CN109603750B - Containing Fe3O4Preparation method of-GQDs composite gel adsorption film - Google Patents

Containing Fe3O4Preparation method of-GQDs composite gel adsorption film Download PDF

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CN109603750B
CN109603750B CN201811610568.XA CN201811610568A CN109603750B CN 109603750 B CN109603750 B CN 109603750B CN 201811610568 A CN201811610568 A CN 201811610568A CN 109603750 B CN109603750 B CN 109603750B
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CN109603750A (en
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杨革
安笑迟
车程川
刘金锋
巩志金
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Qufu Normal University
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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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract

The invention belongs to the field of sewage treatment, and particularly relates to a Fe-containing sewage treatment agent3O4A preparation method and application of a composite gel adsorption film of-GQDs. Containing Fe3O4The preparation method of the composite gel adsorption film of the-GQDs adopts the following steps: preparation of GOQDs dispersion liquid, preparation of amino-modified graphene quantum dots, carboxyl-modified magnetic nanoparticles and Fe3O4The preparation method comprises the steps of preparing a magnetic nanoparticle-graphene quantum dot composite material, preparing a composite embedding carrier aqueous solution, preparing composite gel and preparing a composite gel adsorption film. The composite gel adsorption film prepared by the invention has the advantages of large adsorption capacity, good mechanical strength, recoverability and good biocompatibility.

Description

Containing Fe3O4Preparation method of-GQDs composite gel adsorption film
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a Fe-containing sewage treatment agent3O4A preparation method and application of a composite gel adsorption film of-GQDs.
Background
In recent years, the phenomenon of surface water pollution in China is increasingly serious under the dual influence of natural factors and human factors. Adsorption is considered an economical and efficient process in wastewater treatment. However, the conventional adsorbent has disadvantages of low adsorption capacity, inconvenient separation, and the like, and thus an adsorbent having more powerful adsorption performance is required. For practical sewage treatment, the sewage treatment material is preferably characterized by environmental friendliness, recoverability or degradability, recyclability and the like.
Polyvinyl alcohol gels have received attention for their non-toxic, inexpensive, antimicrobial decomposition, and high mechanical strength. However, the boric acid cross-linking agent used in the preparation process of the polyvinyl alcohol gel has toxic action on microbial cells, and the polyvinyl alcohol carrier is easy to be adhered in the use process, so that the defects of easy breakage of embedded particles, large mass transfer resistance, upward gas generation, large activity loss and the like exist. The preparation of the sodium alginate immobilized material needs calcium ion crosslinking to form gel, which can effectively embed microbial cells, and the activity of the microorganism is high, but the calcified sodium alginate gel has poor stability, is easy to soften under the action of multiple ions or under the condition that calcium ions are diffused and a large amount of potassium and sodium ions are gathered, and has the phenomenon of enzyme leakage.
The carbon nano material adsorbent has the characteristics of high specific surface area, easiness in obtaining, simple synthesis steps, stable physical and chemical structures and the like, and is a hot point of research. Graphene has a certain degree of cytotoxicity, but studies have found that the cytotoxicity of graphene decreases as the size of the sheet decreases. Patent publication No. CN108605983A discloses a Fe3O4The patent utilizes nano material graphene quantum dots and FeCl3Reaction to form Fe3O4The @ GQDs cannot represent the special physical properties of the magnetic nanoparticles such as superparamagnetism and the like.
Therefore, the development of the adsorption film with large adsorption capacity, good mechanical strength, recoverability and excellent biological performance has obvious economic benefit and social benefit.
Disclosure of Invention
The invention provides a Fe-containing composite material with large adsorption capacity, good mechanical strength, recoverability and excellent biological performance3O4-GQDs composite gel adsorption film and preparation method thereof.
In order to achieve the aim, the invention adopts the following technical scheme:
containing Fe3O4The preparation method of the composite gel adsorption film of the-GQDs adopts the following steps:
1) preparing a graphene oxide quantum dot dispersion liquid: dissolving graphene oxide quantum dots in deionized water, performing ultrasonic treatment until dispersion liquid is formed, dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 3500 Da, and diluting the liquid in the dialysis bag until the concentration of the dispersion liquid of the Graphene Oxide Quantum Dots (GOQDs) is 0.25-0.35 mg/mL.
2) Preparing amino modified graphene quantum dots (N-GQDs): mixing the GOQDs dispersion solution of 0.25mg/mL with strong ammonia water, stirring, performing hydrothermal reaction at 100 deg.C for 5 h, cooling to room temperature, taking out the reaction solution, and dialyzing with dialysis bag with molecular weight cutoff of 3500 Da for 4 days. Taking out the solution in the dialysis bag, centrifuging at the rotating speed of 11000 r/min for 15 min to remove precipitates, filtering by using a filter membrane of 0.45 mu m, and freeze-drying to obtain the amino modified graphene quantum dots named as N-GQDs.
3) Carboxyl-modified magnetic nanoparticles: mixing the nano ferroferric oxide dispersion liquid with toluene for later use. Dissolving dimercaptosuccinic acid (DMSA) in dimethyl sulfoxide (DMSO), adding the dimethyl sulfoxide (DMSO) into a toluene solution of ferroferric oxide, stirring for 12 hours at the temperature of 25 ℃ at 120-150 rpm, adding ethyl acetate for precipitation after the reaction is finished, collecting with a magnet, repeating for 2-3 times, cleaning with deionized water for 3 times, finally dissolving in deionized water, and adjusting the pH value to be 7-8 with sodium hydroxide to obtain the magnetic nanoparticles (Fe) with good water solubility and surface carboxylation3O4-DMSA）。
4）Fe3O4Preparing a magnetic nanoparticle-graphene quantum dot composite material: 40mL of Fe was taken3O4DMS, adjusting the pH value to 5-6 by using MES buffer, performing ultrasonic treatment for 10 min, adding 160 mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 240 mg of N-hydroxythiosuccinimide (NHS), performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 ℃ for 15 min, placing the reaction solution in a centrifuge at the rotating speed of 12000 r/min, performing centrifugal treatment for 10 min, and removing the supernatant. Preparing 4 mg/mL N-GQDs suspension, and resuspending Fe by using the N-GQDs solution3O4-DMSA precipitation, adjusting the mixed solution to 7.2-7.5 with PBS buffer, performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 deg.C for 10 h, centrifuging, washing, dialyzing with dialysis bag with molecular weight cutoff of 3500 Da for 2 days, and freeze drying to obtain Fe3O4GQDs powder.
5) Preparing a composite embedding carrier aqueous solution: adding polyvinyl alcohol and sodium alginate into deionized water, sterilizing at high temperature to dissolve completely, and cooling to 28-32 deg.C to obtain polyvinyl alcohol/sodium alginate aqueous solution composite embedding carrier aqueous solution;
6) compoundingPreparation of gel: mixing the Fe prepared in the step (4)3O4Mixing GQDs with the aqueous solution of the composite embedding carrier prepared in the step (5), and uniformly stirring;
7) preparing a composite gel adsorption film: and (3) immersing the polypropylene non-woven fabric into the composite gel prepared in the step (6) at 25-30 ℃ for 3-5 min, taking out, immersing into a calcium chloride/saturated boric acid solution at-5 ℃ to form a film with a single side of 1-3 mm, and carrying out fixed crosslinking at 4 ℃ for 24h to obtain the composite gel adsorption film.
Preferably, the dosage ratio of the GOQDs dispersion liquid and the concentrated ammonia water in the step 2) is 4-6 mL:1 mL.
Preferably, the concentration of the nano ferroferric oxide dispersion liquid in the step 3) is 25%; the dosage ratio of the ferroferric oxide dispersion liquid to the toluene is 1 mL: 0.05-0.1 mL; the dosage ratio of dimercaptosuccinic acid (DMSA) to dimethyl sulfoxide (DMSO) is 10 mg: 1 mL; the dosage ratio of the ferroferric oxide toluene solution to the dimercaptosuccinic acid (DMSA) dimethyl sulfoxide (DMSO) solution is 0.8-1.2 mL: 100 mL; finally obtaining Fe3O4DMSA concentration 0.8 mg/mL.
Preferably, Fe described in step 4)3O4The dosage ratio of the DMSA to the N-GQDs suspension is 2mL:0.8-1.2 mL;
preferably, the temperature of the high-temperature sterilization in the step 5) is 121 ℃, the pressure is 105-110kPa, and the time is 20 min; the dosage ratio of the polyvinyl alcohol, the sodium alginate and the deionized water is 10-14 g: 3-5 g: 100 mL.
Preferably, said Fe in step 6)3O4The dosage ratio of the GQDs to the composite embedding carrier aqueous solution is 3-5 g: 100 mL.
The graphene oxide quantum dots for preparing the composite gel ball composite gel adsorption film are purchased from pioneer nano company, model No. xf074.
A composite gel adsorption film prepared by the preparation method.
An application of the composite gel adsorption film in wastewater treatment.
Preferably, the adding amount of the composite gel adsorption film in the wastewater is the film widthThe ratio of the degree to the bottom area of the wastewater treatment device is 0.1-0.3m:1m2 The membrane height is the same as the wastewater level height in the wastewater treatment plant.
In the invention, Fe3O4and-GQDs is used as an adsorbent, normal saline is used as a surface treating agent, 3% calcium chloride/saturated boric acid solution is used as a cross-linking agent, sodium alginate and polyvinyl alcohol are used as embedding agents, polypropylene water imitation cloth is used as a carrier, and the composite gel adsorption film is prepared by adopting an embedding co-adsorption mode.
Advantageous effects
(1) The composite gel adsorption film prepared by the invention has the advantages of large adsorption capacity, good mechanical strength, recoverability and good biocompatibility.
(2) In the invention, Fe3O4the-GQDs are adsorbents, can remarkably improve the adsorption capacity of the composite gel adsorption film on heavy metals, organic pollutants and the like by chelating surface amino groups of the-GQDs with metal ions, adsorbing aromatic compounds by pi-pi stacking and the like, can also play a role in supporting a framework and can enhance the mechanical strength of the composite gel adsorption film.
Detailed description of the invention
The invention is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the present disclosure, and equivalents fall within the scope of the invention defined by the appended claims.
Example 1
Containing Fe3O4-GQDs composite gel adsorption membranes, prepared by the following steps:
1) preparing a graphene oxide quantum dot dispersion liquid: dissolving graphene oxide quantum dots in deionized water, performing ultrasonic treatment until dispersion liquid is formed, dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 3500 Da, and diluting the liquid in the dialysis bag until the concentration of the dispersion liquid of the Graphene Oxide Quantum Dots (GOQDs) is 0.3 mg/mL.
2) Preparing amino modified graphene quantum dots (N-GQDs): mixing the GOQDs dispersion solution of 0.25mg/mL with strong ammonia water, stirring, performing hydrothermal reaction at 100 deg.C for 5 h, cooling to room temperature, taking out the reaction solution, and dialyzing with dialysis bag with molecular weight cutoff of 3500 Da for 4 days. Taking out the solution in the dialysis bag, centrifuging at the rotating speed of 11000 r/min for 15 min to remove precipitates, filtering by using a filter membrane of 0.45 mu m, and freeze-drying to obtain the amino modified graphene quantum dots named as N-GQDs.
3) Carboxyl-modified magnetic nanoparticles: mixing the nano ferroferric oxide dispersion liquid with toluene for later use. Dissolving dimercaptosuccinic acid (DMSA) in dimethyl sulfoxide (DMSO), adding into a toluene solution of ferroferric oxide, stirring at 25 ℃ and 150rpm for 12h, after the reaction is finished, adding ethyl acetate for precipitation, collecting with a magnet, repeating for 3 times, washing with deionized water for 3 times, finally dissolving in deionized water, and adjusting the pH to 8 with sodium hydroxide to obtain the magnetic nanoparticles (Fe) with good water solubility and surface carboxylation3O4-DMSA）。
4）Fe3O4Preparing a magnetic nanoparticle-graphene quantum dot composite material: 40mL of Fe was taken3O4DMS, adjusting the pH value to 6 by using MES buffer, performing ultrasonic treatment for 10 min, adding 160 mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 240 mg of N-hydroxythiosuccinimide (NHS), performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 ℃ for 15 min, placing the reaction solution in a centrifuge at the rotating speed of 12000 r/min, performing centrifugal treatment for 10 min, and removing the supernatant. Preparing 4 mg/mL N-GQDs suspension, and resuspending Fe by using the N-GQDs solution3O4-DMSA precipitation, adjusting the mixed solution to 7.5 with PBS buffer, performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 deg.C for 10 h, centrifuging and washing after reaction, dialyzing with a dialysis bag with molecular weight cutoff of 3500 Da for 2 days, and freeze-drying to obtain Fe3O4GQDs powder.
5) Preparing a composite embedding carrier aqueous solution: adding polyvinyl alcohol and sodium alginate into deionized water, sterilizing at high temperature to dissolve completely, and cooling to 30 deg.C to obtain polyvinyl alcohol/sodium alginate aqueous solution composite embedding carrier aqueous solution;
6) preparation of composite gel:mixing the Fe prepared in the step (4)3O4Mixing GQDs with the aqueous solution of the composite embedding carrier prepared in the step (5), and uniformly stirring;
7) preparing a composite gel adsorption film: and (3) immersing the polypropylene non-woven fabric into the composite gel prepared in the step (6) at 28 ℃ for 5min, taking out the non-woven fabric, immersing the non-woven fabric into a calcium chloride/saturated boric acid solution at-5 ℃ to form a film with a single side of 3mm, and carrying out fixed crosslinking at 4 ℃ for 24h to obtain the composite gel adsorption film.
The dosage ratio of the GOQDs dispersion liquid to the strong ammonia water in the step 2) is 5 mL:1 mL.
The concentration of the nano ferroferric oxide dispersion liquid in the step 3) is 25 percent; the dosage ratio of the ferroferric oxide dispersion liquid to the toluene is 1 mL: 0.08 mL; the dosage ratio of dimercaptosuccinic acid (DMSA) to dimethyl sulfoxide (DMSO) is 10 mg: 1 mL; the dosage ratio of the ferroferric oxide toluene solution to the dimercaptosuccinic acid (DMSA) dimethyl sulfoxide (DMSO) solution is 1 mL: 100 mL; finally obtaining Fe3O4DMSA concentration 0.8 mg/mL.
Fe described in step 4)3O4The dosage ratio of the DMSA to the N-GQDs suspension is 2mL to 1 mL;
the high-temperature sterilization in the step 5) is carried out at the temperature of 121 ℃ and under the pressure of 105kPa for 20 min; the dosage ratio of the polyvinyl alcohol to the sodium alginate to the deionized water is 12 g: 4 g: 100 mL.
Fe described in step 6)3O4The dosage ratio of GQDs to the composite embedding carrier aqueous solution is 5 g: 100 mL.
The graphene oxide quantum dots for preparing the composite gel adsorption film are purchased from pioneer nano company, model No. xf074.
A composite gel adsorption film prepared by the preparation method.
An application of the composite gel adsorption film in wastewater treatment.
Preferably, the adding amount of the composite gel adsorption film in the wastewater is that the ratio of the film width to the bottom area of the wastewater treatment device is 0.3m:1m2 The membrane height is the same as the wastewater level height in the wastewater treatment plant.
Example 2
Containing Fe3O4-GQDs composite gel adsorption membranes, prepared by the following steps:
1) preparing a graphene oxide quantum dot dispersion liquid: dissolving graphene oxide quantum dots in deionized water, performing ultrasonic treatment until dispersion liquid is formed, dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 3500 Da, and diluting the solution in the dialysis bag until the concentration of the dispersion liquid of the Graphene Oxide Quantum Dots (GOQDs) is 0.25 mg/mL.
2) Preparing amino modified graphene quantum dots (N-GQDs): mixing the GOQDs dispersion solution of 0.25mg/mL with strong ammonia water, stirring, performing hydrothermal reaction at 100 deg.C for 5 h, cooling to room temperature, taking out the reaction solution, and dialyzing with dialysis bag with molecular weight cutoff of 3500 Da for 4 days. Taking out the solution in the dialysis bag, centrifuging at the rotating speed of 11000 r/min for 15 min to remove precipitates, filtering by using a filter membrane of 0.45 mu m, and freeze-drying to obtain the amino modified graphene quantum dots named as N-GQDs.
3) Carboxyl-modified magnetic nanoparticles: mixing the nano ferroferric oxide dispersion liquid with toluene for later use. Dissolving dimercaptosuccinic acid (DMSA) in dimethyl sulfoxide (DMSO), adding into a toluene solution of ferroferric oxide, stirring at 25 ℃ for 12h at 120rpm, after the reaction is finished, adding ethyl acetate for precipitation, collecting with a magnet, repeating for 3 times, washing with deionized water for 3 times, finally dissolving in deionized water, and adjusting the pH to 7 with sodium hydroxide to obtain the magnetic nanoparticles (Fe) with good water solubility and surface carboxylation3O4-DMSA）。
4）Fe3O4Preparing a magnetic nanoparticle-graphene quantum dot composite material: 40mL of Fe was taken3O4DMS, adjusting the pH value to 5 by using MES buffer, performing ultrasonic treatment for 10 min, adding 160 mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 240 mg of N-hydroxythiosuccinimide (NHS), performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 ℃ for 15 min, placing the reaction solution in a centrifuge at the rotating speed of 12000 r/min, performing centrifugal treatment for 10 min, and removing the supernatant. Preparing 4 mg/mL N-GQDs suspension byN-GQDs solution resuspending Fe3O4-DMSA precipitation, adjusting the mixed solution to 7.2 with PBS buffer, performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 deg.C for 10 h, centrifuging and washing after reaction, dialyzing with a dialysis bag with molecular weight cutoff of 3500 Da for 2 days, and freeze-drying to obtain Fe3O4GQDs powder.
5) Preparing a composite embedding carrier aqueous solution: adding polyvinyl alcohol and sodium alginate into deionized water, sterilizing at high temperature to dissolve completely, and cooling to 28 deg.C to obtain polyvinyl alcohol/sodium alginate aqueous solution composite embedding carrier aqueous solution;
6) preparation of composite gel: mixing the Fe prepared in the step (4)3O4Mixing GQDs with the aqueous solution of the composite embedding carrier prepared in the step (5), and uniformly stirring;
7) preparing a composite gel adsorption film: and (3) immersing the polypropylene non-woven fabric into the composite gel prepared in the step (6) at 25 ℃ for 4min, taking out, immersing into a calcium chloride/saturated boric acid solution at-5 ℃ to form a film with a single side of 1mm, and carrying out fixed crosslinking at 4 ℃ for 24h to obtain the composite gel adsorption film.
The dosage ratio of the GOQDs dispersion liquid to the strong ammonia water in the step 2) is 4 mL:1 mL.
The concentration of the nano ferroferric oxide dispersion liquid in the step 3) is 25 percent; the dosage ratio of the ferroferric oxide dispersion liquid to the toluene is 1 mL:1 mL; the dosage ratio of dimercaptosuccinic acid (DMSA) to dimethyl sulfoxide (DMSO) is 10 mg: 1 mL; the dosage ratio of the ferroferric oxide toluene solution to the dimercaptosuccinic acid (DMSA) dimethyl sulfoxide (DMSO) solution is 0.08 mL: 100 mL; finally obtaining Fe3O4DMSA concentration 0.8 mg/mL.
Fe described in step 4)3O4The dosage ratio of the DMSA to the N-GQDs suspension is 2mL to 1.2 mL;
the high-temperature sterilization in the step 5) is carried out at the temperature of 121 ℃ and under the pressure of 110kPa for 20 min; the dosage ratio of the polyvinyl alcohol to the sodium alginate to the deionized water is 10 g: 5 g: 100 mL.
Fe described in step 6)3O4The dosage ratio of GQDs to the composite embedding carrier aqueous solution is 3 g: 100 mL.
The graphene oxide quantum dots for preparing the composite gel adsorption film are purchased from pioneer nano company, model No. xf074.
A composite gel adsorption film prepared by the preparation method.
An application of the composite gel adsorption film in wastewater treatment.
Preferably, the adding amount of the composite gel adsorption film in the wastewater is that the ratio of the film width to the bottom area of the wastewater treatment device is 0.2m:1m2 The membrane height is the same as the wastewater level height in the wastewater treatment plant.
Example 3
Containing Fe3O4-GQDs composite gel adsorption membranes, prepared by the following steps:
1) preparing a graphene oxide quantum dot dispersion liquid: dissolving graphene oxide quantum dots in deionized water, performing ultrasonic treatment until dispersion liquid is formed, dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 3500 Da, and diluting the solution in the dialysis bag until the concentration of the dispersion liquid of the Graphene Oxide Quantum Dots (GOQDs) is 0.35 mg/mL.
2) Preparing amino modified graphene quantum dots (N-GQDs): mixing the GOQDs dispersion solution of 0.25mg/mL with strong ammonia water, stirring, performing hydrothermal reaction at 100 deg.C for 5 h, cooling to room temperature, taking out the reaction solution, and dialyzing with dialysis bag with molecular weight cutoff of 3500 Da for 4 days. Taking out the solution in the dialysis bag, centrifuging at the rotating speed of 11000 r/min for 15 min to remove precipitates, filtering by using a filter membrane of 0.45 mu m, and freeze-drying to obtain the amino modified graphene quantum dots named as N-GQDs.
3) Carboxyl-modified magnetic nanoparticles: mixing the nano ferroferric oxide dispersion liquid with toluene for later use. Dissolving dimercaptosuccinic acid (DMSA) in dimethyl sulfoxide (DMSO), adding into a toluene solution of ferroferric oxide, stirring at the temperature of 25 ℃ at 135rpm for 12h, adding ethyl acetate for precipitation after the reaction is finished, collecting with a magnet, repeating for 2 times, washing with deionized water for 2 times, finally dissolving in deionized water, and adjusting the pH to 7.5 with sodium hydroxide to obtain waterSurface carboxylated magnetic nanoparticles (Fe) with good solubility3O4-DMSA）。
4）Fe3O4Preparing a magnetic nanoparticle-graphene quantum dot composite material: 40mL of Fe was taken3O4DMS, adjusting the pH to 5.5 by using MES buffer, performing ultrasonic treatment for 10 min, adding 160 mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 240 mg of N-hydroxythiosuccinimide (NHS), performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 ℃ for 15 min, placing the reaction solution in a centrifuge at the rotating speed of 12000 r/min, performing centrifugal treatment for 10 min, and removing the supernatant. Preparing 4 mg/mL N-GQDs suspension, and resuspending Fe by using the N-GQDs solution3O4-DMSA precipitation, adjusting the mixed solution to 7.2 with PBS buffer, performing ultrasonic treatment for 10 min, sealing, placing in a shaking table, reacting at 37 deg.C for 10 h, centrifuging and washing after reaction, dialyzing with a dialysis bag with molecular weight cutoff of 3500 Da for 2 days, and freeze-drying to obtain Fe3O4GQDs powder.
5) Preparing a composite embedding carrier aqueous solution: adding polyvinyl alcohol and sodium alginate into deionized water, sterilizing at high temperature, dissolving completely, cooling to 32 deg.C to obtain polyvinyl alcohol/sodium alginate aqueous solution composite embedding carrier aqueous solution;
6) preparation of composite gel: mixing the Fe prepared in the step (4)3O4Mixing GQDs with the aqueous solution of the composite embedding carrier prepared in the step (5), and uniformly stirring;
7) preparing a composite gel adsorption film: and (3) immersing the polypropylene non-woven fabric into the composite gel prepared in the step (6) at 30 ℃ for 3min, taking out, immersing into a calcium chloride/saturated boric acid solution at-5 ℃ to form a film with a single side of 2mm, and carrying out fixed crosslinking at 4 ℃ for 24h to obtain the composite gel adsorption film.
The dosage ratio of the GOQDs dispersion liquid to the strong ammonia water in the step 2) is 6 mL:1 mL.
The concentration of the nano ferroferric oxide dispersion liquid in the step 3) is 25 percent; the dosage ratio of the ferroferric oxide dispersion liquid to the toluene is 1 mL: 0.05 mL; the dosage ratio of dimercaptosuccinic acid (DMSA) to dimethyl sulfoxide (DMSO) is 10 mg: 1 mL; toluene solution of ferroferric oxide and dimercaptoThe dosage ratio of the dimethyl sulfoxide (DMSO) solution of succinic acid (DMSA) is 1.2 mL: 100 mL; finally obtaining Fe3O4DMSA concentration 0.8 mg/mL.
Fe described in step 4)3O4The dosage ratio of the DMSA to the N-GQDs suspension is 2mL to 0.8 mL;
the high-temperature sterilization in the step 5) is carried out at the temperature of 121 ℃ and under the pressure of 108kPa for 20 min; the dosage ratio of the polyvinyl alcohol to the sodium alginate to the deionized water is 14 g: 3 g: 100 mL.
Fe described in step 6)3O4The dosage ratio of GQDs to the composite embedding carrier aqueous solution is 4 g: 100 mL.
The graphene oxide quantum dots for preparing the composite gel adsorption film are purchased from pioneer nano company, model No. xf074.
A composite gel adsorption film prepared by the preparation method.
An application of the composite gel adsorption film in wastewater treatment.
Preferably, the adding amount of the composite gel adsorption film in the wastewater is that the ratio of the film width to the bottom area of the wastewater treatment device is 0.1m:1m2 The membrane height is the same as the wastewater level height in the wastewater treatment plant.
Application example 1
The composite gel adsorption membrane in the embodiment 1-3 is applied to tetracycline wastewater, and the treatment conditions are as follows: the tetracycline wastewater with the initial concentration of 35mg/L is filled into a shake flask with 150 mL/bottle; fixing the composite gel adsorption film from the bottom of the inner side of the shake flask, culturing the shake flask for 5 days on a shaking table with the rotation speed of 150r/min at 30 ℃, sampling every 1d to determine the tetracycline content, and calculating the adsorption rate, wherein the results are shown in Table 2.
The initial concentration is 35mg/L, and the components of the waste water are as follows: 35mg of tetracycline, 0.1g of peptone, 0.01g of yeast powder and 0.05g of sodium chloride, and tap water is added to the volume of 1L.
TABLE 1 adsorption efficiency of composite gel adsorption membranes
Figure DEST_PATH_IMAGE002
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. Containing Fe3O4The preparation method of the composite gel adsorption film of GQDs is characterized by comprising the following steps:
(1) preparation of GOQDs dispersion: dissolving GOQDs in deionized water, performing ultrasonic treatment until dispersion liquid is formed, dialyzing, and diluting to obtain GOQDs dispersion liquid;
(2) preparing the amino-modified graphene quantum dots: mixing the GOQDs dispersion liquid prepared in the step (1) with strong ammonia water, uniformly stirring, carrying out hydrothermal reaction for 5 hours at 100 ℃, cooling to room temperature, taking out reaction liquid, dialyzing, taking out liquid in a dialysis bag, centrifuging to remove precipitates, filtering filtrate, and drying to obtain amino-modified graphene quantum dots, wherein the name of the amino-modified graphene quantum dots is N-GQDs;
(3) carboxyl-modified magnetic nanoparticles: mixing nano ferroferric oxide dispersion liquid with methylbenzene to obtain a methylbenzene solution of nano ferroferric oxide, dissolving DMSA in dimethyl sulfoxide DMSO, adding the DMSA into the methylbenzene solution of nano ferroferric oxide, stirring at 25 ℃ for 12 hours at 120-150 rpm, adding ethyl acetate for precipitation after the reaction is finished, collecting with a magnet, repeating for 2-3 times, cleaning with deionized water for 3 times, finally dissolving in deionized water, adjusting the pH to 7-8 to obtain Fe3O4-DMSA；
（4）Fe3O4Preparing a magnetic nanoparticle-graphene quantum dot composite material: taking 40mL of Fe prepared in step (3)3O4DMSA, adjusting pH to 5-6, sonicating, adding 160 mg of 1- (3-dimethylamino) -acetic acidCarrying out ultrasonic treatment on propyl) -3-ethyl carbodiimide hydrochloride and 240 mg of N-hydroxy thiosuccinimide, sealing, placing in a shaking table, reacting for 15 min at 37 ℃, and centrifuging the reaction solution; resuspending Fe using 4 mg/mL of N-GQDs solution3O4-DMSA precipitation, adjusting pH to 7.2-7.5, ultrasonic treating, placing in a shaker, reacting at 37 deg.C for 10 h, centrifuging, washing, dialyzing, and drying to obtain Fe3O4-GQDs powder;
(5) preparing a composite embedding carrier aqueous solution: adding polyvinyl alcohol and sodium alginate into deionized water, sterilizing at high temperature to dissolve completely, and cooling to 28-32 deg.C to obtain polyvinyl alcohol/sodium alginate aqueous solution composite embedding carrier aqueous solution;
(6) preparation of composite gel: mixing the Fe prepared in the step (4)3O4Mixing GQDs powder with the aqueous solution of the composite embedding carrier prepared in the step (5), and uniformly stirring to obtain composite gel;
(7) preparing a composite gel adsorption film: and (3) immersing the polypropylene non-woven fabric into the composite gel prepared in the step (6) at 25-30 ℃ for 3-5 min, taking out, immersing into a calcium chloride/saturated boric acid solution at-5 ℃ to form a film with a single side of 1-3 mm, and carrying out fixed crosslinking at 4 ℃ for 24h to obtain the composite gel adsorption film.
2. The preparation method according to claim 1, wherein the concentration of the dispersion of GOQDs after dialysis in step (1) is 0.25-0.35 mg/mL; the dosage ratio of the GOQDs dispersion liquid and the strong ammonia water in the step (2) is 4-6 mL:1 mL.
3. The preparation method according to claim 1, wherein the concentration of the nano ferroferric oxide dispersion liquid in the step (3) is 25%; the dosage ratio of the ferroferric oxide dispersion liquid to the toluene is 1 mL: 0.05-0.1 mL; the dosage ratio of DMSA to DMSO is 10 mg: 1 mL; the dosage ratio of the ferroferric oxide toluene solution to the DMSA DMSO solution is 0.8-1.2 mL: 100 mL.
4. The method according to claim 1, wherein Fe is used in the step (4)3O4The dosage ratio of the-DMSA to the N-GQDs solution is 2mL:0.8-1.2 mL.
5. The method according to claim 1, wherein the temperature of the high temperature sterilization in the step (5) is 121 ℃, the pressure is 105kPa and 110kPa, and the time is 20 min; the dosage ratio of the polyvinyl alcohol, the sodium alginate and the deionized water is 10-14 g: 3-5 g: 100 mL.
6. The method according to claim 1, wherein the Fe in the step (6)3O4The dosage ratio of the GQDs to the composite embedding carrier aqueous solution is 3-5 g: 100 mL.
7. A composite gel adsorption film prepared by the preparation method of any one of claims 1 to 6.
8. Use of the composite gel adsorbent film according to claim 7 in wastewater treatment.
9. The use of claim 8, wherein the composite gel adsorption membrane is placed in the wastewater with a membrane width to bottom area ratio of 0.1-0.3m:1m2 The membrane height is the same as the wastewater level height in the wastewater treatment plant.
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CN110013833B (en) * 2019-04-22 2021-08-24 曲阜师范大学 Preparation method of MgO/GQD/chitosan oligosaccharide/PVA composite adsorption film
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102826545A (en) * 2012-09-24 2012-12-19 吴敏 Magnetic graphene material for detecting phthalic acid ester, and preparation and application thereof
CN103613091A (en) * 2013-10-29 2014-03-05 南京邮电大学 GO and magnetic composite material, its preparation method, and its application in water treatment
ES2483598A1 (en) * 2013-02-06 2014-08-06 Acondicionamiento Tarrasense Filter for the treatment of liquids with magnetite nanoparticles and corresponding methods
CN104226281A (en) * 2014-10-13 2014-12-24 江南大学 Composite hydrogel for adsorption of heavy metal ions and preparation method thereof
CN104815337A (en) * 2015-05-14 2015-08-05 临沂大学 Preparation method and antitumor activity of PEG-modified magnetic graphene oxide (GO)
CN105289515A (en) * 2015-11-27 2016-02-03 安徽师范大学 Preparation method and application of magnetic graphene oxide adsorbent material
CN105602013A (en) * 2015-12-21 2016-05-25 西北师范大学 Preparation amino functionalized graphene / chitosan composite and application of the composite to copper ion detection
CN105860153A (en) * 2016-04-26 2016-08-17 福州大学 Composite membrane doped with graphene oxide quantum dots and preparation method thereof
CN107189090A (en) * 2017-06-28 2017-09-22 中国科学院生态环境研究中心 Alginate polyvinyl alcohol nano composite double network gel and preparation method thereof
CN108359663A (en) * 2018-01-23 2018-08-03 曲阜师范大学 A kind of polyP bacteria immobilized spherule and its application

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102826545A (en) * 2012-09-24 2012-12-19 吴敏 Magnetic graphene material for detecting phthalic acid ester, and preparation and application thereof
ES2483598A1 (en) * 2013-02-06 2014-08-06 Acondicionamiento Tarrasense Filter for the treatment of liquids with magnetite nanoparticles and corresponding methods
CN103613091A (en) * 2013-10-29 2014-03-05 南京邮电大学 GO and magnetic composite material, its preparation method, and its application in water treatment
CN104226281A (en) * 2014-10-13 2014-12-24 江南大学 Composite hydrogel for adsorption of heavy metal ions and preparation method thereof
CN104815337A (en) * 2015-05-14 2015-08-05 临沂大学 Preparation method and antitumor activity of PEG-modified magnetic graphene oxide (GO)
CN105289515A (en) * 2015-11-27 2016-02-03 安徽师范大学 Preparation method and application of magnetic graphene oxide adsorbent material
CN105602013A (en) * 2015-12-21 2016-05-25 西北师范大学 Preparation amino functionalized graphene / chitosan composite and application of the composite to copper ion detection
CN105860153A (en) * 2016-04-26 2016-08-17 福州大学 Composite membrane doped with graphene oxide quantum dots and preparation method thereof
CN107189090A (en) * 2017-06-28 2017-09-22 中国科学院生态环境研究中心 Alginate polyvinyl alcohol nano composite double network gel and preparation method thereof
CN108359663A (en) * 2018-01-23 2018-08-03 曲阜师范大学 A kind of polyP bacteria immobilized spherule and its application

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