CN106335890A - Preparation method of phosphorus-doped graphene - Google Patents
Preparation method of phosphorus-doped graphene Download PDFInfo
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- CN106335890A CN106335890A CN201510323544.6A CN201510323544A CN106335890A CN 106335890 A CN106335890 A CN 106335890A CN 201510323544 A CN201510323544 A CN 201510323544A CN 106335890 A CN106335890 A CN 106335890A
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Abstract
The invention relates to a preparation method of phosphorus-doped graphene, and mainly solves the problems of high reaction temperature and high equipment requirement in existing phosphorus-doped graphene preparation. The method provided by the invention comprises the steps of: a) subjecting graphite oxide to ultrasonic peeling in water to obtain a graphene oxide solution; b) mixing the graphene oxide solution with a phosphorous-containing compound, conducting ultrasonic treatment to disperse and mix the substances evenly, thus obtaining a mixture; and c) carrying out hydrothermal reaction on the mixture, thus obtaining the phosphorus-doped graphene. The technical scheme involved in the invention well solves the problems, and can be used for industrial production of phosphorus-doped graphene.
Description
Technical field
The present invention relates to a kind of preparation method of phosphorus doping Graphene.
Background technology
Graphene is with sp by carbon atom2Hybridized orbit forms the two dimensional crystal of hexagonal network structure
Material, has very excellent performance, as high electron mobility, good thermal conductivity, printing opacity
Property and good stability, can be applicable to semi-conducting material, composite, battery electrode material,
The fields such as hydrogen storage material, field emmision material and hypersensor.Doping is to change Graphene electricity
Minor structure and the effective way of chemical property.The graphene-doped lattice of heteroatom, not only can have
The introducing band gap of effect, and the defect of Graphene and the reactivity of local can be increased, thus producing
Raw many new functions.Research finds that nitrogen, boron or element sulphur being capable of graphene-doped lattices effectively
Change its performance, and the research to other element dopings is relatively fewer.
Theoretically P elements are a kind of potential doped chemicals, but phosphorus atoms and carbon atom radius
Difference is more, therefore P elements are not easy to graphene-doped lattice.Document cn201210526363.x
Disclose a kind of preparation method of phosphorus doping Graphene, it is by graphite oxide and organic phosphine compound
Mixture, in 600～1100 DEG C of high-temperature calcinations, realizes reduction and the doping of graphite oxide, but the method
Reaction temperature is high, and equipment requirement is harsh, relatively costly, is unfavorable for realizing large-scale production.Document
Cn201410298769.6 discloses a kind of phosphorus doping Graphene hydrogen-peroxide reduction catalysis of no metal
The preparation method of agent, Graphene and triphenylphosphine are synthesized out phosphorus doping at 900～1000 DEG C by it
Graphene, the method reaction temperature is high, and so that production cost is raised with Graphene for raw material, limits
The popularization of its practical application.
Content of the invention
The technical problem to be solved is that prior art has the preparation reaction of phosphorus doping Graphene
Temperature height and the high problem of equipment requirement, provide a kind of preparation method of new phosphorus doping Graphene.
The method can be used for preparation of industrialization phosphorus doping Graphene, have that reaction temperature is low, equipment simple,
The advantage being easy to industry amplification.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of phosphorus doping stone
The preparation method of black alkene, comprises the following steps:
A) the ultrasonic stripping in water by graphite oxide, obtains graphene oxide solution；
B) described graphene oxide solution and phosphorus-containing compound are mixed, ultrasonically treated make it disperse to mix
Close uniformly, obtain mixture；
C) described mixture, through hydro-thermal reaction, obtains final product described phosphorus doping Graphene.
It is preferable that the ultrasonic splitting time of step a) is 0.5～2 hour in technique scheme.
It is preferable that the concentration of described graphene oxide solution is 0.1～7 milli in technique scheme
Grams per milliliter.It is highly preferred that the concentration of described graphene oxide solution is 0.5～5 mg/ml.
It is preferable that described phosphorus-containing compound is phosphoric acid, pyrophosphoric acid, inclined phosphorus in technique scheme
At least one in acid or phosphorous acid.
In technique scheme it is preferable that hydrothermal temperature be 150～230 DEG C, the time be 5～
24 hours.It is highly preferred that hydrothermal temperature is 180～210 DEG C, the time is 8～20 hours.
It is preferable that oxygen in described phosphorus-containing compound and graphene oxide solution in technique scheme
The weight of graphite alkene is than for 1～50.
It is preferable that step b) sonication treatment time is 5～30 minutes in technique scheme.
In the present invention, with graphite oxide as presoma, homodisperse oxygen is obtained by ultrasonic stripping
Graphite alkene solution；Phosphorus-containing compound phosphoric acid, pyrophosphoric acid, metaphosphoric acid or phosphorous acid are in hydro-thermal mistake
In journey, graphene oxide is reduced into Graphene, realizes the element sulphur doping of Graphene simultaneously.
Phosphorus-containing compound phosphoric acid, pyrophosphoric acid, metaphosphoric acid or phosphorous acid hydrolyze product in water-heat process
Raw hydrogen sulfide and NaOH or potassium hydroxide, the two is respectively provided with good reproducibility, will aoxidize
Graphene is reduced into Graphene；Hydrolyze the hydrogen sulfide producing as sulphur source, in redox graphene
While realize Graphene element sulphur doping.
Compared with prior art, hydrothermal process temperature of the present invention is low, and equipment is simple,
Without the high-temperature services such as chemical vapor deposition stove or high temperature heat treatment furnace, low production cost；Liquid phase water
Thermal process treating capacity is big it is easy to scale is amplified, and can be applicable to the industrial metaplasia of phosphorus doping Graphene
In product, meet the throughput requirements to phosphorus doping Graphene for the field such as absorption, catalysis and energy storage material,
Achieve preferable technique effect.
Brief description
Fig. 1 is native graphite, graphite oxide and phosphorus doping Graphene in the present invention [embodiment 1]
X-ray diffraction composes (xrd) figure.Wherein, a is native graphite, and b is graphite oxide, and c is phosphorus
Doped graphene.
The SEM of the phosphorus doping Graphene that Fig. 2 is prepared for the present invention [embodiment 1]
(sem) figure.
The transmission electron microscope of the phosphorus doping Graphene that Fig. 3 is prepared for the present invention [embodiment 1]
(tem) figure.
The x-ray light of p 2p in the phosphorus doping Graphene that Fig. 4 is prepared for the present invention [embodiment 1]
Electron spectrum (xps) figure.
Fig. 1 is that the x-ray diffraction of native graphite, graphite oxide and phosphorus doping Graphene composes (xrd)
Figure.Phosphorus doping Graphene is belonging at 2 θ=26.6 ° of graphite, and 2 θ=10.8 ° of graphite oxide
Place, all no obvious xrd diffraction maximum, there is Graphene x-ray diffraction feature.
Fig. 2 is SEM (sem) figure of phosphorus doping Graphene.Transparent spun silk shape stone
Black alkene lamella is stacked with, and forms the graphene particles of bulk multi-hole.
Fig. 3 is transmission electron microscope (tem) figure of phosphorus doping Graphene, in electron beam irradiation
A few near-transparent of lower graphene film, surface assumes intrinsic gauffer.
Fig. 4 is x-ray photoelectron spectroscopy (xps) figure of p 2p in phosphorus doping Graphene, wherein
At 132.7ev, peak corresponds to p-c key, and at 133.8ev, peak corresponds to p-o key, shows part phosphorus
Atom has replaced carbon atom and has entered in Graphene lattice.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
[embodiment 1]
By 300 milligrams of graphite oxides, in 100 ml deionized water, ultrasonic stripping is prepared into for 1.5 hours
To 3 mg/ml graphene oxide solution, then add 3 grams of phosphoric acid wherein, ultrasonic 15 minutes
Uniformly, in 200 DEG C of hydro-thermal reactions 15 hours, excess was gone in deionized water eccysis after cooling to dispersion mixing
Phosphorus-containing compound, that is, be obtained phosphorus doping Graphene, wherein the atomic percentage conc of phosphorus be 1.06%.
Prepared phosphorus doping Graphene x-ray diffraction composes (xrd) figure, SEM
(sem) figure, transmission electron microscope (tem) figure, and x-ray photoelectron spectroscopy (xps)
Figure is shown in accompanying drawing, shows that phosphorus atoms have replaced carbon atom and entered in Graphene lattice.
[embodiment 2]
By 50 milligrams of graphite oxides, in 100 ml deionized water, ultrasonic stripping prepares for 1 hour
0.5 mg/ml graphene oxide solution, then wherein add 2.5 grams of phosphoric acid, ultrasonic 10 points
Clock dispersion mixing uniformly, in 180 DEG C of hydro-thermal reactions 20 hours, went by deionized water eccysis after cooling
The phosphorus-containing compound of amount, that is, be obtained phosphorus doping Graphene, the wherein atomic percentage conc of phosphorus is 0.93%.
Prepared phosphorus doping Graphene x-ray diffraction composes (xrd) figure, SEM
(sem) figure, transmission electron microscope (tem) figure, and x-ray photoelectron spectroscopy (xps)
Figure is similar to [embodiment 1].
[embodiment 3]
By 500 milligrams of graphite oxides, in 100 ml deionized water, ultrasonic stripping is prepared into for 2 hours
To 5 mg/ml graphene oxide solution, then add 0.5 gram of phosphoric acid wherein, ultrasonic 10 points
Clock dispersion mixing uniformly, in 210 DEG C of hydro-thermal reactions 8 hours, went by deionized water eccysis after cooling
The phosphorus-containing compound of amount, that is, be obtained phosphorus doping Graphene, the wherein atomic percentage conc of phosphorus is 0.74%.
Prepared phosphorus doping Graphene x-ray diffraction composes (xrd) figure, SEM
(sem) figure, transmission electron microscope (tem) figure, and x-ray photoelectron spectroscopy (xps)
Figure is similar to [embodiment 1].
[embodiment 4]
By 200 milligrams of graphite oxides, in 100 ml deionized water, ultrasonic stripping is prepared into for 1.5 hours
To 2 mg/ml graphene oxide solution, then add 4 grams of metaphosphoric acids wherein, ultrasonic 25
Uniformly, in 200 DEG C of hydro-thermal reactions 12 hours, deionized water eccysis after cooling was gone for minute dispersion mixing
Excessive phosphorus-containing compound, that is, be obtained phosphorus doping Graphene, and the atomic percentage conc of wherein phosphorus is
1.21%.
Prepared phosphorus doping Graphene x-ray diffraction composes (xrd) figure, SEM
(sem) figure, transmission electron microscope (tem) figure, and x-ray photoelectron spectroscopy (xps)
Figure is similar to [embodiment 1].
Claims (9)
1. a kind of preparation method of phosphorus doping Graphene, comprises the following steps:
A) the ultrasonic stripping in water by graphite oxide, obtains graphene oxide solution；
B) described graphene oxide solution and phosphorus-containing compound are mixed, ultrasonically treated make it disperse to mix
Close uniformly, obtain mixture；
C) described mixture, through hydro-thermal reaction, obtains final product described phosphorus doping Graphene.
2. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that step
A) ultrasonic splitting time is 0.5～2 hour.
3. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that described
The concentration of graphene oxide solution is 0.1～7 mg/ml.
4. according to claim 3 the preparation method of phosphorus doping Graphene it is characterised in that described
The concentration of graphene oxide solution is 0.5～5 mg/ml.
5. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that described
Phosphorus-containing compound is at least one in phosphoric acid, pyrophosphoric acid, metaphosphoric acid or phosphorous acid.
6. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that hydro-thermal
Reaction temperature is 150～230 DEG C, and the time is 5～24 hours.
7. according to claim 6 the preparation method of phosphorus doping Graphene it is characterised in that hydro-thermal
Reaction temperature is 180～210 DEG C, and the time is 8～20 hours.
8. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that described
The weight of phosphorus-containing compound and graphene oxide in graphene oxide solution is than for 1～50.
9. according to claim 1 the preparation method of phosphorus doping Graphene it is characterised in that step
B) sonication treatment time is 5～30 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381545A (en) * | 2017-07-20 | 2017-11-24 | 沈阳化工大学 | A kind of preparation method of phosphorous functionalization graphene |
| CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
| CN109524171A (en) * | 2018-10-30 | 2019-03-26 | 天津市职业大学 | A kind of preparation method of graphene and phosphor codoping tin oxide transparent conductive film |
| CN116654919A (en) * | 2023-05-08 | 2023-08-29 | 苏州大学 | Preparation method of phosphorus-doped graphene composite material with adjustable oxidation degree |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381545A (en) * | 2017-07-20 | 2017-11-24 | 沈阳化工大学 | A kind of preparation method of phosphorous functionalization graphene |
| CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
| CN108493424B (en) * | 2018-04-11 | 2020-11-03 | 中科锂电新能源有限公司 | Nitrogen, phosphorus and sulfur co-doped composite carbon material, preparation method thereof and lithium ion battery |
| CN109524171A (en) * | 2018-10-30 | 2019-03-26 | 天津市职业大学 | A kind of preparation method of graphene and phosphor codoping tin oxide transparent conductive film |
| CN116654919A (en) * | 2023-05-08 | 2023-08-29 | 苏州大学 | Preparation method of phosphorus-doped graphene composite material with adjustable oxidation degree |
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