CN106044748A - Method for preparing boron-doped graphene - Google Patents
Method for preparing boron-doped graphene Download PDFInfo
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- CN106044748A CN106044748A CN201610319660.5A CN201610319660A CN106044748A CN 106044748 A CN106044748 A CN 106044748A CN 201610319660 A CN201610319660 A CN 201610319660A CN 106044748 A CN106044748 A CN 106044748A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2002/82—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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a method for preparing boron-doped graphene. The method comprises the steps: introducing nitrogen gas into an ice-bath tetrahydrofuran solvent, adding elemental iodine and sodium borohydride into the solvent, and carrying out mixing and stirring for 2 to 4 hours, so as to obtain a mixed solution; dispersing graphene oxide in a tetrahydrofuran solvent through ultrasonic dispersion, then, adding the obtained solution into the mixed solution, and carrying out a continuous reaction for 2 to 6 days at the temperature of 25 DEG C to 120 DEG C; and after the reaction is stopped, carrying out normal-pressure filtration, carrying out vacuum filtration, carrying out repeated washing by using tetrahydrofuran and water sequentially, and finally, carrying out freeze drying, thereby obtaining the boron-doped graphene, of which the doping content of boron is 1.5% to 3.5%. According to the method, the boron-doped graphene material is prepared through adopting sodium borohydride as a boron source, the method is simple in steps, the cycle of growth is short, the raw materials are wide in source and low in price, the production cost is low, scale production can be achieved, and the economic benefit is good.
Description
Technical field
The present invention relates to Graphene manufacture field, relate more specifically to the preparation method of a kind of boron doped graphene.
Background technology
Graphene has mechanical performance, heat conductivility and the electric conductivity of excellence, plays the work that can not be substituted at a lot of aspects
With, but itself dissolubility in a lot of polymer is poor, and dispersibility in the base also has much room for improvement, in order to improve graphite
Alkene range of application in several cases, needs to be modified it, its performance of modulation and structure.Research shows, at Graphene
Other element of middle doping can improve physical property and the chemical property of Graphene.Owing to boron atom has stronger electrophilic energy
Power, can replace part carbon atom and not change the structure of Graphene, so boron doped graphene is in lithium ion battery, catalysis
Have a wide range of applications in field.For Graphene, boron is a kind of most suitable dopant.The atomic radius of boron is very
Close to carbon atom, after doping, Graphene does not haves the biggest structural aberration；Few 1 electronics of boron atom ratio carbon atom, passes through boron
Doping can realize Graphene by semimetal to the conversion of quasiconductor, make Graphene become p-type semiconductor.Even more important
It is that the incorporation of boron can change the electrical properties of Graphene effectively, is conducive to preparing the excellent electronic device of different performance.
In existing method, CVD and thermal annealing method use boric acid and diboron trioxide as boron source, need higher reaction temperature, and
The relatively low solwution method of temperature uses borine oxolane as boron source, although reaction temperature is relatively low, but boron source price is higher, no
It is suitable for large-scale production and application.
Summary of the invention
It is an object of the invention to provide a kind of low cost, the preparation method of low temperature boron doped graphene.
The technical solution used in the present invention is as follows:
A kind of preparation method of boron doped graphene, it is characterised in that: logical nitrogen in ice bath tetrahydrofuran solvent, by iodine
Simple substance and sodium borohydride mix by a certain percentage, add mixture in ice bath tetrahydrofuran solvent, are sufficiently stirred for reacting 2-4
Hour obtain mixed liquor；Enough Graphene tetrahydrofuran solutions are added to iodo-sodium borohydride reaction mixture, is heated to
Continuing reaction 2-6 days, after question response terminates, natural filtration at 25 DEG C-120 DEG C, sucking filtration, successively with oxolane and water washing number
Secondary, it is dried, obtains boron doped graphene material.The preparation method of described boron doped graphene, it is characterised in that: iodine list used
The mass ratio of matter and sodium borohydride is 1:2-3, sodium borohydride excessive response.
The preparation method of described boron doped graphene, it is characterised in that: the response time of elemental iodine and sodium borohydride is
2.5 hour.
The preparation method of described boron doped graphene, it is characterised in that: elemental iodine used and the mass ratio of sodium borohydride
For 1:2.
The preparation method of described boron doped graphene, it is characterised in that: graphene oxide/oxolane dispersion liquid dense
Degree is 0.5-1.5mg/mL.
The preparation method of described boron doped graphene, it is characterised in that: graphene oxide/oxolane dispersion liquid dense
Degree is 1mg/mL.
The preparation method of described boron doped graphene, it is characterised in that: enough Graphene tetrahydrofuran solutions are added
Enter reacting by heating to iodo-sodium borohydride reaction mixture, the optimal reaction temperature of heating 100 DEG C, optimum reacting time 4 days.
The preparation method of described boron doped graphene, it is characterised in that: the drying mode of end product is lyophilization.
The Graphene boron doping amount that the inventive method is obtained is 3.5%.
The present invention relates to the preparation method of boron doped graphene, the inventive method obtains boron doping stone by a step solwution method
Ink alkene.The method comprise the steps that logical nitrogen in ice bath tetrahydrofuran solvent, add elemental iodine and sodium borohydride mix and blend
Within 2-4 hour, obtain mixed liquor；By graphene oxide ultrasonic disperse in tetrahydrofuran solvent, then it is added into aforementioned mixing
In liquid, 25 DEG C-120 DEG C are continued reaction 2-6 days.After question response terminates, natural filtration, sucking filtration, wash for several times with oxolane,
Rear dry.
The ratio of described sodium borohydride and elemental iodine material amount is 1:2 and 1:3, particularly preferably 1:2.
In a preferred embodiment, the concentration of described graphene oxide/oxolane dispersion liquid is 0.5-1.5mg/
ML, particularly preferably 1mg/mL.
In a preferred embodiment, the temperature of described heating is 25 DEG C-120 DEG C, particularly preferably 100 DEG C.
In a preferred embodiment, the described time continuing reaction is 2-6 days, particularly preferably 4 days.
In a preferred embodiment, described drying mode is that vacuum and heating drying, normal heating are dried and freezing
It is dried, particularly preferably lyophilization.
Beneficial effect:
The present invention, by using a step solwution method to prepare boron doped graphene, obtains not by changing reaction temperature and time
Same boron doping ratio, and the inventive method step is simple, and growth cycle is short, and cost of material is cheap, and production cost is low, can be suitable
Profit accesses existing estate planning and production.Additionally, prepare product photoelectric device, photocatalysis, bio-sensing, fuel cell,
The fields such as lithium ion battery have shown wide prospect.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the boron doped graphene of the embodiment of the present invention 1 preparation；
Fig. 2 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 1 preparation；
Fig. 3 is the Raman scanning spectra of the boron doped graphene of the embodiment of the present invention 1 preparation；
Fig. 4 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 2 preparation；
Fig. 5 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 3 preparation；
Fig. 6 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 4 preparation；
Fig. 7 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 5 preparation；
Fig. 8 is the x-ray photoelectron spectroscopy figure of the boron doped graphene of the embodiment of the present invention 6 preparation.
Detailed description of the invention
The present invention will be further described below, it should be appreciated that these embodiments are only used for citing by the way of embodiment
The purpose of the present invention is described rather than limits the scope of the present invention.
Embodiment 1
The preparation method of a kind of boron doped graphene, specifically comprises the following steps that
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2.5 hours；By the single-layer graphene oxide ultrasonic disperse of 2 times of sodium borohydride quality at tetrahydrochysene
In THF solvent, concentration is 1mg/mL, then is added into aforementioned mixed liquor, and now solution presents dark-brown, 100 DEG C of continuation
React 4 days, after solution colour is black, natural filtration, sucking filtration, washs for several times with oxolane, last lyophilization.
The product obtained is carried out hom ology, the wherein transmission of the boron doped graphene of the present embodiment 1 preparation
Electronic Speculum figure is as shown in Figure 1.It is clear from fig. 1 that, the present embodiment 1 boron doped with oxygen functionalized graphene still remains original oxygen
The ultra-thin two-dimension layer structure of functionalized graphene, but there are more folding and bending.This is likely due in boron doped process
In, create the electron deficiency center of boron, under the effect of Coulomb repulsion, smooth two-dimensional layered structure bends and folds,
On the other hand, the introducing of boron atom makes Graphene create more defect sites, under capillary effect, and carbon plate layer meeting
More bending and folding.Fig. 2 is the XPS spectrum figure of the boron doped graphene that embodiment 1 obtains, and that 192eV is corresponding is the 1s of B
Peak, illustrates that in boron doped with oxygen functionalized graphene, boron is successfully doped in Graphene, and doping is 3.5% (being shown in Table 1).Fig. 3 is
The Raman spectrum of embodiment 1 boron doped graphene, due to the doping of boron atom, boron doping surface of graphene oxide creates more
Avtive spot, be calculated boron doped with oxygen functionalized graphene ID/IG=1.18, higher than the I of graphene oxideD/IG(1.14)。
Embodiment 2
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2.5 hours；By the single-layer graphene oxide ultrasonic disperse of 3 times of sodium borohydride quality at tetrahydrochysene
In THF solvent, concentration is 1.5mg/mL, then is added into aforementioned mixed liquor, and now solution presents dark-brown, and 100 DEG C are continued
Continuous reaction 4 days.After solution colour is black, natural filtration, sucking filtration, washs for several times with oxolane, last lyophilization.Logical
Cross XPS spectrum (Fig. 4) and illustrate that boron is successfully doped in Graphene, and doping is 2.95%.
Embodiment 3
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2.5 hours；By the single-layer graphene oxide ultrasonic disperse of 2 times of sodium borohydride quality at tetrahydrochysene
In THF solvent, concentration is 1.0mg/mL, then is added into aforementioned mixed liquor, and now solution presents dark-brown, and 25 DEG C are continued
Continuous reaction 4 days.Subsequently, natural filtration, sucking filtration, washs for several times with oxolane, last lyophilization.Fig. 5 is that embodiment 3 obtains
The XPS spectrum figure of boron doped graphene, illustrate boron doped with oxygen functionalized graphene is successfully doped in Graphene, and doping be
1.57%.
Embodiment 4
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2.5 hours；By the single-layer graphene oxide ultrasonic disperse of 2 times of sodium borohydride quality at tetrahydrochysene
In THF solvent, concentration is 1.0mg/mL, then is added into aforementioned mixed liquor, and now solution presents dark-brown, and 60 DEG C are continued
Continuous reaction 4 days, solution presents Dark grey.After question response terminates, natural filtration, sucking filtration, wash for several times with oxolane, the coldest
Lyophilizing is dry.Fig. 6 is the XPS spectrum figure of the boron doped graphene that embodiment 4 obtains, and illustrates successfully to mix in boron doped with oxygen functionalized graphene
Miscellaneous enter in Graphene, and doping is 1.82%.
Embodiment 5
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2.5 hours；By the single-layer graphene oxide ultrasonic disperse of 2 times of sodium borohydride quality at tetrahydrochysene
In THF solvent, concentration is 1.0mg/mL, then is added into aforementioned mixed liquor, and 100 DEG C are continued reaction 2 days, and solution presents
Dark grey.After question response terminates, natural filtration, sucking filtration, washs for several times with oxolane, last lyophilization.Fig. 7 is embodiment
The XPS spectrum figure of the 5 boron doped graphenes obtained, illustrates successfully to be doped in Graphene in boron doped with oxygen functionalized graphene, and mixes
Miscellaneous amount is 2.02%.
Embodiment 6
In ice bath tetrahydrofuran solvent, logical nitrogen, adds elemental iodine and the sodium borohydride ratio with thing mass ratio as 1:2
Mix and blend obtains mixed liquor in 2 hours；By the single-layer graphene oxide ultrasonic disperse of 2 times of sodium borohydride quality at tetrahydrochysene furan
Muttering in solvent, concentration is 1.0mg/mL, then is added into aforementioned mixed liquor, and 100 DEG C are continued reaction 2 days, and solution presents deeply
Lycoperdon polymorphum Vitt.After question response terminates, natural filtration, sucking filtration, washs for several times with oxolane, last lyophilization.Fig. 7 is embodiment 5
The XPS spectrum figure of the boron doped graphene obtained, illustrates successfully to be doped in Graphene in boron doped with oxygen functionalized graphene, and doping
Amount is 1.97%.
In the boron doped graphene finished product that embodiment 1 obtains, the percentage composition of each component is shown in Table 1.
Table 1
Can be illustrated that in boron doped with oxygen functionalized graphene, boron is successfully doped in Graphene by table 1, and doping is
3.5%.
Claims (8)
1. the preparation method of a boron doped graphene, it is characterised in that: logical nitrogen in ice bath tetrahydrofuran solvent, by iodine list
Matter and sodium borohydride mix by a certain percentage, add mixture in ice bath tetrahydrofuran solvent, are sufficiently stirred for reacting 2-4 little
Time obtain mixed liquor；Enough Graphene tetrahydrofuran solutions are added to iodo-sodium borohydride reaction mixture, is heated to 25
Continuing reaction 2-6 days, after question response terminates, natural filtration at DEG C-120 DEG C, sucking filtration, successively with oxolane and water washing number
Secondary, it is dried, obtains boron doped graphene material.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that elemental iodine used and hydroboration
The mass ratio of sodium is 1:2-3, sodium borohydride excessive response.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that: elemental iodine and sodium borohydride
Response time is 2.5 hours.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that elemental iodine used and hydroboration
The mass ratio of sodium is 1:2.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that: graphene oxide/tetrahydrochysene furan
The concentration of dispersion liquid of muttering is 0.5-1.5 mg/mL.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that: graphene oxide/tetrahydrochysene furan
The concentration of dispersion liquid of muttering is 1 mg/mL.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that: by enough Graphene tetrahydrochysenes
Reacting by heating in tetrahydrofuran solution addition extremely iodo-sodium borohydride reaction mixture, the optimal reaction temperature of heating 100 DEG C, the most instead
Between Ying Shi 4 days.
The preparation method of boron doped graphene the most according to claim 1, it is characterised in that: the drying mode of end product
For lyophilization.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109835892A (en) * | 2018-12-13 | 2019-06-04 | 华侨大学 | A kind of preparation method of Boron doped semiconductor graphite |
| CN110760081A (en) * | 2019-10-22 | 2020-02-07 | 甘肃微纳科技有限公司 | Preparation method of graphene wave-absorbing patch |
| CN111377457A (en) * | 2020-03-22 | 2020-07-07 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN112076738A (en) * | 2020-09-01 | 2020-12-15 | 齐鲁工业大学 | Boron-doped defective zinc oxide and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787488A (en) * | 2012-07-30 | 2012-11-21 | 哈尔滨工业大学 | Method for preparing graphene oxide grafting surface modification carbon fiber |
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2016
- 2016-05-12 CN CN201610319660.5A patent/CN106044748A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787488A (en) * | 2012-07-30 | 2012-11-21 | 哈尔滨工业大学 | Method for preparing graphene oxide grafting surface modification carbon fiber |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109835892A (en) * | 2018-12-13 | 2019-06-04 | 华侨大学 | A kind of preparation method of Boron doped semiconductor graphite |
| CN110760081A (en) * | 2019-10-22 | 2020-02-07 | 甘肃微纳科技有限公司 | Preparation method of graphene wave-absorbing patch |
| CN110760081B (en) * | 2019-10-22 | 2022-04-19 | 甘肃微纳科技有限公司 | Preparation method of graphene wave-absorbing patch |
| CN111377457A (en) * | 2020-03-22 | 2020-07-07 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN111377457B (en) * | 2020-03-22 | 2022-02-08 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN112076738A (en) * | 2020-09-01 | 2020-12-15 | 齐鲁工业大学 | Boron-doped defective zinc oxide and preparation method and application thereof |
| CN112076738B (en) * | 2020-09-01 | 2022-11-11 | 齐鲁工业大学 | Boron-doped defective zinc oxide and preparation method and application thereof |
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Application publication date: 20161026 |