CN113617339A - GOC/PEI composite adsorbent and preparation method and application thereof - Google Patents
GOC/PEI composite adsorbent and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
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- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 claims description 8
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- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
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- 229910021642 ultra pure water Inorganic materials 0.000 description 9
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- 239000000975 dye Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—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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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a GOC/PEI composite adsorbent and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing carboxylated graphene oxide; coupling polyethyleneimine with diethyltriamine pentaacetic acid to obtain a coupling reaction product; and crosslinking the carboxylated graphene oxide and the coupling reaction product to obtain the GOC/PEI composite adsorbent. According to the invention, the carboxylated graphene oxide is modified to prepare the composite adsorbent with high adsorption capacity for various heavy metal ions and dye molecules, the composite adsorbent can be used for treating the heavy metal ions and the dye molecules in water, and the composite adsorbent has a high cyclic utilization rate and a good engineering application prospect in the treatment process.
Description
Technical Field
The invention relates to the technical field of high polymer composite materials, and particularly relates to a GOC/PEI composite adsorbent and a preparation method and application thereof.
Background
The existing water treatment methods mainly comprise that solid adsorbent adsorption technology is widely accepted by people due to the advantages of simplicity, easiness in operation, low cost and the like in various water treatment technologies. Generally, the factors determining the adsorption performance of the solid adsorbent are mainly influenced by physical properties such as surface chemical structure and specific surface area.
Graphene (Graphene) is sp2The new material with a single-layer two-dimensional honeycomb lattice structure formed by tightly stacking hybridized and connected carbon atoms has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. The abundant oxygen-containing functional groups and the high specific surface area of the graphene-based material enable the graphene-based material to have great development potential in solid adsorbents.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a GOC/PEI composite adsorbent and a preparation method and application thereof.
The technical scheme of the invention is as follows:
on the one hand, the preparation method of the GOC/PEI composite adsorbent comprises the following steps: preparing carboxylated graphene oxide; coupling polyethyleneimine with diethyltriamine pentaacetic acid to obtain a coupling reaction product; and crosslinking the carboxylated graphene oxide and the coupling reaction product to obtain the GOC/PEI composite adsorbent.
Preferably, the preparation of the carboxylated graphene oxide comprises the following steps: preparing a graphene oxide dispersion liquid; adding chloroacetic acid and NaOH into the graphene oxide dispersion liquid, and carrying out stirring reaction at room temperature; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the carboxylated graphene oxide.
Preferably, the preparation of the coupling reaction product comprises the following steps: dissolving polyethyleneimine and diethyltriamine pentaacetic acid in pure water according to the proportion, and adjusting the pH value to be acidic; adding a coupling agent under the stirring condition, and reacting for 12h to obtain the coupling reaction product.
Preferably, the ratio is 1-3: 3-1.
Preferably, the pH is adjusted to 5.5 when the pH is adjusted.
Preferably, the coupling agent is a mixture of carbodiimide hydrochloride and N-hydroxysuccinimide.
Preferably, the preparation of the GOC/PEI composite adsorbent comprises the following steps: preparing a carboxylated graphene oxide solution; adding carbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated graphene oxide solution, stirring for 2 hours, and then dropwise adding the coupling reaction product to perform a crosslinking reaction; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the GOC/PEI composite adsorbent.
Preferably, the crosslinking reaction is carried out by stirring at room temperature for 12 hours.
On the other hand, the GOC/PEI composite adsorbent is prepared by adopting the preparation method of the GOC/PEI composite adsorbent.
On the other hand, the application of the GOC/PEI composite adsorbent in water treatment is also provided.
The invention has the beneficial effects that:
according to the invention, a GOC/PEI composite adsorbent with a multiple network structure is constructed by grafting polyethyleneimine and diethyltriamine pentaacetic acid on carboxylated graphene oxide; the composite adsorbent has good adsorption performance on heavy metal ions and dye molecules, can be used for treating the heavy metal ions and the dye molecules in water, and has high recycling rate and good engineering application prospect in the treatment process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of the preparation method of the GOC/PEI composite adsorbent of the present invention;
FIG. 2 is a scanning electron microscope scanning result of the GOC/PEI composite adsorbent of example 3;
FIG. 3 is a graph showing the Fourier transform infrared spectrum characterization of the GOC/PEI composite adsorbent of example 3;
FIG. 4 is a graph showing the adsorption results of heavy metals and dyes by the GOC/PEI composite adsorbent of example 3;
FIG. 5 is a schematic diagram showing the heavy metal and dye adsorption recycling results of the GOC/PEI composite adsorbent of example 3.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. It should be noted that, in the present application, the embodiments and the technical features of the embodiments may be combined with each other without conflict. It is noted that, unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The use of the terms "comprising" or "including" and the like in the present disclosure is intended to mean that the elements or items listed before the term cover the elements or items listed after the term and their equivalents, but not to exclude other elements or items.
In one aspect, as shown in fig. 1, the present invention provides a preparation method of a GOC/PEI composite adsorbent, comprising the following steps: preparing carboxylated graphene oxide; coupling polyethyleneimine with diethyltriamine pentaacetic acid to obtain a coupling reaction product; and crosslinking the carboxylated graphene oxide and the coupling reaction product to obtain the GOC/PEI composite adsorbent.
In a specific embodiment, the carboxylated graphene oxide is prepared by the following steps: preparing a graphene oxide dispersion liquid; adding chloroacetic acid and NaOH into the graphene oxide dispersion liquid, and carrying out stirring reaction at room temperature; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the carboxylated graphene oxide.
In one specific embodiment, the coupling reaction product is prepared by the following steps: dissolving polyethyleneimine and diethyltriamine pentaacetic acid in pure water according to the proportion, and adjusting the pH value to be acidic; adding a coupling agent under the stirring condition, and reacting for 12h to obtain the coupling reaction product.
Optionally, the ratio is 1-3: 3-1; adjusting the pH to 5.5 when adjusting the pH; the coupling agent is a mixture of carbodiimide hydrochloride and N-hydroxysuccinimide.
It should be noted that, in this example, the mixture of carbodiimide hydrochloride and N-hydroxysuccinimide is used as the coupling agent to promote the-COOH of diethyltriaminepentaacetic acid and the-NH of polyethyleneimine mainly by utilizing the high-activity acylation performance of carbodiimide hydrochloride and the carboxyl activation performance of N-hydroxysuccinimide2The bond forms an amide bond-CO-NH-. In addition to the coupling agent of this embodiment, other coupling agents that can achieve this function in the prior art can also be used.
In a specific embodiment, the GOC/PEI composite adsorbent is prepared by the following steps: preparing a carboxylated graphene oxide solution; adding carbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated graphene oxide solution, stirring for 2 hours, and then dropwise adding the coupling reaction product to perform a crosslinking reaction; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the GOC/PEI composite adsorbent.
Alternatively, the crosslinking reaction is carried out by stirring at room temperature for 12 hours.
On the other hand, the invention also provides a GOC/PEI composite adsorbent, which is prepared by adopting the preparation method of the GOC/PEI composite adsorbent.
On the other hand, the application of the GOC/PEI composite adsorbent in water treatment is also provided.
Example 1
The GOC/PEI composite adsorbent is prepared by the following steps:
(1) preparation of carboxylated Graphene Oxide (GOC): dissolving 0.5g of GO in 50mL of ultrapure water, performing ultrasonic treatment for 30min to obtain GO dispersion liquid, adding 1.2g of chloroacetic acid and 1.8g of NaOH, stirring overnight at room temperature, repeatedly performing centrifugal washing by using a high-speed centrifuge until the mixture is neutral, placing the mixture in a freeze dryer for 12h, and then grinding the mixture into powder to obtain the carboxylated graphene oxide GOC.
(2) Polyethyleneimine PEI and diethyltriaminepentaacetic acid DTPA coupling (PD): 0.5g PEI and 1.5g DTPA were dissolved in 20mL ultrapure water, the pH was adjusted to 5.5 with glacial acetic acid, and 0.3g EDC and 0.25g NHS were added to the mixture under magnetic stirring for 12h to give a pale yellow solution PD of the reaction mass of PEI and DTPA.
(3) Crosslinking of GOC and PD (GOC-g-PD): dissolving 0.5g GOC in 50mL of ultrapure water, performing ultrasonic treatment for 10min, adding 0.3g EDC and 0.25g NHS, and stirring for 2 h; then, dripping the PD solution into the GOC dispersion liquid, and stirring and reacting for 12 hours at room temperature; and after the reaction is finished, repeatedly centrifuging and washing the reaction product by using a high-speed centrifuge to be neutral, placing the reaction product in a freeze dryer for 24 hours, grinding the reaction product into powder, and successfully preparing the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD.
Example 2
The GOC/PEI composite adsorbent is prepared by the following steps:
(1) preparation of carboxylated Graphene Oxide (GOC): dissolving 0.5g of GO in 50mL of ultrapure water, performing ultrasonic treatment for 30min to obtain GO dispersion liquid, adding 1.2g of chloroacetic acid and 1.8g of NaOH, stirring at room temperature overnight, and repeatedly performing centrifugal washing by a high-speed centrifuge until the GO dispersion liquid is neutral. And (3) placing the mixture in a freeze dryer for 12 hours, and grinding the mixture into powder to obtain the carboxylated graphene oxide GOC.
(2) Polyethyleneimine PEI and diethyltriaminepentaacetic acid DTPA coupling (PD): 1.0g PEI and 1.5g DTPA were dissolved in 20mL ultrapure water, the pH was adjusted to 5.5 with glacial acetic acid, and 0.3g EDC and 0.25g NHS were added to the mixture under magnetic stirring for 12h to give a pale yellow solution PD of the reaction mass of PEI and DTPA.
(3) Crosslinking of GOC and PD (GOC-g-PD): 0.5g GOC was dissolved in 50mL ultrapure water and sonicated for 10min, 0.3g EDC and 0.25g NHS were added and stirred for 2 h. Then, the PD solution was added dropwise to the GOC dispersion, and the reaction was stirred at room temperature for 12 hours. And after the reaction is finished, repeatedly centrifuging and washing the reaction product by using a high-speed centrifuge to be neutral, placing the reaction product in a freeze dryer for 24 hours, grinding the reaction product into powder, and successfully preparing the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD.
Example 3
The GOC/PEI composite adsorbent is prepared by the following steps:
(1) preparation of carboxylated Graphene Oxide (GOC): dissolving 0.5g of GO in 50mL of ultrapure water, performing ultrasonic treatment for 30min to obtain GO dispersion liquid, adding 1.2g of chloroacetic acid and 1.8g of NaOH, stirring at room temperature overnight, and repeatedly performing centrifugal washing by a high-speed centrifuge until the GO dispersion liquid is neutral. And (3) placing the mixture in a freeze dryer for 12 hours, and grinding the mixture into powder to obtain the carboxylated graphene oxide GOC.
(2) Polyethyleneimine PEI and diethyltriaminepentaacetic acid DTPA coupling (PD): 1.5g PEI and 0.5g DTPA were dissolved in 20mL ultrapure water, the pH was adjusted to 5.5 with glacial acetic acid, and 0.3g EDC and 0.25g NHS were added to the mixture under magnetic stirring for 12h to give a pale yellow solution PD of the reaction mass of PEI and DTPA.
(3) Crosslinking of GOC and PD (GOC-g-PD): 0.5g GOC was dissolved in 50mL ultrapure water and sonicated for 10min, 0.3g EDC and 0.25g NHS were added and stirred for 2 h. Then, the PD solution was added dropwise to the GOC dispersion, and the reaction was stirred at room temperature for 12 hours. And after the reaction is finished, repeatedly centrifuging and washing the reaction product by using a high-speed centrifuge to be neutral, placing the reaction product in a freeze dryer for 24 hours, grinding the reaction product into powder, and successfully preparing the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD.
Test example 1
The results of scanning the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD prepared in examples 1-3 by a scanning electron microscope are similar, wherein the scanning results of example 3 are shown in FIG. 2. As can be seen from FIG. 2, the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD prepared in example 3 has a two-dimensional wrinkled lamellar structure, and the lamellar structure is curled
Test example 2
The carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD prepared in the embodiments 1-3 is characterized by a Fourier infrared spectrum, and the results of the three are approximate, wherein the characterization result of the embodiment 3 is shown in FIG. 3. As can be seen from FIG. 3, the GOC-g-PD of the carboxylated graphene oxide/polyethyleneimine composite adsorbent prepared in example 3 is 3409cm-1(N-H stretching vibration), 1624cm-1(amide C ═ O stretching vibration) 1453cm-1(NH-of secondary amide), 1394cm-1(C-N stretching vibration), 1240cm-1(C-O stretching vibration of carboxyl) stretching vibration is carried out, which shows that the preparation of the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD is successful.
Test example 3
The adsorption capacity of the carboxylated graphene oxide/polyethyleneimine composite adsorbent prepared in example 3 on heavy metals and dyes is tested, and the method comprises the following steps:
(1) transferring 25mL of heavy metal ion stock solution (the concentration of heavy metal ions is 50-500mg/L represented by Cu (II) and Pb (II)) into a 100mL conical flask by using a pipette, adjusting the pH to 2-7, weighing 0.02g of composite adsorbent GOC-g-PD in the conical flask, sealing the conical flask, oscillating in a 35 ℃ water bath for 12h, taking out the suspension, centrifuging by using a centrifugal machine to obtain supernatant, detecting the concentrations of Cu (II) and Pb (II) in the supernatant by using ICP-OES, and calculating the adsorption capacity.
(2) Transferring 25mL of methylene blue dye stock solution (with the concentration of 50-500mg/L) into a 100mL conical flask by using a pipette, adjusting the pH to 2-10, weighing 0.02g of composite adsorbent GOC-g-PD in the conical flask, sealing, oscillating in a 35 ℃ water bath for 24h, taking out the suspension, centrifuging by using a centrifugal machine to obtain a supernatant, and taking the supernatant and measuring the absorbance by using an ultraviolet spectrophotometer.
The test results are shown in fig. 4. As can be seen from FIG. 4, Cu (II), Pb (II) and MB reached adsorption equilibrium at about 300mg/L and 400mg/L, respectively, and the maximum adsorption equilibrium capacities were 293.8mg/g, 285.61mg/g and 283.74mg/g, respectively. The adsorption capacity is high, and the carboxylic graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD has good adsorption capacity on heavy metals and dyes.
Test example 4
The recycling capability of the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD prepared in example 3 in water treatment of heavy metals and dyes is tested, and the method comprises the following steps:
(1) transferring 25mL of Cu (II) and Pb (II) (50mg/L, pH 7) into a 100mL conical flask by using a pipette, weighing 0.1g of GOC-g-PD adsorbent, oscillating in a water bath for 12h, taking out turbid liquid after the first adsorption experiment is finished, centrifugally separating the adsorbent, adding the adsorbent into the conical flask filled with 25mL of 0.2mol/LHCl solution for desorption for 18h, performing vacuum drying after the desorption for the second adsorption, repeating the experiment to finish 8 times of adsorption and desorption, detecting the concentration in the adsorbed solution by using ICP-OES, and calculating the removal rate of the Cu (II) and the Pb (II) adsorbed each time.
(2) Transferring 25mL of MB (50mg/L, pH 9) into a 100mL conical flask by using a pipette, weighing 0.1g of GOC-g-PD adsorbent, oscillating in a water bath for 12h, taking out turbid liquid after the first adsorption experiment is finished, centrifugally separating the adsorbent, adding the adsorbent into the conical flask filled with 25mL of 0.2mol/LHCl solution for desorption for 18h, and performing vacuum drying for second adsorption after the desorption is finished, thereby repeating the same experiment steps and finishing adsorption and desorption for 8 times. The concentration of methylene blue dye in the solution after adsorption was determined according to the MB standard curve, and the removal rate of each adsorption of MB was calculated.
The test results are shown in fig. 5. As can be seen from FIG. 5, after 6 times of cyclic adsorption, the removal capacity for Cu (II) is 87.9%, the removal capacity for Pb (II) is 84.3%, and the removal capacity for MB is 83.5%, which are all over 80%, indicating that the carboxylated graphene oxide/polyethyleneimine composite adsorbent GOC-g-PD can be recycled and has a good recycling effect in the water treatment process of heavy metals and dyes.
The main reasons for the good adsorption performance of the carboxylated graphene oxide/polyethyleneimine composite adsorbent are as follows: the carboxylated graphene oxide material has a plurality of oxygen-containing functional groups with negative charges, is easy to adsorb organic pollutants containing pi electrons, has good adsorption performance on methylene blue dye molecules, and is strong in deprotonation performance of the carboxyl functional groups, and capable of efficiently combining cations; the polyethyleneimine is a water-soluble high-molecular polymer, and a large number of amino groups are arranged on the molecular chain of the polyethyleneimine and can be coordinated with heavy metal ions; the diethyltriaminepentaacetic acid is used as a high-efficiency chelating agent, and can effectively adsorb heavy metal ions; the carboxylated graphene oxide is grafted and modified by amino/carboxyl organic functional groups, so that the adsorption practicability is improved, and the adsorption active sites of the adsorbent are greatly improved by utilizing the surface structure characteristics of the composite material.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the GOC/PEI composite adsorbent is characterized by comprising the following steps:
preparing carboxylated graphene oxide;
coupling polyethyleneimine with diethyltriamine pentaacetic acid to obtain a coupling reaction product;
and crosslinking the carboxylated graphene oxide and the coupling reaction product to obtain the GOC/PEI composite adsorbent.
2. The method for preparing GOC/PEI composite adsorbent according to claim 1, wherein the preparation of the carboxylated graphene oxide comprises the following steps: preparing a graphene oxide dispersion liquid; adding chloroacetic acid and NaOH into the graphene oxide dispersion liquid, and carrying out stirring reaction at room temperature; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the carboxylated graphene oxide.
3. The method for preparing GOC/PEI composite adsorbent as claimed in claim 1, wherein the coupling reaction product is prepared by the following steps: dissolving polyethyleneimine and diethyltriamine pentaacetic acid in pure water according to the proportion, and adjusting the pH value to be acidic; adding a coupling agent under the stirring condition, and reacting for 12h to obtain the coupling reaction product.
4. The method for preparing the GOC/PEI composite adsorbent as claimed in claim 3, wherein the ratio is 1-3: 3-1.
5. The method for preparing GOC/PEI complex adsorbent as claimed in claim 3, wherein the pH is adjusted to 5.5 when adjusting the pH.
6. The method for preparing a GOC/PEI composite adsorbent according to claim 3, wherein the coupling agent is a mixture of carbodiimide hydrochloride and N-hydroxysuccinimide.
7. The method for preparing GOC/PEI complex adsorbent as claimed in claim 1, wherein the method for preparing GOC/PEI complex adsorbent comprises the following steps: preparing a carboxylated graphene oxide solution; adding carbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated graphene oxide solution, stirring for 2 hours, and then dropwise adding the coupling reaction product to perform a crosslinking reaction; and after the reaction is finished, washing, freeze-drying and grinding into powder to obtain the GOC/PEI composite adsorbent.
8. The method for preparing GOC/PEI composite adsorbent according to claim 7, wherein the cross-linking reaction is carried out under stirring at room temperature for 12 h.
9. A GOC/PEI composite adsorbent, characterized in that it is prepared by the method for preparing a GOC/PEI composite adsorbent according to any one of claims 1-8.
10. Use of the GOC/PEI complex adsorbent of claim 9 in water treatment.
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