CN110614079A - Preparation method and application of net-shaped magnetic graphene oxide - Google Patents
Preparation method and application of net-shaped magnetic graphene oxide Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a net-shaped magnetic graphene oxide. The magnetic graphene has high adsorption capacity on heavy metals, and can quickly remove the magnetic graphene loaded with the heavy metals from water under the action of an external magnetic field after adsorption is completed; the magnetic graphene oxide material has the advantages of easiness in recovery, no pollution, regeneration and the like.
Description
Technical Field
The invention belongs to the field of wastewater treatment; in particular to a rapid preparation method and application of reticular magnetic graphene oxide.
Background
Heavy metals are present in a large amount in many industrial waste water, and not only are environmental pollution caused by the heavy metals, but also serious threats to human health are caused, and the heavy metals are lost. In order to solve the heavy metals in the wastewater, many methods have been developed, such as extraction, precipitation, electrochemical methods, etc., but these methods have some disadvantages, such as extraction, precipitation, etc., which are likely to cause secondary pollution and fail to meet the discharge standard.
Compared with the prior traditional methods, the adsorption is a promising method, and some high molecular materials such as activated carbon, silicon dioxide, resin, polymer and the like are prepared for heavy metals. However, most adsorbents have a problem of low adsorption amount because of small specific surface area, although some adsorbents have large specific surface area and high removal rate. However, how to separate these adsorbents is a problem to be solved. In order to solve the above problems, we have prepared a magnetic graphene material in a net shape, which has magnetism and can be rapidly separated under the action of an external magnetic field. The preparation process is simple, the synthesis can be carried out quickly, and the problems of complex process and high cost of magnetic graphene preparation in the past are solved. The adsorbent has a large specific surface area, can quickly adsorb and desorb, and has a high adsorption capacity. Therefore, the material is a material with potential application and has potential value for realizing industrialization.
Disclosure of Invention
The invention aims to solve the defects that the prior extraction and precipitation method for removing heavy metals in wastewater easily causes secondary pollution and can not reach the discharge standard.
The invention aims to provide a preparation method of reticular magnetic graphene oxide, which is carried out according to the following steps:
step one, FeCl3.6H2O, sodium acetate anddissolving polyethylene glycol in ethylene glycol, stirring, reacting by a solvothermal method, washing with water under the action of a magnetic field for at least 3 times, and drying in vacuum to prepare superparamagnetic ferroferric oxide nanoparticles;
step two, dispersing the superparamagnetic ferroferric oxide nanoparticles prepared in the step one in ethanol water solution, carrying out ultrasonic treatment, adding ammonia water solution, adding a silicon source while stirring, continuously stirring after the silicon source is added, washing for at least 3 times under the action of a magnetic field, and carrying out vacuum drying to obtain Fe3O4/SiO2A nanoparticle;
step three, Fe prepared in the step two3O4/SiO2Respectively ultrasonically dispersing nano particles and graphene oxide in water under the stirring condition, then mixing to obtain a suspension, dropwise adding a silane coupling agent while stirring, continuously stirring, washing for at least 3 times under the action of a magnetic field, and freeze-drying to obtain the reticular magnetic graphene oxide.
Further defined, the FeCl of step one3.6H2The mass ratio of O to sodium acetate is 1: (8-11); the polyethylene glycol and FeCl3.6H2The quantity ratio of the O substances is 1: (24-28); the mass ratio of the polyethylene glycol to the ethylene glycol is 1 (5-8).
Further limiting, the temperature of the solvothermal method in the step one is 190-200 ℃, and the time is 8-12 h; the temperature of the vacuum drying is 50-60 ℃, and the time of the vacuum drying is 10-12 h.
Further, the silicon source in the second step is tetraethoxysilane.
Further limiting, in the second step, the ethanol water solution is prepared by ethanol and water according to the volume ratio of 50 (1-7); and taking 80-100 mL of ethanol aqueous solution as a reference, wherein the addition amount of the superparamagnetic ferroferric oxide nanoparticles prepared in the step one in the reaction system is 0.8-0.9 g, the mass percentage concentration of the ammonia aqueous solution is 25%, the addition amount of the ammonia aqueous solution is 1.5-2.0 mL, and the addition amount of the silicon source is 1-1.2 mL.
Further limiting, the ultrasonic treatment time in the step two is 1-2 h; and after the silicon source is added, continuously stirring for 6-10 hours at 50-60 ℃, and vacuum drying for 10-12 hours at 50-60 ℃.
Further limiting, the Fe is added in the third step according to the proportion of 1g/100mL3O4/SiO2Dispersing nano particles in water, dispersing Graphene Oxide (GO) in water according to the proportion of 1g/100mL, and dispersing Fe in suspension liquid3O4/SiO2The mass ratio of the nano particles to the graphene oxide is 1:1, and the dosage of the silane coupling agent in each 200mL of water is 7-9 mL.
Further limiting, the ultrasonic dispersion time in the third step is 2-3h, the stirring is continued for 30-60min at 40-50 ℃, and the freeze-drying time is 12-15h at-50 ℃.
Further, the silane coupling agent in the third step is one of methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, mercaptopropyltri (ethyl) oxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, or any combination of several of them.
Fe in the product of the invention3O4/SiO2The nano particles and the graphene oxide are fully combined to form a compound with a net structure;
another objective of the present invention is to provide an application of the magnetic graphene oxide in a net shape prepared by the above method of the present invention in removing heavy metals in wastewater, specifically in treating heavy metals such as lead and cadmium in wastewater, wherein the treatment of heavy metals in wastewater is performed according to the following steps: adjusting the pH value of the wastewater to 4-8, adding 50-80 mg of reticular magnetic graphene oxide into the wastewater according to the proportion that every 100mL of wastewater to be treated is added, and treating for 3-6h to complete the removal of heavy metals in the wastewater.
The preparation method of the reticular magnetic graphene oxide has the advantages of simple preparation process, low preparation cost, mild preparation conditions and the like.
The net-shaped magnetic graphene oxide has the advantages of superparamagnetism, easiness in magnetic separation, large specific surface area, no secondary pollution and the like.
The reticular magnetic graphene oxide can be used for treating lead and cadmium in wastewater, has high adsorption rate and can be repeatedly used.
The reticular magnetic graphene oxide has high adsorption capacity on heavy metals, and the magnetic graphene loaded with the heavy metals can be quickly removed from water under the action of an external magnetic field after adsorption is finished, so that the defects of the conventional solvent extraction method and other methods are overcome, the solvent in the solvent extraction is generally an organic solvent, most of the organic solvent is toxic, and secondary pollution is easily caused; the magnetic graphene oxide material has the advantages of easiness in recovery, no pollution, regeneration and the like.
The magnetic graphene oxide of the present invention is regenerated using hydrochloric acid.
Drawings
FIG. 1 is a transmission electron microscope image of the magnetic graphene oxide network prepared by the method of example 3;
FIG. 2 is a graph showing the relationship between the concentration of heavy metal and the amount of adsorption in example 3.
Detailed Description
Example 1: the rapid preparation method of the magnetic graphene oxide network described in this embodiment is performed according to the following steps:
step one, FeCl3.6H2Dissolving O, sodium acetate and polyethylene glycol in ethylene glycol, stirring for 1h at 1000 r/min, transferring the mixture to a reaction kettle, then placing the reaction kettle in an air-blowing drying oven, heating to 190 ℃, keeping the temperature for 8h, washing with water for three times under the action of a magnetic field (namely the action of the magnetic field) after the reaction is finished, and drying in vacuum for 10h at 50 ℃ to obtain Fe3O4A nanoparticle; FeCl described in step (1)3.6H2The mass ratio of O to sodium acetate is 1: 8; the polyethylene glycol and FeCl3.6H2The quantity ratio of the O substances is 1: 24; the mass ratio of polyethylene glycol to ethylene glycol is 1: 5;
step two, 0.8g of Fe obtained in the step one3O4The nanoparticles were dispersed in 80mL ethanol solution (volume of ethanol and water)The ratio is 4: 1) carrying out ultrasonic treatment for 1 hour at 40Hz, then adding 1.5mL of ammonia water solution with the mass percentage concentration of 25%, adding 1mL of ethyl orthosilicate while stirring for 1000 revolutions per minute, continuously stirring for 6 hours at 50 ℃, washing with water for three times under the action of a magnetic field after the reaction is finished, and carrying out vacuum drying for 10 hours at 50 ℃ to obtain Fe3O4/SiO2A nanoparticle;
step three, 1g of Fe obtained in the step two3O4/SiO2Dispersing nanoparticles in 100mL of water under continuous stirring by ultrasonic waves, dispersing 1g of Graphene Oxide (GO) in 100mL of water under continuous stirring with 40Hz ultrasonic dispersion time controlled at 2h, and mixing to obtain suspension (Fe)3O4/SiO2The mass ratio of the nano particles to the graphene oxide is 1:1), then methacryloxypropyltrimethoxysilane is dropwise added, the using amount of the methacryloxypropyltrimethoxysilane is 7mL, the mixture is continuously stirred at 40 ℃ for 30min, after the reaction is finished, the mixture is washed with water for three times under the action of a magnetic field (namely the action of the magnetic field), and then the mixture is freeze-dried at-50 ℃ for 12h to obtain the reticular Fe3O4/SiO2a/GO material.
In the application of the obtained magnetic graphene oxide in treating heavy metals such as lead and cadmium in wastewater, the concentrations of lead and cadmium in wastewater are respectively 100mg/L, the pH value of the wastewater is adjusted to be 4, 50mg of the prepared material is respectively added into the wastewater with the volume of 100mL of lead and chromium, the mixture is stirred and reacted in a thermostatic water bath at the temperature of 25 ℃ for 3 hours, after the reaction is finished, the magnetic graphene oxide adsorbing the heavy metals is rapidly removed under the action of an external magnetic field, and then the concentration of lead or cadmium in the residual solution is detected by ICP-OES. The removal rates of lead and cadmium were 87% and 78%, respectively.
Example 2: the rapid preparation method of the magnetic graphene oxide network described in this embodiment is performed according to the following steps:
step one, FeCl3.6H2Dissolving O, sodium acetate and polyethylene glycol in ethylene glycol, stirring at 1000 rpm for 1 hr, transferring the mixture to a reaction kettle, and air dryingHeating to 195 deg.C in a box, maintaining for 9h, washing with water under the action of magnetic field for three times after reaction, and vacuum drying at 55 deg.C for 11h to obtain Fe3O4A nanoparticle; the FeCl3.6H2The mass ratio of O to sodium acetate is 1: 9; the polyethylene glycol and FeCl3.6H2The quantity ratio of the O substances is 1: 25; the mass ratio of polyethylene glycol to ethylene glycol is 1: 6;
step two, 0.85g of Fe obtained in the step one3O4Dispersing the nano particles in 90mL of ethanol solution (the volume ratio of ethanol to water is 4: 1), carrying out ultrasonic treatment for 1.5h at 40Hz, then adding 1.8mL of ammonia water solution with the mass percentage concentration of 25%, adding 1.1mL of ethyl orthosilicate while stirring at 1000 rpm, continuously stirring for 8h at 55 ℃, washing with water for three times under the action of a magnetic field after the reaction is finished, and carrying out vacuum drying for 11h at 55 ℃ to obtain Fe3O4/SiO2A nanoparticle;
step three, 1g of Fe obtained in the step two3O4/SiO2Ultrasonically dispersing nano particles in 100mL of water under continuous stirring, simultaneously ultrasonically dispersing 1g of Graphene Oxide (GO) in 100mL of water under continuous stirring, controlling the ultrasonic dispersion time of 40Hz to be 3h, mixing to prepare a suspension, dropwise adding 8mL of vinyltriethoxysilane, continuously stirring at 45 ℃ for 50min, washing with water for three times under the action of a magnetic field after the reaction is finished, and freeze-drying for 14h to obtain reticular Fe3O4/SiO2a/GO material;
in the application of the obtained magnetic graphene oxide in treating heavy metals such as lead and cadmium in wastewater, the concentrations of lead and cadmium in wastewater are respectively 100mg/L, the pH value of the wastewater is adjusted to 6, 60mg of the prepared material is respectively added into lead and chromium wastewater with the volume of 100mL, the mixture is stirred and reacted in a constant-temperature water bath at the temperature of 35 ℃ for 4 hours, the magnetic graphene oxide adsorbing the heavy metals is rapidly removed under the action of an external magnetic field after the reaction is finished, and then the concentration of lead or cadmium in the residual solution is detected by ICP-OES. The removal rates of lead and cadmium were 94% and 85%, respectively.
Example 3: the rapid preparation method of the magnetic graphene oxide network described in this embodiment is performed according to the following steps:
step one, FeCl3.6H2Dissolving O, sodium acetate and polyethylene glycol in ethylene glycol, stirring for 2h at 1000 r/min, transferring the mixture to a reaction kettle, then placing the reaction kettle in an air-blowing drying oven, heating to 200 ℃, keeping the temperature for 12h, washing with water for three times under the action of a magnetic field after the reaction is finished, and drying in vacuum for 12h at 60 ℃ to obtain Fe3O4A nanoparticle; the FeCl3.6H2The mass ratio of O to sodium acetate is 1: 11; the polyethylene glycol and FeCl3.6H2The quantity ratio of the O substances is 1: 28; the mass ratio of polyethylene glycol to ethylene glycol is 1: 8;
step two, 0.9g of Fe obtained in the step one3O4Dispersing the nano particles in 100mL of ethanol solution (the volume ratio of ethanol to water is 4: 1), carrying out ultrasonic treatment for 2h at 40Hz, then adding 2.0mL of ammonia water solution with the mass percentage concentration of 25%, adding 1.2mL of silicon source while stirring at 1000 rpm, continuously stirring for 10h at 60 ℃, washing with water for three times under the action of a magnetic field after the reaction is finished, and carrying out vacuum drying for 12h at 60 ℃ to obtain Fe3O4/SiO2A nanoparticle;
step three, 1g of Fe obtained in the step two3O4/SiO2Ultrasonically dispersing nano particles in 100mL of water under continuous stirring, simultaneously ultrasonically dispersing 1g of Graphene Oxide (GO) in 100mL of water under continuous stirring, controlling the ultrasonic dispersion time of 40Hz to be 3h, and then ultrasonically dispersing the nano particles in the 100mL of water according to Fe3O4/SiO2Mixing nano particles and graphene oxide together according to the mass ratio of 1:1 to prepare a suspension, dropwise adding 3-aminopropyltriethoxysilane, wherein the dosage of the 3-aminopropyltriethoxysilane is 9mL, continuously stirring at 50 ℃ for 60min, washing with water for three times under the action of a magnetic field (namely assisted by a magnet) after the reaction is finished, and freeze-drying at-50 ℃ for 15h to obtain the reticular Fe3O4/SiO2a/GO material.
In the application of the obtained magnetic graphene oxide in treating heavy metals such as lead and cadmium in wastewater, the concentrations of lead and cadmium in wastewater are respectively 100mg/L, the pH value of the wastewater is adjusted to 7, 80mg of the prepared material is respectively added into lead and chromium wastewater with the volume of 100mL, the wastewater is stirred and reacted for 5 hours in a constant-temperature water bath at the temperature of 45 ℃, after the reaction is finished, the magnetic graphene oxide adsorbing the heavy metals is rapidly removed under the action of an external magnetic field, and then the concentration of lead or cadmium in the residual solution is detected by ICP-OES. The removal rates of lead and cadmium were 99.5% and 97%, respectively.
Fig. 1 is a transmission electron microscope image of the magnetic graphene oxide network prepared in this embodiment, and it can be seen that the magnetic material and the graphene oxide are fully combined to form a complex with a network structure.
Fig. 2 is a graph showing a relationship between the concentration of heavy metal and the adsorption amount, and it can be seen that the magnetic graphene oxide of the embodiment has a large adsorption amount to heavy metal lead and cadmium.
Claims (10)
1. A preparation method of net-shaped magnetic graphene oxide is characterized by comprising the following steps:
step one, FeCl3.6H2Dissolving O, sodium acetate and polyethylene glycol in ethylene glycol, stirring, reacting by a solvothermal method, washing for at least 3 times under the action of a magnetic field, and drying in vacuum to prepare superparamagnetic ferroferric oxide nanoparticles;
step two, dispersing the superparamagnetic ferroferric oxide nanoparticles prepared in the step one in ethanol water solution, carrying out ultrasonic treatment, adding ammonia water solution, adding a silicon source while stirring, continuously stirring after the silicon source is added, washing for at least 3 times under the action of a magnetic field, and carrying out vacuum drying to obtain Fe3O4/SiO2A nanoparticle;
step three, Fe prepared in the step two3O4/SiO2Respectively ultrasonically dispersing nano particles and graphene oxide in water under the stirring condition, then mixing to obtain a suspension, dropwise adding a silane coupling agent while stirring, continuously stirring, and performing magnetic fieldWashing with water for at least 3 times, and freeze-drying to obtain the net-shaped magnetic graphene oxide.
2. The method for preparing magnetic graphene oxide in net shape according to claim 1, wherein the FeCl in step one3.6H2The mass ratio of O to sodium acetate is 1: (8-11); the polyethylene glycol and FeCl3.6H2The quantity ratio of the O substances is 1: (24-28); the mass ratio of the polyethylene glycol to the ethylene glycol is 1 (5-8).
3. The method for preparing the reticular magnetic graphene oxide according to claim 2, wherein the temperature of the solvothermal method in the step one is 190-200 ℃ and the time is 8-12 h; the temperature of the vacuum drying is 50-60 ℃, and the time of the vacuum drying is 10-12 h.
4. The method according to claim 1, wherein the silicon source in step two is tetraethoxysilane.
5. The method for preparing magnetic graphene oxide with network shape according to claim 4, wherein in the second step, the ethanol aqueous solution is prepared by ethanol and water according to a volume ratio of 50 (1-7); and taking 80-100 mL of ethanol aqueous solution as a reference, wherein the addition amount of the superparamagnetic ferroferric oxide nanoparticles prepared in the step one in the reaction system is 0.8-0.9 g, the mass percentage concentration of the ammonia aqueous solution is 25%, the addition amount of the ammonia aqueous solution is 1.5-2.0 mL, and the addition amount of the silicon source is 1-1.2 mL.
6. The method for preparing the reticular magnetic graphene oxide according to claim 1, wherein the ultrasonic treatment time in the second step is 1-2 h; and after the silicon source is added, continuously stirring for 6-10 hours at 50-60 ℃, and vacuum drying for 10-12 hours at 50-60 ℃.
7. The method of claim 1The preparation method of the reticular magnetic graphene oxide is characterized in that Fe is added according to the proportion of 1g/100mL in the third step3O4/SiO2Dispersing nano particles in water, dispersing Graphene Oxide (GO) in water according to the proportion of 1g/100mL, and dispersing Fe in suspension liquid3O4/SiO2The mass ratio of the nano particles to the graphene oxide is 1:1, and the dosage of the silane coupling agent in every 200mL of water is 7-9 mL.
8. The preparation method of the reticular magnetic graphene oxide according to claim 7, characterized in that the ultrasonic dispersion time in the third step is 2-3h, the stirring is continued for 30-60min at 40-50 ℃, and the freeze-drying time at-50 ℃ is 12-15 h.
9. The method according to claim 7, wherein the silane coupling agent in step three is one or more selected from methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane (ethylthio) oxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane.
10. The reticular magnetic graphene oxide prepared by the preparation method of the magnetic material according to any one of claims 1 to 8 is used for removing heavy metals in wastewater; the heavy metal in the wastewater is treated by the following steps: adjusting the pH value of the sewage to 4-8, adding 50-80 mg of reticular magnetic graphene oxide into the wastewater according to the proportion that every 100mL of wastewater to be treated is added with the reticular magnetic graphene oxide, and treating for 3-6h to complete the removal of heavy metals in the wastewater.
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| CN111458429A (en) * | 2020-04-07 | 2020-07-28 | 江苏海洋大学 | Preparation and application of chitosan modified magnetic nano material |
| CN111657295A (en) * | 2020-06-17 | 2020-09-15 | 邓天生 | Magnetic renewable antibacterial agent and preparation method thereof |
| CN112745860A (en) * | 2021-02-23 | 2021-05-04 | 潍坊科技学院 | Acidified soil conditioner based on graphene |
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