CN103738953A - Preparation method for carbon nano tube-graphene composite foam - Google Patents
Preparation method for carbon nano tube-graphene composite foam Download PDFInfo
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- CN103738953A CN103738953A CN201310713369.2A CN201310713369A CN103738953A CN 103738953 A CN103738953 A CN 103738953A CN 201310713369 A CN201310713369 A CN 201310713369A CN 103738953 A CN103738953 A CN 103738953A
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Abstract
The invention belongs to a preparation method of a nano composite material and particularly relates to the field of a microwave preparation method for a grapheme-based composite material. A preparation method for carbon nano tube-graphene composite foam comprises the following steps: firstly, loading ferrocene on graphene foam; and then carrying out microwave treatment on the graphene foam loaded with the ferrocene and decomposing the ferrocene on the graphene foam by a high temperature which is instantly generated, so as to generate a catalyst and a carbon source to realize carbon nano tube in-situ growth and obtain the carbon nano tube-graphene composite foam. A carbon nano tube in the composite material vertically and epitaxially grows on the surface of a hole wall of the graphene foam; the super-hydrophobic and super-lipophilic surface chemical characteristics are represented; the preparation method has a wide application prospect in the aspects of adsorption, oil-water separation and the like; the method has the characteristics that operation is simple and convenient, cost is low, and industrial production is easily realized, and is an important preparation method for nano carbon materials.
Description
Technical field
The invention belongs to the preparation method of nano composite material, relate in particular to the microwave preparation technical field of graphene-based matrix material.
Background technology
Grapheme foam is the novel three-dimension integrally functional materials of a class.This class material has specific surface area and the excellent conductive characteristic of flourishing pore texture, super large, at numerous areas such as energy storage, environment protection and catalysis, has broad application prospects.The method of preparing grapheme foam of report comprises the several different methods such as hydrothermal reduction method, chemical reduction method and chemical Vapor deposition process at present.Although grapheme foam has shown the performance of a series of excellences, the character of some aspect particularly hydrophobic performance is not ideal enough, and the hydrophobic performance that how effectively to improve grapheme foam becomes an important challenge.
One of important channel of improving material hydrophobic performance is the roughness that increases material surface.As a kind of material typically with high length-diameter ratio, carbon nanotube particularly vertical orientated carbon nano pipe array is used for improving surperficial hydrophobic property, initiative super hydrophobic surface widely.Utilize the grapheme foam of chemical vapour deposition as substrate, after catalyst deposit, again carry out chemical vapor deposition processes and successfully realized the preparation of super-hydrophobic carbon nanotube-grapheme foam, but the loaded down with trivial details process of the method and extremely low productive rate have limited the possibility of this foam practical application greatly.And by introduce carbon nanotube in the process of chemical preparation grapheme foam, can obtain efficiently, cheaply graphene-carbon nano tube foam, but in this foam, carbon nanotube is often coated by graphene nanometer sheet, to the hydrophobic improvement of material not obvious.How at grapheme foam hole wall surface, to introduce vertical orientated carbon nano pipe array and be still a difficult problem.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation method of carbon nanotube-Graphene composite foam, the method is dispersed in ferrocene on the surface of grapheme foam, and there is the grapheme foam of ferrocene to carry out microwave treatment to load, induction ferrocene cracking catalysis Formed nanotube, rapidly and efficiently obtain carbon nanotube-Graphene composite foam.
The technical solution adopted in the present invention is as follows: a kind of preparation method of carbon nanotube-Graphene composite foam, and this preparation method carries out in accordance with the following steps:
(1) ferrocene is dispersed in lower boiling organic solvent and obtains ferrocene solution, the concentration range of ferrocene solution is 5 ~ 20 mg/mL;
(2) grapheme foam is inserted in above-mentioned ferrocene solution, fully dipping;
(3) grapheme foam after dipping is taken out, is dried, obtaining load has the grapheme foam of ferrocene;
(4) load there is is the grapheme foam of ferrocene be placed in microwave reactor; after utilizing non-oxide protective gas to purge, carry out microwave treatment; the high temperature that grapheme foam and microwave action produce makes ferrocene decompose carbon nano-tube, and naturally cooling obtains carbon nanotube-Graphene composite foam after being down to room temperature.
In described (1), lower boiling organic solvent is selected from one or more mixing in acetone, ethanol, gasoline, sherwood oil, benzene, ether, hexanaphthene and ethyl acetate.
The grapheme foam that described raw material grapheme foam is chemical preparation or the standby grapheme foam of hydrothermal reduction legal system.
Described chemical preparation grapheme foam is to adopt reductive agent quadrol, sodium bisulfite, xitix, sodium sulphite, hydrogen iodide or Resorcinol reduction to prepare gained; It is that additional reducing agent hydrothermal treatment consists is not prepared gained that described hydrothermal reduction is prepared grapheme foam, or additionally adds reductive agent hydrazine hydrate, sodium bisulfite, xitix or sodium sulphite hydrothermal reduction and prepare gained.
The protective gas in described (4) without oxidisability is selected from one or more mixing in the low-carbon (LC) hydrocarbon gas such as nitrogen, argon gas, helium, hydrogen and methane, ethene.
Described microwave treatment power is 800 W, and the treatment time is 5 ~ 600 seconds.
Described carbon nanotube is vertical orientated to be grown on grapheme foam hole wall, has good super-hydrophobic super oil-wet behavior, at aspects such as absorption, oily water separations, has broad application prospects.
Compared with prior art, the present invention has following remarkable advantage:
1. technique is simple, and raw material is cheap and easy to get;
2. under microwave exposure, ferrocene is at grapheme foam hole wall surface original position pyrolysis Formed nanotube;
3. generated in-situ carbon nanotube vertical-growth, on Graphene hole wall, can improve the wettability of original grapheme foam effectively;
4. under microwave exposure, carbon nanotube has very high growth efficiency, and only the microwave treatment of 5 s just can realize the growth of carbon nanotube.
Accompanying drawing explanation
Fig. 1 is carbon nanotube-Graphene composite foam preparation flow figure;
Fig. 2 is the digital photograph of carbon nanotube-Graphene composite foam, and the ferrocene strength of solution of using is 15 mg/mL, and microwave treatment time is 1 minute;
Fig. 3 is the electron scanning micrograph of carbon nanotube-Graphene composite foam, and the ferrocene strength of solution of using is 15 mg/mL, and microwave treatment time is 1 minute;
Fig. 4 is the selective adsorption process of carbon nanotube-Graphene composite foam to oil and water;
Fig. 5 is the electron scanning micrograph of carbon nanotube-Graphene composite foam, and the ferrocene strength of solution of using is 15 mg/mL, and microwave treatment time was 5 seconds;
Fig. 6 is the electron scanning micrograph of carbon nanotube-Graphene composite foam, and the ferrocene strength of solution of using is 20 mg/mL, and microwave treatment time was 30 seconds.
Embodiment
Fig. 1 is the preparation flow schematic diagram of carbon nanotube-Graphene composite foam in the present invention, and concrete preparation process is as described below:
(1) in lower boiling organic solvent, disperse ferrocene to make ferrocene solution, the concentration range of ferrocene solution is 5 ~ 20 mg/mL; Low boiling point organic solvent used comprises one or more mixing in acetone, ethanol, gasoline, sherwood oil, benzene, ether, hexanaphthene, ethyl acetate;
(2) grapheme foam is inserted in above-mentioned ferrocene solution, fully dipping; The grapheme foam using comprises grapheme foam and the standby grapheme foam of hydrothermal reduction legal system of chemical preparation; The reductive agent of chemical preparation grapheme foam can be quadrol, sodium bisulfite, xitix, sodium sulphite, hydrogen iodide and Resorcinol etc.; When preparing grapheme foam, can additionally add hydrothermal reduction reductive agent as hydrazine hydrate, sodium bisulfite, xitix, sodium sulphite etc., also additional reducing agent not;
(3) grapheme foam after dipping is taken out, is dried, obtaining load has the grapheme foam of ferrocene;
(4) load there is is the grapheme foam of ferrocene be placed in microwave reactor; after utilizing protective gas to purge, carry out microwave treatment; the high temperature that grapheme foam and microwave action produce makes ferrocene decompose carbon nano-tube, and naturally cooling obtains carbon nanotube-Graphene composite foam after being down to room temperature.The protective gas using is non-oxidizing gas, comprises one or more mixing in the low-carbon (LC) hydrocarbon gas such as nitrogen, argon gas, helium, hydrogen and methane, ethene; Microwave treatment power is 800 W, and the time is 5 ~ 600 seconds.
Carbon nanotube-Graphene composite foam prepared by aforesaid method, carbon nanotube is vertical orientated on grapheme foam hole wall, and the material obtaining has good ultra-hydrophobicity.The method is simple to operate, easily amplifies.Below will by several specific embodiments, the invention will be further described:
embodiment 1:
By in the ultrasonic acetone that is dispersed in 40 mL of 0.6 g ferrocene, obtaining concentration is the ferrocene acetone soln of 15 mg/mL.The grapheme foam that quadrol assisted Reduction is prepared is inserted in the acetone soln of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, place seasoning, after acetone volatilization completely, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in argon replaces reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 1min, obtains carbon nanotube-Graphene composite foam.Thermogravimetric analysis shows that the content of carbon nanotube in composite foam is 32 wt%.Figure 2 shows that the composite foam digital photograph obtaining, Figure 3 shows that the electron scanning micrograph of composite foam, as can be seen from the figure the both sides uniform loading of grapheme foam hole wall a large amount of vertical orientated carbon nanotubes, the length of carbon nanotube is in 5 about μ m.Fig. 4 has shown the selective adsorption capacity of gained carbon nanotube-Graphene composite foam to oil and water, water droplet can present spherical state and rest on for a long time the surface of foam, and oil droplet just penetrated in the space of foam completely in the moment that touches foam, reflect super-hydrophobic, the super oil-wetted surface characteristic of this composite foam.
embodiment 2:
By in the ultrasonic acetone that is dispersed in 50 mL of 0.75 g ferrocene, obtaining concentration is the ferrocene acetone soln of 15 mg/mL.The grapheme foam that quadrol assisted Reduction is prepared is inserted in the acetone soln of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, place seasoning, after acetone volatilization completely, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in argon replaces reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 5 s, obtains carbon nanotube-Graphene composite foam.Thermogravimetric analysis shows that the content of carbon nanotube in mixture is 8 wt%.Figure 5 shows that the electron scanning micrograph of the composite foam obtaining, the length of carbon nanotube of as can be seen from the figure growing in this embodiment is shorter, is hundreds of nanometers.
embodiment 3:
By in the ultrasonic gasoline that is dispersed in 30 mL of 0.6 g ferrocene, obtaining concentration is the ferrocene gasoline solution of 20 mg/mL.The grapheme foam that xitix assisted Reduction is prepared is inserted in the solution of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, place seasoning, after gasoline volatilization is complete, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in nitrogen replacement reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 30 s, obtains carbon nanotube-Graphene composite foam.In mixture, the content of carbon nanotube is 42 wt%.
embodiment 4:
By in the ultrasonic ethanol that is dispersed in 40 mL of 0.4 g ferrocene, obtaining concentration is the ferrocene ethanolic soln of 10 mg/mL.The grapheme foam that hydro-thermal assisted Reduction is prepared is inserted in the solution of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, be placed in stink cupboard and be dried, after ethanol volatilization completely, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in hydrogen exchange reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 15 s, obtains carbon nanotube-Graphene composite foam.In mixture, the content of carbon nanotube is 23 wt.%
embodiment 5:
By in the ultrasonic acetone that is dispersed in 40 mL of 0.2 g ferrocene, obtaining concentration is the ferrocene acetone soln of 5 mg/mL.Quadrol is reduced to the grapheme foam preparing inserts in the solution of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, be placed in stink cupboard and be dried, after acetone volatilization completely, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in hydrogen/argon gas gas mixture metathesis reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 40 s, obtains carbon nanotube-Graphene composite foam.In mixture, the content of carbon nanotube is 17 wt%.Figure 6 shows that the electron scanning micrograph of the composite foam obtaining.
embodiment 6:
By in the ultrasonic sherwood oil that is dispersed in 50 mL of 0.5 g ferrocene, obtaining concentration is the ferrocene petroleum ether solution of 10 mg/mL.Quadrol is reduced to the grapheme foam preparing inserts in the solution of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, be placed in stink cupboard and be dried, after sherwood oil volatilization completely, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in argon gas gas mixture metathesis reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 600 s, obtains carbon nanotube-Graphene composite foam.In mixture, the content of carbon nanotube is 28 wt%.
embodiment 7:
By ultrasonic 0.3 g ferrocene, be dispersed in the sherwood oil of 20mL and the mixing solutions of 20mL gasoline, obtaining concentration is the ferrocene solution of 7.5 mg/mL.Quadrol is reduced to the grapheme foam preparing inserts in the solution of above-mentioned ferrocene.Impregnated grapheme foam is taken out, under room temperature, be placed in stink cupboard and be dried, after solvent evaporates is complete, obtain supporting the grapheme foam of ferrocene.The grapheme foam that supports ferrocene is placed in to microwave reactor, passes into the air in nitrogen mixture metathesis reactor.Microwave reactor is opened, carried out microwave exposure processing, the power of microwave reactor is 800 W, and the treatment time is 30 s, obtains carbon nanotube-Graphene composite foam.In mixture, the content of carbon nanotube is 15 wt.%.
Claims (7)
1. a preparation method for carbon nanotube-Graphene composite foam, is characterized in that: this preparation method carries out in accordance with the following steps:
(1) ferrocene is dispersed in lower boiling organic solvent and obtains ferrocene solution, the concentration range of ferrocene solution is 5 ~ 20 mg/mL;
(2) grapheme foam is inserted in above-mentioned ferrocene solution, fully dipping;
(3) grapheme foam after dipping is taken out, is dried, obtaining load has the grapheme foam of ferrocene;
(4) load there is is the grapheme foam of ferrocene be placed in microwave reactor; after utilizing non-oxide protective gas to purge, carry out microwave treatment; the high temperature that grapheme foam and microwave action produce makes ferrocene decompose carbon nano-tube, and naturally cooling obtains carbon nanotube-Graphene composite foam after being down to room temperature.
2. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 1, is characterized in that: in described (1), lower boiling organic solvent is selected from one or more mixing in acetone, ethanol, gasoline, sherwood oil, benzene, ether, hexanaphthene and ethyl acetate.
3. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 1, is characterized in that: the grapheme foam that described raw material grapheme foam is chemical preparation or the standby grapheme foam of hydrothermal reduction legal system.
4. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 3, is characterized in that: described chemical preparation grapheme foam is to adopt reductive agent quadrol, sodium bisulfite, xitix, sodium sulphite, hydrogen iodide or Resorcinol reduction to prepare gained; It is that additional reducing agent hydrothermal treatment consists is not prepared gained that described hydrothermal reduction is prepared grapheme foam, or additionally adds reductive agent hydrazine hydrate, sodium bisulfite, xitix or sodium sulphite hydrothermal reduction and prepare gained.
5. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 1, is characterized in that: the protective gas in described (4) without oxidisability is selected from one or more mixing in the low-carbon (LC) hydrocarbon gas such as nitrogen, argon gas, helium, hydrogen and methane, ethene.
6. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 1, is characterized in that: described microwave treatment power is 800 W, and the time is 5 ~ 600 seconds.
7. the preparation method of a kind of carbon nanotube-Graphene composite foam according to claim 1, is characterized in that: described carbon nanotube is vertical orientated to be grown on grapheme foam hole wall, has good super-hydrophobic super oil-wet behavior.
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| CN116535124A (en) * | 2023-05-09 | 2023-08-04 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
| CN116535124B (en) * | 2023-05-09 | 2024-04-12 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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