CN108380177B - Preparation method of magnetic modified graphene oxide hydrogel - Google Patents
Preparation method of magnetic modified graphene oxide hydrogel Download PDFInfo
- Publication number
- CN108380177B CN108380177B CN201810198040.XA CN201810198040A CN108380177B CN 108380177 B CN108380177 B CN 108380177B CN 201810198040 A CN201810198040 A CN 201810198040A CN 108380177 B CN108380177 B CN 108380177B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- modified graphene
- reacting
- oxide hydrogel
- hydrogel
- 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.)
- Active
Links
Images
Classifications
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to the field of hydrogel adsorption materials, and aims to solve the problems that most of the existing hydrogel adsorption materials are difficult to separate and regenerate, difficult to degrade, lack in adsorption performance and the like. The prepared modified magnetic graphene oxide hydrogel has good separation and regeneration performance and adsorption performance on heavy metal ions, and realizes synchronous adsorption of various heavy metal ions and rapid separation of the adsorption material and wastewater.
Description
Technical Field
The invention relates to the field of hydrogel adsorption materials, in particular to a preparation method of a material for identifying various heavy metal ions.
Background
With the rapid development of urbanization and industrialization, increasingly serious environmental pollution threatens the harmony of human health and society, and the environmental quality problem draws unprecedented attention, wherein the treatment of industrial wastewater containing heavy metal ions is widely concerned. At present, methods for removing heavy metal ions include an ion exchange method, a chemical precipitation method, a membrane separation method, an adsorption method, an electrochemical method and the like, wherein the adsorption method is widely applied, and the selection of an adsorption material is critical. The hydrogel has good water permeability, adsorbability, biocompatibility and degradability, can sense and respond to environmental changes simultaneously, and is a good environment-friendly adsorption material. The raw material selection of the hydrogel directly influences the adsorption performance of the hydrogel, and the magnetic graphene oxide becomes a current research hotspot due to the advantages of the magnetic graphene oxide. The magnetic graphene oxide keeps the excellent adsorption performance of the graphene oxide with high specific surface area and a large number of oxygen-containing functional groups on the surface, has magnetism, can be quickly separated and regenerated, but is lack of identification intelligence, especially for heavy metal ions with multiple redox valence states, so that the preparation of the intelligently identifiable redox bifunctional group compound by using an organic synthesis method is a very meaningful research.
For example, patent No. CN 104043396B discloses a method for preparing magnetic aminated graphene oxide by grafting diethylenetriamine onto the surface of magnetic graphene oxide for removing divalent copper ions in water; patent No. CN 103601899B discloses a graphene oxide reinforced magnetic hydrogel prepared from graphene oxide, ferroferric oxide and polyvinyl alcohol. In conclusion, most of the adsorbing materials in the prior patents have the problems of difficult separation and regeneration, difficult degradation, poor adsorption performance and the like.
Disclosure of Invention
In order to solve the problems that most of the existing adsorbing materials are difficult to separate and regenerate, difficult to degrade, lack in adsorption performance and the like, the invention provides a preparation method of magnetic modified graphene oxide hydrogel, the prepared modified magnetic graphene oxide hydrogel has good separation and regeneration performance and adsorption performance on heavy metal ions, and synchronous adsorption of various heavy metal ions and rapid separation of various heavy metal ions from wastewater are realized.
The invention is realized by the following technical scheme: the preparation method of the magnetic modified graphene oxide hydrogel comprises the following steps:
(1) mixing graphite powder and sodium nitrite, placing the mixture in a water bath at 0-5 ℃, adding concentrated sulfuric acid, reacting for 1-2 hours, adding potassium dichromate, reacting for 1-2 hours, then adding dichloromethane serving as a solvent and m-chloroperoxybenzoic acid, reacting for 1-2 hours, heating to 20-25 ℃, adding deionized water, continuing to react for 0.5-1 hour, filtering, washing to neutrality, and performing vacuum drying at 40-45 ℃ to obtain graphene oxide;
preferably, the mass ratio of the graphite powder to the sodium nitrite is 3-5: 1, the mass ratio of graphite powder to potassium dichromate is 1: 5-8, wherein the mass ratio of the graphite powder to the m-chloroperoxybenzoic acid is 1: 5 to 6.
Dichloromethane is used as solvent, and the amount is used for dissolving solute.
Preferably, the mass fraction of the concentrated sulfuric acid is 95-98%, and the volume ratio of the graphite powder to the concentrated sulfuric acid is 1 g: 20-25 mL.
Preferably, the volume ratio of the deionized water to the concentrated sulfuric acid is 4-6: 1.
preferably, the washing is performed by using dilute hydrochloric acid, saturated sodium bicarbonate solution and deionized water. The mass fraction of the dilute hydrochloric acid is 3-5%. The mass fraction of the saturated sodium bicarbonate is 10-20%.
(2) Under the protection of inert gas, dissolving the graphene oxide and thiourea prepared in the step (1) in hydrobromic acid, reacting for 20-30 min, refluxing for 12-15 h at 50-60 ℃, cooling to room temperature, reacting for 20-30 min at 0-5 ℃, adding a sodium hydroxide solution, reacting for 8-12 h, adjusting the pH of the solution to 2.0-3.0, recrystallizing with deionized water, and performing vacuum drying at 45-50 ℃ to obtain sulfhydryl graphene oxide;
preferably, the mass ratio of the graphene oxide to the thiourea is 1: 10-15, wherein the volume ratio of the mass of the thiourea to the volume of the hydrobromic acid is 1 g: 15-20 mL, wherein the mass fraction of hydrobromic acid is 30-40%.
Sodium hydroxide is preferably used in an amount of 10 to 20% by mass in order to provide an alkaline environment.
(3) Adding L-cysteine and the mercapto graphene oxide prepared in the step (2) into a phosphate buffer solution with the pH of 7.4-8.0, reacting for 3-4 h, taking out a product, soaking the product in deionized water for 2-3 days, and drying at 40-50 ℃ to obtain modified graphene oxide hydrogel;
preferably, the mass ratio of the mercapto graphene oxide to the L-cysteine is 9-11: 1, the volume ratio of the mass of the mercapto graphene oxide to the volume of the phosphate buffer solution is 1 g: 10-12 mL.
Phosphate buffer solution as solvent for dissolving the protecting agent is prepared from NaCl, KCl and Na2HPO4、KH2PO4Preferably, the concentration of all phosphate radicals in the buffer solution is 0.01 mol/L.
(4) Under the protection of inert gas, FeCl is added3·6H2O and FeSO4·7H2Dissolving and mixing O, adding the mixture into the modified graphene oxide hydrogel prepared in the step (3), adjusting the pH to 8.0-10.0, reacting for 3-4 h at 30-40 ℃, separating the hydrogel, washing with deionized water, and drying in vacuum at 45-50 ℃ to obtain the magnetic modified graphene oxide hydrogel.
Preferably, FeCl3·6H2O and FeSO4·7H2The molar ratio of O is 1.4-2.0: 1.0 FeCl3·6H2The mass ratio of the O to the modified graphene oxide hydrogel is 4.0-6.0: 1.0.
preferably, the inert gas is selected from nitrogen.
According to the method, an oxidant is used for replacing a traditional Hummers method to synthesize graphene oxide, thiourea is used for sulfhydrylation to obtain sulfhydrylated graphene oxide, L-cysteine is subjected to copolymerization reaction with the sulfhydrylated graphene oxide, and finally, the magnetic modified graphene oxide hydrogel is synthesized through a chemical coprecipitation method.
The application of the magnetic modified graphene oxide hydrogel in identifying various heavy metal ions can be used for adsorbing various heavy metal ions in a sewage system. According to the invention, amino and disulfide bonds are copolymerized and grafted on the magnetic graphene oxide through sulfhydrylation and L-cysteine, so that the complexing effect of the composite material and heavy metal ions is enhanced, and the composite material has outstanding heavy metal ion adsorption performance.
Compared with the prior art, the invention has the beneficial effects that: the modified magnetic graphene oxide hydrogel has good separation and regeneration performance and adsorption performance on heavy metal ions, and realizes synchronous adsorption of various heavy metal ions and rapid separation from wastewater.
Drawings
FIG. 1 is an infrared spectrum of a magnetically modified graphene oxide hydrogel of example 1;
fig. 2 is a nuclear magnetic resonance hydrogen spectrum of the magnetic modified graphene oxide hydrogel in example 1.
Detailed description of the invention
The invention is further illustrated by the accompanying drawings and specific examples, in which the starting materials are commercially available or may be prepared by conventional methods. The following examples are intended to illustrate the invention but are not intended to limit the invention further.
The phosphate buffer solution was prepared from 7.9g NaCl, 0.2g KCl, 0.24g KH2PO4，1.8g K2HPO4Dissolving in 800ml of distilled water, adjusting the pH value of the solution to 7.4 by using HCl, finally adding distilled water to a constant volume of 1L, wherein the concentration is 0.01mol/L, and then storing in a refrigerator at 4 ℃.
Example 1
(1) Mixing 2g of graphite powder and 0.5g of sodium nitrite, placing the mixture in an ice bath at 0 ℃, slowly adding 50mL of 95% concentrated sulfuric acid, reacting for 2 hours, slowly adding 10g of potassium dichromate, reacting for 2 hours, adding 100mL of dichloromethane and 10g of m-chloroperoxybenzoic acid, reacting for 2 hours, heating to 20 ℃, slowly adding 200mL of deionized water, continuing to react for 1 hour, filtering, washing 5% of dilute hydrochloric acid, 10% of saturated sodium bicarbonate solution and deionized water to be neutral, and drying in vacuum at 45 ℃ to obtain graphene oxide 1.
(2) Under the protection of nitrogen, 0.1g of graphene oxide 1 and 1g of thiourea are dissolved in 15mL of 40% hydrobromic acid, the reaction is carried out for 20min, the reflux is carried out at 50 ℃ for 12h, the temperature is cooled to room temperature, the reaction is carried out at 0 ℃ for 30min, 40mL of 20% sodium hydroxide solution is added for reaction for 8h, the pH of the solution is adjusted to 2.0, and after the recrystallization in deionized water, the vacuum drying is carried out at 50 ℃ to obtain the sulfhydryl graphene oxide 1.
(3) Adding 0.5g L-cysteine and 5g of mercapto graphene oxide 1 into 50mL of phosphate buffer solution with the pH value of 7.4, reacting for 4h, taking out a product, soaking the product in deionized water for 2 days, and drying at 50 ℃ to obtain the modified graphene oxide hydrogel 1.
(4) Under the protection of nitrogen, 2.7g of FeCl3·6H2O and 1.98g FeSO4·7H2Dissolving and mixing O, adding the mixture into a solution in which 0.5g of modified graphene oxide hydrogel 1 is dissolved, adjusting the pH value to 9.0, reacting for 4 hours at 40 ℃, separating hydrogel, washing with deionized water, and drying in vacuum at 45 ℃ to obtain the magnetic modified graphene oxide hydrogel 1.
An infrared spectrogram of the magnetic modified graphene oxide hydrogel 1 is shown in fig. 1, and a nuclear magnetic resonance hydrogen spectrogram of the magnetic modified graphene oxide hydrogel 1 is shown in fig. 2.
Example 2
(1) Mixing 2g of graphite powder and 0.4g of sodium nitrite, placing the mixture in an ice bath at 0 ℃, slowly adding 45mL of 98% concentrated sulfuric acid, reacting for 1h, slowly adding 12g of potassium dichromate, reacting for 1h, adding 100mL of dichloromethane and 12g of m-chloroperoxybenzoic acid, reacting for 1h, heating to 25 ℃, slowly adding 250mL of deionized water, continuing to react for 1h, filtering, washing 5% of dilute hydrochloric acid, 10% of saturated sodium bicarbonate solution and deionized water to be neutral, and drying in vacuum at 45 ℃ to obtain graphene oxide 2.
(2) Under the protection of nitrogen, 0.1g of graphene oxide 2 and 1.2g of thiourea are dissolved in 18mL of 35% hydrobromic acid, the mixture is reacted for 30min, the reflux is carried out at 40 ℃ for 15h, the mixture is cooled to room temperature, the reaction is carried out at 0 ℃ for 30min, 40mL of 20% sodium hydroxide solution is added for reaction for 8h, the pH value of the solution is adjusted to 3.0, and the solution is recrystallized by deionized water and then dried in vacuum at 50 ℃ to obtain the graphene oxide 2.
(3) Adding 0.5g L-cysteine and 5.5g of mercapto graphene oxide 2 into 55mL of phosphate buffer solution with the pH value of 8.0, reacting for 4h, taking out a product, soaking the product in deionized water for 3 days, and drying at 45 ℃ to obtain the modified graphene oxide hydrogel 2.
(4) Under the protection of nitrogen, 2g of FeCl3·6H2O and 1gFeSO4·7H2Dissolving and mixing O, adding the mixture into a solution in which 0.5g of modified graphene oxide hydrogel 2 is dissolved, adjusting the pH value to 10.0, reacting for 4 hours at 30 ℃, separating hydrogel, washing with deionized water, and drying in vacuum at 45 ℃ to obtain the magnetic modified graphene oxide hydrogel 2.
Example 3
(1) Mixing 2g of graphite powder and 0.6g of sodium nitrite, placing the mixture in a water bath at 5 ℃, slowly adding 40mL of 98% concentrated sulfuric acid, reacting for 2 hours, slowly adding 14g of potassium dichromate, reacting for 2 hours, adding 100mL of dichloromethane and 11g of m-chloroperoxybenzoic acid, reacting for 2 hours, heating to 20 ℃, slowly adding 240mL of deionized water, continuing to react for 0.5 hour, filtering, washing 5% of dilute hydrochloric acid, 10% of saturated sodium bicarbonate solution and deionized water to be neutral, and drying in vacuum at 45 ℃ to obtain graphene oxide 3.
(2) Under the protection of nitrogen, 0.1g of graphene oxide 3 and 1.5g of thiourea are dissolved in 30mL of 30% hydrobromic acid, the reaction is carried out for 25min, the reflux is carried out at 45 ℃ for 13h, the cooling is carried out to the room temperature, the reaction is carried out at 5 ℃ for 20min, 40mL of 10% sodium hydroxide solution is added for reaction for 12h, the pH of the solution is adjusted to 2.5, and the vacuum drying is carried out at 40 ℃ after the recrystallization of deionized water, so that the graphene oxide 3 with sulfhydryl groups is obtained.
(3) Adding 0.5g L-cysteine and 4.5g of mercapto graphene oxide 3 into 45mL of phosphate buffer solution with the pH value of 7.4, reacting for 3h, taking out a product, soaking the product in deionized water for 2 days, and drying at 40 ℃ to obtain the modified graphene oxide hydrogel 3.
(4) Under the protection of nitrogen, 3g of FeCl3·6H2O and 1.73g FeSO4·7H2Dissolving and mixing O, adding the mixture into a solution in which 0.5g of modified graphene oxide hydrogel 3 is dissolved, adjusting the pH value to 10.0, reacting for 3 hours at 40 ℃, separating hydrogel, washing with deionized water, and drying in vacuum at 50 ℃ to obtain the magnetic modified graphene oxide hydrogel 3.
Test example
The table 1 shows the adsorption performance of the magnetic modified graphene oxide hydrogel 1-3 prepared in examples 1-3. Table 1 table of adsorption properties of magnetic modified graphene oxide hydrogel prepared by three groups of examples
The magnetic modified graphene oxide hydrogel prepared by the invention can be obtained by testing examples, and has good adsorption performance on various heavy metal ion pollutants, wherein the adsorption performance is good for Pb2+The adsorption performance of (2) is best.
Claims (9)
1. The preparation method of the magnetic modified graphene oxide hydrogel is characterized by comprising the following steps:
(1) mixing graphite powder and sodium nitrite, placing the mixture in a water bath at 0-5 ℃, adding concentrated sulfuric acid, reacting for 1-2 hours, adding potassium dichromate, reacting for 1-2 hours, then adding dichloromethane serving as a solvent and m-chloroperoxybenzoic acid, reacting for 1-2 hours, heating to 20-25 ℃, adding deionized water, continuing to react for 0.5-1 hour, filtering, washing to neutrality, and performing vacuum drying at 40-45 ℃ to obtain graphene oxide;
the mass ratio of the graphite powder to the sodium nitrite is 3-5: 1, the mass ratio of graphite powder to potassium dichromate is 1: 5-8, wherein the mass ratio of the graphite powder to the m-chloroperoxybenzoic acid is 1: 5-6;
(2) under the protection of inert gas, dissolving graphene oxide and thiourea in hydrobromic acid, reacting for 20-30 min, refluxing for 12-15 h at 50-60 ℃, cooling to room temperature, reacting for 20-30 min at 0-5 ℃, adding a sodium hydroxide solution, reacting for 8-12 h, adjusting the pH of the solution to 2.0-3.0, recrystallizing with deionized water, and performing vacuum drying at 45-50 ℃ to obtain sulfhydryl graphene oxide;
the mass ratio of the graphene oxide to the thiourea is 1: 10-15, wherein the volume ratio of the mass of the thiourea to the volume of the hydrobromic acid is 1 g: 15-20 mL;
(3) adding L-cysteine and sulfhydryl graphene oxide into a phosphate buffer solution with the pH of 7.4-8.0, reacting for 3-4 h, taking out a product, soaking the product in deionized water for 2-3 days, and drying at 40-50 ℃ to obtain modified graphene oxide hydrogel;
the mass ratio of the mercapto graphene oxide to the L-cysteine is (9-11): 1;
(4) under the protection of inert gas, FeCl is added3·6H2O and FeSO4·7H2Dissolving and mixing O, adding the mixture into a modified graphene oxide hydrogel solution, adjusting the pH to 8.0-10.0, reacting at 30-40 ℃ for 3-4 h, separating hydrogel, washing with deionized water, and drying at 45-50 ℃ in vacuum to obtain magnetic modified graphene oxide waterAnd (4) gelling.
2. The preparation method of the magnetically modified graphene oxide hydrogel according to claim 1, wherein the mass fraction of the concentrated sulfuric acid in the step (1) is 95% -98%, and the volume ratio of the mass of the graphite powder to the volume of the concentrated sulfuric acid is 1 g: 20-25 mL.
3. The preparation method of the magnetic modified graphene oxide hydrogel according to claim 1 or 2, wherein the volume ratio of deionized water to concentrated sulfuric acid in the step (1) is 4-6: 1.
4. the method for preparing the magnetically modified graphene oxide hydrogel according to claim 1, wherein the step (1) is performed by washing with dilute hydrochloric acid, saturated sodium bicarbonate solution and deionized water.
5. The method for preparing the magnetically modified graphene oxide hydrogel according to claim 1, wherein the hydrobromic acid mass fraction in the step (2) is 30-40%.
6. The method for preparing the magnetically modified graphene oxide hydrogel according to claim 1, wherein the sodium hydroxide is present in the step (2) in an amount of 10-20% by weight.
7. The method for preparing the magnetically modified graphene oxide hydrogel according to claim 1, wherein the ratio of the mass of the mercapto graphene oxide to the volume of the phosphate buffer solution in the step (3) is 1 g: 10-12 mL.
8. The method for preparing magnetically modified graphene oxide hydrogel according to claim 1, wherein FeCl is added in the step (4)3·6H2O and FeSO4·7H2The molar ratio of O is 1.4-2.0: 1, FeCl3·6H2The mass ratio of the O to the modified graphene oxide hydrogel is 4-6: 1.
9. an application of the magnetic modified graphene oxide hydrogel obtained by the preparation method of the magnetic modified graphene oxide hydrogel according to claim 1 in identification of various heavy metal ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198040.XA CN108380177B (en) | 2018-03-09 | 2018-03-09 | Preparation method of magnetic modified graphene oxide hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198040.XA CN108380177B (en) | 2018-03-09 | 2018-03-09 | Preparation method of magnetic modified graphene oxide hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108380177A CN108380177A (en) | 2018-08-10 |
| CN108380177B true CN108380177B (en) | 2020-10-27 |
Family
ID=63066507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810198040.XA Active CN108380177B (en) | 2018-03-09 | 2018-03-09 | Preparation method of magnetic modified graphene oxide hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108380177B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109520648B (en) * | 2018-10-22 | 2020-09-22 | 华南理工大学 | Wearable piezoresistive pressure sensor and preparation method and application thereof |
| CN109502581B (en) * | 2018-12-13 | 2020-06-30 | 浙江农林大学 | Preparation method and application of graphene-based aerogel |
| CN109880122A (en) * | 2019-01-15 | 2019-06-14 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | A kind of supersonically preparation method of magnetic response graphene oxide hydrogel |
| CN109659111B (en) * | 2019-02-01 | 2020-12-08 | 杭州高烯科技有限公司 | Graphene-ferrite magnetic composite film and preparation method thereof |
| TWI704109B (en) * | 2019-09-20 | 2020-09-11 | 國立臺灣大學 | Method of recovering gold using thiourea graphene |
| CN112537818A (en) * | 2019-09-20 | 2021-03-23 | 席行正 | Method for recovering gold by using thiourea graphene |
| CN114797783B (en) * | 2022-03-23 | 2023-06-27 | 山东大学 | Adsorbent for selectively removing Cr (VI) and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004064518A1 (en) * | 2003-01-23 | 2004-08-05 | Nippon Soda Co., Ltd. | Water dispersible granules for agricultural and horticultural use |
| JP2011224532A (en) * | 2010-04-16 | 2011-11-10 | Hisaaki Nagasaki | Carbon dioxide fixation method using human hair as support and recycling method therefor |
| CN103991864B (en) * | 2014-05-16 | 2016-01-20 | 中国科学技术大学 | A kind of preparation method of graphene aerogel |
| CN104556012B (en) * | 2015-01-07 | 2016-04-27 | 浙江碳谷上希材料科技有限公司 | A kind of sulfhydryl modified graphene oxide and preparation method thereof |
| CN105597689A (en) * | 2016-03-30 | 2016-05-25 | 湖南师范大学 | Preparation for magnetic nanoparticle with breakable oxygen ammonia functional groups and application to separation and enrichment of glycoprotein |
| CN105699454A (en) * | 2016-02-26 | 2016-06-22 | 厦门大学 | Preparing method for graphene-nanogold hydrogel electrode |
| CN107759808A (en) * | 2017-09-18 | 2018-03-06 | 同济大学 | The preparation method of sodium alginate/L cysteines/redox graphene magnetic water/aeroge |
-
2018
- 2018-03-09 CN CN201810198040.XA patent/CN108380177B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004064518A1 (en) * | 2003-01-23 | 2004-08-05 | Nippon Soda Co., Ltd. | Water dispersible granules for agricultural and horticultural use |
| JP2011224532A (en) * | 2010-04-16 | 2011-11-10 | Hisaaki Nagasaki | Carbon dioxide fixation method using human hair as support and recycling method therefor |
| CN103991864B (en) * | 2014-05-16 | 2016-01-20 | 中国科学技术大学 | A kind of preparation method of graphene aerogel |
| CN104556012B (en) * | 2015-01-07 | 2016-04-27 | 浙江碳谷上希材料科技有限公司 | A kind of sulfhydryl modified graphene oxide and preparation method thereof |
| CN105699454A (en) * | 2016-02-26 | 2016-06-22 | 厦门大学 | Preparing method for graphene-nanogold hydrogel electrode |
| CN105597689A (en) * | 2016-03-30 | 2016-05-25 | 湖南师范大学 | Preparation for magnetic nanoparticle with breakable oxygen ammonia functional groups and application to separation and enrichment of glycoprotein |
| CN107759808A (en) * | 2017-09-18 | 2018-03-06 | 同济大学 | The preparation method of sodium alginate/L cysteines/redox graphene magnetic water/aeroge |
Non-Patent Citations (2)
| Title |
|---|
| Dynamical roles of metal ions and the disulfide;Feng Ding et.al;《PNAS》;20081216;第16卷;全文 * |
| 二硫键交联的巯基化壳聚糖水凝胶;李义等;《精细化工》;20170131;第34卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108380177A (en) | 2018-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108380177B (en) | Preparation method of magnetic modified graphene oxide hydrogel | |
| CN112441572B (en) | Method for recovering waste lithium iron phosphate anode material | |
| CN105056719B (en) | The preparation method and desulfurizing agent obtained by this method of a kind of FeOOH low-temp desulfurization agent | |
| CN108976430B (en) | Acylhydrazone-linked covalent organic framework material and preparation method and application thereof | |
| CN103506065B (en) | A kind of Magnetic heavy metal adsorbent with casing-core structure and preparation method thereof | |
| CN114212803B (en) | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material | |
| CN110862631B (en) | Preparation method of efficient recyclable lithium extraction membrane material for salt lake brine | |
| CN112897627A (en) | Method for removing heavy metal wastewater | |
| CN101857923A (en) | Method for recovering copper, zinc and iron from sulphide ore calcine pickle liquor containing gold and silver | |
| CN105131329A (en) | Preparation method and application of macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with metal ions | |
| CN106841479A (en) | A kind of method of detection soil Zhong bioxin residual | |
| CN110180489B (en) | Sulfur-doped lithium-rich manganese lithium adsorbent and preparation method and application thereof | |
| CN106984137B (en) | CO absorption device capable of realizing rapid phase separation2Preparation and use method of polyamino acid ionic liquid type phase separation absorbent | |
| CN103611503A (en) | Alpha-ketoglutaric acid modified magnetic chitosan and preparation method and application thereof in field of cadmium-containing wastewater treatment | |
| CN112892502A (en) | Preparation method of polydopamine-containing ion chelating agent and obtained product | |
| CN104992850B (en) | A kind of Fe3O4/MnO2/ RGO materials and preparation method and application | |
| CN111514861B (en) | Preparation method and application of tridentate ligand heavy metal ion imprinting material | |
| CN110314667A (en) | A kind of preparation and its application of metal organic polymer material | |
| CN110394166A (en) | A kind of crown ether type Lignin-Based Adsorption Material and preparation method thereof | |
| CN113695353B (en) | Preparation method and application of calcite-rhombohedral cadmium ore solid solution | |
| CN115254034A (en) | Preparation method and adsorption application of malic acid-kaolinite nano-composite | |
| CN114807979A (en) | Preparation method and application of copper-vacancy-rich sulfide-based electrocatalyst | |
| CN113274991A (en) | Method for removing hexavalent chromium ions in wastewater | |
| KR20140001123A (en) | Lithium-manganese complex oxides, lithium-manganese adsorption precursor and method for preparing the same, and lithium adsorbent using the same | |
| CN112717886A (en) | Rare earth element adsorbent and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |