CN109174023A - A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application - Google Patents
A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application Download PDFInfo
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- CN109174023A CN109174023A CN201811032482.3A CN201811032482A CN109174023A CN 109174023 A CN109174023 A CN 109174023A CN 201811032482 A CN201811032482 A CN 201811032482A CN 109174023 A CN109174023 A CN 109174023A
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—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
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The present invention relates to a kind of nano-cellulose cross-linked graphene/chitosan aeroges and preparation method thereof, application, belong to the Dye Adsorption field of aeroge.Nano-cellulose cross-linked graphene/chitosan aeroge of the invention is made of the mixing crosslinking of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan.Nano-cellulose cross-linked graphene/chitosan aeroge of the invention, both there is graphene and the excellent absorption property of chitosan, it is avoided again using toxic cross-linking agents, the advantages of nano-cellulose large specific surface area can be played simultaneously, separation easy to accomplish with water body, it not will cause secondary pollution, it is a kind of environmental-friendly novel absorption material, through showing the test of organic dyestuff absorption property, nano-cellulose cross-linked graphene/chitosan aeroge of the invention is to Congo red, amino black has good adsorption effect, removal rate reaches 92% or more, and adsorption process is fast, it is easily isolated after absorption, it has a good application prospect.
Description
Technical field
The present invention relates to a kind of nano-cellulose cross-linked graphene/chitosan aeroges and preparation method thereof, application, belong to
The Dye Adsorption field of aeroge.
Background technique
With the fast development of domestic dyeing, largely the sewage containing dyestuff is discharged into water body environment, is caused
Water pollution seriously threatens the water body safety in China, and the method for water process has very much, and absorption method is a kind of side being simple and efficient
Method.Aeroge uses the processing for being used for sewage frequently as absorption due to its own high-specific surface area and superelevation pore volume rate.
In the prior art, Authorization Notice No. is that the Chinese invention patent of CN105566659B discloses a kind of graphite oxide
Alkene/nano-cellulose aerogel, the aeroge are to be prepared using nano-cellulose and graphene oxide as raw material by hydro-thermal reaction
Hydrogel is further obtained by freeze-drying.The aeroge can be used for organic dye molecule in sewage or other impurities
The purification of sewage is realized in removal, but the aeroge is only capable of by hydroxyl, carboxylic group and the cellulose on graphene molecules chain
Oxygen-containing group on chain enhances its adsorption capacity to organic pollutant, and adsorption effect is poor；And graphene oxide and poly-
Closing between object matrix does not have chemical bond crosslinking, and stability is low, is easy to move to from sorbent systems in absorption swelling process
In aqueous systems, the adsorption effect of adsorbent material is not only reduced, also can therefore cause the nanometer toxicity of graphene oxide.
Summary of the invention
Nano-cellulose friendship high the object of the present invention is to provide a kind of stability and good to Adsorption of Organic effect
Join graphene/chitosan aeroge.
The present invention also provides a kind of cross-linked graphene of above-mentioned fiber/chitosan aeroge preparation method and its going
Application in terms of except organic dyestuff in wastewater.
In order to achieve the goal above, skill used by nano-cellulose cross-linked graphene/chitosan aeroge of the invention
Art scheme is:
A kind of nano-cellulose cross-linked graphene/chitosan aeroge aoxidizes stone by dialdehyde nano-cellulose, amino modified
Black alkene and chitosan mixing crosslinking are made.
Nano-cellulose cross-linked graphene/chitosan aeroge of the invention, is by dialdehyde nano-cellulose, amino modified
Graphene oxide mixes crosslinking with chitosan and is made, and chitosan is as a kind of natural water-soluble Biodegradable high-molecular material
Material has the characteristics that inexpensive, abundance and reproducible, and containing a large amount of amino and hydroxyl in strand, these groups can
To be acted on organic dyestuff with electrostatic attraction and Hyarogen-bonding, to improve adsorption effect.Graphene is a kind of with single former
The nano material of sublayer structure, has biggish specific surface area, and graphene after modified contains organic group, increases its water
Dispersibility；In addition, the modifying agent of graphene contains a large amount of amine groups, can be reacted with the aldehyde radical of dialdehyde nano-cellulose,
To realize the chemical crosslinking of graphene oxide layer and polymeric groups, the stability and absorption property of aeroge are improved.
Dialdehyde nano-cellulose maintains the advantages of nano-cellulose large specific surface area, and obtained aeroge both has graphene and shell
The excellent absorption property of glycan, and avoid using toxic crosslinking agent, while nano-cellulose large specific surface area can be played
Advantage, it is a kind of environmental-friendly novel absorption material, tool that the separation easy to accomplish with water body, which not will cause without secondary pollution,
There are higher research and practical application value.By showing that nano-cellulose of the invention is handed over to the test of organic dyestuff absorption property
Joining graphene/chitosan aeroge has good adsorption effect to Congo red, amino black, and removal rate reaches 92% or more, and
And adsorption process is fast, is easily isolated after absorption, has a good application prospect.
The present invention is not particularly limited the dialdehyde nano-cellulose of use, and the dialdehyde nano-cellulose of the prior art is equal
It can be used for the present invention.Preferably, the dialdehyde nano-cellulose is dialdehyde nanocrystalline cellulose.
Preferably, the dialdehyde nanofiber is prepared using the method included the following steps: by nano-cellulose with
Sodium metaperiodate according to mass ratio be 1:1~5 ratio mix, be protected from light to get.
Preferably, the time being protected from light be 4~for 24 hours.The nano-cellulose is nanocrystalline cellulose (NCC).
Preferably, the mass ratio of the dialdehyde nano-cellulose and the amino modified graphene oxide is 1:0.25~3.
Preferably, the mass ratio of the dialdehyde nano-cellulose and the chitosan is 1:0.5~3.
Preferably, the temperature of the mixing crosslinking is 15~40 DEG C.It is further preferred that the temperature of the mixing crosslinking is
Room temperature.
Preferably, the time of the mixing crosslinking is 2~8h.
The present invention is not particularly limited used amino modified graphene oxide, amino modified in the prior art
Graphene oxide is suitable for the invention technical solution.Preferably, the amino modified graphene oxide is polyethyleneimine
Modified graphene oxide.
Preferably, the amino modified graphene oxide is prepared using the method included the following steps: amido is changed
Property agent and graphite oxide according to mass ratio be 1~8:1 ratio mix, 85~90 DEG C of 4~6h of reaction to get.It is further excellent
Choosing, amino modified dose is 2~5.5:1 with the mass ratio of graphene oxide.
Preferably, the amino modified agent is polyethyleneimine.
Technical solution used by nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the invention
Are as follows:
A kind of preparation method of above-mentioned nano-cellulose cross-linked graphene/chitosan aeroge, comprising the following steps: will be double
The mixed solution of aldehyde nano-cellulose, amino modified graphene oxide and chitosan reacts in a mold, it is dry to get.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the invention, preparation flow is simple, raw material
It is easy to get, resulting aeroge has good adsorption effect to Congo red, amino black, and removal rate reaches 92% or more, and inhales
Attached procedure block is easily isolated after absorption, has a good application prospect.
Preferably, the drying is freeze-drying.The time of the freeze-drying is 12~48h.
Preferably, the mixed solution is made using the method included the following steps: providing dialdehyde nano-cellulose and amine
The composite solution of base modified graphene oxide；Will the composite solution be added chitosan solution in, be uniformly mixed to get.
Preferably, the mass fraction of dialdehyde nano-cellulose is 0.2~2% in the composite solution.
Preferably, the mass fraction of chitosan is 0.02~3% in the chitosan solution.It is further preferred that described
The mass fraction of chitosan is 3% in chitosan solution.
Preferably, the chitosan solution is dissolved the chitosan in obtained in acetic acid aqueous solution.The acetic acid is water-soluble
The mass fraction of acetic acid is 0.5~2% in liquid.
Nano-cellulose cross-linked graphene/chitosan aeroge answering in terms of removing organic dyestuff in wastewater of the invention
With used technical solution are as follows:
A kind of above-mentioned nano-cellulose cross-linked graphene/chitosan aeroge is in terms of removing organic dyestuff in wastewater
Using.
Nano-cellulose cross-linked graphene/chitosan aeroge of the invention imitates organic dyestuff with good absorption
Fruit can reach 92% or more especially for Congo red removal rate, have wide application in terms for the treatment of of dyeing wastewater
Prospect.
Detailed description of the invention
Fig. 1 is the XRD spectrum of nano-cellulose oxidation front and back in embodiment 1；In figure, NCC: nanocrystalline cellulose；DAC:
Dialdehyde nano-cellulose；
Fig. 2 is that nano-cellulose cross-linked graphene/chitosan aeroge SEM of embodiment 1 schemes.
Specific embodiment
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
The nano-cellulose used in specific embodiment is nanocrystalline cellulose (NCC).
Embodiment 1
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 3:1:3.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 1.2g sodium metaperiodate is taken to be dissolved in 20mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 0.6g nanometers
Cellulose is protected from light 4h at 40 DEG C, is filtered, washed, and removes unreacted sodium metaperiodate, obtains dialdehyde nano-cellulose；
2) after taking 1g polyethyleneimine to mix with 0.2g graphene oxide, 4h is reacted in 90 DEG C of heating, film is crossed and filters, remove
Unreacted polyethyleneimine obtains polyethyleneimine-modified graphene oxide；
3) it disperses dialdehyde nano-cellulose in distilled water, it is molten that the dialdehyde nano-cellulose that mass fraction is 2% is made
Liquid；It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 1% is made and aoxidizes stone
Black alkene solution；
The ratio for being 3:1 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 0.6g chitosan is weighed to be added in the acetic acid solution of 19.4g 1%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 3:1:3, takes
The resulting composite solution of step 3) is added dropwise in chitosan solution dropwise, is uniformly mixed, and dialdehyde nano-cellulose/amine is obtained
Base modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 4h at room temperature is freeze-dried 12h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Dialdehyde obtained in the step 1) of nano-cellulose used by the present embodiment and above-mentioned preparation method is received respectively
Rice cellulose carries out XRD test, and gained XRD spectrum is shown in Fig. 1, and nano-cellulose NCC is in 2 θ=16 ° and 2 θ=22 ° as shown in Figure 1
Diffraction maximum is presented, shows that sample is cellulose I type crystal.From the point of view of comparison, the above-mentioned diffraction peak intensity of dialdehyde nano-cellulose DAC
It is greatly lowered, shows that the crystallinity of DAC significantly reduces since hydroxyl is converted into aldehyde radical in NCC.Due to the generation of aldehyde radical in DAC,
Be conducive to the chemical crosslinking of dialdehyde nano-cellulose Yu modified graphene oxide and chitosan.
SEM test is carried out to the nano-cellulose cross-linked graphene/chitosan aeroge of the present embodiment, resulting SEM shines
Piece is shown in Fig. 2, and as shown in Figure 2, three-dimensional net structure is presented in gained aeroge, has big specific surface area.Graphene oxide layer
It is dispersed in polymeric matrix, has no obvious reunion.
Embodiment 2
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 2:1:3.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 1.0g sodium metaperiodate is taken to be dissolved in 20mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 0.6g nanometers
Cellulose is protected from light 6h at 40 DEG C, is filtered, washed, and removes unreacted sodium metaperiodate, obtains dialdehyde nano-cellulose；
2) after taking 1g polyethyleneimine to mix with 0.3g graphene oxide, 4h is reacted in 90 DEG C of heating, film is crossed and filters, remove
Unreacted polyethyleneimine obtains polyethyleneimine-modified graphene oxide；
3) it disperses dialdehyde nano-cellulose in distilled water, it is molten that the dialdehyde nano-cellulose that mass fraction is 1% is made
Liquid；
It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 1% is made
Graphene oxide solution；
The ratio for being 2:1 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 0.9g chitosan is weighed to be added in the acetic acid solution of 29.1g 1%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 2:1:3, takes
The resulting composite solution of step 3) is added dropwise in chitosan solution dropwise, is uniformly mixed, and dialdehyde nano-cellulose/amine is obtained
Base modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 6h at room temperature is freeze-dried 20h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Embodiment 3
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:2:3.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 1.0g sodium metaperiodate is taken to be dissolved in 20mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 0.5g nanometers
Cellulose is protected from light 8h at 40 DEG C, is filtered, washed, and removes unreacted sodium metaperiodate, obtains dialdehyde nano-cellulose；
2) after taking 4g polyethyleneimine to mix with 1g graphene oxide, 4h is reacted in 90 DEG C of heating, film is crossed and filters, remove not
The polyethyleneimine of reaction obtains polyethyleneimine-modified graphene oxide；
3) it disperses dialdehyde nano-cellulose in distilled water, it is molten that the dialdehyde nano-cellulose that mass fraction is 2% is made
Liquid；
It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 1% is made
Graphene oxide solution；
The ratio for being 1:2 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 1.5g chitosan is weighed to be added in the acetic acid solution of 48.5g 1%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:2:3, takes
The resulting composite solution of step 3) is added dropwise in chitosan solution dropwise, is uniformly mixed, and dialdehyde nano-cellulose/amine is obtained
Base modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 8h at room temperature is freeze-dried 40h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Embodiment 4
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:3:3.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 2.5g sodium metaperiodate is taken to be dissolved in 40mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 0.5g nanometers
Cellulose is protected from light for 24 hours at 40 DEG C, is filtered, washed, and unreacted sodium metaperiodate is removed, and obtains dialdehyde nano-cellulose；
2) after taking 8g polyethyleneimine to mix with 1.5g graphene oxide, 6h is reacted in 85 DEG C of heating, film is crossed and filters, remove
Unreacted polyethyleneimine obtains polyethyleneimine-modified graphene oxide；
3) it disperses dialdehyde nano-cellulose in distilled water, the dialdehyde nano-cellulose that mass fraction is 1.5% is made
Solution；
It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 1% is made
Graphene oxide solution；
The ratio for being 1:3 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 1.5g chitosan is weighed to be added in the acetic acid solution of 48.5g 1%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:3:3, takes
The resulting composite solution of step 3) is added dropwise in chitosan solution dropwise, is uniformly mixed, and dialdehyde nano-cellulose/amine is obtained
Base modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 2h at room temperature is freeze-dried 48h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Embodiment 5
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 4:1:12.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 2.0g sodium metaperiodate is taken to be dissolved in 40mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 0.5g nanometers
Cellulose is protected from light 16h at 40 DEG C, is filtered, washed, and removes unreacted sodium metaperiodate, obtains dialdehyde nano-cellulose；
2) after taking 0.5g polyethyleneimine to mix with 0.125g graphene oxide, 5h is reacted in 85 DEG C of heating, film is crossed and filters,
Unreacted polyethyleneimine is removed, polyethyleneimine-modified graphene oxide is obtained；
3) it disperses dialdehyde nano-cellulose in distilled water, it is molten that the dialdehyde nano-cellulose that mass fraction is 2% is made
Liquid；
It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 1% is made
Graphene oxide solution；
The ratio for being 4:1 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 1.5g chitosan is weighed to be added in the acetic acid solution of 48.5g 1%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 4:1:12,
Take the resulting composite solution of step 3) to be added dropwise in chitosan solution dropwise, be uniformly mixed, obtain dialdehyde nano-cellulose/
Amino modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 5h at room temperature is freeze-dried 30h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Embodiment 6
Nano-cellulose cross-linked graphene/chitosan the aeroge of the present embodiment, by dialdehyde nano-cellulose, amino modified
Graphene oxide and chitosan mixing crosslinking are made；Amino modified graphene oxide is polyethyleneimine-modified graphene oxide；
The mass ratio of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:1:0.5.
Nano-cellulose cross-linked graphene/chitosan aeroge preparation method of the present embodiment, comprising the following steps:
1) 2.0g sodium metaperiodate is taken to be dissolved in 40mL distilled water, the sulphur acid for adjusting pH that 1M is added is 4, is then added 1.0g nanometers
Cellulose is protected from light 16h at 40 DEG C, is filtered, washed, and removes unreacted sodium metaperiodate, obtains dialdehyde nano-cellulose；
2) after taking 2.0g polyethyleneimine to mix with 1.0g graphene oxide, 5h is reacted in 85 DEG C of heating, film is crossed and filters, remove
Unreacted polyethyleneimine is removed, polyethyleneimine-modified graphene oxide is obtained；
3) it disperses dialdehyde nano-cellulose in distilled water, it is molten that the dialdehyde nano-cellulose that mass fraction is 4% is made
Liquid；
It disperses polyethyleneimine-modified graphene oxide in distilled water, the amino modified that mass fraction is 4% is made
Graphene oxide solution；
The ratio for being 1:1 according to dialdehyde nano-cellulose and polyethyleneimine-modified graphene oxide mass ratio, takes dialdehyde
Nano-cellulose solution and the mixing of amino modified graphene oxide solution, ultrasound obtain uniform composite solution；
4) 0.5g chitosan is weighed to be added in the acetic acid solution of 19.4g 2%, heating dissolves chitosan all at 50 DEG C,
Obtain chitosan solution；
The ratio that mass ratio according to dialdehyde nano-cellulose, amino modified graphene oxide and chitosan is 1:1:0.5,
Take the resulting composite solution of step 3) to be added dropwise in chitosan solution dropwise, be uniformly mixed, obtain dialdehyde nano-cellulose/
Amino modified graphene oxide/chitosan mixed solution；
5) above-mentioned dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution is fitted into mold,
Then cross-linking reaction 5h at room temperature is freeze-dried 30h, obtain dialdehyde nano-cellulose cross-linked graphene/compound airsetting of chitosan
Glue to get.
Experimental example
This experimental example is to Examples 1 to 6 resulting nano-cellulose cross-linked graphene/chitosan aeroge to organic dyestuff
Absorption property detected.Detection method are as follows: the sample for accurately weighing 5mg is added to the Congo red molten of 10mL 100mg/mL
(30 DEG C, 100rmin in liquid, are put into water-bath constant temperature oscillator-1) oscillation, after reaching adsorption equilibrium, use uv-spectrophotometric
The absorbance that dye solution is measured under the wavelength of 497nm is counted, it is Congo red so as to find out what is be adsorbed to calculate dye strength
Amount, then calculates Congo red removal rate, the results are shown in Table 1.
The absorption property testing result of cellulose crosslinked graphene oxide/chitosan aeroge obtained by 1 Examples 1 to 6 of table
As it can be seen from table 1 nano-cellulose cross-linked graphene/chitosan composite aerogel is to Congo red with good
Adsorption effect.1~6 pair of Congo red removal rate of experimental example is 92% or more.The experimental results showed that present invention gained Nanowire
Tieing up plain cross-linked graphene/chitosan composite aerogel has good adsorption effect to congo red, in the suction of dyeing waste water
Attached dose of field, has broad application prospects.
Claims (10)
1. a kind of nano-cellulose cross-linked graphene/chitosan aeroge, it is characterised in that: by dialdehyde nano-cellulose, amido
Modified graphene oxide and chitosan mixing crosslinking are made.
2. nano-cellulose cross-linked graphene/chitosan aeroge according to claim 1, it is characterised in that: described double
Aldehyde nano-cellulose is dialdehyde nanocrystalline cellulose.
3. nano-cellulose cross-linked graphene/chitosan aeroge according to claim 1, it is characterised in that: described double
The mass ratio of aldehyde nano-cellulose and the amino modified graphene oxide is 1:0.25~3.
4. nano-cellulose cross-linked graphene/chitosan aeroge according to claim 1, it is characterised in that: described double
The mass ratio of aldehyde nano-cellulose and the chitosan is 1:0.5~3.
5. nano-cellulose cross-linked graphene/chitosan aeroge according to claim 1, it is characterised in that: described mixed
The temperature for closing crosslinking is 15~40 DEG C.
6. nano-cellulose cross-linked graphene/chitosan aeroge according to claim 1, it is characterised in that: the amine
Base modified graphene oxide is polyethyleneimine-modified graphene oxide.
7. a kind of preparation method of nano-cellulose cross-linked graphene/chitosan aeroge as described in claim 1, feature
It is: the following steps are included: by the mixed solution of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan in mold
Middle reaction, it is dry to get.
8. the preparation method of nano-cellulose cross-linked graphene/chitosan aeroge according to claim 7, feature exist
In: the mixed solution is made using the method included the following steps: providing dialdehyde nano-cellulose and amino modified oxidation stone
The composite solution of black alkene；Will the composite solution be added chitosan solution in, be uniformly mixed to get.
9. the preparation method of nano-cellulose cross-linked graphene/chitosan aeroge according to claim 8, feature exist
In: the mass fraction of chitosan is 0.02~3% in the chitosan solution.
10. a kind of nano-cellulose cross-linked graphene/chitosan aeroge as described in claim 1 is organic in removal waste water
Application in terms of dyestuff.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811032482.3A CN109174023B (en) | 2018-09-05 | 2018-09-05 | Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof |
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| CN111001394A (en) * | 2019-12-26 | 2020-04-14 | 武汉工程大学 | Graphene oxide/sodium alginate composite aerogel efficient adsorbent and preparation method and application thereof |
| CN111499929A (en) * | 2020-04-26 | 2020-08-07 | 魏步龙 | Graphene-nano silver modified chitosan-cellulose antibacterial film and preparation method thereof |
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| CN112897629A (en) * | 2021-04-21 | 2021-06-04 | 铜陵博锋实业有限公司 | Plant cellulose modified adsorption material and preparation process thereof |
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