool down, be separated by filtration to obtain solid product, while after gained solid product is alternately washed using deionized water and ethanol, dividing again
It is dissipated in 80mL acid ethanol solutions, 12h is heated at reflux under the conditions of 60 DEG C and sloughs pore template, obtains intermediate II；After
Filter separation of intermediates II, after being then separated by filtration the intermediate II for finishing using deionized water and ethanol washing, in 60 DEG C of bars
Sieved after 48h is vacuum dried under part, obtain the amidoxim mesoporous silicon dioxide micro-sphere adsorbent that particle diameter is 90~150 microns.
In the present invention, in step (2), the pore template is PEO-PPOX-PEO
Triblock copolymer, abbreviation P123.
In the present invention, in step (2), silicic acid sodium content is 10.0g in the 50mL sodium silicate solutions.
In the present invention, in step (2), the amidoxim organosilan functionalized reagent is with the mass ratio of sodium metasilicate
10wt.%~30wt.%.
Beneficial effect：
1) it is primary raw material that the present invention uses sodium metasilicate to substitute tetraethyl orthosilicate, because sodium metasilicate cost of material only has positive silicon
The 1/10 of acetoacetic ester cost of material, therefore can effectively reduce production cost；And utilize microwave-hydrothermal method synthesis amidoximization mesoporous
Silicon dioxide microsphere adsorbent can shorten the reaction time to 12~18h, significantly improve production efficiency；Additionally, microwave-hydrothermal method is closed
Into that can promote spontaneous nucleation, gained amidoxim mesoporous silicon dioxide micro-sphere adsorbent granularity is evenly；
2) it is of the invention while microwave-hydrothermal method synthesizing mesoporous silicon dioxide microsphere adsorbent, further with copolycondensation
Method introduces functional group (amidoxime group) and adsorbent is modified, therefore can significantly improve mesoporous silicon dioxide micro-sphere to uranium
Adsorption capacity；
3) amidoxim mesoporous silicon dioxide micro-sphere adsorbent prepared by the present invention has good mechanical strength and chemistry
Stability, can be short from uranium-containing waste water quick adsorption uranium, time of equilibrium adsorption, and uranium absorption capacity is high, and can reuse 6 times with
On, it is adaptable to the separation and recovery of uranium in uranium-containing waste water.
Brief description of the drawings
Fig. 1 is the preparation flow figure of presently preferred embodiments of the present invention.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Conjunction is specifically illustrating, and the present invention is expanded on further.
Embodiment 1
A kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method, comprises the following steps that：
(1) synthesis amidoxim organosilan functionalized reagent (AOES)
In 20mL alcohol-water mixture (ethanol：Water=1.6:120mg (3- cyanogen propyl group) triethoxysilane is added in 5v/v)
(CP-TES), 387.2mg azanols (AO) and 275mg Na2CO3, reaction 12h is heated at reflux under the conditions of 70 DEG C, extract through Soxhlet
Purification is taken, amidoxim organosilan functionalized reagent ((3- amidoxime groups propyl group) triethoxysilane) is obtained, reaction equation is as follows：
(2) amidoxim mesoporous silicon dioxide micro-sphere adsorbent is prepared (by AOES/Na2SiO3Mass ratio 10wt.% is implemented)
Take 60mL absolute ethyl alcohols, 80mL deionized waters, 30mL acetums (25wt.%) and 2.0mL P123 and be placed in container
In quick stirring mixing, side stirring, while to adding 50mL sodium silicate solutions (sodium metasilicate containing 10.0g) and 1.0g in the container
AOES fully mixes to obtain mixture；Gained mixture is placed in reactor again, the stir about 2.5h under the conditions of 40 DEG C, then heated up
Microwave hydrothermal treatment 10h is carried out under the conditions of to 90 DEG C and obtains intermediate compound I；Then by this intermediate compound I through cooling down, being separated by filtration and obtaining solid
Product, while after gained solid product is alternately washed using deionized water and ethanol, 80mL acidic ethanols are dispersed to again molten
In liquid, 12h is heated at reflux under the conditions of 60 DEG C, to slough pore template (P123), obtains intermediate II；Refilter in the middle of separation
Body II, after being then separated by filtration the use deionized water and ethanol washing for finishing, sieves after being vacuum dried 48h under the conditions of 60 DEG C
Point, obtain the amidoxim mesoporous silicon dioxide micro-sphere adsorbent that particle diameter is 90-150 microns.
The amidoxim mesoporous silicon dioxide micro-sphere adsorbent can be used for uranium absorption capacity upto 97mg/g after testing
The separation and recovery of uranium in uranium-containing waste water, in 1h, amidoxim mesoporous silicon dioxide micro-sphere adsorbent can be again for time of equilibrium adsorption
Use more than 6 times again, uranium absorption capacity declines 11.6%.
Embodiment 2
A kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method, comprises the following steps that：
(1) synthesis amidoxim organosilan functionalized reagent (AOES)
In 20mL alcohol-water mixture (ethanol：Water=1.6:120mg (3- cyanogen propyl group) triethoxysilane is added in 5v/v)
(CP-TES), 387.2mg azanols (AO) and 275mg Na2CO3, reaction 12h is heated at reflux under the conditions of 70 DEG C, extract through Soxhlet
Purification is taken, amidoxim organosilan functionalized reagent ((3- amidoxime groups propyl group) triethoxysilane) is obtained, reaction equation is as follows：
(2) amidoxim mesoporous silicon dioxide micro-sphere adsorbent is prepared (by AOES/Na2SiO3Mass ratio 20wt.% is implemented)
Take 60mL absolute ethyl alcohols, 80mL deionized waters, 30mL acetums (25wt.%) and 2.0mL P123 and be placed in container
In quick stirring mixing；Side is stirred, while to addition 50mL sodium silicate solutions (sodium metasilicate containing 10.0g) and 2.0g in the container
AOES fully mixes to obtain mixture；Gained mixture is placed in reactor again, the stir about 2.5h under the conditions of 40 DEG C, then heated up
Microwave hydrothermal treatment 10h is carried out under the conditions of to 90 DEG C and obtains intermediate compound I；Then by this intermediate compound I through cooling down, being separated by filtration and obtaining solid
Product, while after gained solid product is alternately washed using deionized water and ethanol, 80mL acidic ethanols are dispersed to again molten
In liquid, 12h is heated at reflux under the conditions of 60 DEG C, to slough pore template (P123), obtains intermediate II；Refilter in the middle of separation
Body II, after being then separated by filtration the intermediate II for finishing using deionized water and ethanol washing, vacuum is done under the conditions of 60 DEG C
Sieved after dry 48h, obtain the amidoxim mesoporous silicon dioxide micro-sphere adsorbent that particle diameter is 90-150 microns.
The amidoxim mesoporous silicon dioxide micro-sphere adsorbent can be used uranium absorption capacity upto 160mg/g after testing
The separation and recovery of uranium in uranium-containing waste water, in 1h, amidoxim mesoporous silicon dioxide micro-sphere adsorbent can for time of equilibrium adsorption
Reuse more than 6 times, uranium absorption capacity declines 9.5%.
Embodiment 3
A kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method, comprises the following steps that：
(1) synthesis amidoxim organosilan functionalized reagent (AOES)
In 20mL alcohol-water mixture (ethanol：Water=1.6:120mg (3- cyanogen propyl group) triethoxysilane is added in 5v/v)
(CP-TES), 387.2mg azanols (AO) and 275mg Na2CO3, reaction 12h is heated at reflux under the conditions of 70 DEG C, extract through Soxhlet
Purification is taken, amidoxim organosilan functionalized reagent ((3- amidoxime groups propyl group) triethoxysilane) is obtained, reaction equation is as follows：
(2) amidoxim mesoporous silicon dioxide micro-sphere adsorbent is prepared (by AOES/Na2SiO3Mass ratio 30wt.% is implemented)
Take 60mL absolute ethyl alcohols, 80mL deionized waters, 30mL acetums (25wt.%) and 2.0mL P123 and be placed in container
In quick stirring mixing, side stirring, while to adding 50mL sodium silicate solutions (sodium metasilicate containing 10.0g) and 3.0g in the container
AOES fully mixes to obtain mixture；Gained mixture is placed in reactor again, the stir about 2.5h under the conditions of 40 DEG C, then heated up
Microwave hydrothermal treatment 10h is carried out under the conditions of to 90 DEG C and obtains intermediate compound I；Then by this intermediate compound I through cooling down, being separated by filtration and obtaining solid
Product, while after gained solid product is alternately washed using deionized water and ethanol, 80mL acidic ethanols are dispersed to again molten
In liquid, 12h is heated at reflux under the conditions of 60 DEG C, to slough pore template (P123), obtains intermediate II；Refilter in the middle of separation
Body II, after being then separated by filtration the intermediate II for finishing using deionized water and ethanol washing, vacuum is done under the conditions of 60 DEG C
Sieved after dry 48h, obtain the amidoxim mesoporous silicon dioxide micro-sphere adsorbent that particle diameter is 90-150 microns.
The amidoxim mesoporous silicon dioxide micro-sphere adsorbent can be used uranium absorption capacity upto 135mg/g after testing
The separation and recovery of uranium in uranium-containing waste water, in 1h, amidoxim mesoporous silicon dioxide micro-sphere adsorbent can for time of equilibrium adsorption
Reuse more than 6 times, uranium absorption capacity declines 10.4%.
Detected by the amidoxim mesoporous silicon dioxide micro-sphere adsorbent prepared to 1~embodiment of embodiment 3, most
Good adsorption conditionses are：AOES/Na2SiO330 DEG C of mass ratio 20wt.%, adsorption temp, Optimal pH 5.0-5.5, adsorbent amount
1.0g/L。
General principle of the invention, principal character and major advantage has been shown and described above.The technical staff of the industry
It should be appreciated that the present invention is not limited to the above embodiments, the present invention is simply illustrated described in above-described embodiment and specification
Principle, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these change and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appending claims and its equivalent
Thing is defined.
Claims (9)
1. a kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent, it is characterised in that general formula of molecular structure is：SiO2
[O3SiCH2CH2C(NH2)NOH]x(x=0.06~0.13).
2. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method, it is characterised in that comprise the following steps that：
(1) amidoxim organosilan functionalized reagent is synthesized
120mg (3- cyanogen propyl group) triethoxysilane, 387.2mg azanols and 275mg is added in 20mL alcohol-water mixtures
Na2CO3, reaction 12h is heated at reflux under the conditions of 70 DEG C, purified through soxhlet extraction, obtain the examination of amidoxim organosilan functionalization
Agent, reaction equation is as follows：
(2) amidoxim mesoporous silicon dioxide micro-sphere adsorbent is prepared
60mL absolute ethyl alcohols, 80mL deionized waters, 30mL acetums and 2.0mL pore templates is taken to be placed in container and quickly stir
Mixing, side stirring are mixed, while being tried to addition 50mL sodium silicate solutions in the container and quantitative amidoxim organosilan functionalization
Agent is sufficiently mixed to obtain mixture；Gained mixture is placed in reactor again, 2~3h is stirred under the conditions of 40 DEG C, then be warming up to
Microwave hydrothermal treatment 10h is carried out under the conditions of 90 DEG C and obtains intermediate compound I；Then by this intermediate compound I through cooling down, being separated by filtration and obtaining solid product
Thing, while after gained solid product is alternately washed using deionized water and ethanol, 80mL acid ethanol solutions are dispersed to again
In, 12h is heated at reflux under the conditions of 60 DEG C and sloughs pore template, obtain intermediate II；Separation of intermediates II is refiltered, then will
After the intermediate II for finishing is separated by filtration using deionized water and ethanol washing, sieved after being vacuum dried 48h under the conditions of 60 DEG C,
Obtain the amidoxim mesoporous silicon dioxide micro-sphere adsorbent that particle diameter is 90~150 microns.
3. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (1), ethanol and the volume ratio of water are 1.6 in the alcohol-water mixture:5.
4. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (1), the amidoxim organosilan functionalized reagent is (3- amidoxime groups propyl group) triethoxysilane.
5. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (2), acetic acid quality point rate is 25% in the acetum.
6. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (2), the pore template is PEO-PPOX-PEO triblock copolymer.
7. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (2), silicic acid sodium content is 10.0g in the 50mL sodium silicate solutions.
8. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (2), the amidoxim organosilan functionalized reagent is 10~30% with the mass ratio of sodium metasilicate.
9. a kind of amidoxim mesoporous silicon dioxide micro-sphere sorbent preparation method according to claim 2, its feature exists
In in step (2), the amidoxim organosilan functionalized reagent added in the container is 1.0~3.0g.
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| CN107899553A (en) * | 2017-11-28 | 2018-04-13 | 西南石油大学 | A kind of adsorbent containing imidazoline structure and preparation method thereof |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of amidoxim-silica resin preparation method for adsorbing gallium |
| CN109954484A (en) * | 2019-04-04 | 2019-07-02 | 哈尔滨工程大学 | The uranium absorption material and preparation method of mesoporous silica gel particulate load amidoxim polymer |
| GB2590792A (en) * | 2019-11-11 | 2021-07-07 | Univ Jiangsu | Method for preparing amidoxime functionalized hollow porous polymer microsphere by using CO2 as emulsion template |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899553A (en) * | 2017-11-28 | 2018-04-13 | 西南石油大学 | A kind of adsorbent containing imidazoline structure and preparation method thereof |
| CN107899553B (en) * | 2017-11-28 | 2020-03-03 | 西南石油大学 | Adsorbent containing imidazoline structure and preparation method thereof |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of amidoxim-silica resin preparation method for adsorbing gallium |
| CN109776744B (en) * | 2019-01-12 | 2021-08-03 | 广西大学 | Preparation method of amidoxime-silicon dioxide resin for adsorbing gallium |
| CN109954484A (en) * | 2019-04-04 | 2019-07-02 | 哈尔滨工程大学 | The uranium absorption material and preparation method of mesoporous silica gel particulate load amidoxim polymer |
| CN109954484B (en) * | 2019-04-04 | 2022-03-18 | 哈尔滨工程大学 | Uranium adsorbing material of mesoporous silica gel particle loaded amidoxime polymer and preparation method |
| GB2590792A (en) * | 2019-11-11 | 2021-07-07 | Univ Jiangsu | Method for preparing amidoxime functionalized hollow porous polymer microsphere by using CO2 as emulsion template |
| JP2022511183A (en) * | 2019-11-11 | 2022-01-31 | 江▲蘇▼大学 | A method for preparing amidoxime-functionalized hollow porous polymer microbeads using CO2 as an emulsion template. |
| GB2590792B (en) * | 2019-11-11 | 2022-06-08 | Univ Jiangsu | Method for preparing amidoxime functionalized hollow porous polymer microspheres using CO2 as emulsion template |
| JP7207765B2 (en) | 2019-11-11 | 2023-01-18 | 江▲蘇▼大学 | A Method for Preparing Amidoxime-Functionalized Hollow Porous Polymeric Microbeads as Emulsion Templates |
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