CN110817849A - Sulfhydrylation graphene aerogel and preparation method and application thereof - Google Patents
Sulfhydrylation graphene aerogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN110817849A CN110817849A CN201911204465.8A CN201911204465A CN110817849A CN 110817849 A CN110817849 A CN 110817849A CN 201911204465 A CN201911204465 A CN 201911204465A CN 110817849 A CN110817849 A CN 110817849A
- Authority
- CN
- China
- Prior art keywords
- graphene
- heavy metal
- sulfhydrylation
- graphene aerogel
- hydrosulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a sulfhydrylation graphene aerogel, wherein an adsorbent of the sulfhydrylation graphene aerogel takes oxidized graphene and hydrosulfide as raw materials, the oxidized graphene and the hydrosulfide react to obtain sulfhydrylation graphene hydrogel, and then the sulfhydrylation graphene hydrogel is dried to obtain the sulfhydrylation graphene aerogel. The invention also provides a preparation method of the sulfhydrylation graphene aerogel and application of the sulfhydrylation graphene aerogel in preparation of a heavy metal ion adsorbent. The sulfhydrylation graphene aerogel has an interconnected network structure, a large specific surface area and abundant active adsorption sites, and the adsorption capacity of the sulfhydrylation graphene aerogel on copper ions is remarkably improved. The sulfhydrylation graphene aerogel disclosed by the invention has a very good application prospect in preparation of a high-efficiency adsorbent for removing heavy metal ions in industrial wastewater.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a sulfhydrylation graphene aerogel and a preparation method and application thereof.
Background
In recent decades, with the rapid development of economy and society, human activities increasingly interfere with the environment, causing serious environmental pollution. Heavy metal elements, which are major pollutants in industrial wastewater, are difficult to degrade and have high toxicity. They not only destroy the aquatic environment, but can also be harmful to aquatic life and human health through the food chain. Among them, copper is one of the essential trace elements in the organism, and is involved in the metabolic process of the organism. However, excessive copper ions in surface and ground water pose a serious threat to human health and other organisms. In view of this, there is an urgent need to develop a cost-effective and high-performance adsorbent for efficiently removing excessive copper ions from wastewater. Until now, a great deal of research has been devoted to the purification of contaminated water containing heavy metal ions, and various corresponding wastewater treatment methods, such as adsorption, ion exchange, membrane separation, flocculation coagulation, and chemical precipitation. At present, the adsorption method is considered to be one of the most effective methods for treating the polluted water containing heavy metal ions due to the characteristics of wide adaptability, high efficiency, low price and the like. Therefore, various adsorbents such as chitosan, activated carbon, silica, zeolite, granular activated carbon, and carbon-based materials have been widely studied for removing heavy metal contaminants from aqueous solutions.
Graphene and graphene-based nanomaterials are used as a novel carbon-based adsorption material, have extremely large specific surface area, high mechanical strength and feasible chemical modification capacity, and therefore become high-performance adsorbents for removing heavy metals from wastewater solutions. In addition, rich oxygen-containing functional groups on the graphene oxide are beneficial to providing more modification sites for the graphene aerogel, so that inorganic elements such as nitrogen and sulfur are introduced to improve the adsorption capacity of the graphene aerogel, and the graphene oxide aerogel has a wider application prospect in the field of heavy metal removal.
Chinese patent application CN106179277A discloses a sulfhydrylated graphene oxide/polyvinyl alcohol macroporous composite sphere adsorbent and a preparation method and application thereof. Firstly, preparing graphite oxide by adopting an improved Hummers method, obtaining graphene oxide through ultrasonic stripping, preparing sulfhydrylated graphene oxide through covalent modification of 4-aminothiophenol, and embedding the sulfhydrylated graphene oxide in polyvinyl alcohol to prepare the sulfhydrylated graphene oxide/polyvinyl alcohol macroporous composite sphere adsorbent. The macroporous composite ball adsorbent in the patent application introduces sulfydryl, reduces water solubility, is easy for solid-liquid separation, and improves the adsorption capacity of the product to pollutants. However, the application takes 4-aminothiophenol as a raw material, the preparation cost is high, and the adsorption capacity (maximum adsorption capacity of 88.90mg/g) of the macroporous composite ball adsorbent to heavy metal ions cannot meet the requirement and needs to be further improved. Therefore, the preparation of the adsorbent with lower preparation cost and better adsorption capacity on heavy metal ions has very important significance.
Disclosure of Invention
The invention aims to provide a sulfhydrylation graphene aerogel adsorbent which is lower in preparation cost and better in adsorption capacity on heavy metal ions and a preparation method thereof.
The invention provides a sulfhydrylation graphene aerogel, wherein an adsorbent of the sulfhydrylation graphene aerogel takes oxidized graphene and hydrosulfide as raw materials, the oxidized graphene and the hydrosulfide react to obtain sulfhydrylation graphene hydrogel, and then the sulfhydrylation graphene hydrogel is dried to obtain the sulfhydrylation graphene aerogel.
Further, the hydrosulfide is sodium hydrosulfide.
Further, the mass ratio of the graphene oxide to the hydrogen sulfide is (1-5): 1, preferably 2: 1.
the invention also provides a preparation method of the sulfhydrylation graphene aerogel, which comprises the following steps:
(1) adding graphene oxide into water, and dispersing to obtain a graphene oxide dispersion liquid; dissolving hydrosulfide in water to obtain hydrosulfide aqueous solution;
(2) adding the hydrosulfide aqueous solution obtained in the step (1) into the graphene oxide dispersion liquid, and reacting to obtain sulfhydrylation graphene hydrogel;
(3) and (3) drying the sulfhydrylation graphene hydrogel obtained in the step (2) to obtain sulfhydrylation graphene aerogel.
Further, in the step (1), the concentration of the graphene oxide dispersion liquid is 4-6mg/mL, preferably 6 mg/mL; the concentration of the hydrosulfide aqueous solution is 0.10-0.20 mg/mL, preferably 0.15 mg/mL;
and/or, in the step (2), the reaction conditions are as follows: reacting for 5-20 hours at 55-85 ℃ under vacuum, and preferably, the reaction conditions are as follows: reacting for 7 hours at 65 ℃ in a vacuum state;
and/or, in the step (3), the drying method is freeze drying, preferably, the freeze drying temperature is below-40 ℃ and the time is 48-60 hours.
Further, in the step (2), after the reaction is finished, the following purification steps are included: transferring the reacted system into a container filled with ethanol water solution, soaking in the ethanol water solution, and removing unreacted hydrosulfide in the system; preferably, the soaking time is 48 hours, during which the aqueous ethanol solution is replaced every 4 hours, and the volume of ethanol in the aqueous ethanol solution is 20%.
The invention also provides application of the sulfhydrylation graphene aerogel in preparation of a heavy metal ion adsorbent.
Further, the heavy metal ion is Cu2+。
Further, the dosage of the heavy metal ion adsorbent is 7-30mg per 50mL of heavy metal ion solution;
the concentration of the heavy metal ion solution is 50-550 mg/L;
the pH value of the heavy metal ion solution is 1.5-5.5.
Further, the dosage of the heavy metal ion adsorbent is 7mg per 50mL of heavy metal ion solution;
the concentration of the heavy metal ion solution is50 mg/L;
the pH of the heavy metal ion solution is 5.5.
Experimental results show that the sulfhydrylation graphene aerogel disclosed by the invention has an interconnected network structure, a larger specific surface area and abundant active adsorption sites (including residual oxygen-containing functional groups and grafted sulfhydryl groups), the maximum adsorption capacity of the sulfhydrylation graphene aerogel on copper ions is up to 421.21mg/g, and the maximum adsorption capacity is improved by 433.18% compared with that of the sulfhydryl group-free graphene aerogel. Meanwhile, after the sulfhydrylation graphene aerogel disclosed by the invention is complexed with copper ions, the water solubility is extremely low, the solid-liquid separation after adsorption is facilitated, and the use value of the sulfhydrylation graphene aerogel is improved.
The preparation method disclosed by the invention is simple in preparation process, cheap and easily available in raw materials, mild in experimental conditions, safe and controllable, and the prepared sulfhydrylation graphene aerogel has excellent adsorption capacity on copper ions in an aqueous solution, and can be used as a novel efficient adsorbent for removing heavy metal ions from industrial wastewater.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
Fig. 1 is a process route for preparing a thiolated graphene aerogel (TFGA).
FIG. 2 is an SEM photograph of TFGA-1.
FIG. 3 is an infrared spectrum of GO and TFGA-1.
FIG. 4 is a spectrum S2p of TFGA-1.
FIG. 5 is a graph showing the change in adsorption capacity of TFGA for copper ions at different amounts of TFGA.
FIG. 6 is a graph showing the change in adsorption capacity of TFGA for copper ions under different pH conditions.
FIG. 7 is a graph showing the change in the adsorption capacity of TFGA for copper ions at different copper ion concentrations.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
According to the preparation process route shown in fig. 1, the thiolated graphene aerogel TFGA of the present invention is prepared.
Example 1 preparation of a thiolated graphene aerogel (TFGA-1)
Adding 0.6g of graphite oxide powder (GO, purchased from Hexagon, science and technology Co., Ltd.) into deionized water at room temperature, and magnetically stirring uniformly to obtain a graphene oxide colloidal suspension; and carrying out ultrasonic treatment on the graphene oxide colloidal suspension for 1 hour to form a uniform and stable graphene oxide dispersion liquid of 6 mg/mL. Dissolving 0.3g of sodium hydrosulfide in 2mL of deionized water to obtain a sodium hydrosulfide aqueous solution, slowly dropwise adding the sodium hydrosulfide aqueous solution into a sample bottle filled with the graphene oxide dispersion liquid while stirring to obtain a mixture, transferring the sample bottle filled with the mixture into a vacuum drying oven at 65 ℃, and reacting for 7 hours to obtain the thiolated graphene hydrogel.
And transferring the obtained thiolated graphene hydrogel into a large beaker, transferring the thiolated graphene hydrogel into an ethanol aqueous solution (wherein the volume of the ethanol accounts for 20%), soaking the thiolated graphene hydrogel in the ethanol aqueous solution for two days, and replacing the ethanol aqueous solution every 4 hours until the surplus sodium hydrosulfide which does not participate in the reaction is washed clean. And then placing the sulfhydrylation graphene hydrogel after soaking in a freeze dryer, and freeze-drying for 48 hours at the temperature of minus 40 ℃ to obtain the sulfhydrylation graphene aerogel, which is named as TFGA-1.
Example 2 preparation of thiolated graphene aerogel (TFGA-2)
Adding 0.4g of graphite oxide powder into deionized water at room temperature, and magnetically stirring uniformly to obtain a graphene oxide colloidal suspension; and carrying out ultrasonic treatment on the graphene oxide colloidal suspension for 1 hour to form a uniform and stable 4mg/mL graphene oxide dispersion liquid. Dissolving 0.2g of sodium hydrosulfide in 2mL of deionized water to obtain a sodium hydrosulfide aqueous solution, slowly dropwise adding the sodium hydrosulfide aqueous solution into a sample bottle filled with the graphene oxide dispersion liquid while stirring to obtain a mixture, transferring the sample bottle filled with the mixture into a vacuum drying oven at 55 ℃, and reacting for 11 hours to obtain the thiolated graphene hydrogel.
And transferring the obtained thiolated graphene hydrogel into a large beaker, transferring the thiolated graphene hydrogel into an ethanol aqueous solution (wherein the volume of the ethanol accounts for 20%), soaking the thiolated graphene hydrogel in the ethanol aqueous solution for two days, and replacing the ethanol aqueous solution every 4 hours until the surplus sodium hydrosulfide which does not participate in the reaction is washed clean. And (3) placing the sulfhydrylation graphene hydrogel after soaking in a freeze dryer, and freeze-drying for 48 hours at the temperature of-40 ℃ to obtain sulfhydrylation graphene aerogel, which is named as TFGA-2.
Example 3 preparation of thiolated graphene aerogel (TFGA-3)
Adding 0.5g of graphite oxide powder into deionized water at room temperature, and magnetically stirring uniformly to obtain a graphene oxide colloidal suspension; and carrying out ultrasonic treatment on the graphene oxide colloidal suspension for 1 hour to form a uniform and stable 5mg/mL graphene oxide dispersion liquid. Dissolving 0.25g of sodium hydrosulfide in 2mL of deionized water to obtain a sodium hydrosulfide aqueous solution, slowly dropwise adding the sodium hydrosulfide aqueous solution into a sample bottle filled with the graphene oxide dispersion liquid while stirring to obtain a mixture, transferring the sample bottle filled with the mixture into a vacuum drying oven at 75 ℃, and reacting for 7 hours to obtain the thiolated graphene hydrogel.
And transferring the obtained thiolated graphene hydrogel into a large beaker, adding an ethanol aqueous solution (wherein the volume of the ethanol accounts for 20%) into the beaker, soaking the thiolated graphene hydrogel in the ethanol aqueous solution for two days, and replacing the ethanol aqueous solution every 4 hours until the surplus sodium hydrosulfide which does not participate in the reaction is washed clean. And (3) placing the sulfhydrylation graphene hydrogel after soaking in a freeze dryer, and freeze-drying for 48 hours at the temperature of-40 ℃ to obtain the sulfhydrylation graphene aerogel, which is named as TFGA-3.
Example 4 preparation of thiolated graphene aerogel (TFGA-4)
Adding 0.5g of graphite oxide powder into deionized water at room temperature, and magnetically stirring uniformly to obtain a graphene oxide colloidal suspension; and carrying out ultrasonic treatment on the graphene oxide colloidal suspension for 1 hour to form a uniform and stable 5mg/mL graphene oxide dispersion liquid. Dissolving 0.25g of sodium hydrosulfide in 2mL of deionized water to obtain a sodium hydrosulfide aqueous solution, slowly dropwise adding the sodium hydrosulfide aqueous solution into a sample bottle filled with the graphene oxide dispersion liquid while stirring to obtain a mixture, transferring the sample bottle filled with the mixture into a vacuum drying oven at 85 ℃, and reacting for 5 hours to obtain the thiolated graphene hydrogel.
And transferring the obtained thiolated graphene hydrogel into a large beaker, adding an ethanol aqueous solution (wherein the volume of the ethanol accounts for 20%) into the beaker, soaking the thiolated graphene hydrogel in the ethanol aqueous solution for two days, and replacing the ethanol aqueous solution every 4 hours until the surplus sodium hydrosulfide which does not participate in the reaction is washed clean. And (3) placing the sulfhydrylation graphene hydrogel after soaking in a freeze dryer, and freeze-drying for 48 hours at the temperature of-40 ℃ to obtain sulfhydrylation graphene aerogel, which is named as TFGA-4.
Comparative example 1 preparation of graphene aerogel containing no mercapto group
Graphene aerogel containing no mercapto group was prepared by replacing sodium hydrosulfide with ascorbic acid in the same manner as in example 1.
The beneficial effects of the present invention are demonstrated by the following experimental examples.
Experimental example 1 structural characterization of thiolated graphene aerogel according to the present invention
1. Experimental methods
SEM, Quanta 250, testing at 20kV accelerating voltage; fourier transform Infrared (FT-IR) Spectroscopy (Nicolet iS50) analyzed the chemical composition of the sample surface in the range of 4000 to 400cm-1XPS analysis of sulfur-containing groups, KRATOS XSAM800, with AlK α as the X-ray source and a power of 150W.
2. Experimental sample
Thiolated graphene aerogel TFGA-1 prepared in example 1, raw material graphene oxide GO in example 1.
3. Results of the experiment
SEM results of the sulfhydrylated graphene aerogel are shown in FIG. 2, and it can be seen that the aerogel TFGA-1 has a highly interconnected three-dimensional porous structure, and the structure increases the number of active sites of the TFGA-1, so that the adsorption capacity of the TFGA-1 adsorbent on copper ions in a water body can be improved.
FIG. 3 is an infrared spectrum of GO and TFGA-1, the hydroxyl peak of the thiolated graphene aerogel is significantly reduced, while the peak intensity of the epoxy group is not significantly reduced, compared to pure graphite oxide GO, and the newly appeared 669cm-1And 808cm-1Peaks, which are associated with C-S stretch and C-SH bending. Also in the S2p spectrum of FIG. 4, the peak was at 163.8eV, due to H-C-S in the aerogel.
The characterization results show that the aerogel prepared by the invention contains rich oxygen-containing functional groups and sulfydryl, and the success of preparing the sulfhydrylation graphene aerogel is proved.
Experimental example 2 screening of copper ion adsorption conditions by using thiolated graphene aerogel according to the present invention
1. Experimental methods
(a) Determination of adsorption Capacity for copper ions at different amounts of TFGA
Adding 7-35mg of graphene aerogel into 50ml of 250mg/L copper ion aqueous solution, adjusting the pH to 5.5, oscillating for 720min, testing the copper ion concentration of the residual solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity of the copper ion concentration.
(b) Determination of adsorption Capacity for copper ions under different pH conditions
Adding 7mg of graphene aerogel into 50ml of 250mg/L copper ion aqueous solution, adjusting the pH to 1.5-5.5, oscillating for 720min, testing the copper ion concentration of the residual solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity of the copper ion concentration.
2. Experimental sample
Example 1 the thiolated graphene aerogel TFGA-1 prepared.
3. Results of the experiment
The effect on the adsorption capacity for copper ions at different amounts of TFGA is shown in fig. 5, where it can be seen that the adsorption capacity for copper ions decreases with increasing TFGA mass. Therefore, when 50mL of the copper ion solution was adsorbed, the optimum mass of TFGA selected was 7 mg.
The effect on the adsorption capacity of copper ions under different pH conditions is shown in FIG. 6, and it can be seen that the adsorption capacity of TFGA for copper ions gradually increases as the pH in the aqueous solution increases from 1.5 to 5.5, and the maximum adsorption amount is obtained at pH 5.5, indicating that the adsorption amount strongly depends on the pH of the solution. To avoid the effect of copper ion hydrolysis, pH 5.5 was chosen as the optimum.
Experimental example 3 test of copper ion adsorption capacity of thiolated graphene aerogel according to the present invention
1. Experimental methods
Adding 7mg of graphene aerogel into 50ml of copper ion aqueous solutions with different concentrations (50-550 mg/L), adjusting the pH to 5.5, oscillating for 720min, testing the copper ion concentration of the rest solution by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity of the rest solution.
2. Experimental sample
The sulfhydrylation graphene aerogel TFGA-1-TFGA-4 prepared in the examples 1-4 and the graphene aerogel without sulfhydryl groups prepared in the comparative example 1.
3. Results of the experiment
For the sulfhydrylation graphene aerogel, the adsorption capacity of the sulfhydrylation graphene aerogel on copper ions is increased along with the increase of the copper ion concentration, and finally, an equilibrium state is reached, and when the copper ion concentration is 550mg/L, the adsorption capacity of the sulfhydrylation graphene aerogel is the maximum. Wherein the maximum adsorption capacity of TFGA-1 is 421.21mg/g (as shown in FIG. 7), the maximum adsorption capacity of TFGA-2 is 361.68mg/g, the maximum adsorption capacity of TFGA-3 is 212.92mg/g, and the maximum adsorption capacity of TFGA-4 is 138.84mg/g
In contrast, in the case of the graphene aerogel containing no mercapto group prepared in comparative example 1, the maximum adsorption capacity was only 79.00mg/g at a copper ion concentration of 550 mg/L.
Therefore, the sulfhydrylation graphene aerogel prepared by the invention can obviously improve the Cu content in the aqueous solution2+The maximum adsorption capacity of the TFGA prepared in example 1 of the present invention, in particular, was increased by 433.18% compared to the graphene aerogel without thiol groups.
In summary, in the invention, graphene oxide and a hydrosulfide are used as raw materials, a thiol group is grafted to graphene oxide through a covalent reaction, and the thiolated graphene aerogel is prepared through freeze drying. The sulfhydrylation graphene aerogel has an interconnected network structure, a large specific surface area and abundant active adsorption sites, and the adsorption capacity of the sulfhydrylation graphene aerogel on copper ions is remarkably improved. The sulfhydrylation graphene aerogel disclosed by the invention has a very good application prospect in preparation of a high-efficiency adsorbent for removing heavy metal ions in industrial wastewater.
Claims (10)
1. A sulfhydrylation graphene aerogel is characterized in that: the sulfhydrylation graphene aerogel adsorbent is prepared by taking graphene oxide and hydrosulfide as raw materials, reacting to obtain sulfhydrylation graphene hydrogel, and drying.
2. The thiolated graphene aerogel according to claim 1, wherein: the hydrosulfide is sodium hydrosulfide.
3. The thiolated graphene aerogel according to claim 1 or 2, characterized in that: the mass ratio of the graphene oxide to the hydrosulfide is (1-5): 1, preferably 2: 1.
4. the method for preparing a thiolated graphene aerogel according to any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) adding graphene oxide into water, and dispersing to obtain a graphene oxide dispersion liquid; dissolving hydrosulfide in water to obtain hydrosulfide aqueous solution;
(2) adding the hydrosulfide aqueous solution obtained in the step (1) into the graphene oxide dispersion liquid, and reacting to obtain sulfhydrylation graphene hydrogel;
(3) and (3) drying the sulfhydrylation graphene hydrogel obtained in the step (2) to obtain sulfhydrylation graphene aerogel.
5. The method of claim 4, wherein: in the step (1), the concentration of the graphene oxide dispersion liquid is 4-6mg/mL, preferably 6 mg/mL; the concentration of the hydrosulfide aqueous solution is 0.10-0.20 mg/mL, preferably 0.15 mg/mL;
and/or, in the step (2), the reaction conditions are as follows: reacting for 5-20 hours at 55-85 ℃ under vacuum, and preferably, the reaction conditions are as follows: reacting for 7 hours at 65 ℃ in a vacuum state;
and/or, in the step (3), the drying method is freeze drying, preferably, the freeze drying temperature is below-40 ℃ and the time is 48-60 hours.
6. The method according to claim 4 or 5, characterized in that: in the step (2), after the reaction is finished, the method further comprises the following purification steps: transferring the reacted system into a container filled with ethanol water solution, soaking in the ethanol water solution, and removing unreacted hydrosulfide in the system; preferably, the soaking time is 48 hours, during which the aqueous ethanol solution is replaced every 4 hours, and the volume of ethanol in the aqueous ethanol solution is 20%.
7. Use of the thiolated graphene aerogel according to any one of claims 1 to 3, for the preparation of an adsorbent for heavy metal ions.
8. Use according to claim 7, characterized in that: the heavy metal ion is Cu2+。
9. Use according to claim 7 or 8, characterized in that: the dosage of the heavy metal ion adsorbent is 7-30mg per 50mL of heavy metal ion solution;
the concentration of the heavy metal ion solution is 50-550 mg/L;
the pH value of the heavy metal ion solution is 1.5-5.5.
10. Use according to claim 9, characterized in that: the dosage of the heavy metal ion adsorbent is 7mg of heavy metal ion solution per 50 mL;
the concentration of the heavy metal ion solution is50 mg/L;
the pH of the heavy metal ion solution is 5.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911204465.8A CN110817849A (en) | 2019-11-29 | 2019-11-29 | Sulfhydrylation graphene aerogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911204465.8A CN110817849A (en) | 2019-11-29 | 2019-11-29 | Sulfhydrylation graphene aerogel and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110817849A true CN110817849A (en) | 2020-02-21 |
Family
ID=69543351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911204465.8A Pending CN110817849A (en) | 2019-11-29 | 2019-11-29 | Sulfhydrylation graphene aerogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110817849A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578255A (en) * | 2021-08-17 | 2021-11-02 | 日月光半导体制造股份有限公司 | Method for treating porous silica |
| CN117106360A (en) * | 2023-10-13 | 2023-11-24 | 韬禾(天津)技术开发有限公司 | Waterproof, anti-corrosion and heat-insulating composite coating for high polymer metal and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006616A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of high-adsorbability graphene aerogel |
| CN106179277A (en) * | 2016-08-31 | 2016-12-07 | 武汉大学 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
| CN106861762A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The synthesis of metal oxide nano cluster and nano-cluster and the application in water oxygen |
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
| CN108178152A (en) * | 2018-03-01 | 2018-06-19 | 济南开发区星火科学技术研究院 | It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method |
| CN108423654A (en) * | 2018-03-28 | 2018-08-21 | 陕西科技大学 | A kind of amination graphene aeroge high-efficiency adsorbent, preparation method and applications |
-
2019
- 2019-11-29 CN CN201911204465.8A patent/CN110817849A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861762A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The synthesis of metal oxide nano cluster and nano-cluster and the application in water oxygen |
| CN106006616A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of high-adsorbability graphene aerogel |
| CN106179277A (en) * | 2016-08-31 | 2016-12-07 | 武汉大学 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
| CN108178152A (en) * | 2018-03-01 | 2018-06-19 | 济南开发区星火科学技术研究院 | It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method |
| CN108423654A (en) * | 2018-03-28 | 2018-08-21 | 陕西科技大学 | A kind of amination graphene aeroge high-efficiency adsorbent, preparation method and applications |
Non-Patent Citations (2)
| Title |
|---|
| MINGXI CHEN 等: "《A one-step method for reduction and self-assembling of graphene oxide into reduced graphene oxide aerogels》", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| SANTHAKUMAR KANNAPPAN 等: "《Thiolatede-graphene-based supercapacitors with high energy density and stable cycling performance》", 《CARBON》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578255A (en) * | 2021-08-17 | 2021-11-02 | 日月光半导体制造股份有限公司 | Method for treating porous silica |
| CN117106360A (en) * | 2023-10-13 | 2023-11-24 | 韬禾(天津)技术开发有限公司 | Waterproof, anti-corrosion and heat-insulating composite coating for high polymer metal and preparation method thereof |
| CN117106360B (en) * | 2023-10-13 | 2024-02-20 | 韬禾(天津)技术开发有限公司 | Waterproof, anti-corrosion and heat-insulating composite coating for high polymer metal and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bashir et al. | Removal of heavy metal ions from aqueous system by ion-exchange and biosorption methods | |
| Krstić et al. | A review on adsorbents for treatment of water and wastewaters containing copper ions | |
| Hadavifar et al. | Removal of mercury (II) and cadmium (II) ions from synthetic wastewater by a newly synthesized amino and thiolated multi-walled carbon nanotubes | |
| Rangsayatorn et al. | Cadmium biosorption by cells of Spirulina platensis TISTR 8217 immobilized in alginate and silica gel | |
| Matheickal et al. | Biosorption of cadmium (II) from aqueous solutions by pre-treated biomass of marine alga Durvillaea potatorum | |
| Akar et al. | Enhanced biosorption of nickel (II) ions by silica-gel-immobilized waste biomass: biosorption characteristics in batch and dynamic flow mode | |
| Gupta et al. | Biosorption of lead from aqueous solutions by green algae Spirogyra species: kinetics and equilibrium studies | |
| Yaqubi et al. | Adsorptive removal of tetracycline and amoxicillin from aqueous solution by leached carbon black waste and chitosan-carbon composite beads | |
| Wierzba | Biosorption of lead (II), zinc (II) and nickel (II) from industrial wastewater by Stenotrophomonas maltophilia and Bacillus subtilis | |
| Akar et al. | Removal of copper (II) ions from synthetic solution and real wastewater by the combined action of dried Trametes versicolor cells and montmorillonite | |
| Khakpour et al. | Two-stage biosorption of selenium from aqueous solution using dried biomass of the baker's yeast Saccharomyces cerevisiae | |
| Mahmoud et al. | Enhanced biosorptive removal of cadmium from aqueous solutions by silicon dioxide nano-powder, heat inactivated and immobilized Aspergillus ustus | |
| CN103769058B (en) | The preparation method of carbonization chitosan absorbent, product and application process | |
| Tabatabaeian et al. | Cross-linked bionanocomposites of hydrolyzed guar gum/magnetic layered double hydroxide as an effective sorbent for methylene blue removal | |
| Peter et al. | Removal of thallium from aqueous solutions by modified Aspergillus niger biomass | |
| Akar et al. | Nickel removal characteristics of an immobilized macro fungus: equilibrium, kinetic and mechanism analysis of the biosorption | |
| Khan et al. | Isotherm and kinetics modeling of Pb (II) and Cd (II) adsorptive uptake from aqueous solution by chemically modified green algal biomass | |
| Yuqian et al. | Adsorption of La3+ and Ce3+ by poly-γ-glutamic acid crosslinked with polyvinyl alcohol | |
| Xu et al. | Adsorption of Rare Earths (Ⅲ) Using an efficient sodium alginate hydrogel cross-linked with poly-γ-glutamate | |
| Nguyen et al. | Adsorptive removal of iron using SiO 2 nanoparticles extracted from rice husk ash | |
| He et al. | Effective remediation of cadmium and zinc co-contaminated soil by electrokinetic-permeable reactive barrier with a pretreatment of complexing agent and microorganism | |
| Xu et al. | Antibacterial property and biocompatibility of Chitosan/Poly (vinyl alcohol)/ZnO (CS/PVA/ZnO) beads as an efficient adsorbent for Cu (II) removal from aqueous solution | |
| CN110817849A (en) | Sulfhydrylation graphene aerogel and preparation method and application thereof | |
| Yang et al. | Adsorption behavior of cross-linked chitosan modified by graphene oxide for Cu (II) removal | |
| Zare et al. | Dried activated sludge as an appropriate biosorbent for removal of copper (II) ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230404 Address after: 210000 room 2108-2110, tower a, Tengfei building, No. 88, Jiangmiao Road, yanchuangyuan, Jiangbei new area, Nanjing, Jiangsu Applicant after: Nanjing standard spectrum detection technology service Co.,Ltd. Address before: No. 311 Yanxin Road, Huishan District, Wuxi City, Jiangsu Province, 214100 Applicant before: WUXI CITY HUISHAN DISTRICT CHUANDA GRAPHITE ALKENE APPLICATION RESEARCH CENTER |
|
| TA01 | Transfer of patent application right |