CN116161653A - Method for modifying amino on surface of graphene oxide sheet - Google Patents
Method for modifying amino on surface of graphene oxide sheet Download PDFInfo
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- CN116161653A CN116161653A CN202310158696.XA CN202310158696A CN116161653A CN 116161653 A CN116161653 A CN 116161653A CN 202310158696 A CN202310158696 A CN 202310158696A CN 116161653 A CN116161653 A CN 116161653A
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- graphene oxide
- oxide sheet
- turbid liquid
- coupling agent
- amino groups
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical group CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 claims 2
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
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Classifications
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
In the anhydrous condition, toluene is used as a dispersing agent to prepare a turbid liquid of the graphene oxide sheet; adding an aminosilane coupling agent into the graphene oxide sheet turbid liquid, and stirring and uniformly mixing; heating and refluxing the system obtained in the previous step at a controlled temperature, and continuously introducing protective gas in the heating process; the product was washed by centrifugation with absolute ethanol and stored dispersed in absolute ethanol. The invention can successfully modify more amino groups in GO, and the GO after surface modification has better dispersibility and stability. Meanwhile, the anhydrous environment and inert atmosphere strictly maintained in the preparation process prevent the problem of the sedimentation of the common hydrolysis products modified by the coupling agent method GO, so that the operability and the repeatability of the experimental process are stronger.
Description
Technical Field
The invention belongs to the technical field of graphene oxide modification, and particularly relates to a method for coupling amino-containing groups on the surface of a graphene oxide sheet by using 3-aminopropyl trimethoxy silane (APTMS).
Background
Graphene Oxide (GO) is a commonly used inorganic material with excellent thermal and chemical stability. Graphene oxide has the characteristics of small size effect, surface interface effect, quantum size effect, high strength, toughness, high stability and the like, and is widely applied to preparation and modification of materials such as plastics, rubber, ceramics, paint, cosmetics, drug carriers and the like. However, the graphene oxide sheet (GO) has high surface energy, strong hydrophilicity and poor compatibility and dispersibility with an organic matrix due to the fact that the surface of the graphene oxide sheet (GO) contains a large number of hydroxyl (-OH), and the GO surface must be subjected to organic modification to reduce the surface energy and improve the dispersibility, so that the excellent characteristics of GO can be endowed to the composite material.
The silane coupling agent is the most commonly used one of a plurality of material surface modifying agents, and the surface of GO modified by the aminosilane coupling agent contains amino (-NH) 2 ) The active amino group can react with a plurality of molecules, and can obviously improve the dispersibility and stability of GO in an organic matrix, thereby expanding and improving the application performance of GO. If the modified GO is used as a reinforcing filler to be added into materials such as rubber, plastic and the like in the field of materials, the tensile strength, wear resistance, rheological property, ageing resistance and the like of a composite matrix can be effectively improved; in the catalytic field, the amination-modified GO is easy to separate and reuse.
Disclosure of Invention
The technical problems to be solved are as follows: the invention provides a method for modifying amino groups on the surface of a graphene oxide sheet, which can successfully modify more amino groups on GO, and the GO subjected to surface modification has better dispersibility and stability. Meanwhile, the anhydrous environment and inert atmosphere strictly maintained in the preparation process prevent the problem of the sedimentation of the common hydrolysis products modified by the coupling agent method GO, so that the operability and the repeatability of the experimental process are stronger.
The technical scheme is as follows: a method for modifying amino on the surface of graphene oxide sheet comprises the following steps: a. under anhydrous condition, toluene is used as a dispersing agent to prepare 0.4mg/mL graphene oxide sheet (GO) turbid liquid; b. adding an aminosilane coupling agent accounting for not less than 0.5 percent of the volume fraction of the graphene oxide sheet turbid liquid into the graphene oxide sheet turbid liquid, and stirring and uniformly mixing; c. c, heating and refluxing the system obtained in the step b at the control temperature of 85-105 ℃ for 12-15 h, and continuously introducing protective gas in the heating process; d. the product was washed by centrifugation with absolute ethanol and stored dispersed in absolute ethanol.
Preferably, the aminosilane coupling agent is APTMS, and the volume ratio of the APTMS in the system is 0.5%.
Preferably, in the preparation process b-c, the volume fraction of water in the reaction system is less than 0.01%.
The protective gas is nitrogen or inert gas.
The amino-modified graphene oxide sheet prepared by the method is prepared.
The beneficial effects are that: the aminosilane coupling agent used in the invention is APTMS, and the system is strictly controlled to be anhydrous and continuously protected by nitrogen. The anhydrous environment and the inert atmosphere can effectively avoid the hydrolysis of the silane coupling agent and the mutual condensation of hydrolysis products to form polysiloxane substances or the condensation of the polysiloxane substances on the GO surface to form an irregular multi-molecule modification layer. In addition, compared with GO modified by using classical silane coupling agent 3-aminopropyl triethoxy silane (APTES) on the surface under the same control condition, the IR and SEM characterization results show that the efficiency of amination of GO by using APTMS is higher, and the modified GO has better dispersibility and stability. The modification scheme has the advantages of simple process and strong operability, and GO with the surface modified by the APTMS has better dispersivity and stability. Meanwhile, the strictly anhydrous and inert atmosphere environment controlled in the invention effectively prevents the hydrolysis of the silane coupling agent, and ensures the high yield of the reaction.
Drawings
FIG. 1 is an infrared spectrum of APTMS aminated GO surface example 1, showing samples 3500-3300 cm -1 The characteristic peaks of free N-H are obvious.
Fig. 2 is the particle diameter of the APTMS aminated GO surface examples 1, 4 and 5, showing that example 1 is most uniform.
Description of the embodiments
Example 1
30mL of pure toluene is taken as a dispersing agent, 12mg of GO with the particle size of 200nm after suction filtration and drying is dispersed, 150 mu L (about 0.5% by volume of the system) of APTMS is added into the turbid liquid, heating is carried out, the temperature is controlled at 95 ℃, condensation reflux is carried out, a magnetic stirrer is used for continuously stirring the system in the heating process, and nitrogen is continuously introduced into the solution for protection. After 12h the reaction was stopped and the sample was recovered and used withoutWashed 3 times with aqueous ethanol and stored dispersed in ethanol. The glass instruments used in the preparation process are strictly washed and dried. The infrared spectrum characterization shows that GO 3500-3300 cm with surface modified is obtained -1 The characteristic peaks of free N-H are obvious. SEM characterization results show that the GO subjected to surface modification has uniform particle size and good dispersibility.
Example 2
30mL of pure toluene is taken as a dispersing agent to disperse 12mg of GO with the particle size of 400nm after suction filtration and drying, 150 mu L (about 0.5% by volume of the system) of APTMS is added into the turbid liquid, the system is heated, the temperature is controlled at 95 ℃, and the mixture is condensed and refluxed. The system is continuously stirred by a magnetic stirrer in the heating process, and nitrogen is continuously introduced into the solution for protection. After 12h the reaction was terminated, the samples were recovered and washed 3 times with absolute ethanol and stored dispersed in ethanol. The glass instruments used in the preparation process are strictly washed and dried. The infrared spectrum characterization shows that GO 3500-3300 cm with surface modified is obtained -1 The characteristic peaks of free N-H are obvious. SEM characterization results show that the GO subjected to surface modification has uniform particle size and good dispersibility.
Example 3
30mL of pure toluene is taken as a dispersing agent to disperse 12mg of GO with the particle size of 200nm after suction filtration and drying, 75 mu L (about 0.25% by volume of the system) of APTMS is added into the turbid liquid, the system is heated, the temperature is controlled at 95 ℃, and the mixture is condensed and refluxed. The system is continuously stirred by a magnetic stirrer in the heating process, and nitrogen is continuously introduced into the solution for protection. After 12h the reaction was terminated, the samples were recovered and washed 3 times with absolute ethanol and stored dispersed in ethanol. The glass instruments used in the preparation process are strictly washed and dried. Infrared spectra showed no free N-H characteristic peaks for the surface modified GO. SEM characterization results showed that the particles were uniformly dispersed well.
Example 4
30mL of pure toluene is taken as a dispersing agent, 12mg of GO with the particle size of 200nm after suction filtration and drying is dispersed, 50 mu L (about 0.17% by volume of the system) of APTMS is added into the turbid liquid, heating is carried out, the temperature is controlled at 95 ℃, condensation reflux is carried out, a magnetic stirrer is used for continuously stirring the system in the heating process, and nitrogen is continuously introduced into the solution for protection. After 12h the reaction was terminated, the samples were recovered and washed 3 times with absolute ethanol and stored dispersed in ethanol. The particle size value of GO in ethanol solution is observed to be large by the nano particle size analyzer, and GO dispersibility is proved to be poor.
Example 5
30mL of pure toluene is taken as a dispersing agent, 12mg of GO with the particle size of 200nm after suction filtration and drying is dispersed, 250 mu L (accounting for about 0.84% of the volume of the system) of APTMS is added into the turbid liquid, heating is carried out, the temperature is controlled at 95 ℃, condensation reflux is carried out, the system is continuously stirred by a magnetic stirrer in the heating process, and nitrogen is continuously introduced into the solution for protection. After 12h the reaction was terminated, the samples were recovered and washed 3 times with absolute ethanol and stored dispersed in ethanol. The particle size value of GO in ethanol solution is observed to be large by the nano particle size analyzer, and GO dispersibility is proved to be poor.
Claims (5)
1. The method for modifying amino groups on the surface of the graphene oxide sheet is characterized by comprising the following steps: a. under anhydrous condition, toluene is used as a dispersing agent to prepare 0.4mg/mL graphene oxide sheet (GO) turbid liquid; b. adding an aminosilane coupling agent accounting for not less than 0.5 percent of the volume fraction of the graphene oxide sheet turbid liquid into the graphene oxide sheet turbid liquid, and stirring and uniformly mixing; c. c, heating and refluxing the system obtained in the step b at the control temperature of 85-105 ℃ for 12-15 h, and continuously introducing protective gas in the heating process; d. the product was washed by centrifugation with absolute ethanol and stored dispersed in absolute ethanol.
2. The method for modifying amino groups on the surface of graphene oxide sheets according to claim 1, wherein the aminosilane coupling agent is APTMS, and the volume ratio of the APTMS in the system is 0.5%.
3. The method for modifying amino groups on the surface of graphene oxide sheets according to claim 1, wherein in the preparation process b-c, the volume fraction of water in a reaction system is less than 0.01%.
4. The method for modifying amino groups on the surface of a graphene oxide sheet according to claim 1, wherein the shielding gas is nitrogen or inert gas.
5. The amino-modified graphene oxide sheet produced by the method of any one of claims 1 to 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310158696.XA CN116161653A (en) | 2023-02-20 | 2023-02-20 | Method for modifying amino on surface of graphene oxide sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310158696.XA CN116161653A (en) | 2023-02-20 | 2023-02-20 | Method for modifying amino on surface of graphene oxide sheet |
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| Publication Number | Publication Date |
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| CN116161653A true CN116161653A (en) | 2023-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310158696.XA Withdrawn CN116161653A (en) | 2023-02-20 | 2023-02-20 | Method for modifying amino on surface of graphene oxide sheet |
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| CN (1) | CN116161653A (en) |
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2023
- 2023-02-20 CN CN202310158696.XA patent/CN116161653A/en not_active Withdrawn
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Application publication date: 20230526 |