CN103638894A - Preparation method of modified graphene-based iron oxide nano-composite material - Google Patents
Preparation method of modified graphene-based iron oxide nano-composite material Download PDFInfo
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- CN103638894A CN103638894A CN201310668638.8A CN201310668638A CN103638894A CN 103638894 A CN103638894 A CN 103638894A CN 201310668638 A CN201310668638 A CN 201310668638A CN 103638894 A CN103638894 A CN 103638894A
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Abstract
The invention relates to a modified graphene-based iron oxide composite and particularly relates to a preparation method of a modified graphene-based iron oxide nano-composite material. The technical scheme for realizing the preparation method provided by the invention is as follows: graphene-based iron oxide nano-particles are prepared by taking graphite oxide, soluble high-iron salt, diethylene glycol and sodium hydroxide as raw materials; then, 3-mercaptopropyl triethoxysilane is used for modifying the prepared nano-particles to prepare the modified graphene-based iron oxide nano-composite material. When the modified graphene-based iron oxide nano-composite material is used for treating heavy metals in sewage, the adsorption capacity is great; simultaneously, the preparation requirements are relatively simple, and the application prospect is great.
Description
Technical field
The present invention relates to a kind of modified graphite thiazolinyl ferroferric oxide compound, particularly a kind of preparation method of modified graphite thiazolinyl ferriferrous oxide nano composite.
Background technology
Grapheme material is that its structure is similar to not curling CNT by a kind of carbonaceous material with large π key conjugated system of the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape lattice structure; Grapheme material, with its unique physical arrangement feature and excellent mechanics, electric property, is with a wide range of applications in nanoelectronics, microelectronics, energy storage material and prepare composite; The means of preparing at present Graphene are a lot, comprise mechanical stripping method, epitaxy method, heating SiC method, graphite graft process, thermal expansion stripping method, electrochemical process, chemical vapour deposition technique and graphite oxide reducing process etc.
Research shows that Graphene is the ideal carrier of functional materials anchor loads, and after compound with metal, metal oxide, sulfide etc., the performance of material of main part is improved; Magnetic Nano material and Graphene is compound, can obtain thering is excellent absorption property, composite that again can Magnetic Isolation, has potential application at aspects such as sewage disposal, organic matter enrichments.
Vimlesh Chandra, Jaesung Park etc. are by preparing dispersible magnetic oxygenated Graphene particle in water, and the removal of research to trivalent in waste water and pentavalent arsenic ion can reach more than 99.9% clearance under ppb concentration; Yunjin Yao, Shiding Miao etc. is carried in tri-iron tetroxide particle on Graphene by chemical deposition, prepare graphene-based ferriferrous oxide nano-particle, and study it for the absorption of methylene blue and congo red, obtained good removal effect; Graphene and the ferriferrous oxide composite material of the preparations such as Yan-Ping Chang have good Adsorption effect to aniline and parachloroanilinum.
Summary of the invention
The present invention proposes a kind of new method, to graphene-based ferriferrous oxide material modifying surface, prepares modified graphite thiazolinyl ferriferrous oxide nanometer material, thereby realizes the raising for the absorption property of heavy metal ion.
The present invention is achieved by the following technical programs:
(1) graphite oxide is dispersed in diethylene glycol (DEG), ultrasonic dispersion, is configured to the dispersion liquid of 1.5mg/mL, adds solubility ferric salt, and in solubility ferric salt and dispersion liquid, the mass ratio of graphite oxide is 4:1, stirs, at N
2under protection, be heated to 220 ℃, continue to stir, react 30 minutes;
(2) diethylene glycol solution of the NaOH of configuration 10mg/mL, at N
2under protection, be heated to 120 ℃ reaction 1 hour after, be cooled to 70 ℃ standby;
(3) solution of being prepared by step (2) adds rapidly in solution prepared by step (1), and volume ratio is 1:4, and the product that obtains is centrifugal to be cleaned afterwards with ethanol, and vacuum drying, obtains graphene-based ferroferric oxide nano granules;
(4) 3-mercaptopropyltriethoxysilane is dissolved in solvent, volume ratio is 1:150, with glacial acetic acid, regulates pH value, hydrolysis;
(5) graphene-based ferroferric oxide nano granules is dispersed in solution 4, concentration is 1 g/L, reacts respectively under room temperature and heating condition, and product cleans with ethanol, and vacuum drying obtains modified graphite thiazolinyl ferriferrous oxide nano composite.
In described step (1), solubility ferric salt used is iron chloride or ferric nitrate.
Solvent in described step (4) is ethanol or DMF.
In described step (4), regulating the scope of pH value is 2-6.
In described step (4), hydrolysis time is 1-3 hour.
Graphene-based tri-iron tetroxide was evenly spread in solution in described step (5) ultrasonic 0.5-1 hour.
In described step (5), heating condition temperature is 40-60 ℃, and the reaction time is 4-6h.
Beneficial effect:
(1) this method preparation is simple, by regulating pH to promote silane coupler hydrolysis to form silanol group, can with burning deposits yields strong bonded, thereby realize the modification to matrix surface, the mercapto groups of 3-mercaptopropyltriethoxysilane end can practical function modification.
(2) modified graphite thiazolinyl ferriferrous oxide nano compound has that the specific area of Graphene is large simultaneously, the superparamagnetism of tri-iron tetroxide and finishing functional group be for the binding function of heavy metal ion, when cadmium ion adsorbs in to the aqueous solution, there is larger adsorption capacity and good adsorption effect.
(3) the modified Nano material of preparing has good recycling property, can realize the recycling for material by desorption.
Accompanying drawing explanation
Fig. 1 is the TEM comparison diagram before and after the obtained graphene-based ferriferrous oxide nano composite modification of embodiment 1; (a) for before modification; (b) for after modification.
Fig. 2 is the FT-IR figure of the obtained modified graphite thiazolinyl of embodiment 1 ferriferrous oxide nano composite.
Fig. 3 is the adsorption capacity figure to cadmium ion in the aqueous solution before and after the obtained graphene-based ferriferrous oxide nano composite modification of embodiment 1; (a) for before modification; (b) for after modification.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail; But should understand, these embodiment are only not used in and limit the scope of the invention for explanation, in addition should understand, after having read the content of the present invention's instruction, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1:
(1) 30mg graphite oxide is dispersed in 20mL diethylene glycol (DEG), ultrasonic 1 hour, adds 120mg iron chloride to stir 1 hour, at N
2under protection, be heated to 220 ℃, continue to stir, react 30 minutes;
(2) in 20mL diethylene glycol (DEG), add 200mg NaOH, at N
2under protection, be heated to 120 ℃ reaction 1 hour after, be cooled to 70 ℃ standby;
(3) in (1) solution, add rapidly 5mL(2) storing solution, the product obtaining is centrifugal rear with ethanol cleaning, and vacuum drying, obtains graphene-based ferroferric oxide nano granules;
(4) 1mL 3-mercaptopropyltriethoxysilane is dissolved in 150ml ethanol, with glacial acetic acid, pH value is adjusted to 2, be hydrolyzed 1 hour;
(5) ultrasonic 0.5h, graphene-based ferroferric oxide nano granules is dispersed in the solution of step 4, reacts 4 hours respectively under room temperature and 40 ℃ of conditions, product cleans with ethanol, vacuum drying, obtains modified graphite thiazolinyl ferriferrous oxide nano composite.
Embodiment 2:
(1) 30mg graphite oxide is dispersed in 20mL diethylene glycol (DEG), ultrasonic 1 hour, adds 120mg ferric nitrate to stir 1 hour, at N
2under protection, be heated to 220 ℃, continue to stir, react 30 minutes;
(2) in 20mL diethylene glycol (DEG), add 200mg NaOH, at N
2under protection, be heated to 120 ℃ reaction 1 hour after, be cooled to 70 ℃ standby;
(3) in the solution of step 1 preparation, add rapidly the storing solution of 5mL step 2 preparation, the product obtaining is centrifugal rear with ethanol cleaning, and vacuum drying, obtains graphene-based ferroferric oxide nano granules;
(4) 1mL 3-mercaptopropyltriethoxysilane is dissolved in 150ml ethanol, with glacial acetic acid, pH value is adjusted to 4, be hydrolyzed 2 hours;
(5) ultrasonic 45min, graphene-based ferroferric oxide nano granules is dispersed in the solution of step 4 preparation, reacts 5 hours respectively under room temperature and 50 ℃ of conditions, product cleans with ethanol, vacuum drying, obtains modified graphite thiazolinyl ferriferrous oxide nano composite.
Embodiment 3:
(1) 30mg graphite oxide is dispersed in 20mL diethylene glycol (DEG), ultrasonic 1 hour, adds 120mg iron chloride to stir 1 hour, at N
2under protection, be heated to 220 ℃, continue to stir, react 30 minutes;
(2) in 20mL diethylene glycol (DEG), add 200mg NaOH, at N
2under protection, be heated to 120 ℃ reaction 1 hour after, be cooled to 70 ℃ standby;
(3) in the solution of step 1 preparation, add rapidly the storing solution of 5mL step 2 preparation, the product obtaining is centrifugal rear with ethanol cleaning, and vacuum drying, obtains graphene-based ferroferric oxide nano granules;
(4) 2mL 3-mercaptopropyltriethoxysilane is dissolved in to 300mLN, in dinethylformamide, with glacial acetic acid, pH value is adjusted to 6, be hydrolyzed 3 hours;
(5) ultrasonic 1h, graphene-based ferroferric oxide nano granules is dispersed in the solution of step 4 preparation, reacts 5 hours respectively under room temperature and 60 ℃ of conditions, product cleans with ethanol, vacuum drying, obtains modified graphite thiazolinyl ferriferrous oxide nano composite.
The TEM figure that Fig. 1 (a) is unmodified graphene-based ferriferrous oxide composite material, show that ferriferrous oxide nano-particle is successfully anchored at at graphene-based the end, the TEM figure that Fig. 1 (b) is the graphene-based ferriferrous oxide composite material after modification, nano particle diameter has had obvious increase, shows that silane coupler successfully realized the modification to nanoparticle surface.
Fig. 2 is the FI-IR figure of the graphene-based ferriferrous oxide composite material after modification, 568cm
-1be the feature stretching vibration peak of Fe-O, proved that ferriferrous oxide nano-particle is successfully fixed on Graphene.1633 peak cm
-1and 1390cm
-1the characteristic absorption peak of 3-mercaptopropyltriethoxysilane, at 1080cm
-1the peak that place occurs is at Si-O stretching vibration peak, has disclosed silane coupler graphene-based ferriferrous oxide nano-particle is successfully realized to modification.
In to water, cadmium ion adsorbs, the adsorption effect of the graphene-based ferriferrous oxide composite material before and after modification is respectively as shown in Fig. 3 (a), (b), and the graphene-based ferriferrous oxide composite material after modification improves before than modification to the adsorption effect of cadmium ion.
Claims (9)
1. a preparation method for modified graphite thiazolinyl ferriferrous oxide nano composite, described modified graphite thiazolinyl ferriferrous oxide nano composite, for Adsorption of Heavy Metal Ions, is characterized in that comprising the steps:
(1) 3-mercaptopropyltriethoxysilane is dissolved in solvent, volume ratio is 1:150, with glacial acetic acid, regulates pH value, hydrolysis;
(2) graphene-based ferroferric oxide nano granules is dispersed in the hydrating solution of step 1 preparation, concentration is 1 g/L, reacts respectively under room temperature and heating condition, and product cleans with ethanol, vacuum drying, obtains modified graphite thiazolinyl ferriferrous oxide nano composite.
2. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: the solvent in described step (1) is ethanol or DMF.
3. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: the pH value scope regulating in described step (1) is 2-6.
4. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: in described step (1), hydrolysis time is 1-3 hour.
5. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as described in claim 1, is characterized in that: in described step (2), graphene-based tri-iron tetroxide iron nano-particle was evenly spread in ultrasonic 0.5-1 hour in the hydrating solution of step 1 preparation.
6. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: in described step (2), heating condition temperature is 40-60 ℃, and the reaction time is 4-6 hour.
7. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: described heavy metal ion is cadmium ion.
8. the preparation method of a kind of graphene-based ferriferrous oxide nano composite as claimed in claim 1, is characterized in that: the preparation method of described graphene-based ferroferric oxide nano granules is as follows:
(3) graphite oxide is dispersed in diethylene glycol (DEG), ultrasonic dispersion, is configured to the dispersion liquid of 1.5mg/mL, adds solubility ferric salt, and in solubility ferric salt and dispersion liquid, the mass ratio of graphite oxide is 4:1, stirs, at N
2under protection, be heated to 220 ℃, continue to stir, react 30 minutes;
(4) diethylene glycol solution of the NaOH of configuration 10mg/mL, at N
2under protection, be heated to 120 ℃ reaction 1 hour after, be cooled to 70 ℃ standby;
(5) solution of being prepared by step (2) adds rapidly in solution prepared by step (1), and volume ratio is 1:4, and the product that obtains is centrifugal to be cleaned afterwards with ethanol, and vacuum drying, obtains graphene-based ferroferric oxide nano granules.
9. the preparation method of a kind of modified graphite thiazolinyl ferriferrous oxide nano composite as claimed in claim 7, is characterized in that: in described step (3), solubility ferric salt used is iron chloride or ferric nitrate.
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Cited By (6)
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| CN105510416A (en) * | 2016-01-07 | 2016-04-20 | 上海第二工业大学 | Preparation method of electrochemical sensor based on magnetic nanocomposite |
| CN107127351A (en) * | 2017-05-03 | 2017-09-05 | 广州特种承压设备检测研究院 | Graphene and ferroso-ferric oxide@metal/composite materials and its preparation method and application |
| CN108795238A (en) * | 2018-06-26 | 2018-11-13 | 常州二维碳素科技股份有限公司 | A kind of pyrographite alkene conductive coating and its application |
| CN110614079A (en) * | 2018-06-20 | 2019-12-27 | 李克非 | Preparation method and application of net-shaped magnetic graphene oxide |
| CN110652986A (en) * | 2018-06-28 | 2020-01-07 | 李克非 | Reticular magnetic Fe3O4Preparation method and application of/GO/ZnO catalyst |
| CN113546630A (en) * | 2021-07-30 | 2021-10-26 | 华东理工大学 | Graphite-based supported iron-based catalyst and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105510416A (en) * | 2016-01-07 | 2016-04-20 | 上海第二工业大学 | Preparation method of electrochemical sensor based on magnetic nanocomposite |
| CN107127351A (en) * | 2017-05-03 | 2017-09-05 | 广州特种承压设备检测研究院 | Graphene and ferroso-ferric oxide@metal/composite materials and its preparation method and application |
| CN107127351B (en) * | 2017-05-03 | 2019-03-19 | 广州特种承压设备检测研究院 | Graphene and ferroso-ferric oxide@metal/composite material and its preparation method and application |
| CN110614079A (en) * | 2018-06-20 | 2019-12-27 | 李克非 | Preparation method and application of net-shaped magnetic graphene oxide |
| CN108795238A (en) * | 2018-06-26 | 2018-11-13 | 常州二维碳素科技股份有限公司 | A kind of pyrographite alkene conductive coating and its application |
| CN110652986A (en) * | 2018-06-28 | 2020-01-07 | 李克非 | Reticular magnetic Fe3O4Preparation method and application of/GO/ZnO catalyst |
| CN113546630A (en) * | 2021-07-30 | 2021-10-26 | 华东理工大学 | Graphite-based supported iron-based catalyst and preparation method and application thereof |
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Application publication date: 20140319 |