CN108212117A - A kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material - Google Patents

A kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material Download PDF

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CN108212117A
CN108212117A CN201611157496.9A CN201611157496A CN108212117A CN 108212117 A CN108212117 A CN 108212117A CN 201611157496 A CN201611157496 A CN 201611157496A CN 108212117 A CN108212117 A CN 108212117A
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polyethyleneimine
graphene oxide
composite material
carboxymethyl cellulose
cellulose composite
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林雪梅
孟晗
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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Abstract

The invention discloses a kind of preparation methods of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material, nucleophilic displacement of fluorine occurs and acts on by the amino on polyethyleneimine strand and the carboxyl of surface of graphene oxide, epoxy group, prepare graphene oxide/polyethyleneimine composite material, again using glutaraldehyde as coupling agent, with the further modified graphene oxide/polyethyleneimine of carboxymethyl cellulose, three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material is obtained.The present invention increases the oxygen-containing adsorption site quantity of negatively charged of material, and form three-D space structure, further improves absorption property by introducing carboxymethyl cellulose.Under mild acid conditions, three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material of the invention is to Pb2+There is good adsorption effect, compared with graphene oxide/polyethyleneimine, adsorbance improves 34.6%, can be applied to heavy metal adsorption processing.

Description

A kind of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material Preparation method
Technical field
The present invention relates to a kind of preparation sides of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material Method belongs to technical field of material.
Background technology
The exploitation of heavy metal, smelting, process cause heavy metal such as lead, mercury, cadmium, cobalt etc. to enter big gas and water, soil In, cause serious environmental pollution, and heavy metal ion and its compound are sufficiently stable in the environment, there is enriching, no Can its harmfulness be reduced by the purification of nature.Therefore, that how to administer that heavy metal pollution is that industrial development faces important chooses War.
Absorption method is the most commonly used method of heavy metal containing wastewater treatment.Biomaterial type is enriched, cheap to be easy to get, and can be given birth to Object is degraded, and cellulose, pectic substance, lignin and chitosan rich in hydroxyl, carboxyl and amido etc. can occur with metal ion Physical absorption or chelant effect have the potential of larger removal metal ion, are obtained extensively in absorbing heavy metal ions Concern.
Derivative of the graphene oxide (GO) as graphene, containing a large amount of acid oxygen-containing in large specific surface area and lamella Functional group, have preferable absorption property, additionally many material exhibits are gone out with very strong compatibility, can via with oxygen-containing function Group reaction and be modified.Sui Zhu silver et al. is prepared for graphene oxide/polyethyleneimine composite material, is formed by being freeze-dried Three-dimensional hole, for adsorbing dyestuff and carbon dioxide, but this method is material to be made to form opening structure using external physical means, Increase material preparation cost (Sui Z Y, et al.Preparation of Three-Dimensional Graphene Oxide-Polyethylenimine Porous Materials as Dye and Gas Adsorbents[J].ACS Appl.Mater.Interfaces 2013,5,9172-9179).King family is macro et al. to use polyethyleneimine-modified graphene oxide, And it is had studied to Cr2+Absorption property, maximal absorptive capacity 56.99mg/g, adsorbance with pH value increase and reduce (Wang Jia It is macro to wait polyethyleneimine-modifieds graphite oxide to Cr in water2+Absorption [J] Chinese Journal of Inorganic Chemistries, 2015,31 (6), 1185- 1193.)。
Although graphene oxide and its composite material show heavy metal ion good absorption property, generally existing Adsorption capacity is relatively low and cost is higher, reuses the problems such as performance is poor.
Invention content
For it is existing based on the composite adsorbing material of graphene oxide there are the problem of, the present invention provides a kind of three-dimensionals The preparation method of graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material.The method passes through polyethyleneimine point Nucleophilic displacement of fluorine effect occurs for the carboxyl on amino and surface of graphene oxide in subchain, epoxy group, prepares graphene oxide/poly- Aziridine (GO/PEI) composite material, then using glutaraldehyde as coupling agent, with the further modified graphite oxide of carboxymethyl cellulose Alkene/polyethyleneimine obtains three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose (GO/PEI/CMC) composite material. The present invention increases the adsorption site of material, and unexpectedly form three-D space structure by introducing carboxymethyl cellulose, into Improve absorption property to one step.
Technical scheme is as follows：
A kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material, specific steps It is as follows：
Step 1, graphite oxide is placed in water ultrasonic disperse and obtains graphene oxide dispersion, adjust graphene oxide point The pH of dispersion liquid to 8.0 ± 0.5 is 1 by the mass ratio of polyethyleneimine and graphene oxide：1~3 addition polyethyleneimine is molten Liquid reacts at room temperature after ultrasonic mixing is uniform, obtains graphene oxide/polyethyleneimine complex liquid；
Step 2, it is 1 by the mass ratio of graphene oxide, polyethyleneimine and sodium carboxymethylcellulose:1~3:0.5~1, Carboxymethylcellulose sodium solution is added in graphene oxide/polyethyleneimine complex liquid, is uniformly mixed, 800~ Glutaraldehyde is slowly added dropwise under 1000rpm mixing speeds, after completion of dropwise addition, the reaction was continued under 500~600rpm mixing speeds, washes It washs, is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material.
Preferably, in step 1, reaction time 20-24h.
Preferably, in step 2, the mass ratio 1 of the graphene oxide, polyethyleneimine and sodium carboxymethylcellulose: 2:1, the reaction was continued, and the time is 4h.
The present invention also provides three-dimensional graphene oxide/polyethyleneimine/carboxymethyl celluloses that the above method is prepared Composite material.
Further, three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose that the above method is prepared is compound Application of the material in heavy metal ion adsorbed, concrete application method are：The pH of heavy metal ion-containing waste water is adjusted to 2~7, Three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material is added in be adsorbed.
Preferably, the pH of the heavy metal ion-containing waste water is 5.5.
Preferably, the adsorption time is 4-5h.
The present invention prepares graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material by necleophilic reaction, system Preparation Method is easy, at low cost.Containing a large amount of carboxyl and hydroxyl in carboxymethyl cellulose strand, can be generated with heavy metal ion Stronger coordination improves composite material to Pb2+Absorption property.The three-dimensional graphite oxide that the method for the present invention is prepared Alkene/polyethyleneimine/carboxymethyl cellulose composite material surface contains a large amount of oxygen-containing adsorption site, and with three dimensions Structure, while the thermal stability enhancing of material.Under synergistic effect both ways, graphene oxide/polyethyleneimine/carboxymethyl Cellulose shows good absorption property as adsorbent in absorbing heavy metal ions.
Description of the drawings
Fig. 1 is GO/PEI/CMC composite structure figures.
Fig. 2 is that the SEM of GO/PEI and GO/PEI/CMC composite materials schemes.
Fig. 3 is that the TGA of GO/PEI and GO/PEI/CMC composite materials schemes.
Fig. 4 is that solution initial PH value influences knot to the adsorbance of the GO/PEI/CMC composite material adsorpting lead ions of GO/PEI Fruit is schemed.
Fig. 5 is that adsorption time influences result to the adsorbance of the GO/PEI/CMC composite material adsorpting lead ions of GO/PEI Figure.
Specific embodiment
With reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.2g, ultrasonic 1min react 20h, obtain graphene oxide/polyethyleneimine at room temperature Amine complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.1g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 800rpm mixing speeds, after completion of dropwise addition, 600rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 0.5h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 53.8mg/g.
Embodiment 2
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.4g, ultrasonic 1min react 20h, obtain graphene oxide/polyethyleneimine at room temperature Amine complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.1g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 1000rpm mixing speeds, after completion of dropwise addition, 500rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 4.0h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 68.4mg/g.
Embodiment 3
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.6g, ultrasonic 1min react for 24 hours at room temperature, obtain graphene oxide/polyethyleneimine Amine complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.1g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 1000rpm mixing speeds, after completion of dropwise addition, 500rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 4.0h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 83.2mg/g.
Embodiment 4
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.2g, ultrasonic 1min react 20h, obtain graphene oxide/polyethyleneimine at room temperature Amine complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.2g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 800rpm mixing speeds, after completion of dropwise addition, 600rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 4.0h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 64.0mg/g.
Embodiment 5
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.4g, ultrasonic 1min, react at room temperature for 24 hours, obtain graphene oxide/polyethylene Imines complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.2g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 1000rpm mixing speeds, after completion of dropwise addition, 600rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 4.0h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 95.4mg/g.
Embodiment 6
(1) preparation of graphene oxide/polyethyleneimine：0.2g graphite oxides are placed in the obtained oxygen of ultrasound in deionized water Graphite alkene dispersion liquid adjusts the pH to 8.0 of GO dispersion liquids with the NaOH of 0.1M, and the quality for then adding in polyethyleneimine is The polyethylenimine solution for waiting GO volumes of 0.6g, ultrasonic 1min react for 24 hours at room temperature, obtain graphene oxide/polyethyleneimine Amine complex liquid.
(2) preparation of graphene oxide/polyethyleneimine/carboxymethyl cellulose：Graphene oxide/polyethyleneimine is multiple The quality that conjunction liquid is added to sodium carboxymethylcellulose is in the carboxymethylcellulose sodium solution equal with GO concentration of 0.2g, quickly 30min is stirred, then, at room temperature, glutaraldehyde is slowly added dropwise under 800rpm mixing speeds, after completion of dropwise addition, 600rpm stirring speed Degree is lower the reaction was continued 4h, finally, washing is dried to obtain three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite wood Material.
(3) absorption of the composite material to heavy metal ion:At 25 DEG C, by 20mg graphene oxides/polyethyleneimine/carboxylic first Base cellulose composite material, the pH for being added to 50mL is the Pb of 5.5 a concentration of 50mg/L2+In heavy metal ion solution, stirring is inhaled Attached 4.0h.Heavy metal ion solution concentration in solution after atomic absorption method detection absorption, calculates graphene oxide/polyethyleneimine Amine/carboxymethyl cellulose composite material is to the adsorption rate of heavy metal ion.The result shows that graphene oxide/polyethyleneimine/carboxylic Methylcellulose is to Pb2+Adsorbance be 94.7mg/g.
Comparative example 1
The preparation of graphene oxide/polyethyleneimine composite material, preparation process and adsorption process are measured with embodiment 1 Graphene oxide/polyethyleneimine composite material to Pb2+Adsorbance be 45.2mg/g.
Comparative example 2
The preparation of graphene oxide/polyethyleneimine composite material, preparation process and adsorption process are measured with embodiment 2 Graphene oxide/polyethyleneimine composite material to Pb2+Adsorbance be 57.1mg/g.
Comparative example 3
The preparation of graphene oxide/polyethyleneimine composite material, preparation process and adsorption process are measured with embodiment 3 Graphene oxide/polyethyleneimine composite material to Pb2+Adsorbance be 76.5mg/g.
Table 1 is GO/PEI the and GO/PEI/CMC composite materials in comparative example and embodiment to Pb2+Absorption result.Compare GO/PEI and GO/PEI/CMC composite materials are to Pb in table 12+Adsorption effect, it is known that, when the mass ratio of GO and PEI is constant, Addition CMC can increase GO/PEI/CMC composite material adsorption capacities, be primarily due to introducing CMC and increase adsorption site quantity and material Expect the influence of surface topography.In the case where GO contents are constant, GO/PEI/CMC is higher than GO/PEI to the adsorbance of lead, this is because CMC More electronegative oxygen-containing functional groups are introduced, and the irregular holes structure of GO/PEI/CMC is also beneficial to adsorpting lead ion. The oxygen-containing functional group on GO surfaces is limited, can only connect a certain number of PEI, therefore continues to increase the mass ratio of GO and PEI It is nonsensical.Similarly, the CMC quantity that GO/PEI can be connected is also limited, therefore the best in quality of GO, PEI and CMC Than being 1:2:1.
Table 1GO/PEI and GO/PEI/CMC composite material is to Pb2+Absorption result
Fig. 1 is the structure chart of GO/PEI/CMC composite materials.Fig. 2 is GO/PEI (A) and GO/PEI/CMC (B) composite material SEM, it can be clearly seen that, GO/PEI composite materials are in the rougher two-dimensional structure in surface；GO/PEI/CMC composite materials have There is certain hole, in three-dimensional structure.Fig. 3 is that the TGA of GO/PEI and GO/PEI/CMC composite materials schemes, as seen from the figure, at 400 DEG C Before, the mainly decomposition of the functional group of GO/PEI and GO/PEI/CMC composite material surfaces, PEI and CMC, it is clear that GO/PEI/ The stability higher of CMC composite materials.Fig. 4 be solution initial PH value to the GO/PEI/CMC composite materials Adsorption of Lead of GO/PEI from The influence result figure of the adsorbance of son, under different solutions initial pH, GO/PEI/CMC is all higher than GO/ to the adsorbance of lead ion The adsorbance of PEI.Fig. 5 is adsorption time to influence knot of the GO/PEI and GO/PEI/CMC composite materials to the adsorbance of lead ion Fruit is schemed, it is known that GO/PEI composite materials about reach balance, GO/PEI/CMC composite materials to the absorption of lead ion after 120min Adsorpting lead ion then reaches balance after 240min, and GO/PEI/CMC composite materials are advisable to the adsorption time of lead ion in 4-5h.
In conclusion the more existing composite material phase based on graphene oxide of GO/PEI/CMC composite materials of the present invention Than (such as GO/PEI), on the one hand the addition of carboxymethyl cellulose obtains the composite material with three-D space structure, the opposing party The group on face carboxymethyl cellulose surface further increases the quantity in the oxygen-containing site of negatively charged.In addition, composite material is steady It is qualitative to have promotion.By the improvement of the three-D space structure and more adsorption sites of GO/PEI/CMC composite materials, significantly improve Adsorption effect of the composite material to heavy metal ion, and the promotion of stability so that GO/PEI/CMC of the invention is compound Materials'use is stablized, and suitable environment is more extensive, can be applied to heavy metal adsorption processing.

Claims (8)

1. a kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material, feature exist In being as follows：
Step 1, graphite oxide is placed in water ultrasonic disperse and obtains graphene oxide dispersion, adjust graphene oxide dispersion PH to 8.0 ± 0.5, by the mass ratio of polyethyleneimine and graphene oxide be 1：1~3 adds in polyethylenimine solution, surpasses Sound reacts at room temperature after mixing, obtains graphene oxide/polyethyleneimine complex liquid；
Step 2, it is 1 by the mass ratio of graphene oxide, polyethyleneimine and sodium carboxymethylcellulose:1~3:0.5~1, in oxygen Carboxymethylcellulose sodium solution is added in graphite alkene/polyethyleneimine complex liquid, is uniformly mixed, 800~1000rpm is stirred It mixes and glutaraldehyde is slowly added dropwise under speed, after completion of dropwise addition, the reaction was continued under 500~600rpm mixing speeds, and washing is dried to obtain Three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material.
2. preparation method according to claim 1, which is characterized in that in step 1, reaction time 20-24h.
3. preparation method according to claim 1, which is characterized in that in step 2, the graphene oxide, polyethylene The mass ratio 1 of imines and sodium carboxymethylcellulose:2:1, the reaction was continued, and the time is 4h.
4. three-dimensional graphene oxide/polyethyleneimine/carboxylic first made from preparation method according to any one of claims 1 to 3 Base cellulose composite material.
5. three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material according to claim 4 is in a huge sum of money Belong to the application in ionic adsorption.
6. three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material according to claim 5 is in a huge sum of money Belong to the application in ionic adsorption, which is characterized in that concrete application method is：The pH of heavy metal ion-containing waste water is adjusted to 2~ 7, it adds in three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material and is adsorbed.
7. three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material according to claim 6 is in a huge sum of money Belong to the application in ionic adsorption, which is characterized in that the pH of the heavy metal ion-containing waste water is 5.5.
8. three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material according to claim 6 is in a huge sum of money Belong to the application in ionic adsorption, which is characterized in that the adsorption time is 4-5h.
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