CN108525615B - Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel - Google Patents
Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel Download PDFInfo
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Abstract
The invention relates to preparation and application of a three-dimensional foam nickel-based nitrogen-doped graphene aerogel. The preparation method comprises the following steps: preparing graphene oxide by adopting an improved Hummers method, cleaning and etching foamed nickel, adding the cleaned and etched foamed nickel into a mixed solution of the graphene oxide, a nitrogen source, a reducing agent and a crosslinking agent to perform graphene self-assembly reaction, and freeze-drying the generated graphene hydrogel to obtain the foamed nickel-based nitrogen-doped graphene aerogel. The composite catalyst is added into high-salt dye wastewater, so that the dye adsorbed on the aerogel can be degraded, and harmless degradation is realized. The catalyst disclosed by the invention has the advantages of high catalytic efficiency, good reusability and the like, particularly solves the technical problems that the traditional nano/micron cobalt catalyst is not easy to recover, the graphene aerogel is low in mechanical strength, high-toxicity organic halogenated byproducts are easy to generate in the free radical oxidative degradation of high-salt dye wastewater and the like, and can be applied to the field of high-salt dye wastewater treatment.
Description
Technical Field
The invention relates to a composite catalytic material applied to the technical field of high-salt dye wastewater treatment, in particular to preparation of a three-dimensional foam nickel-based nitrogen-doped graphene aerogel and application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treatment of high-salt dye wastewater.
Background
The high-salt dye wastewater (the salinity is more than 1 percent) belongs to industrial wastewater which is difficult to biodegrade and has great harm. The transition metal cobalt catalyzes the potassium monoperoxysulfate to generate strong oxidizing species such as sulfuric acid free radicals, hydroxyl free radicals and the like, and the most of organic pollutants difficult to degrade are efficiently degraded. However, when the technology is applied to treat high-salt dye wastewater, chloride ions in the wastewater can capture sulfuric acid radicals and hydroxyl radicals to generate chlorine radicals with lower activity, so that the mineralization efficiency of the dye is low. More seriously, the chlorine free radicals are easy to react with dye molecules and their intermediate degradation products to generate organic halogenated byproducts with higher toxicity and even carcinogenicity, which seriously restricts the large-scale application of the technology in high-salt dye wastewater (Ruixia Y., et al. effects of chlorine on degradation of Acid organic 7 by sulfate and adsorbed oxidation processes: injections for formation of chlorine organic compounds [ J ]. Hazard. matrix, 2011,96: 173-.
In addition, the traditional ionic cobalt catalyst also has the problem of secondary pollution. In recent years, a nanometer or micron heterogeneous catalyst is prepared in Chinese patent CN 106694052A (a cellulose-based composite catalyst for catalyzing persulfate to degrade dye methyl orange and a preparation method thereof), Chinese patent CN 102583692B (a method for catalyzing persulfate to treat organic pollutants in water by heterogeneous copper oxide) and the like. Although the catalysts can realize effective degradation of organic pollutants, the recovery requires complex processes such as filtration, centrifugation and drying, and the recovery cost is high.
Disclosure of Invention
The invention provides a three-dimensional foam nickel-based nitrogen-doped graphene aerogel and a preparation method thereof, aiming at overcoming the problems that the traditional nano/micron cobalt catalyst is not easy to recover and the mechanical strength of the graphene aerogel is low in the background technology. The three-dimensional foam nickel-based nitrogen-doped graphene aerogel catalyst has the advantages of high catalytic efficiency, good reusability, simple recovery mode, high mechanical strength and the like, and particularly solves the technical problems that the traditional nano/micron-sized cobalt catalyst is not easy to recover, the graphene aerogel has low mechanical strength, high-toxicity organic halogenated byproducts are easy to generate in the free radical oxidative degradation of high-salt dye wastewater and the like. The invention also provides application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treatment of high-salt dye wastewater.
The invention can solve the problems by the following technical scheme:
the three-dimensional foam nickel-based nitrogen-doped graphene aerogel comprises the following components in percentage by weight: 4.0-10.9% of graphene oxide, 8.3-21.7% of nitrogen source, 1.7-5.4% of cross-linking agent, 8.3-10.9% of reducing agent and 51.1-77.7% of foamed nickel. .
Further, the nitrogen source is at least one of urea, ammonia water and melamine, the crosslinking agent is at least one of sodium tetraborate and polyvinyl alcohol, and the reducing agent is at least one of ascorbic acid, sodium bisulfite, sodium borohydride and hydroquinone.
The invention also discloses a preparation method of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel, which comprises the following steps:
(1) adding graphene oxide into distilled water according to a proportion, and ultrasonically stirring and dispersing;
(2) adding a nitrogen source, a cross-linking agent and a reducing agent into the graphene oxide solution obtained in the step (1) in proportion, and ultrasonically stirring uniformly;
(3) soaking the pretreated foamed nickel into the mixed solution obtained in the step (2), and reacting the mixed solution at 90 ℃ for 12 hours;
(4) and after the reaction is finished, obtaining the foam nickel-based nitrogen-doped graphene hydrogel, taking out the foam nickel-based nitrogen-doped graphene hydrogel, washing the foam nickel-based nitrogen-doped graphene hydrogel with distilled water to remove impurities, and freeze-drying to obtain the foam nickel-based nitrogen-doped graphene aerogel.
Further, the pretreatment method of the foamed nickel comprises the following steps:
(1) putting the foamed nickel into an acetone solvent, and performing ultrasonic treatment for 10 minutes to remove trace oil stains on the foamed nickel matrix, so that the hydrophilicity of the matrix is increased;
(2) ultrasonically cleaning the processed foam nickel for 10 minutes by using distilled water;
(3) etching the foamed nickel subjected to ultrasonic cleaning by using distilled water for 15 minutes by using 6.0 mol/L hydrochloric acid to remove an oxide layer on the surface of the matrix and form a micro-rough surface on the surface layer of the foamed nickel, so that the bonding force between the foamed nickel and graphene is enhanced;
(4) ultrasonically cleaning the foamed nickel treated by hydrochloric acid for 15 minutes by using distilled water, and then washing the foamed nickel by using the distilled water for several times;
(5) the treated nickel foam is dried in an oven at 60 ℃ for 3 h.
Further, the preparation method of the graphene oxide comprises the following steps:
(1) adding 1 g of graphite powder (1200 meshes) and 23 mL of concentrated sulfuric acid into a triangular flask in sequence, carrying out ice bath and stirring for 10 min;
(2) slowly adding 3 g of potassium permanganate into the flask, placing the flask in a 35 ℃ water bath kettle, and stirring for 2 hours;
(3) adding 50 mL of distilled water into the flask, placing the flask in a water bath kettle at the temperature of 95 ℃, and stirring for 15 min;
(4) transferring the mixed solution in the flask into a beaker filled with 150 mL of distilled water, dropwise adding hydrogen peroxide (the mass concentration is 30%), stirring while dropwise adding until the solution turns from brown to yellow;
(5) filtering the mixture, and dialyzing the mixture for 3 times by using 50 mL of HCl (10 mass percent) to remove impurities;
(6) and filtering the solution, and freeze-drying filter residues at the temperature of minus 40 ℃ to obtain the graphene oxide.
Further, the concentration of the graphene oxide is 0.5-2 g/L, the concentration of the nitrogen source is 1-4 g/L, the concentration of the cross-linking agent is 0.2-1 g/L, the concentration of the reducing agent is 1-2 g/L, the freeze-drying temperature is-40 ℃, and the freeze-drying time is 12 hours.
The invention also discloses application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treatment of high-salt dye wastewater.
Further, the application process comprises the following steps:
(1) adding the foam nickel-based nitrogen-doped graphene aerogel into high-salt dye wastewater, stirring, and completely adsorbing dye molecules on the surface of the graphene aerogel under a certain temperature condition;
(2) taking out the foam nickel-based nitrogen-doped graphene aerogel, and cleaning with distilled water to remove surface salt ions;
(3) adding the foam nickel-based nitrogen-doped graphene aerogel into a solution containing potassium monoperoxysulfate to generate strong oxidation species such as sulfuric acid free radicals and hydroxyl free radicals and the like to degrade dyes adsorbed on the surface of the graphene aerogel.
Further, in the high-salt dye wastewater in the step (1), the concentration of sodium chloride is 10-50 g/L, the concentration of dye is 0.1-0.5 mmol/L, and the molar concentration ratio of potassium monoperoxysulfate to dye is (10-50): 1; in the step (1), the adsorption temperature is 30-50 ℃, and the adsorption time is 30-90 min; and (3) degrading at 10-40 ℃ for 30-60 min.
Compared with the background technology, the invention has the following beneficial effects: according to the invention, the foam nickel with excellent mechanical properties, strong chemical stability, high temperature resistance, strong conductivity, large porosity and specific surface area is used as the template of the nitrogen-doped graphene aerogel, so that the mechanical strength and the catalytic performance of the nitrogen-doped graphene aerogel can be improved. The prepared foam nickel-based nitrogen-doped graphene aerogel is a metal-free catalyst, the problem of secondary pollution caused by cobalt loss is solved, and the macroscopic composite nano catalyst also has the advantages of large specific surface area, high catalytic efficiency and easiness in recycling.
The method for degrading the high-salt dye wastewater by catalyzing the potassium monoperoxysulfate with the foam nickel-based nitrogen-doped graphene aerogel also has the following beneficial effects: the prepared composite catalyst has large specific surface area and strong adsorption performance, can efficiently adsorb dye molecules, and realizes the separation of the dye molecules and salt ions in high-salt dye wastewater; the prepared composite catalyst has strong catalytic performance, can catalyze potassium monoperoxysulfate to generate a large amount of sulfate radicals and hydroxyl radicals, and realizes the degradation of dye molecules.
Drawings
Fig. 1 is a graph of an adsorption effect of a foam nickel-based nitrogen-doped graphene aerogel on acid orange 7 in example 1 of the present invention;
fig. 2 is a graph of the adsorption effect of the foamed nickel-based nitrogen-doped graphene aerogel catalyst on acid orange 7 after five times of recycling in example 1 of the invention;
fig. 3 is a graph of an adsorption effect of the foam nickel-based nitrogen-doped graphene aerogel on methyl orange in embodiment 2 of the invention.
The specific implementation mode is as follows:
the invention will be further described with reference to the following drawings and specific embodiments:
example 1
Urea is used as a nitrogen source, sodium tetraborate is used as a crosslinking agent, ascorbic acid is used as a reducing agent, and the foamed nickel-based nitrogen-doped graphene aerogel (4.0% of graphene oxide, 8.3% of nitrogen source, 1.7% of crosslinking agent, 8.3% of reducing agent and 77.7% of foamed nickel) and acid orange 7 (with the concentration of 0.2 mmol/L) wastewater with the treatment salinity (NaCl) of 20 g/L are prepared. The specific preparation and use method of the foam nickel-based nitrogen-doped graphene aerogel comprises the following steps:
(1) pretreatment of nickel foam
Immersing foamed nickel (2 cm multiplied by 4 cm multiplied by 0.6 cm) into acetone, and carrying out ultrasonic treatment for 10 minutes to remove trace oil stains on the foamed nickel substrate, so as to increase the hydrophilicity of the substrate; performing ultrasonic treatment on the processed foamed nickel by using distilled water for 10 minutes, and then etching the foamed nickel by using 6.0 mol/L hydrochloric acid for 15 minutes to remove an oxide layer on the surface of a matrix and form a micro-rough surface on the surface layer of the foamed nickel, so that the bonding force between the foamed nickel and graphene is enhanced; and ultrasonically cleaning the foamed nickel treated by hydrochloric acid by using distilled water for 15 minutes, then washing the foamed nickel by using the distilled water for a plurality of times, and finally drying the treated foamed nickel in an oven at the temperature of 60 ℃ for 3 hours.
(2) Preparation of graphene oxide
Adding 1 g of graphite powder (1200 meshes) and 23 mL of concentrated sulfuric acid into a triangular flask in sequence, carrying out ice bath and stirring for 10 min; slowly adding 3 g of potassium permanganate into the flask, placing the flask in a 35 ℃ water bath kettle, and stirring for 2 hours; adding 50 mL of distilled water into the flask, placing the flask in a water bath kettle at the temperature of 95 ℃, and stirring for 15 min; transferring the mixed solution in the flask into a beaker filled with 150 mL of distilled water, dropwise adding hydrogen peroxide (the mass concentration is 30%), stirring while dropwise adding until the solution turns from brown to yellow; filtering the mixture, and dialyzing the mixture for 3 times by using 50 mL of HCl (10 mass percent) to remove impurities; and filtering the solution, and freeze-drying filter residues at the temperature of minus 40 ℃ to obtain the graphene oxide.
(3) Preparation of foam nickel-based nitrogen-doped graphene oxide
Adding graphene oxide (25 mg) into 50 mL of distilled water, and ultrasonically stirring for 1 h to obtain a uniformly dispersed graphene suspension; adding 0.05 g of urea, 0.01 g of sodium tetraborate and 0.05 g of ascorbic acid into the suspension, and ultrasonically stirring for 1 h; immersing the pretreated foamed nickel into the mixed solution, and reacting the mixed solution at 90 ℃ for 12 hours to obtain foamed nickel-based nitrogen-doped graphene hydrogel; and taking out the foam nickel-based nitrogen-doped graphene hydrogel, washing the foam nickel-based nitrogen-doped graphene hydrogel for multiple times by using distilled water to remove impurities, and finally, carrying out freeze drying for 12 hours at the temperature of minus 40 ℃ to obtain the foam nickel-based nitrogen-doped graphene aerogel.
(4) Harmless degradation of acid orange 7 high-salinity wastewater
The dye in the selected high-salt dye wastewater is acid orange 7, the concentration is 50 mg/L, and the NaCl concentration is 20 g/L. When the waste water is degraded by adopting the traditional cobalt ion to catalyze the potassium monoperoxysulfate, the degradation efficiency is low, and various high-toxicity even carcinogenic organic halogenated byproducts such as chlorophenols, chlorobenzenes and the like are generated in the degradation process.
The specific process for catalytically degrading the acid orange 7 high-salt wastewater by adopting the prepared foam nickel-based nitrogen-doped graphene aerogel is as follows: adding the foam nickel-based nitrogen-doped graphene aerogel into acid orange 7 wastewater (100 mL), stirring, setting the adsorption temperature to be 40 ℃, sampling at regular intervals, measuring absorbance, and calculating the adsorption amount of the dye on the surface of the foam nickel-based nitrogen-doped graphene aerogel. As shown in fig. 1, after 70 min, acid orange 7 in the solution is completely adsorbed on the surface of the graphene aerogel. Taking the foam nickel-based nitrogen-doped graphene aerogel out of the solution, and washing the solution with distilled water to remove surface salt ions; then adding the mixture into a solution containing potassium monoperoxysulfate (5 mmol/L) and stirring, and completely degrading the acid orange 7 after reacting for 60 min. The detection of the microcoulomb method shows that no organic halogenated byproducts are generated in the degradation process.
When the foam nickel-based nitrogen-doped graphene aerogel is reused after being used, the foam nickel-based nitrogen-doped graphene aerogel is washed by distilled water to remove impurities and is reused for 5 times, and the adsorption and degradation efficiency of the foam nickel is not obviously reduced (see figure 2)。
Example 2
Ammonia water is used as a nitrogen source, polyvinyl alcohol is used as a cross-linking agent, sodium bisulfite is used as a reducing agent, foam nickel-based nitrogen-doped graphene aerogel (10.9% of graphene oxide, 21.7% of nitrogen source, 5.4% of cross-linking agent, 10.9% of reducing agent and 51.1% of foam nickel) is prepared, and methyl orange (with the concentration of 0.2 mmol/L) wastewater with the treatment salinity (NaCl) of 30 g/L is treated. The specific preparation and use method of the foam nickel-based nitrogen-doped graphene aerogel comprises the following steps:
(1) pretreatment of nickel foam (2 cm. times.5 cm. times.0.6 cm) was carried out in accordance with the method of example 1;
(2) preparing graphene oxide according to the method of example 1;
(3) and preparing the foam nickel-based nitrogen-doped graphene oxide.
Adding graphene oxide (100 mg) into 100 mL of distilled water, and ultrasonically stirring for 1 h to obtain a uniformly dispersed graphene suspension; adding 0.2 g of ammonia water, 0.05 g of polyvinyl alcohol and 0.1 g of sodium bisulfite into the suspension, and ultrasonically stirring for 1 h; reacting the mixed solution at 90 ℃ for 12 h to obtain foam nickel-based nitrogen-doped graphene hydrogel; and taking out the foam nickel-based nitrogen-doped graphene hydrogel, washing the foam nickel-based nitrogen-doped graphene hydrogel for multiple times by using distilled water to remove impurities, and finally, freeze-drying the foam nickel-based nitrogen-doped graphene hydrogel for 12 hours at the temperature of minus 40 ℃ to obtain the foam nickel-based nitrogen-doped graphene aerogel.
The specific process for catalytically degrading methyl orange high-salt wastewater by adopting the prepared foam nickel-based nitrogen-doped graphene aerogel comprises the following steps: adding the foam nickel-based nitrogen-doped graphene aerogel into methyl orange wastewater (100 mL), stirring for 80 min at 30 ℃, and adsorbing all dye molecules on the surface of the graphene aerogel (shown in figure 3); taking out the foam nickel-based nitrogen-doped graphene aerogel, and cleaning with distilled water to remove surface salt ions; adding the foam nickel-based nitrogen-doped graphene aerogel into a solution containing potassium monoperoxysulfate (10 mmol/L), and stirring for 60 min to completely degrade methyl orange adsorbed by the graphene aerogel. The detection of the microcoulomb method shows that no organic halogenated byproducts are generated in the degradation process.
Claims (9)
1. The three-dimensional foam nickel-based nitrogen-doped graphene aerogel comprises the following components in percentage by weight: 4.0-10.9% of graphene oxide, 8.3-21.7% of nitrogen source, 1.7-5.4% of cross-linking agent, 8.3-10.9% of reducing agent and 51.1-77.7% of foamed nickel; the nitrogen source is at least one of urea, ammonia water and melamine, the cross-linking agent is sodium tetraborate, and the reducing agent is at least one of ascorbic acid, sodium bisulfite and hydroquinone;
the preparation method comprises the following steps:
(1) adding graphene oxide into distilled water according to a proportion, and ultrasonically stirring and dispersing;
(2) adding a nitrogen source, a cross-linking agent and a reducing agent into the graphene oxide solution obtained in the step (1) in proportion, and ultrasonically stirring uniformly;
(3) soaking the pretreated foamed nickel into the mixed solution obtained in the step (2), and reacting the mixed solution at 90 ℃ for 12 hours;
(4) and after the reaction is finished, obtaining the foam nickel-based nitrogen-doped graphene hydrogel, taking out the foam nickel-based nitrogen-doped graphene hydrogel, washing the foam nickel-based nitrogen-doped graphene hydrogel with distilled water to remove impurities, and freeze-drying to obtain the foam nickel-based nitrogen-doped graphene aerogel.
2. The preparation method of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
(1) adding graphene oxide into distilled water according to a proportion, and ultrasonically stirring and dispersing;
(2) adding a nitrogen source, a cross-linking agent and a reducing agent into the graphene oxide solution obtained in the step (1) in proportion, and ultrasonically stirring uniformly;
(3) soaking the pretreated foamed nickel into the mixed solution obtained in the step (2), and reacting the mixed solution at 90 ℃ for 12 hours;
(4) and after the reaction is finished, obtaining the foam nickel-based nitrogen-doped graphene hydrogel, taking out the foam nickel-based nitrogen-doped graphene hydrogel, washing the foam nickel-based nitrogen-doped graphene hydrogel with distilled water to remove impurities, and freeze-drying to obtain the foam nickel-based nitrogen-doped graphene aerogel.
3. The preparation method of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel according to claim 2, characterized by comprising the following steps: the pretreatment method of the foamed nickel comprises the following steps:
(1) putting the foamed nickel into an acetone solvent, and performing ultrasonic treatment for 10 minutes to remove trace oil stains on the foamed nickel matrix, so that the hydrophilicity of the matrix is increased;
(2) ultrasonically cleaning the processed foam nickel for 10 minutes by using distilled water;
(3) etching the foamed nickel subjected to ultrasonic cleaning by using distilled water for 15 minutes by using 6.0 mol/L hydrochloric acid to remove an oxide layer on the surface of the matrix and form a micro-rough surface on the surface layer of the foamed nickel, so that the bonding force between the foamed nickel and graphene is enhanced;
(4) ultrasonically cleaning the foamed nickel treated by hydrochloric acid for 15 minutes by using distilled water, and then washing the foamed nickel by using the distilled water for several times;
(5) the treated nickel foam is dried in an oven at 60 ℃ for 3 h.
4. The preparation method of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel according to claim 2, characterized by comprising the following steps: the preparation method of the graphene oxide comprises the following steps:
(1) adding 1 g of 1200-mesh graphite powder and 23 mL of concentrated sulfuric acid into a triangular flask in sequence, carrying out ice bath and stirring for 10 min;
(2) slowly adding 3 g of potassium permanganate into the flask, placing the flask in a 35 ℃ water bath kettle, and stirring for 2 hours;
(3) adding 50 mL of distilled water into the flask, placing the flask in a water bath kettle at the temperature of 95 ℃, and stirring for 15 min;
(4) transferring the mixed solution in the flask into a beaker filled with 150 mL of distilled water, dropwise adding hydrogen peroxide with the mass concentration of 30%, and stirring while dropwise adding until the solution turns from brown to yellow;
(5) filtering the mixture, and dialyzing for 3 times by using 50 mL of HCl with the HCl mass concentration of 10% to remove impurities;
(6) and filtering the solution, and freeze-drying filter residues at the temperature of minus 40 ℃ to obtain the graphene oxide.
5. The preparation method of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel according to claim 2, characterized by comprising the following steps: the graphene oxide concentration is 0.5-2 g/L, the nitrogen source concentration is 1-4 g/L, the cross-linking agent concentration is 0.2-1 g/L, the reducing agent concentration is 1-2 g/L, the freeze-drying temperature is-40 ℃, and the freeze-drying time is 12 hours.
6. The application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel according to claim 1 in treatment of high-salt dye wastewater.
7. The application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treating high-salt dye wastewater according to claim 6 is characterized in that: the application process comprises the following steps:
(1) adding the foam nickel-based nitrogen-doped graphene aerogel into high-salt dye wastewater, stirring, and completely adsorbing dye molecules on the surface of the graphene aerogel under a certain temperature condition;
(2) taking out the foam nickel-based nitrogen-doped graphene aerogel, and cleaning with distilled water to remove surface salt ions;
(3) adding the foam nickel-based nitrogen-doped graphene aerogel into a solution containing potassium monoperoxysulfate to generate strong oxidizing species of sulfuric acid radicals and hydroxyl radicals so as to degrade dyes adsorbed on the surface of the graphene aerogel.
8. The application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treating high-salt dye wastewater according to claim 7 is characterized in that: the concentration of sodium chloride in the high-salt dye wastewater in the step (1) is 10-50 g/L, the concentration of dye is 0.1-0.5 mmol/L, and the molar concentration ratio of potassium monoperoxysulfate to dye is 10-50: 1.
9. the application of the three-dimensional foam nickel-based nitrogen-doped graphene aerogel in treating high-salt dye wastewater according to claim 7 is characterized in that: in the step (1), the adsorption temperature is 30-50 ℃, and the adsorption time is 30-90 min; and (3) degrading at 10-40 ℃ for 30-60 min.
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| CN110240149B (en) * | 2019-06-27 | 2021-04-02 | 中素新科技有限公司 | Production method of graphene |
| CN112886028B (en) * | 2019-11-29 | 2022-03-08 | 中国科学院大连化学物理研究所 | Self-supporting porous air electrode material and preparation and application thereof |
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