Method for preparing fluorinated graphene nanoribbons

Abstract

A method for preparing fluorinated graphene nanoribbons by using fluorine gas as a fluorine source, which includes a step of: fluorinating anhydrous carbon nanotubes in a fluorine gas atmosphere under a pressure of 0.070 MPa and a temperature of 280450 C. to obtain the fluorinated graphene nanoribbons. The method provided is operationally simple, and has a wide variety of raw material sources, low cost, and high production which can reach up to tens of milligrams and even up to hundreds of grams; moreover, the method has simple post-treatment, and can produce fluorinated graphene nanoribbons by a one-step reaction. The prepared fluorinated graphene nanoribbons have very good superhydrophobic properties and chemical stability, and thus can be applied to the anti-icing and other fields, having a very good application prospect.

Claims

1. A method for preparing a fluorinated graphene nanoribbon, comprising fluorinating an anhydrous carbon nanotube in a fluorine gas atmosphere under a pressure of 0.070 MPa and a temperature of 280450 C. to obtain the fluorinated graphene nanoribbon.

2. The method according to claim 1, wherein the carbon nanotube is single-walled carbon nanotube, double-walled carbon nanotube, or multi-walled carbon nanotube.

3. The method according to claim 1, wherein the anhydrous carbon nanotubes are dehydrated by: placing the carbon nanotubes and a desiccant in a vacuum oven and performing vacuum drying at 80120 C.

4. The method according to claim 3, wherein the desiccant is selected from the group consisting of anhydrous phosphorus pentoxide, molecular sieve, and activated carbon.

5. The method according to claim 1, wherein the anhydrous carbon nanotubes are subjected to a secondary drying before use by: placing the anhydrous carbon nanotubes in a reactor under vacuum at 280450 C. for 30300 min.

6. The method according to claim 1, wherein the fluorine gas atmosphere is fluorine gas, or a mixed gas of fluorine gas and an inert gas.

7. The method according to claim 6, wherein the volume percentage of the fluorine gas in the mixed gas is 10%50%.

8. The method according to claim 6, wherein the inert gas is nitrogen gas.

9. The method according to claim 1, wherein the fluorinating is performed for 412 hours.

10. The method according to claim 1, further comprising a purification step: purifying the carbon nanotubes or the anhydrous carbon nanotubes under an H.sub.2 atmosphere at a temperature of 500800 C. for a duration of 510 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a transmission electron micrograph of fluorinated graphene nanoribbons;

(2) FIG. 2 is a view of a contact angle test of fluorinated graphene nanoribbons;

(3) FIG. 3 is Fourier transform infrared spectra of fluorinated graphene nanoribbons; and

(4) FIG. 4 is X-ray photoelectron spectra of fluorinated graphene nanoribbons.

DETAILED DESCRIPTION OF EMBODIMENTS

(5) The present invention provides a method for preparing fluorinated graphene nanoribbons, comprising a step of:

(6) fluorinating an anhydrous carbon nanotube in a fluorine gas atmosphere under a pressure of 0.070 MPa and a temperature of 280450 C. to obtain the fluorinated graphene nanoribbon.

(7) In the present invention, single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes can be used as a raw material of the carbon nanotubes.

(8) In order to ensure the smooth progress of the fluorination process, the carbon nanotubes must be anhydrous. The anhydrous carbon nanotubes are dehydrated preferably by:

(9) placing the carbon nanotubes and a desiccant into a vacuum oven to perform vacuum drying at 80120 C.

(10) The drying is performed for preferably 48 hours.

(11) The desiccant is preferably one or more of anhydrous phosphorus pentoxide, a molecular sieve, and activated carbon.

(12) In the present invention, preferably, the anhydrous carbon nanotubes are subjected to secondary drying before use by: keeping the anhydrous carbon nanotubes in a reactor under vacuum at 280450 C. for 30300 min, then evacuating to vacuum and introducing fluorine gas thereto.

(13) The fluorine gas atmosphere is fluorine gas, or a mixed gas of fluorine gas with an inert gas.

(14) The volume ratio of the fluorine gas in the mixed gas is preferably 10%50%.

(15) The inert gas is preferably nitrogen gas.

(16) The fluorination is performed for preferably 412 hours.

(17) After the fluorination, in the present invention, preferably, the resulting material is dried. The drying is performed for preferably 812 hours.

(18) In the present invention, preferably, the preparation method further comprises a purification operation of: purifying carbon nanotubes or anhydrous carbon nanotubes under an H.sub.2 atmosphere to remove impurities such as oxides therein.

(19) The purification operation on the carbon nanotubes allows the resulting fluorinated graphene nanoribbons to have a less amount of oxygen and to be more homogeneous, thereby improving the subsequent hydrophobic properties thereof.

(20) The purification is performed at a temperature of preferably 500800 C. for a period of preferably 510 hours.

(21) The aforementioned purification operation may be performed after the carbon nanotubes are dried and before the secondary drying; or after the secondary drying; or before the carbon nanotubes are dried, and is not particularly limited in the present invention.

(22) The method provided in the present invention is operationally simple, and has a wide variety of raw material sources, low cost, and high production which can reach up to tens of milligrams and even up to hundreds of grams; moreover, the method has simple post-treatment, and can produce fluorinated graphene nanoribbons by a one-step reaction. The prepared fluorinated graphene nanoribbons have very good superhydrophobic properties and chemical stability, and thus can be applied into the anti-icing and other fields, having a very good application prospect.

(23) Hereinafter, the method for preparing fluorinated graphene nanoribbons of the present invention will be described in detail in combination with examples in order to further illustrate the present invention.

Example 1

(24) (1) 10 mg of single-walled carbon nanotubes were placed into a tube furnace, and H.sub.2 was introduced thereto to perform purification at 500 C. for 5 hours.

(25) (2) 10 mg of the purified single-walled carbon nanotubes were placed into a vacuum oven at 100 C., with anhydrous phosphorus pentoxide being placed at the bottom of the vacuum oven. After 4 hours, the resultant was taken out and sealed until use.

(26) (3) 10 mg of the dried single-walled carbon nanotubes obtained in (2) were placed into a reactor and evacuated to vacuum. After the reactor was heated to a reaction temperature of 300 C., it was maintained at this temperature for 240 min, and then evacuated to vacuum. A mixed gas of 20% fluorine gas with nitrogen gas was introduced thereto up to 0.07 MPa, to perform a reaction for 4 hours.

(27) (4) The product obtained in (3) was placed into a vacuum oven and dried for 10 hours, to obtain 8.3 mg of fluorinated graphene nanoribbons having a fluorine-to-carbon ratio of 0.97.

(28) The microstructure of the prepared fluorinated graphene nanoribbons was characterized by using transmission electron microscopy. FIG. 1 is a transmission electron micrograph of the fluorinated graphene nanoribbons. As can be seen from FIG. 1, highly uniform fluorinated graphene nanoribbons are prepared in the present invention.

(29) The fluorinated graphene nanoribbons were tested for the contact angle. FIG. 2 is a view of a contact angle test thereof. As can be seen from FIG. 2, the contact angle of the fluorinated graphene nanoribbons was 1702, demonstrating that the fluorinated graphene nanoribbons have very good superhydrophobic properties.

(30) The fluorinated graphene nanoribbons were also tested for the infrared absorption, and the results are shown in FIG. 3. FIG. 3 is infrared absorption spectra of the fluorinated graphene nanoribbon, in which, from top to bottom and sequentially, curve a is for carbon tubes fluorinated at 300 C., curve b is for carbon tubes fluorinated at 280 C., curve c is for carbon tubes fluorinated at 250 C., and curve d is for carbon tubes fluorinated at 200 C. As can be seen from FIG. 3, a C=C absorption peak appears at 1530, and at 300 C., the carbon tubes are cut apart and this peak disappears.

(31) The fluorinated graphene nanoribbons were subjected to XPS analysis, and the results are shown in FIG. 4. FIG. 4 is X-ray photoelectron spectra of the fluorinated graphene nanoribbon. As can be seen from FIG. 4, the fluorinated graphene nanoribbons prepared in the present invention contain C, O, and F elements.

Example 2

(32) (1) 50 mg of single-walled carbon nanotubes were placed into a tube furnace, and H.sub.2 was introduced thereto to perform purification at 500 C. for 5 hours.

(33) (2) 50 mg of the purified single-walled carbon nanotubes were placed into a vacuum oven at 90 C., with anhydrous phosphorus pentoxide being placed at the bottom of the vacuum oven. After 6 hours, the resultant was taken out and sealed until use.

(34) (3) 50 mg of the dried single-walled carbon nanotubes obtained in (2) were placed into a reactor and evacuated to vacuum. After the reactor was heated to a reaction temperature of 320 C., it was maintained at this temperature for 240 min, and then evacuated to vacuum. A mixed gas of 20% fluorine gas with nitrogen gas was introduced thereto up to 0 MPa, to perform a reaction for 4 hours.

(35) (4) The product obtained in (3) was placed into a vacuum oven and dried for 10 hours, to obtain 42.6 mg of fluorinated graphene nanoribbons having a fluorine-to-carbon ratio of 1.08.

Example 3

(36) (1) 12 mg of double-walled carbon nanotubes were placed into a vacuum oven at 100 C., with anhydrous phosphorus pentoxide being placed at the bottom of the vacuum oven. After 6 hours, the resultant was taken out and sealed until use.

(37) (2) 12 mg of the dried double-walled carbon nanotubes obtained in (1) were placed into a reactor and evacuated to vacuum. After the reactor was heated to a reaction temperature of 350 C., it was maintained at this temperature for 240 min, and then evacuated to vacuum. A mixed gas of 20% fluorine gas with nitrogen gas was introduced thereto up to 0 MPa, to perform a reaction for 5 hours.

(38) (3) The product obtained in (2) was placed into a vacuum oven and dried for 10 hours, to obtain 10.2 mg of fluorinated graphene nanoribbons having a fluorine-to-carbon ratio of 0.87.

Example 4

(39) (1) 40 mg of double-walled carbon nanotubes were placed into a tube furnace, and H.sub.2 was introduced thereto to perform purification at 700 C. for 5 hours.

(40) (2) 40 mg of the purified double-walled carbon nanotubes were placed into a vacuum oven at 100 C., with anhydrous phosphorus pentoxide being placed at the bottom of the vacuum oven. After 5 hours, the resultant was taken out and sealed until use.

(41) (3) 40 mg of the dried double-walled carbon nanotubes obtained in (2) were placed into a reactor and evacuated to vacuum. After the reactor was heated to a reaction temperature of 380 C., it was maintained at this temperature for 300 min, and then evacuated to vacuum. A mixed gas of 20% fluorine gas with nitrogen gas was introduced thereto up to 0 MPa, to perform a reaction for 6 hours.

(42) (4) The product obtained in (3) was placed into a vacuum oven and dried for 10 hours, to obtain 33.2 mg of fluorinated graphene nanoribbons having a fluorine-to-carbon ratio of 0.96.

Example 5

(43) (1) 10 mg of multi-walled carbon nanotubes were placed into a vacuum oven at 100 C., with anhydrous phosphorus pentoxide being placed at the bottom of the vacuum oven. After 6 hours, the resultant was taken out and sealed until use.

(44) (2) 10 mg of the dried multi-walled carbon nanotubes obtained in (1) were placed into a reactor and evacuated to vacuum. After the reactor was heated to a reaction temperature of 450 C., it was maintained at this temperature for 300 min, and then evacuated to vacuum. A mixed gas of 20% fluorine gas with nitrogen gas was introduced thereto up to 0 MPa, to perform a reaction for 6 hours.

(45) (3) The product obtained in (2) was placed into a vacuum oven and dried for 10 hours, to obtain 7.8 mg of fluorinated graphene nanoribbons having a fluorine-to-carbon ratio of 0.82.

(46) As can be seen from the above examples, in the present invention, fluorinated graphene nanoribbons can be prepared by only one step, and the preparation method is simple.

(47) The foregoing description of the examples is provided merely to help understanding the method of the present invention and the core idea thereof. It should be pointed out that those skilled in the art can also make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.