CN106902778A - A kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof - Google Patents
A kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof 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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- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof.Chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material, it is characterised in that：It is shitosan is made into main material and graphene oxide and polyvinyl alcohol to carry out preliminary cross-linking modified rear vacuum freeze drying in acid condition to obtain.Composite adsorbing material preparation process of the invention is simple to operation, low cost, and the composite adsorbing material has loose structure, and structural behaviour stabilization, porosity is high, and water absorbing properties are good, and heavy metal ion has good adsorption effect.
Description
Technical field
The present invention relates to a kind of chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material and preparation method thereof, can use
In treatment Adsorption of Heavy Metals ion, belong to field of functional polymer composites.
Background technology
Graphene oxide (GO) is the oxidation product and its derivative of Graphene, based on Graphene or graphene oxide
Carbon nano-composite material there is the performances such as good mechanical flexibility, chemical stability.Graphene oxide has specific surface area
Greatly, various structures, pore size be adjustable and metal complexing groups.Simultaneously it compared with Graphene, surface contain more hydroxyls,
The oxygen-containing functional group such as carboxyl, carbonyl, can be well dispersed in the aqueous solution.On the one hand it can be straight using Surface oxygen-containing groups
Connect with target metal ions phase separation, on the other hand it can be connected and be modified with other functional groups such as amino, increase
The adsorption capacity of big its heavy metal ion.
Shitosan (CTS) is a kind of nontoxic, free of contamination material, and can with hydrophily, biocompatibility and biology
Xie Xing.Compared to chitin, substantial amounts of active group, such as amino, hydroxyl and hydroxyl are contained in chitosan molecule, chemical property is lived
Sprinkle, be more conducive to chemical modification.Shitosan surface carries substantial amounts of amino and hydroxyl simultaneously, so that it can be with numerous heavy metals
Ion forms the chelate of stabilization, so having good heavy metals removal effect.Using the amino on shitosan and oxidation stone
The characteristics of hydroxyl on black alkene easily reacts, so that the very excellent shell of absorption property can be prepared by both are crosslinked together
Glycan/graphene oxide composite adsorption material.And polyvinyl alcohol (PVA) is nontoxic, biodegradable water the most frequently used at present
Soluble macromolecular material.Contain substantial amounts of hydroxyl on its strand, and show certain chemism, while its material is showed
Go out good water imbibition, with good film forming, caking property and emulsibility.Therefore PVA has been widely studied for adsorbing
The preparation of material (such as water/gas gel), achieves good effect.
Different excellent properties are just shown respectively due to GO, CTS, PVA, so there are many scholars to consider triplicity
Prepare the more excellent composite of absorption property.As patent No. CN201410540016 disclose a kind of Adsorption of Heavy Metals from
Son composite aquogel and its preparation, patent No. CN201410123913 disclose a kind of hydrogel for sewage disposal and its
Preparation method, the two patents are first to prepare GO/CTS/PVA/ mixed solution of sodium alginate, then by be added dropwise calcium chloride-
Boric acid saturated solution is chemically crosslinked and is prepared composite aquogel.But hydrogel porosity prepared by the method is universal not
Height, and aperture it is small, without stabilization pore structure.Also patent No. CN201610038032 discloses a kind of graphene oxide
The preparation method of polyvinyl alcohol hybrid aerogel, patent No. CN201610034533 discloses a kind of polyvinyl alcohol-shitosan-oxygen
Graphite alkene sponge and preparation method thereof, the two patents be all then by using various chemical reagent for example crosslinking agent, foaming agent,
Be blended together for GO, CTS, PVA by catalyst etc., then the curing molding in die material.But the absorption that the method is prepared
Material loose structure is easily influenceed by foaming agent, the consumption of crosslinking agent and moulding process and the low feelings of porosity is easily occurred
Condition, and generally require PVA and occupy larger proportion just beneficial to being solidified into stabilization composite construction, and the method medicine using various
Increased production cost.
The content of the invention
For above-mentioned existing technical problem and defect, there is provided a kind of improved chitosan/oxidized Graphene/poly-
Vinyl alcohol (CTS/GO/PVA) composite adsorbing material and preparation method thereof, the ternary blend systems of the composite adsorbing material make use of
GO, CTS, PVA each functional group feature and carry out blended cross linking and be modified, it is to avoid the use of crosslinking agent and its to co-mixing system
Influence.Employing Vacuum Freezing ＆ Drying Technology solves the shortcomings of sample porosity is not high, loose structure is unstable simultaneously, keeps away
Exempt from influence of the content of sample component to its curing molding, so that it is material of main part that shitosan may be selected, to increase compound system
The adsorption capacity of heavy metal.The sorbing material that the method is prepared has porosity high, good water absorption and heavy metal ion
The features such as adsorption effect is protruded, and its structural behaviour stabilization, can repeatedly use and non-secondary pollution.
Chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material, it is that shitosan is made into main material and graphite oxide
Alkene and polyvinyl alcohol carry out preliminary cross-linking modified rear vacuum freeze drying and obtain in acid condition.
By such scheme, graphene oxide consumption is the 3%~5% of chitosan mass；Polyvinyl alcohol consumption is shitosan
The 5%~10% of quality.
By such scheme, the preliminary cross-linking modified temperature of step (2) is 60~80 DEG C, and the modified-reaction time is 4~5h.
By such scheme, pre-freezing temperature is not higher than -10 DEG C；Vacuum refrigeration temperature is not higher than -50 DEG C, during vacuum freeze drying
Between be 36~48h.
The preparation method of chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material of the present invention, specific steps
It is as follows：
(1) oxidation stripping method prepares the graphene oxide solution of acetoxylation, is added thereto to quantitative shitosan and stirs
Mix to it and be completely dissolved, then be placed in sonic oscillation under normal temperature environment and obtain GO/CTS homogeneous blends；
(2) quantitative poly-vinyl alcohol solution is added to above-mentioned co-mixing system, stirs and ultrasound is to homogeneous；The system is put again
In constant speed blended under agitation reaction certain hour in thermostat water bath, and sulfuric acid solution is slowly added dropwise within the half an hour of starting
To be catalyzed esterification, the acetalation between GO, CTS, PVA three, the GO/CTS/PVA after cross-linking reaction is can obtain homogeneously altogether
Mixed system.
(3) reaction is obtained in (2) co-mixing system is placed in refrigerator pre-freeze to solidifying state, after in vacuum freeze drier
Middle vacuum freeze drying certain hour, taking-up obtains final product the composite adsorbing material.
By such scheme, the 30~40min of sonic oscillation time of step (1), supersonic frequency is not less than 40KHz.
By such scheme, the graphene oxide described in step (1) is to prepare graphite oxide using improvement Hummers, so
Obtained after fully being peeled off through normal temperature ultrasound in acetic acid solution, graphene oxide solution concentration is 1.5~2.5mg/ml.
By such scheme, above-mentioned acetic acid solution concentration is 0.8~1.0%.
By such scheme, the shitosan described in step (1) is excellent pure level powder, and its deacetylation is more than 90%.
By such scheme, the polyvinyl alcohol degree of polymerization described in step (2) is 1700~1800, and its solution concentration is 5%
~10%.
By such scheme, the sulfuric acid solution concentration described in step (2) is 60%~80%, and consumption is co-mixing system volume
1~2%.
By such scheme, the ultrasonic time of step (2) is 20~30min, and supersonic frequency is not less than 40KHz.
By such scheme, the vacuum freeze drier vacuum described in step (3) is not higher than 20Pa.
Compared with prior art, the present invention has following distinguishing feature：
(1) composite adsorbing material that the method for the invention is obtained, it utilizes amino and hydroxyl, oxidation stone on shitosan
The hydroxyl reactive group on carboxyl and aldehyde radical and polyvinyl alcohol on black alkene is esterified by under sulphuric acid environment, acetalation etc.
Reaction preliminary cross-linking modified formation tri compound homogeneous blend, it is to avoid the use of crosslinking agent and its to co-mixing system each group
Divide the influence of performance.And then coordinating Vacuum Freezing ＆ Drying Technology, directly freezed is dried and reached in material knot under vacuum conditions
The purpose of many stomatas is formed in structure, solves that common sample porosity in ternary system chemical crosslink technique is high, porous knot
The shortcomings of structure is unstable.And make use of and can keep well during vacuum freeze drying sample original chemical composition and physical property
The characteristics of, and avoid influence of the content of sample component to its formation problems.
(2) in blending reaction, there is acetalation production acetal compound in the hydroxyl on PVA, on the one hand with GO aldehyde radicals
The water absorbing capacity of the co-mixing system can be improved, the emulsibility of another aspect PVA can reduce co-mixing system shitosan film forming to inhaling
The porous influence of enclosure material, it is ensured that have good compatibility between co-mixing system each component, so as to obtain, structure is more stable, hole
Gap rate composite adsorbing material high.
(3) the composite adsorbing material knot that the proportioning consumption of the chitosan/oxidized Graphene/polyvinyl alcohol of present invention regulation and control is obtained
Structure stabilization, there is loose structure, and porosity can be up to more than 90%, and its water absorption rate can also be up to 2300%, and have well
The effect of Adsorption of Heavy Metals ion, the highest adsorbance to copper ion can reach 92.5mg/g, to the highest adsorbance of lead ion
77.3mg/g can be reached.Apparently higher than sorbing material prepared by under equal conditions other conventional chemical cross-linking methods.
(4) chitosan/oxidized Graphene prepared by the method for the invention/polyvinyl alcohol sorbing material preparation technology letter
It is single, environment-friendly, can largely prepare, and easy to operate, production cost is relatively low, and the adsorption material can be arbitrarily adjusted according to demand
The size dimension of material.
Brief description of the drawings
Fig. 1 is the porous composite adsorbing material scanning electron microscope (SEM) photograph of present invention preparation in embodiment 1；
Fig. 2 is the porous composite adsorbing material scanning electron microscope (SEM) photograph of present invention preparation in embodiment 2；
Fig. 3 is the porous composite adsorbing material scanning electron microscope (SEM) photograph of present invention preparation in embodiment 3.
Specific embodiment
In order to better illustrate the present invention, with reference to comparative example and the embodiment content that the present invention is furture elucidated, but
Present disclosure is not only limited to the following examples.
Comparative example 1
A kind of preparation method of common chitosan/oxidized Graphene/polyvinyl alcohol composite hydrogel, main process is as follows：
Graphite oxide is prepared using Hummers is improved, is then filled through normal temperature ultrasound in the acetic acid solution of 0.9% concentration
Divide the graphene oxide solution for obtaining that concentration is 2.0mg/ml after peeling off.Weigh the oxidation under 2g shitosans add the 40ml concentration
In graphene solution, stir and ultrasound 35min is to being completely dissolved, then it is molten to the polyvinyl alcohol that system addition 2ml concentration is 8%
First ultrasound 25min and the stirring of liquid and 1g sodium alginates is to homogeneous.The above-mentioned mixed liquor for preparing is instilled into 3% chlorine with syringe
Particle diameter is prepared in change calcium-boric acid saturated solution for the chitosan/oxidized Graphenes of 3~5mm/polyvinyl alcohol composite hydrogel microballoon,
And 24h is soaked, finally with deionized water rinsing 5 times and soaking water.
Comparative example 2
A kind of preparation method of common chitosan/oxidized Graphene/polyvinyl alcohol compound sponge, main process is as follows：
Graphite oxide is prepared using Hummers is improved, is then filled through normal temperature ultrasound in the acetic acid solution of 0.9% concentration
Divide the graphene oxide solution for obtaining that concentration is 2.0mg/ml after peeling off.Weigh the oxidation under 2g shitosans add the 40ml concentration
In graphene solution, stir and ultrasound is to being completely dissolved, then the poly-vinyl alcohol solution that 2ml concentration is 8% is added to the system, so
Add mass ratio to be respectively 15% and 3% crosslinking agent formaldehyde and foaming agent n-hexane afterwards, and be to system addition mass ratio
6% sulfuric acid, first by co-mixing system stirring mixing 30 minutes at 30 DEG C.Then the mixed solution is poured into mould
In, and solidifying 10 hours at 70 DEG C, solidification completes to take out the chitosan/oxidized Graphene that obtains final product foaming cross-linking method and prepare/poly-
Vinyl alcohol composite sponge.
Embodiment 1
Graphite oxide is prepared using Hummers is improved, is then filled through normal temperature ultrasound in the acetic acid solution of 0.8% concentration
Divide the graphene oxide solution for obtaining that concentration is 1.5mg/ml after peeling off.Weigh the oxidation under 2g shitosans add the 40ml concentration
In graphene solution, stir and ultrasound 30min is to being completely dissolved, then it is molten to the polyvinyl alcohol that system addition 2ml concentration is 5%
Stirring and ultrasound 20min is to homogeneous after liquid.Then the blend solution is placed in 70 DEG C of water-baths, and is slowly dripped within half an hour
After adding 1% sulfuric acid (concentration 60%) and constant speed stirring reaction 4h of blending volume, composite crosslinking co-mixing system is can obtain, should
GO accounts for 3%, PVA of chitosan mass and accounts for the 5% of chitosan mass in system.Will be pre- in the blend solution -10 DEG C of refrigerators of placement
Freeze to solidification shape, then be placed in freeze-drying 36 hours in vacuum freeze drier, taking-up obtains final product cavernous chitosan/oxidized
Graphene/polyvinyl alcohol composite adsorbing material.
Embodiment 2
Graphite oxide is prepared using Hummers is improved, is then filled through normal temperature ultrasound in the acetic acid solution of 0.9% concentration
Divide the graphene oxide solution for obtaining that concentration is 2.0mg/ml after peeling off.Weigh the oxidation under 2g shitosans add the 40ml concentration
In graphene solution, stir and ultrasound 35min is to being completely dissolved, then it is molten to the polyvinyl alcohol that system addition 2ml concentration is 8%
Liquid stirring and ultrasound 25min is to homogeneous.Then the blend solution is placed in 75 DEG C of water-baths, and is slowly added dropwise within half an hour
After 1.5% sulfuric acid (concentration 70%) and constant speed stirring reaction 4.5h of complete blending volume, composite crosslinking co-mixing system is can obtain,
GO accounts for 4%, PVA of chitosan mass and accounts for the 8% of chitosan mass in the system.By in the blend solution -15 DEG C of refrigerators of placement
Pre-freeze is to after solidifying shape, then is placed in freeze-drying 42 hours in vacuum freeze drier, and taking-up obtains final product cavernous shitosan/oxygen
Graphite alkene/polyvinyl alcohol composite adsorbing material.
Embodiment 3
Graphite oxide is prepared using Hummers is improved, is then filled through normal temperature ultrasound in the acetic acid solution of 1.0% concentration
Divide the graphene oxide solution for obtaining that concentration is 2.5mg/ml after peeling off.Weigh the oxidation under 2g shitosans add the 40ml concentration
In graphene solution, stir and ultrasound 40min is to being completely dissolved, then to the polyvinyl alcohol that system addition 2ml concentration is 10%
Solution stirring and ultrasound 30min is to homogeneous.Then the blend solution is placed in 80 DEG C of water-baths, and is slowly dripped within half an hour
After adding 2% sulfuric acid (concentration 80%) and constant speed stirring reaction 5h of blending volume, composite crosslinking co-mixing system is can obtain, should
GO accounts for 5%, PVA of chitosan mass and accounts for the 10% of chitosan mass in system.Will be pre- in the blend solution -20 DEG C of refrigerators of placement
Freeze to solidification shape, then be placed in freeze-drying 48 hours in vacuum freeze drier, taking-up obtains final product cavernous chitosan/oxidized
Graphene/polyvinyl alcohol composite adsorbing material.
The absorption property excellent in order to illustrate composite adsorbing material of the present invention, compared for same ternary system and identical respectively
Corresponding absorption property (the comparative example of composite sponge prepared by the hydrogel and foaming cross-linking method that under ratio prepared by chemical crosslink technique
1 and comparative example 2).
Heavy metal ion adsorbed amount test process：Comparative example 1,2 and the sorbing material prepared by embodiment 1,2,3 are taken respectively
0.1g, is respectively placed in 250ml conical flasks, and sequentially adds the Cu that 100ml concentration is 100mg/L2+Solution, separately takes one group of difference
It is the Pb of 100mg/L to add 100ml concentration2+Solution, then the 12h of slowly vibrating absorption at normal temperatures, heavy before and after test absorption
Concentration of metal ions changes and draws the adsorbance (reference formula 3) of respective material.
The porosity and water absorption rate of every kind of sorbing material are calculated according to formula (1) and formula (2).
The specific data of every group of test experiments are as shown in table 1.
The surface scan electron microscope of every kind of sorbing material is as shown in drawings.
The properties test data of composite adsorbing material under the different preparation conditions of table 1
| Porosity (%) | Water absorption rate (%) | |||
| Comparative example 1 | 65.1 | 1430 | 61.7 | 58.8 |
| Comparative example 2 | 58.8 | 1390 | 53.6 | 47.3 |
| Embodiment 1 | 87.3 | 2180 | 87.2 | 73.6 |
| Embodiment 2 | 90.1 | 2300 | 92.5 | 74.5 |
| Embodiment 3 | 88.2 | 2210 | 88.2 | 77.3 |
, it is apparent that chitosan/oxidized Graphene/polyvinyl alcohol cellular prepared by the present invention is combined and inhales from table 1
Enclosure material is in porosity, water absorption rate and heavy metal ion Cu2+And Pb2+Adsorbance under equal conditions is substantially all higher than same
Composite sponge prepared by the hydrogel and foaming cross-linking method that under sample ternary system, same ratio prepared by chemical crosslink technique, explanation
The technical method of use of the present invention can be efficiently modified the absorption property of the three-component compound system, and also be entered by scanning electron microscope (SEM) photograph
One step illustrates that composite adsorbing material pore structure of the invention is obvious, aperture is big and close and is evenly distributed, and sees Fig. 1-Fig. 3.
When the present invention relates to porosity (%), water absorption rate (%), heavy metal ion adsorbed amount (mg/g) etc., its survey
Fixed, computational methods are as follows respectively：
(1)
In formula, m is sample mass (g), and V is volume of sample (cm3), ρ is the skeletal density (g/cm of sample material3)。
(2)
In formula, m1Quality after fully being absorbed water for sample material, m0It is sample initial mass.
(3)
In formula, C, Ce(mg/L) concentration after the original concentration of heavy metal ion and adsorption equilibrium is respectively, V is molten to be taken
Liquid is accumulated, m0It is the quality (g) of composite adsorbing material for being consumed.
Claims (10)
1. chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material, it is characterised in that：It is that shitosan is made into main material
Preliminary cross-linking modified rear vacuum freeze drying is carried out in acid condition with graphene oxide and polyvinyl alcohol to obtain.
2. chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material according to claim 1, it is characterised in that：Oxygen
Graphite alkene consumption is the 3%~5% of chitosan mass；Polyvinyl alcohol consumption is the 5%~10% of chitosan mass.
3. chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material according to claim 1, it is characterised in that：Just
It is 60~80 DEG C to walk cross-linking modified temperature, and the modified-reaction time is 4~5h.
4. chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material according to claim 1, it is characterised in that：In advance
Freeze temperature and be not higher than -10 DEG C；Vacuum refrigeration temperature is not higher than -50 DEG C, and the vacuum freeze drying time is 36~48h.
5. the preparation method of the chitosan/oxidized Graphene/polyvinyl alcohol composite adsorbing material described in claim 1, its is specific
Step is as follows：
(1) oxidation stripping method prepares the graphene oxide solution of acetoxylation, is added thereto to quantitative shitosan and stirs extremely
It is completely dissolved, then is placed in sonic oscillation under normal temperature environment and obtains GO/CTS homogeneous blends；
(2) quantitative poly-vinyl alcohol solution is added to above-mentioned co-mixing system, stirs and ultrasound is to homogeneous；The system is placed in perseverance again
Constant speed blended under agitation reaction certain hour in warm water bath, and be slowly added dropwise sulfuric acid solution to urge within the half an hour of starting
Change esterification, the acetalation between GO, CTS, PVA three, can obtain the homogeneous mixtures of the GO/CTS/PVA after cross-linking reaction
System.
(3) reaction is obtained in (2) co-mixing system is placed in refrigerator pre-freeze to solidifying state, after it is true in vacuum freeze drier
Vacuum freecing-dry certain hour, taking-up obtains final product the composite adsorbing material.
6. preparation method according to claim 5, it is characterised in that：30~the 40min of sonic oscillation time of step (1),
Supersonic frequency is not less than 40KHz；
The ultrasonic time of step (2) is 20~30min, and supersonic frequency is not less than 40KHz；
The vacuum freeze drier vacuum not higher than 20Pa of vacuum freeze drying in step (3).
7. preparation method according to claim 5, it is characterised in that：Graphene oxide described in step (1) is to use to change
Enter Hummers and prepare graphite oxide, obtained after then fully being peeled off through normal temperature ultrasound in acetic acid solution, graphene oxide is molten
Liquid concentration is 1.5~2.5mg/ml.
8. preparation method according to claim 7, it is characterised in that：Acetic acid solution concentration is 0.8~1.0%.
9. preparation method according to claim 5, it is characterised in that：Shitosan described in step (1) is excellent pure level powder,
Its deacetylation is more than 90%；
The polyvinyl alcohol degree of polymerization described in step (2) is 1700~1800, and its solution concentration is 5%~10%.
10. preparation method according to claim 5, it is characterised in that：Sulfuric acid solution concentration described in step (2) is
60%~80%, consumption is the 1~2% of co-mixing system volume.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108176383A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of antibacterial absorption sponge material |
| CN110124627A (en) * | 2019-06-27 | 2019-08-16 | 中素新科技有限公司 | Graphene oxide and alginate composite aerogel and its preparation method and application |
| CN110624515A (en) * | 2019-10-22 | 2019-12-31 | 泸州老窖股份有限公司 | Fruit wine clarifying agent and preparation method thereof |
| CN110937598A (en) * | 2019-11-08 | 2020-03-31 | 宁波锋成先进能源材料研究院 | Modified graphene oxide and preparation method and application thereof |
| CN111097065A (en) * | 2019-12-29 | 2020-05-05 | 苏州阿德旺斯新材料有限公司 | Carbon fiber-based porous material, preparation method and application thereof |
| CN111871391A (en) * | 2020-07-09 | 2020-11-03 | 清华大学 | Preparation and application of polyvinyl alcohol/graphene oxide/manganese dioxide adsorbent |
| CN112495435A (en) * | 2020-11-23 | 2021-03-16 | 北京联合大学 | Chitosan-based graphene/TiO2Composite microsphere and preparation method thereof |
| CN112875693A (en) * | 2021-03-26 | 2021-06-01 | 忆净空气技术(上海)有限公司 | Nano-silver odor-removing and formaldehyde-removing preparation and preparation method thereof |
| CN112871138A (en) * | 2019-11-29 | 2021-06-01 | 合肥杰事杰新材料股份有限公司 | Chitosan composite film adsorbent material and preparation method and application thereof |
| CN113683786A (en) * | 2021-08-03 | 2021-11-23 | 武汉理工大学 | Dual self-healing antibacterial hydrogel and preparation method and application thereof |
| CN113679660A (en) * | 2020-05-19 | 2021-11-23 | 北京智慧客科技创新有限公司 | Slow-release drug carrier and preparation method and application thereof |
| CN114262034A (en) * | 2021-12-31 | 2022-04-01 | 合肥工业大学 | Method for separating rubidium from salt lake brine by using polyvinyl alcohol/chitosan/graphene/nickel copper hexacyanide complex |
| CN115634718A (en) * | 2022-08-17 | 2023-01-24 | 湖北工程学院 | Preparation method and application of graphene oxide/chitosan/polyvinyl alcohol composite microsphere solid-supported copper catalyst |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108176383A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of antibacterial absorption sponge material |
| CN110124627A (en) * | 2019-06-27 | 2019-08-16 | 中素新科技有限公司 | Graphene oxide and alginate composite aerogel and its preparation method and application |
| CN110624515A (en) * | 2019-10-22 | 2019-12-31 | 泸州老窖股份有限公司 | Fruit wine clarifying agent and preparation method thereof |
| CN110937598A (en) * | 2019-11-08 | 2020-03-31 | 宁波锋成先进能源材料研究院 | Modified graphene oxide and preparation method and application thereof |
| CN112871138A (en) * | 2019-11-29 | 2021-06-01 | 合肥杰事杰新材料股份有限公司 | Chitosan composite film adsorbent material and preparation method and application thereof |
| CN111097065A (en) * | 2019-12-29 | 2020-05-05 | 苏州阿德旺斯新材料有限公司 | Carbon fiber-based porous material, preparation method and application thereof |
| CN111097065B (en) * | 2019-12-29 | 2021-09-07 | 苏州阿德旺斯新材料有限公司 | Carbon fiber-based porous material, preparation method and application thereof |
| CN113679660A (en) * | 2020-05-19 | 2021-11-23 | 北京智慧客科技创新有限公司 | Slow-release drug carrier and preparation method and application thereof |
| CN111871391A (en) * | 2020-07-09 | 2020-11-03 | 清华大学 | Preparation and application of polyvinyl alcohol/graphene oxide/manganese dioxide adsorbent |
| CN111871391B (en) * | 2020-07-09 | 2022-06-07 | 清华大学 | Preparation and application of polyvinyl alcohol/graphene oxide/manganese dioxide adsorbent |
| CN112495435B (en) * | 2020-11-23 | 2023-05-16 | 北京联合大学 | Chitosan-based graphene/TiO 2 Composite microsphere and preparation method thereof |
| CN112495435A (en) * | 2020-11-23 | 2021-03-16 | 北京联合大学 | Chitosan-based graphene/TiO2Composite microsphere and preparation method thereof |
| CN112875693A (en) * | 2021-03-26 | 2021-06-01 | 忆净空气技术(上海)有限公司 | Nano-silver odor-removing and formaldehyde-removing preparation and preparation method thereof |
| CN113683786A (en) * | 2021-08-03 | 2021-11-23 | 武汉理工大学 | Dual self-healing antibacterial hydrogel and preparation method and application thereof |
| CN113683786B (en) * | 2021-08-03 | 2023-12-12 | 武汉理工大学 | Double self-healing antibacterial hydrogel and preparation method and application thereof |
| CN114262034A (en) * | 2021-12-31 | 2022-04-01 | 合肥工业大学 | Method for separating rubidium from salt lake brine by using polyvinyl alcohol/chitosan/graphene/nickel copper hexacyanide complex |
| CN114262034B (en) * | 2021-12-31 | 2022-12-02 | 合肥工业大学 | Method for separating rubidium from salt lake brine by using polyvinyl alcohol/chitosan/graphene/nickel copper hexacyanide complex |
| CN115634718A (en) * | 2022-08-17 | 2023-01-24 | 湖北工程学院 | Preparation method and application of graphene oxide/chitosan/polyvinyl alcohol composite microsphere solid-supported copper catalyst |
| CN115634718B (en) * | 2022-08-17 | 2024-02-06 | 湖北工程学院 | Preparation method and application of graphene oxide/chitosan/polyvinyl alcohol composite microsphere immobilized copper catalyst |
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