CN107497404B - Preparation method of modified graphene oxide adsorption material - Google Patents
Preparation method of modified graphene oxide adsorption material Download PDFInfo
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- CN107497404B CN107497404B CN201710969875.6A CN201710969875A CN107497404B CN 107497404 B CN107497404 B CN 107497404B CN 201710969875 A CN201710969875 A CN 201710969875A CN 107497404 B CN107497404 B CN 107497404B
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- 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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- 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
Abstract
A preparation method of a modified graphene oxide adsorption material comprises the following steps: (1) ultrasonically dispersing graphene oxide in anhydrous N, N-dimethylformamide, adding diphenylmethane diisocyanate, and reacting; (2) uniformly mixing the diphenylmethane diisocyanate functionalized graphene oxide with ethylene diamine tetraacetic acid, grinding, washing, and freeze-drying to obtain the graphene oxide. The invention takes isocyanate as a bridging body, and prepares a composite material through amidation and carbamation reaction; the adsorbent prepared by the method has both a multi-carboxyl functional group and a multi-hydroxyl functional group, has excellent adsorption performance on heavy metal ions in wastewater, and can overcome the defect that chelates dissolved in water cannot be separated when EDTA (ethylene diamine tetraacetic acid) is used for removing heavy metals alone.
Description
Technical Field
The invention relates to a preparation method of a modified graphene oxide adsorption material.
Background
The graphene oxide is a carbon-based material which is formed by tightly stacking single-layer carbon atoms and has a two-dimensional plane honeycomb-shaped lattice structure, has a large specific surface area, has rich active oxygen-containing groups such as-COOH, -OH, epoxy groups and the like on the surface, and is an economic and efficient heavy metal ion adsorbent. The oxygen-containing functional groups can perform a chelating action with heavy metal ions, can also form a reticular cage molecule with an adsorbate through hydrogen bonds, and simultaneously provide chemical reaction active sites for the functionalized modification of the surface of the graphene oxide, so that the graphene oxide has the excellent performances of relatively active physicochemical properties, easiness in chemical modification and the like. However, the dispersibility of graphene oxide is poor, and when the graphene oxide is applied to the adsorption field, due effects cannot be exerted due to material agglomeration, and subsequent treatment of graphene oxide cannot be realized due to difficulty in collection.
Ethylene Diamine Tetraacetic Acid (EDTA) is a good metal ion chelating agent, has six coordination atoms in molecules, can form stable complexes with most metal ions such as alkali metal, rare earth metal, transition metal and the like, and has larger load capacity on heavy metal ions.
Shenkeyan and the like, preparation of silane modified graphene oxide nanocomposite [ D ], university of China, 2011, n-butylamine and toluene are used as solvents, the silane modified graphene oxide nanocomposite reacts with a certain amount of graphene oxide under the protection of nitrogen at room temperature or 30 ℃ for 48 hours, and after methanol precipitation, the graphene oxide nanocomposite is sequentially washed by anhydrous toluene, n-butane, ethanol, acetone, a mixed solution of ethanol and water and acetone to prepare different silanization reagent modified graphene oxide composites. However, as with the existing method for modifying graphene oxide by EDTA, most of the methods use a silylation reagent as an intermediate, and the silylation method generally has the defects of long reaction period, high requirements for conditions and the like.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, especially the defects of long reaction period and multiple organic solvents needed in the prior art, and provides a preparation method of a modified graphene oxide adsorption material.
A preparation method of a modified graphene oxide adsorption material comprises the following steps:
(1) ultrasonically dispersing 100mg of graphene oxide in anhydrous N, N-Dimethylformamide (DMF), adding 1-3mL of diphenylmethane diisocyanate (MDI), stirring at 40-80 ℃, reacting for 1-4h, cooling, washing a reaction product with the anhydrous N, N-Dimethylformamide (DMF) for more than 3 times (preferably, more than 15 mL of the anhydrous N, N-dimethylformamide is used each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) uniformly mixing the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) with Ethylene Diamine Tetraacetic Acid (EDTA) according to a weight ratio of 1:20-40, placing the mixture in a ball mill, controlling the ball-material ratio to be 1.5-3:1, and the rotating speed to be 60-100rad/min, grinding for 1-6h, washing with a sodium bicarbonate (NaHCO 3) solution with the pH value of 7.5-8.5 until no bubbles emerge, and freeze-drying to obtain the ethylene diamine tetraacetic acid/diphenylmethane diisocyanate/graphene oxide composite material (EDTA/MDI/graphene oxide composite material).
According to the invention, through research, the optimum reaction time and the optimum raw material ratio are selected, and if the raw materials exceed the ratio range, incomplete reaction or waste of the raw materials can be caused; if the reaction time is exceeded, the degree of reaction does not increase, and the efficiency is reduced.
Compared with the prior art, the EDTA/MDI/graphene oxide composite material is obtained by reacting hydroxyl and carboxyl on graphene oxide with high-activity-NCO on one of MDI intermediates and reacting the other high-activity-NCO group on the MDI intermediates with carboxyl on EDTA. The composite material shows good stability in organic solvent and water, and when the composite material is applied to the field of adsorption, the composite material has the structural characteristics of rich oxygen-containing functional groups, large pore diameter and uniform pore channel distribution, so that the chelating capacity of the composite material on various heavy metal ions and cationic dyes is enhanced.
According to the invention, the EDTA and the graphene oxide are combined by adopting a solid-phase grinding method and an isocyanate grafting method, so that the adsorption capacity of the obtained adsorption material on heavy metal ions is enhanced, the adsorption material is particularly suitable for the field of heavy metal wastewater treatment, and the separation, recovery and reutilization of later-stage materials are facilitated.
According to the invention, isocyanate (MDI) is taken as a bridging body, and an EDTA/MDI modified graphene oxide adsorption new material-EDTA/MDI/graphene oxide composite material is prepared through amidation and carbamation reaction; the adsorbent prepared by the method has both a multi-carboxyl functional group and a multi-hydroxyl functional group, has excellent adsorption performance on heavy metal ions in wastewater, and can overcome the defect that chelates dissolved in water cannot be separated when EDTA (ethylene diamine tetraacetic acid) is used for removing heavy metals alone.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
The embodiment comprises the following steps:
(1) placing 100mg of graphene oxide (sold in the market) into a three-neck round-bottom flask, adding 50mL of anhydrous DMF, performing ultrasonic dispersion for 1h, adding 1mL of MDI, and stirring at 60 ℃ for 4 h; after the reaction is finished, cooling, washing the reaction product with anhydrous DMF for 3 times (using 15 ml of anhydrous N, N-dimethylformamide each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) and (2) grinding and uniformly mixing 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 2g of EDTA in an agate mortar, placing the mixture in a ball mill, controlling the ball-to-material ratio to be 3:1 and the rotating speed to be 60rad/min, carrying out ball milling for 6h, washing the mixture by using a sodium bicarbonate (NaHCO 3) solution with the pH value of 8.0 until no bubbles emerge, and carrying out freeze drying to obtain the ethylenediamine tetraacetic acid/diphenylmethane diisocyanate/graphene oxide composite material (EDTA/MDI/graphene oxide composite material).
Example 2
The embodiment comprises the following steps:
(1) placing 100mg of graphene oxide (sold in the market) into a three-neck round-bottom flask, adding 50mL of anhydrous DMF (dimethyl formamide) for ultrasonic dispersion for 1h, adding 3mL of MDI (diphenyl-methane-diisocyanate), and stirring at 60 ℃ for reaction for 4 h; after the reaction is finished, cooling, washing the reaction product with anhydrous DMF for 3 times (using 15 ml of anhydrous N, N-dimethylformamide each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) and (2) grinding 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 4g of EDTA in an agate mortar, uniformly mixing, placing in a ball mill, controlling the ball-to-material ratio to be 3:1 and the rotating speed to be 60rad/min, carrying out ball milling for 6h, washing with a sodium bicarbonate (NaHCO 3) solution with the pH value of 8.0 until no bubbles emerge, and carrying out freeze drying to obtain the EDTA/MDI/graphene oxide composite material.
Example 3
The embodiment comprises the following steps:
(1) placing 100mg of graphene oxide (sold in the market) into a three-neck round-bottom flask, adding 50mL of anhydrous DMF, performing ultrasonic dispersion for 1h, adding 3mL of MDI, and stirring at 80 ℃ for 2 h; after the reaction is finished, cooling, washing the reaction product with anhydrous N, N-Dimethylformamide (DMF) for 3 times (15 ml of anhydrous N, N-dimethylformamide is used each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) and (2) grinding and uniformly mixing 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 2g of EDTA in an agate mortar, then placing the mixture in a ball mill, controlling the ball-to-material ratio to be 3:1, the rotating speed to be 100rad/min, carrying out ball milling for 3h, washing the mixture by using a sodium bicarbonate (NaHCO 3) solution with the pH value of 8.0 until no bubbles emerge, and then carrying out freeze drying to obtain the EDTA/MDI/graphene oxide composite material.
Example 4
The embodiment comprises the following steps:
(1) placing 100mg of graphene oxide (sold in the market) into a three-neck round-bottom flask, adding 50mL of anhydrous DMF, performing ultrasonic dispersion for 1h, adding 2mL of MDI, and stirring at 80 ℃ for 2 h; cooling after the reaction is finished, washing the reaction product with anhydrous N, N-Dimethylformamide (DMF) for 3 times (15 ml of anhydrous N, N-dimethylformamide is used each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) grinding 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 4g of EDTA in an agate mortar, uniformly mixing, placing in a ball mill, controlling the ball-to-material ratio to be 2:1, controlling the rotating speed to be 100rad/min, and carrying out ball milling for 6 h; and washing with a sodium bicarbonate (NaHCO 3) solution with the pH of 8.0 until no bubbles emerge, and freeze-drying to obtain the EDTA/MDI/graphene oxide composite material.
Example 5
The embodiment comprises the following steps:
(1) placing 100mg of graphene oxide (sold in the market) into a three-neck round-bottom flask, adding 50mL of anhydrous DMF, performing ultrasonic dispersion for 1h, adding 3mL of MDI, and stirring at 80 ℃ for 4 h; cooling after the reaction is finished, washing the reaction product with anhydrous N, N-Dimethylformamide (DMF) for 3 times (15 ml of anhydrous N, N-dimethylformamide is used each time), centrifugally separating, and drying in vacuum to obtain the diphenylmethane diisocyanate functionalized graphene oxide;
(2) and (2) putting 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 4g of EDTA in an agate mortar, grinding and uniformly mixing, putting the mixture in a ball mill, controlling the ball-to-material ratio to be 1.5:1 and the rotating speed to be 100rad/min, carrying out ball milling for 3h, washing the mixture by using a sodium bicarbonate (NaHCO 3) solution with the pH value of 8.0 until no bubbles emerge, and carrying out freeze drying to obtain the EDTA/MDI/graphene oxide composite material.
Application examples
And (3) detection of adsorption performance: the raw material Graphene Oxide (GO) and the composite material obtained in each embodiment are respectively subjected to adsorption performance detection.
1. Mother liquor preparation
Accurately weighing NiSO4.6H2O (2.2393 g) and CuSO4.5H2O (1.9644 g) required by the experiment respectively, adding distilled water to dissolve, transferring to a 1000mL volumetric flask for constant volume, and obtaining mother liquor with the concentration of 500mg/L for later use. Solutions with various concentrations used in the experiment are all prepared by diluting the mother liquor
2. Experiment of adsorption Capacity
25mL of Cu2+ and Ni2+ solutions with the concentrations of 30, 60, 90, 120, 150, 180, 210 and 240 mg/L are taken, 25mg of GO and EDTA/MDI/GO composite materials are respectively added, the pH value of the Cu2+ solution is adjusted to be 5.0-5.5, the pH value of the Ni2+ solution is adjusted to be 6.5, the mixture is magnetically stirred and reacted for 150min at room temperature, the mixture is filtered and separated after the reaction, the concentrations of Cu2+ and Ni2+ in the filtrate are measured by flame atomic absorption spectrometry, and the adsorption capacity Qe is calculated, and the result is shown in Table 1.
The formula for the calculation of the adsorption capacity is:
c0: initial concentration (mg/L)
Ce: equilibrium concentration is the concentration after reaction (mg/L)
V: volume of solution (L)
M: amount of adsorbent (g)
3. Recovery experiment
Taking Cu2+ in the solution as a research object, respectively adding an adsorbing material GO adsorbing Cu2+ and an EDTA/MDI/GO composite material into 100ml of 1M HCl solution, soaking for 12h at room temperature, then carrying out centrifugal separation, water washing and drying, and obtaining the experimental material for researching the recycling performance of the adsorbent. The adsorption experiment was performed again using the two materials, and after adsorption, centrifugal separation was performed, and the Cu2+ concentration in the supernatant was measured by flame atomic absorption spectrometry, and the adsorption capacity Qe thereof was calculated. The steps are repeated, and the recycling rate of the materials after 10 times of recycling tests is explored. The results are shown in Table 2.
Claims (1)
1. A preparation method of a modified graphene oxide adsorption material is characterized by comprising the following steps:
(1) taking 100mg of graphene oxide, adding 50mL of anhydrous DMF (dimethyl formamide) for ultrasonic dispersion for 1h, adding 3mL of MDI (diphenyl methane diisocyanate), and stirring at 80 ℃ for 2 h; after the reaction is finished, cooling, washing the reaction product for 3 times by using anhydrous N, N-dimethylformamide, wherein 15 ml of anhydrous N, N-dimethylformamide is used each time; centrifugally separating and drying in vacuum to obtain diphenylmethane diisocyanate functionalized graphene oxide;
(2) and (2) grinding and uniformly mixing 0.1g of the diphenylmethane diisocyanate functionalized graphene oxide obtained in the step (1) and 2g of EDTA, placing the mixture in a ball mill, controlling the ball-to-material ratio to be 3:1, the rotating speed to be 100rad/min, carrying out ball milling for 3h, washing the mixture by using a sodium bicarbonate solution with the pH value of 8.0 until no bubbles emerge, and then carrying out freeze drying to obtain the EDTA/MDI/graphene oxide composite material.
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