CN111036176A - Magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material and preparation method thereof - Google Patents
Magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic graphene oxide/sodium alginate/carboxymethyl cellulose composite material and a preparation method thereof. The method comprises the steps of firstly preparing magnetic graphene oxide by adopting a chemical coprecipitation method, and then preparing the magnetic graphene oxide/sodium carboxymethylcellulose/sodium alginate composite material by adopting an ion exchange method together with sodium carboxymethylcellulose and sodium alginate. The composite material disclosed by the invention contains abundant active functional groups, can generate a stronger coordination effect with heavy metal ions, improves the adsorption performance of the composite material on the heavy metal ions, has the maximum adsorption capacity of 92.6mg/g, and is suitable for heavy metal ion adsorption treatment.
Description
Technical Field
The invention relates to a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material and a preparation method thereof, and belongs to the technical field of preparation of adsorption materials.
Background
The traditional adsorbents such as activated carbon, resin and biological adsorbents have small pore channels, so that for some macromolecular organic pollutants, the pore blocking effect causes the blockage of the pore channels and reduces the adsorption quantity. Meanwhile, the adsorbent has high adsorption cost, poor adsorption effect and low regeneration efficiency, and further application of the adsorbent is restricted.
Cellulose, chitosan, sodium alginate, soy protein and the like are common organic materials of the graphene/natural polymer adsorbent. The natural polymers are widely existed in nature, are low in price, have rich oxygen-containing functional groups on the surface, and have excellent hydrophilicity and biocompatibility. For example, graphene oxide is compounded on the surface of cellulose nanofibrils to prepare a graphene/natural polymer composite adsorbent which has excellent biocompatibility and regeneration capability. The graphene/alginic acid composite adsorbent has excellent hydrophilic capacity and affinity for dye pollutants. The adsorbent which takes graphene as a matrix and is compounded with natural high-molecular soybean protein has excellent hydrophilic performance, contains rich active functional groups and can be used for treating antibiotics.
At present, the application of graphene/organic matter composite adsorbent in water treatment has been advanced to a certain extent, but corresponding attention is still lacking in the following important aspects.
1) Optimizing the composite proportion of organic matter and graphene
The compounding ratio of the organic matter and the graphene affects the performance and the cost of the composite adsorbent. In the composite adsorbent, graphene plays a main adsorption role. When the graphene exceeds a certain proportion, the layers of the graphene are overlapped, so that the material is wasted. The proportion of organic matters influences the structural stability, hydrophilicity, biocompatibility and the like of the adsorbent, and the cost of the composite adsorbent can be reduced due to the lower price of the adsorbent relative to graphene.
2) Improve the contact effect and adsorption rate of the material and the pollutants
Compared with a dispersed adsorbent, the graphene/organic matter composite adsorbent has the advantage of easy separation and regeneration, but the existence of a macroscopic body also limits the contact efficiency of the graphene/organic matter composite adsorbent and pollutants in water, and reduces the adsorption rate. How to effectively improve the contact effect of the graphene/organic matter composite adsorbent and pollutants in water and shorten the equilibrium adsorption time by means of improving the structure of the composite adsorbent, modifying functional groups and the like is the key for improving the actual treatment capacity of the composite adsorbent.
Disclosure of Invention
The invention aims to provide a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material and a preparation method thereof. According to the method, sodium carboxymethylcellulose, sodium alginate and magnetic graphene oxide are combined to prepare the magnetic graphene oxide/sodium carboxymethylcellulose/sodium alginate composite material, the composite material maintains good mechanical properties, meanwhile, the high-efficiency adsorption effect is kept, and the magnetic graphene oxide/sodium carboxymethylcellulose/sodium alginate composite material can be magnetically separated and recycled.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material comprises the following specific steps:
step 1, adding ferric trichloride and ferrous chloride into a graphene oxide dispersion solution, stirring and mixing uniformly, adjusting the pH to 9.5 +/-0.5, and reacting at room temperature to obtain magnetic graphene oxide;
and 2, ultrasonically dissolving sodium alginate and sodium carboxymethylcellulose in the magnetic graphene oxide dispersion liquid according to the mass ratio of 1-5: 10: 5-10 of the magnetic graphene oxide, sodium alginate and sodium carboxymethylcellulose, uniformly stirring and mixing, dripping the mixed solution into a calcium chloride solution with the mass fraction of 5 +/-2%, soaking at room temperature, washing with water, and drying to obtain the magnetic graphene oxide/sodium carboxymethylcellulose/sodium alginate composite material.
Preferably, in the steps 1 and 2, the stirring speed is 800-1000 rpm.
Preferably, in the step 1, the molar ratio of the ferric trichloride to the ferrous chloride is 2: 1.
Preferably, in the step 1, the reaction time is 20-24 h.
Preferably, in the step 2, the mass ratio of the magnetic graphene oxide to the sodium alginate to the sodium carboxymethyl cellulose is 3:10: 5.
The invention also provides the magnetic graphene oxide/sodium carboxymethyl cellulose/sodium alginate composite material prepared by the preparation method.
Further, the invention provides an application of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material in heavy metal ion adsorption, and the specific application method comprises the following steps: adjusting the pH value of the wastewater containing heavy metal ions to 3-10, and adding a magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material for adsorption.
Preferably, the heavy metal ion is Cu2+。
Preferably, the pH value of the wastewater containing heavy metal ions is 7.
Preferably, the adsorption time is 2-4 h.
The magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material is prepared through a polymerization reaction. The magnetic graphene oxide surface contains rich active functional groups such as carbonyl, hydroxyl, carboxyl and the like, is easily soluble in water and various solvents, can adsorb cations, and can also be separated and recovered. The sodium alginate has the advantages of good biocompatibility, wide source, low toxicity, low cost, biodegradability, and the like, and the guluronic acid cross-linkable divalent metal ions (such as Cu) in the structure2+). The molecular chain of the sodium carboxymethyl cellulose contains a large amount of carboxyl and hydroxyl, and can generate stronger coordination with heavy metal ions, so that the Cu coordination of the composite material is improved2+The adsorption performance of (3).
Compared with the prior art, the invention has the following advantages:
the surface of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material contains a large number of active adsorption sites, and the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material has a large specific surface area and a proper pore structure, is stable in quality in the adsorption process, has good mechanical strength, can be recycled, and can be used as an adsorbent in the field of heavy metal ion adsorption.
Drawings
Fig. 1 is a synthesis diagram of a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material.
Fig. 2 is a diagram of a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material.
Fig. 3 is an SEM image of the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material.
Fig. 4 is a TG diagram of magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose and graphene oxide/sodium alginate.
FIG. 5 shows magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose and Fe3O4A VSM map of.
FIG. 6 is an XPS survey spectrum of magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose
Fig. 7 is a graph showing the effect of the initial pH value of the solution on the adsorption amount of copper ions adsorbed by the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material prepared in example 1.
Fig. 8 is a graph showing the effect of adsorption time on the adsorption amount of copper ions adsorbed by the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material prepared in example 1.
Fig. 9 is a graph of the result of a recycling experiment of the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material prepared in example 1 with respect to adsorption time.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Comparative example 1
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 1g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 1g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a calcium chloride solution with the mass fraction of 5%, soaking for 24 hours, washing with deionized water for 3 times, and freeze-drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 38.8 mg/g.
Comparative example 2
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 0.1g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 0.1g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing with deionized water for 3 times, and performing freeze drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 73.1 mg/g.
Comparative example 3
(1) Preparing magnetic graphene oxide: 1.0g of synthesized oxygenThe graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 0.3g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 0.1g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing for 3 times by using deionized water, and performing freeze drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 76.3 mg/g.
Comparative example 4
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 0.3g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 1g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing with deionized water for 3 times, and performing freeze drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 78.4 mg/g.
Example 1
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 0.3g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 0.5g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing for 3 times by using deionized water, and performing freeze drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The results show that the graphene oxide/polyethyleneimine/carboxymethyl cellulose pairCu2+The amount of adsorbed was 92.6 mg/g.
Example 2
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to a pH of 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 0.1g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 0.5g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dripping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing for 3 times by using deionized water, and performing freeze drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 88.4 mg/g.
Example 3
(1) Preparing magnetic graphene oxide: 1.0g of the synthesized graphene oxide was ultrasonically dispersed in 100mL of ultrapure water. Under the protection of nitrogen, 1.3g of FeCl3、0.5g FeCl2(molar ratio 2:1) was dissolved in 100mL of ultrapure water, and 25% aqueous ammonia was rapidly added to adjust pH to 10. The mixture was stirred at high temperature for 1 h. Cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol three times respectively, and vacuum drying for 12 h.
(2) Preparing magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose: adding 1g of magnetic graphene oxide into a beaker filled with 100ml of ultrapure water, performing ultrasonic dispersion for 2 hours, adding 1g of sodium alginate and 0.5g of sodium carboxymethylcellulose into the magnetic graphene oxide aqueous solution uniformly dispersed by ultrasonic dispersion, stirring at a constant speed for 1 hour, dropping the mixed solution into a 5% calcium chloride solution by mass fraction, soaking for 24 hours, washing with deionized water for 3 times, and freeze-drying.
(3) Adsorption of the composite material on heavy metal ions: at 25 ℃, adding 4g of graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material into 100mL of Cu with pH of 7 and concentration of 100mg/L2+Stirring and adsorbing the heavy metal ion solution for 2.5 h. And detecting the concentration of the heavy metal ion solution in the adsorbed solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption rate of the composite material to the heavy metal ions. The result shows that the graphene oxide/polyethyleneimine/carboxymethyl cellulose is paired with Cu2+The amount of adsorbed was 85.7 mg/g.
Maximum adsorption capacity at different raw material ratios
| Name (R) | Mass ratio of the components | Cu2+Adsorption amount mg/g |
| Comparative example 1 | 10:10:10 | 38.8 |
| Comparative example 2 | 1:10:1 | 73.1 |
| Comparative example 3 | 3:10:1 | 76.3 |
| Comparative example 4 | 3:10:10 | 78.4 |
| Example 1 | 3:10:5 | 92.6 |
| Example 2 | 1:10:5 | 88.4 |
| Example 3 | 10:10:5 | 85.7 |
Fig. 1 is a synthesis diagram of a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material.
Fig. 2 is a diagram of a magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material. The adsorbing material can be gathered by an external magnetic field, and the recovery is simple and rapid.
Fig. 3 is an SEM of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material, and it is apparent from a that the surface of the mixture has many wrinkles. From B, it can be seen that the surface of the sample is irregular and has a lot of white particles polymerized, indicating Fe3O4Compounding has been successful. C is a partial enlarged view of the surface of the sphere of the composite material, the surface of the sphere is not smooth and has a large number of wrinkles and a certain pore structure, and pollutant molecules can permeate into the interior through the pore structure on the surface of the colloidal beads, so that the further adsorption of the pollutant molecules is facilitated. D is the internal section view of the sphere, and the figure shows that the inside of the rubber bead presents a complex network structure, the porous structure is very obvious, and the rubber bead has a large specific surface area。
Fig. 4 is a thermogravimetric curve of magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose and graphene oxide/sodium alginate. The thermogravimetric curve of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose is shown in a figure a, and the thermal decomposition is mainly divided into 3 stages. The weight loss at 200 ℃ is 8.7 percent respectively, which is caused by volatilization of water molecules on the surfaces of the microspheres and physically combined water molecules; the weight loss between 200 and 300 ℃ is caused by CO generated by the decomposition of oxygen-containing functional groups2And the dehydration of hydroxyl and carboxyl in the microspheres and the decomposition of part of sodium carboxymethylcellulose into intermediate products; mass loss at 300 ℃ 450 ℃ corresponds to further decomposition of the intermediate product and decarboxylation to CO2And the product is partially carbonized. There is also a residue at 550 ℃ as a result of the good thermal stability of the magnetic graphene oxide, as well as the strong intermolecular interactions. The thermogravimetric curve of the graphene oxide/sodium alginate is shown in a graph b, and the weight loss rate is about 40 percent and is obviously greater than that of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose within the range of 300 ℃. The improvement of the thermal stability performance is mainly attributed to the fact that the introduction of the sodium carboxymethyl cellulose enables a larger network to be formed among the three components, and therefore the thermal stability of the material is improved.
FIG. 5 shows magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose and Fe3O4A VSM map of. In which a is Fe3O4B is the magnetic hysteresis curve of magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose. As shown in the figure, the hysteresis curve is in a typical S shape, and the magnetic saturation intensity of the magnetic composite material is 16.8 emu/g. The magnetic hysteresis loop passes through the original point, and almost no remanence phenomenon exists by taking the original point as the center, which shows that the graphene oxide/magnetic chitosan has excellent magnetic performance.
Fig. 6 is an XPS survey of magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose. The characteristic peaks at C1s, N1s and O1s were at 285ev, 400ev and 532ev binding energies, respectively.
Fig. 7 is a graph showing the effect of the initial pH of the solution on the amount of copper ions adsorbed by the composite material, and the adsorption amount reached the maximum at pH 7.
Fig. 8 is a graph showing the effect of adsorption time on the amount of copper ions adsorbed by the composite material, and it is understood that the adsorption of lead ions by the composite material reaches equilibrium after about 120 min.
Fig. 9 is a graph of the result of a recycling experiment of the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material prepared in example 1 with respect to adsorption time. Obviously, after three repeated experiments, the adsorption amount is reduced by 6.7mg/g, 15.9mg/g and 22.3mg/g respectively. This is probably because the surface of the composite material contains many electronegative carboxyl active sites, and the carboxyl negative ions and copper ions are physically adsorbed, and the activation energy required for adsorption is low and reversible.
The composition of the magnetic graphene oxide, the sodium alginate and the sodium carboxymethyl cellulose enables the material to have a three-dimensional space structure on one hand, and further increases the number of functional groups and adsorption active points on the other hand. In addition, the stability of the composite material is improved to a certain extent, the adsorption effect of the composite material on heavy metal ions is obviously improved, and the stability is improved, so that the composite material disclosed by the invention is stable in use, is more widely applicable to environments, and can be applied to heavy metal adsorption treatment.
Claims (10)
1. The preparation method of the magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material is characterized by comprising the following specific steps of:
step 1, adding ferric trichloride and ferrous chloride into a graphene oxide dispersion solution, stirring and mixing uniformly, adjusting the pH to 9.5 +/-0.5, and reacting at room temperature to obtain magnetic graphene oxide;
and 2, ultrasonically dissolving sodium alginate and sodium carboxymethylcellulose in the magnetic graphene oxide dispersion liquid according to the mass ratio of 1-5: 10: 5-10 of the magnetic graphene oxide, sodium alginate and sodium carboxymethylcellulose, uniformly stirring and mixing, dripping the mixed solution into a calcium chloride solution with the mass fraction of 5 +/-2%, soaking at room temperature, washing with water, and drying to obtain the magnetic graphene oxide/sodium carboxymethylcellulose/sodium alginate composite material.
2. The method according to claim 1, wherein the stirring speed in steps 1 and 2 is 800 to 1000 rpm.
3. The method according to claim 1, wherein in step 1, the molar ratio of ferric trichloride to ferrous chloride is 2: 1.
4. The preparation method according to claim 1, wherein in the step 1, the reaction time is 20-24 h.
5. The preparation method according to claim 1, wherein in the step 2, the mass ratio of the magnetic graphene oxide to the sodium alginate to the sodium carboxymethyl cellulose is 3:10: 5.
6. The prepared magnetic graphene oxide/sodium carboxymethyl cellulose/sodium alginate composite material according to any one of claims 1 to 5.
7. The application of the magnetic graphene oxide/sodium alginate/sodium carboxymethyl cellulose composite material according to claim 6 in heavy metal ion adsorption.
8. The application of claim 7, wherein the specific application method is as follows: adjusting the pH value of the wastewater containing heavy metal ions to 3-10, and adding a magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material for adsorption.
9. The use according to claim 8, wherein the heavy metal ion is Cu2+。
10. The application of claim 8, wherein the pH of the wastewater containing heavy metal ions is 7, and the adsorption time is 2-4 h.
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