CN105645392A - Preparation method and application of aminated graphene - Google Patents
Preparation method and application of aminated graphene Download PDFInfo
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- CN105645392A CN105645392A CN201610012813.1A CN201610012813A CN105645392A CN 105645392 A CN105645392 A CN 105645392A CN 201610012813 A CN201610012813 A CN 201610012813A CN 105645392 A CN105645392 A CN 105645392A
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C01B2204/02—Single layer graphene
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- 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
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- 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
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a preparation method of aminated graphene, particularly a preparation method and application of aminated graphene, belonging to the field of environmental functional materials. The preparation method comprises the following steps: dissolving graphene oxide powder in a dimethylformamide solution, respectively adding ethylenediamine and an N,N'-dicyclohexylcarbodiimide tetrahydrofuran solution, and reacting to obtain the monoatomic-lamellar-structure aminated graphene. The preparation method is simple, and has the advantages of mild preparation reaction and high safety. The obtained aminated graphene is a monoatomic lamellar structure, has the advantages of high amination degree and higher nitrogen content than the products of other preparation methods, is beneficial to adsorbing heavy metal ions in wastewater, and has favorable application prospects in the aspect of heavy metal wastewater treatment.
Description
The application obtains the subsidy of Tianjin institution of higher education " innovation team's training plan " (TD12-5037) and Tianjin Normal University's doctor's fund (52XB1403).
Technical field
The invention belongs to environment functional material field, be specifically related to the preparation method of a kind of amination Graphene and the application in processing heavy metal containing sewage thereof.
Background technology
Graphene, since within 2004, being found, has received significant attention because of its electricity highlighted and mechanical property. Owing to Graphene has the monatomic lamellar structure of uniqueness, its specific surface area is huge, therefore the pollutant in water environment is had very strong absorbability. But, Graphene is susceptible to reunite in aqueous, it is unfavorable for the pollutant absorption on its surface, and the surface of functionalization graphene (such as graphene oxide, amination Graphene etc.) has the functional groups such as carboxyl, hydroxyl, amino, its surface hydrophilicity is made to strengthen, substantially increase its dispersibility in aqueous, it is possible to the pollutant in active adsorption water environment. Owing to amino can with heavy metal ion generation complexing, the interaction with heavy metal ion is higher, and therefore compared to other functionalization graphenes, amination Graphene is higher to the absorption property of Heavy Metals in Water Environment ion. The amination Graphene of synthesized high-performance is significant for the heavy metal pollution processed in water environment.
In existing research, the method for modified acquisition amination Graphene is various. As the third dicyan is directly grafted on surface of graphene oxide by patent 201410339486, obtain amination Graphene by reducing. Patent 201210569837 adopts electrolysis, prepares amination Graphene with graphene oxide and ammonia for raw material. Patent 201410124106 will prepare a kind of amino modified graphene oxide compound forward osmosis membrane after blended to graphene oxide, dimethylformamide, organic amine and Dicyclohexylcarbodiimide supersound process. But, the most process of these methods is complicated at present, requires higher to the operation requirement in preparation process and environmental condition, and products therefrom cannot ensure that as monatomic lamellar structure. For this, the present invention proposes a kind of method preparing monatomic lamellar structure amination Graphene. The method is simple to operate, reaction temperature and, temperature requirement is low, and environmental pollution is little, solves the additive method high request to operating environment and equipment, and ensure that monatomic lamellar structure and the high nitrogen content of product.Amination Graphene prepared by the method is removed heavy metal ion efficiency in water and is significantly improved.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of amination Graphene and be applied to the removal of heavy metal ions in wastewater.
The most process of current existing amination graphene preparation method is complicated, requires higher to the operation requirement in preparation process and environmental condition, and products therefrom cannot ensure that as monatomic lamellar structure. For this, the present invention proposes a kind of method preparing monatomic lamellar structure amination Graphene, and its feature comprises the following steps:
(1) taking graphene oxide powder and dimethylformamide that mass ratio is 1:15 ~ 1:300, mix homogeneously forms it into stable suspension;
(2) by oxolane and N, N '-dicyclohexylcarbodiimide with mass ratio 5:1 ~ 10:1 mixing, stir;
(3) in the suspension that step (1) is prepared, add and N, N ' ethylenediamine of-dicyclohexylcarbodiimide equal mass and step 2) N for preparing, the tetrahydrofuran solution of N '-dicyclohexylcarbodiimide, stirring 3 ~ 5d, sucking filtration, namely complete the amination of graphene oxide;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed repeatedly, to remove the residual organic matter in operating process;
(5) adding appropriate ultra-pure water in the amination Graphene obtained in step (4), water bath sonicator is so as to be uniformly dispersed;
(6) by gained amination Graphene colloid solution lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained. In step (1) and (2), the method for described mix homogeneously is the method adopting water bath sonicator, and the time is 15��20min. In step (3), described ethylenediamine, N, N ' mass ratio of-dicyclohexylcarbodiimide and graphene oxide is 10:10:1��40:40:1. In step (3), described stirring means is magnetic stirrer, carries out under room temperature; The organic facies filter membrane using filter membrane to be 0.22 ��m in described sucking filtration process. In step (4), described cleaning way is clean according to the order of distilled water after first methanol, at least by every kind of solvent clean 4 times, it is ensured that residual organic matter all cleans up; In step (5), the temperature of water bath sonicator not can exceed that 50oC, and the time is 2h��4h.
The preparation method of amination Graphene of the present invention, graphene oxide powder used is single-layer graphene oxide.
The present invention further discloses the application in absorption heavy metal ions in wastewater of the amination Graphene of preparation; Described heavy metal ion refers to Cu2+��Cd2+��Pb2+��Zn2+Deng. The results show: amination Graphene prepared by the present invention has significant effect in absorption heavy metal ions in wastewater, particularly amination Graphene Adsorption of Cu2+Ability on improve about 2 times than regular oxidation Graphene.
More detailed description of the present invention is as follows:
(1) taking graphene oxide powder and dimethylformamide that mass ratio is 1:15,1:50,1:100,1:300, mix homogeneously forms it into stable suspension;
(2) by oxolane and N, N '-dicyclohexylcarbodiimide with mass ratio 5:1,7:1,8:1,10:1 mix, stir;
(3) in the suspension that step (1) is prepared, add and N, N ' ethylenediamine of-dicyclohexylcarbodiimide equal mass and step 2) N for preparing, the tetrahydrofuran solution of N '-dicyclohexylcarbodiimide, stirring 3d, sucking filtration, namely complete the amination of graphene oxide;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed repeatedly, to remove the residual organic matter in operating process;
(5) adding appropriate ultra-pure water in the amination Graphene obtained in step (4), water bath sonicator is so as to be uniformly dispersed;
(6) by gained amination Graphene colloid solution lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
In a preferred embodiment of the present invention, it is characterised in that in step (1) and (2), the method for described mix homogeneously is adopt ultrasonic method, and the time is 20min.
In a preferred embodiment of the present invention, it is characterised in that in step (3), the mass ratio of described ethylenediamine, N, N '-dicyclohexylcarbodiimide and graphene oxide is 20:20:1; Described stirring is magnetic stirrer, and room temperature carries out; Organic filter membrane that described sucking filtration uses filter membrane to be 0.22 ��m.
In a preferred embodiment of the present invention, it is characterised in that in step (4), the way of described cleaning is clean according to the order of distilled water after first methanol, at least by every kind of solvent clean 4 times. Purpose is to remove the residual organic matter in previous action process.
In a preferred embodiment of the present invention, it is characterised in that in step (5), the temperature of described water-bath is less than 50oC, and the time is 2h.
In a preferred embodiment of the present invention, it is characterised in that in step (6), described freeze-drying time is 3d.
In a preferred embodiment of the present invention, it is characterised in that graphene oxide powder used selects single-layer graphene oxide.
Compared with prior art, the invention have the advantages that
(1) operating procedure of the present invention is simple, reaction temperature and, reaction can be completed under room temperature condition, it is not necessary to higher reaction temperature, safety is high and environmental pollution is little;
(2) being known by x-ray photoelectron (XPS) profiling results, the nitrogen content of amination Graphene is greatly improved, and the form adding nitrogen is many with the existence of amino state.
(3) by high power transmission electron microscope (TEM) collection of illustrative plates it can be seen that the product obtained is monatomic laminated structure, there is better dispersibility, be conducive to the absorption of Pollutants in Wastewater.
(4) for the copper ion in waste water, amination Graphene is greatly improved than the absorbability of native oxide Graphene, can be used for the removal of heavy metal ions in wastewater.
Accompanying drawing explanation
Fig. 1 is x-ray photoelectron (XPS) collection of illustrative plates of amination Graphene and graphene oxide;
Fig. 2 is infrared (FTIR) collection of illustrative plates of amination Graphene and graphene oxide;
Fig. 3 is transmission electron microscope (TEM) collection of illustrative plates of amination Graphene and graphene oxide;
Fig. 4 is copper ion adsorption isotherm on amination Graphene and graphene oxide.
Specific embodiments
Below in conjunction with specific embodiment, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various change or amendment by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally. The chemical reagent such as wherein used graphene oxide powder, dimethylformamide, ethylenediamine are commercially available.
Embodiment 1
(1) 0.1g graphene oxide powder is dissolved in 1.6mL dimethylformamide, stirs and form it into stable suspension;
(2) by N, the N of 11mL oxolane Yu 1.6mL ' mixing of-dicyclohexylcarbodiimide, stir;
(3) in the suspension of step 1) preparation, 2.2mL ethylenediamine and step 2 are added) N, the N that prepare ' tetrahydrofuran solution of-dicyclohexylcarbodiimide, stirs 3d, sucking filtration, obtains amination Graphene;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed several times, to remove the residual organic matter in operating process;
(5) the amination Graphene obtained in step (4) adds appropriate ultra-pure water, water bath sonicator 20min;
(6) by gained amination Graphene lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
Embodiment 2
(1) 0.1g graphene oxide powder is dissolved in 5.2mL dimethylformamide, stirs and form it into stable suspension;
(2) by N, the N of 15.7mL oxolane Yu 1.6mL ' mixing of-dicyclohexylcarbodiimide, stir;
(3) in the suspension of step 1) preparation, 2.2mL ethylenediamine and step 2 are added) N, the N that prepare ' tetrahydrofuran solution of-dicyclohexylcarbodiimide, stirs 3d, sucking filtration, obtains amination Graphene;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed several times, to remove the residual organic matter in operating process;
(5) the amination Graphene obtained in step (4) adds appropriate ultra-pure water, water bath sonicator 20min;
(6) by gained amination Graphene lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
Embodiment 3
(1) 0.1g graphene oxide powder is dissolved in 10mL dimethylformamide, stirs and form it into stable suspension;
(2) by N, the N of 18mL oxolane Yu 1.5mL ' mixing of-dicyclohexylcarbodiimide, stir;
(3) in the suspension of step 1) preparation, 2.2mL ethylenediamine and step 2 are added) N, the N that prepare ' tetrahydrofuran solution of-dicyclohexylcarbodiimide, stirs 3d, sucking filtration, obtains amination Graphene;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed several times, to remove the residual organic matter in operating process;
(5) the amination Graphene obtained in step (4) adds appropriate ultra-pure water, water bath sonicator 20min;
(6) by gained amination Graphene lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
Embodiment 4
(1) 0.1g graphene oxide powder is dissolved in 32mL dimethylformamide, stirs and form it into stable suspension;
(2) by N, the N of 22.5mL oxolane Yu 1.7mL ' mixing of-dicyclohexylcarbodiimide, stir;
(3) in the suspension of step 1) preparation, 2.2mL ethylenediamine and step 2 are added) N, the N that prepare ' tetrahydrofuran solution of-dicyclohexylcarbodiimide, stirs 3d, sucking filtration, obtains amination Graphene;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed several times, to remove the residual organic matter in operating process;
(5) the amination Graphene obtained in step (4) adds appropriate ultra-pure water, water bath sonicator 20min;
(6) by gained amination Graphene lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
Embodiment 5
Application Example
Amination Graphene is greatly improved than the absorbability of native oxide Graphene heavy metal ion, can be used for the removal of bivalent cupric ion in waste water.
Taking volume is 20ml, initial concentration is 4,8,12,22, the copper ion of 50mg/L, adding HCl/NaOH, to regulate pH value be 5.4, and each sample adds the amination graphene/graphene oxide 10mg of embodiment 3 preparation. Amination graphene/graphene oxide is separated with aqueous solution as after reacting 3 days in impeller by reaction bulb, completes Cu in aqueous solution2+Adsorption treatment. Solution remains Cu2+Concentration use inductively coupled plasma atomic emission spectrometry instrument (ICP-OES) be measured, calculated adsorption isotherm is shown in Fig. 4.
Conclusion:
(1) Cu2+When low concentration (4mg/L), the adsorption isothermequation on amination GrapheneK dIt is 15000, and the adsorption isothermequation on graphene oxideK dIt is 32000.
(2) Cu2+When high concentration (50mg/L), the adsorption isothermequation on amination GrapheneK dIt is 6600, and the adsorption isothermequation on graphene oxideK dIt is 3500.
(3) Adsorption of Cu on amination Graphene2+Energy force rate graphene oxide improve about 2 times.
Below being only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment, with present inventive concept without the various process programs of substantial differences all in protection scope of the present invention.
Claims (7)
1. the preparation method of an amination Graphene, it is characterised in that concretely comprise the following steps:
(1) taking graphene oxide powder and dimethylformamide that mass ratio is 1:15 ~ 300, mix homogeneously forms it into stable suspension;
(2) by oxolane and N, N '-dicyclohexylcarbodiimide with mass ratio 5:1 ~ 10:1 mixing, stir;
(3) in the suspension that step (1) is prepared, add and N, N ' ethylenediamine of-dicyclohexylcarbodiimide equal mass and step 2) N for preparing, the tetrahydrofuran solution of N '-dicyclohexylcarbodiimide, stirring 3 ~ 5d, sucking filtration, namely complete the amination of graphene oxide;
(4) the amination Graphene methanol of step (3) gained and distilled water are respectively washed repeatedly, to remove the residual organic matter in operating process;
(5) adding appropriate ultra-pure water in the amination Graphene obtained in step (4), water bath sonicator is so as to be uniformly dispersed;
(6) by gained amination Graphene colloid solution lyophilization in step (5), the amination Graphene of monatomic lamellar structure is obtained.
2. the preparation method of amination Graphene according to claim 1, it is characterised in that in step (1) and (2), the method for described mix homogeneously is the method adopting water bath sonicator, and the time is 15��20min.
3. the preparation method of amination Graphene according to claim 1, it is characterised in that in step (3), described ethylenediamine, N, N ' mass ratio of-dicyclohexylcarbodiimide and graphene oxide is 10:10:1��40:40:1.
4. the preparation method of amination Graphene according to claim 1, it is characterised in that in step (3), described stirring means is magnetic stirrer, carries out under room temperature; The organic facies filter membrane using filter membrane to be 0.22 ��m in described sucking filtration process.
5. the preparation method of amination Graphene according to claim 1, it is characterised in that in step (4), described cleaning way is clean according to the order of distilled water after first methanol, at least by every kind of solvent clean 4 times, it is ensured that residual organic matter all cleans up;In step (5), the temperature of water bath sonicator not can exceed that 50oC, and the time is 2h��4h.
6. the preparation method of amination Graphene according to claim 1, it is characterised in that graphene oxide powder used is single-layer graphene oxide.
7. the amination Graphene that prepared by employing method described in claim 1 application in absorption heavy metal ions in wastewater; Described heavy metal ion refers to Cu2+��Cd2+��Pb2+��Zn2��
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215722A (en) * | 2016-08-08 | 2016-12-14 | 贵阳时代沃顿科技有限公司 | A kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof |
| CN108417403A (en) * | 2018-03-09 | 2018-08-17 | 西安交通大学 | A kind of preparation method of the porous nitrogen-doped graphene membrane electrodes of 3D |
| CN108505049A (en) * | 2018-05-28 | 2018-09-07 | 中国科学院理化技术研究所 | Graphite oxide corrosion inhibitor and preparation and application thereof |
| CN109942868A (en) * | 2019-02-25 | 2019-06-28 | 王雪峰 | A kind of preparation method of waterproof tensile fiber type element packaging film |
| CN110538672A (en) * | 2019-07-25 | 2019-12-06 | 广东工业大学 | Composite visible light response photocatalyst material and preparation method and application thereof |
| CN113244890A (en) * | 2021-05-25 | 2021-08-13 | 成都师范学院 | Preparation method and application of halloysite nanotube/graphene oxide composite material |
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| CN103861565A (en) * | 2012-12-14 | 2014-06-18 | 吉首大学 | Preparation of linear amino modified graphene oxide adsorption material |
| CN104923156A (en) * | 2015-05-20 | 2015-09-23 | 东华大学 | Carbon-base loaded adsorbent for removing heavy metal in wastewater and preparation and use thereof |
| WO2015170124A1 (en) * | 2014-05-09 | 2015-11-12 | The University Of Manchester | Functionalised graphene |
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- 2016-01-11 CN CN201610012813.1A patent/CN105645392B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103861565A (en) * | 2012-12-14 | 2014-06-18 | 吉首大学 | Preparation of linear amino modified graphene oxide adsorption material |
| WO2015170124A1 (en) * | 2014-05-09 | 2015-11-12 | The University Of Manchester | Functionalised graphene |
| CN104923156A (en) * | 2015-05-20 | 2015-09-23 | 东华大学 | Carbon-base loaded adsorbent for removing heavy metal in wastewater and preparation and use thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215722A (en) * | 2016-08-08 | 2016-12-14 | 贵阳时代沃顿科技有限公司 | A kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof |
| CN108417403A (en) * | 2018-03-09 | 2018-08-17 | 西安交通大学 | A kind of preparation method of the porous nitrogen-doped graphene membrane electrodes of 3D |
| CN108505049A (en) * | 2018-05-28 | 2018-09-07 | 中国科学院理化技术研究所 | Graphite oxide corrosion inhibitor and preparation and application thereof |
| CN108505049B (en) * | 2018-05-28 | 2019-12-10 | 中国科学院理化技术研究所 | Graphite oxide corrosion inhibitor and preparation and application thereof |
| CN109942868A (en) * | 2019-02-25 | 2019-06-28 | 王雪峰 | A kind of preparation method of waterproof tensile fiber type element packaging film |
| CN110538672A (en) * | 2019-07-25 | 2019-12-06 | 广东工业大学 | Composite visible light response photocatalyst material and preparation method and application thereof |
| CN113244890A (en) * | 2021-05-25 | 2021-08-13 | 成都师范学院 | Preparation method and application of halloysite nanotube/graphene oxide composite material |
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