CN106276865A - The method producing phosphorus doping Graphene - Google Patents
The method producing phosphorus doping Graphene Download PDFInfo
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- CN106276865A CN106276865A CN201510324797.5A CN201510324797A CN106276865A CN 106276865 A CN106276865 A CN 106276865A CN 201510324797 A CN201510324797 A CN 201510324797A CN 106276865 A CN106276865 A CN 106276865A
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Abstract
The present invention relates to a kind of method producing phosphorus doping Graphene, mainly there is phosphorus doping Graphene and prepare reaction temperature height, response time length, equipment requirements height, cost height, uneven problem of adulterating in solution prior art.The present invention is comprised the following steps by employing: a) by the most ultrasonic for graphite oxide stripping, obtain graphene oxide solution；B) described graphene oxide solution and phosphorus-containing matter being mixed, supersound process makes its dispersion mixing uniform, obtains liquid mixture；It is dried described liquid mixture, obtains solid mixture；C) being processed by described solid mixture microwave exposure under inert gas shielding, be cooled to room temperature, the technical scheme obtaining described phosphorus doping Graphene preferably resolves this problem, can be used in the commercial production of phosphorus doping Graphene.
Description
Technical field
The present invention relates to a kind of method producing phosphorus doping Graphene.
Background technology
Graphene is with sp by carbon atom2The two dimensional crystal of hybrid orbital composition hexagonal network structure
Material, has the most excellent performance, such as high electron mobility, good heat 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 lattice that heteroatom is graphene-doped, not only can have
The introducing band gap of effect, and the defect of Graphene and the reactivity of local can be increased, thus produce
Raw many new functions.Research finds that nitrogen, boron or element sulphur can graphene-doped lattices effectively
Change its performance, and the research to other element doping is relatively fewer.
P elements is a kind of potential doped chemical theoretically, but phosphorus atoms and carbon atom radius
Differ more, therefore P elements is not easy to graphene-doped lattice.Document CN201210526363.X
Disclosing the preparation method of a kind of phosphorus doping Graphene, it is by graphite oxide and organic phosphine compound
Mixture is 600～1100 DEG C of high-temperature calcinations, it is achieved the reduction of graphite oxide and doping, but the method
Need to use high temperature reaction stove, equipment requirements is high, and reaction temperature is high, and the response time is long, and with oxidation
Graphite is raw material, it is impossible to realizes the haptoreaction of its internal graphene planes and triphenylphosphine, therefore produces
In thing, P elements doping is uneven.Document CN201410298769.6 discloses a kind of phosphorus without metal
The preparation method of doped graphene hydrogen-peroxide reduction catalyst, Graphene and triphenylphosphine are existed by it
900～1000 DEG C are synthesized out phosphorus doping Graphene, and the method reaction temperature is high, and the response time is long,
And make production cost raise with Graphene for raw material, limit the popularization of its actual application.
Summary of the invention
The technical problem to be solved is that prior art exists the preparation reaction of phosphorus doping Graphene
Temperature height, response time length, equipment requirements height, cost are high, uneven problem of adulterating, it is provided that
A kind of new method producing phosphorus doping Graphene.The method can be used for preparation of industrialization phosphorus doping stone
Ink alkene, has that reaction temperature is low, the response time is short, equipment is simple, low cost, a uniform doping
Advantage.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of phosphorus that produces is mixed
The method of miscellaneous Graphene, comprises the following steps:
A) by the most ultrasonic for graphite oxide stripping, graphene oxide solution is obtained；
B) described graphene oxide solution and phosphorus-containing matter being mixed, supersound process makes it disperse to mix
Close uniformly, obtain liquid mixture；It is dried described liquid mixture, obtains solid mixture；
C) described solid mixture microwave exposure under inert gas shielding is processed, is cooled to room temperature,
Obtain described phosphorus doping Graphene.
In technique scheme, it is preferable that the ultrasonic splitting time of step a) is 0.5～2 hour.
In technique scheme, it is preferable that step b) sonication treatment time is 5～30 minutes.
In technique scheme, it is preferable that the concentration of described graphene oxide solution is 0.1～7 millis
Grams per milliliter.It is highly preferred that the concentration of described graphene oxide solution is 0.5～5 mg/ml.
In technique scheme, it is preferable that described solvent be water, ethanol, isopropanol, hexamethylene,
Benzene, acetone, oxolane, methyl pyrrolidone, ethyl pyrrolidone, dimethylformamide or
Dimethyl acetylamide.
In technique scheme, it is preferable that described phosphorus-containing compound is triphenylphosphine, triphenyl oxygen
Change phosphine, three (o-tolyl) phosphine, to methyl triphenyl phosphine, tert-butyl diphenyl phosphine, pi-allyl hexichol
Base phosphine, ethyldiphenylphosphine, diphenyl ethyoxyl phosphine, benzyldiphenylphosphine, diphenylcyclo base
Phosphine, isopropyl biphenyl phosphine, diamyl Phenylphosphine, phenyldicyclohexylphosphine, tricyclohexyl phosphine, three
At least one in cyclohexyl phosphine oxide, tert-butyl group dicyclohexylphosphontetrafluoroborate or tribenzyl phosphine.
In technique scheme, it is preferable that microwave exposure processes and carries out in microwave reactor.
In technique scheme, it is preferable that the power of described microwave reactor is 350～1200 watts
Spy, exposure time is 30 seconds～10 minutes.
In technique scheme, it is preferable that described phosphorus-containing compound and oxygen in graphene oxide solution
The weight ratio of functionalized graphene is 1～50.
In technique scheme, it is preferable that described noble gas is in nitrogen, argon or helium
At least one.
In the present invention, with graphite oxide as presoma, obtain homodisperse oxygen by ultrasonic stripping
Functionalized graphene solution；Under microwave exposure effect, the hydroxyl of surface of graphene oxide, carboxyl, carbonyl
The oxygen-containing luminous energy such as base group decomposes rapidly, releases amount of heat, makes system temperature rise rapidly to
500～1000 DEG C, phosphorus-containing matter decomposes becomes the gas of the phosphorus element-containings such as hydrogen phosphide, itself and oxygen
Functionalized graphene reacts, and generates phosphorus doping Graphene while redox graphene.
Compared with prior art, the present invention utilizes the polarity oxygen-containing functional group pair of surface of graphene oxide
Strong from exothermic effect when the strong Absorption of selectivity of microwave and oxygen-containing functional group decompose, it is to avoid
Conventional Convective Heating mode heat transfer rate is slow, the shortcoming of length preheating time, when shortening reaction
Between, decrease energy consumption of reaction；In the present invention phosphorus-containing compound decompose, the reduction of graphene oxide and
Doping is the most quickly carried out, it is not necessary to pre-reduction graphene oxide, and technique is simpler,
Equipment cost and preparation cost are lower；The present invention is by phosphorus-containing compound with graphene oxide in the solution
Mix homogeneously, it is achieved phosphorus-containing compound is fully contacted with graphene oxide plane, it is to avoid oxidation
Graphene planes within graphite granule is difficult to the shortcoming contacted with phosphorus-containing compound, phosphorus unit in product
Element uniform doping, can be applicable in the industrialized production of phosphorus doping Graphene, meets absorption, catalysis
With field throughput requirements to phosphorus doping Graphene such as energy storage materials, achieve preferable technique effect.
Accompanying drawing explanation
Fig. 1 is native graphite, graphite oxide and phosphorus doping Graphene in the present invention [embodiment 1]
X-ray diffraction spectrum (XRD) figure.Wherein, A is native graphite, and B is graphite oxide, and C is phosphorus
Doped graphene.
Fig. 2 is the scanning electron microscope of phosphorus doping Graphene prepared by the present invention [embodiment 1]
(SEM) figure.
Fig. 3 is the transmission electron microscope of phosphorus doping Graphene prepared by the present invention [embodiment 1]
(TEM) figure.
Fig. 4 is the X-ray light of P 2p in phosphorus doping Graphene prepared by the present invention [embodiment 1]
Electron spectrum (XPS) figure.
Fig. 1 is the X-ray diffraction spectrum (XRD) of native graphite, graphite oxide and phosphorus doping Graphene
Figure.Phosphorus doping Graphene is belonging at 2 θ=26.6 ° of graphite, and 2 θ=10.8 ° of graphite oxide
Place, all without obvious XRD diffraction maximum, has Graphene X ray diffracting characteristic.
Fig. 2 is scanning electron microscope (SEM) figure of phosphorus doping Graphene.Transparent spun silk shape stone
Ink alkene lamella is stacked with, and forms the Graphene granule of bulk multi-hole.
Fig. 3 is transmission electron microscope (TEM) figure of phosphorus doping Graphene, at electron beam irradiation
Lower a few near-transparent of graphene film, surface presents intrinsic gauffer.
Fig. 4 is x-ray photoelectron power spectrum (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.
Detailed description of the invention
[embodiment 1]
The ultrasonic stripping in 100 milliliters of ethanol of 300 milligrams of graphite oxides is prepared 3 in 1.5 hours
Mg/ml graphene oxide solution, the most wherein 3 grams of triphenylphosphines of addition, ultrasonic 15 minutes
Dispersion mixing is uniform, is dried to obtain solid mixture；By solid mixture under inert gas shielding,
Power is radiation treatment 1 minute in 1200 watts of microwave reactors, is cooled to room temperature, i.e. prepares phosphorus
Doped graphene, wherein the atomic percentage conc of phosphorus is 1.45%.
Prepare phosphorus doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electron microscope
(SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS)
Figure is shown in accompanying drawing, shows that phosphorus atoms has replaced carbon atom and entered in Graphene lattice.
[embodiment 2]
The ultrasonic stripping in 100 milliliters of ethanol of 50 milligrams of graphite oxides is prepared 0.5 in 1 hour
Mg/ml graphene oxide solution, the most wherein 2.5 grams of triphenylphosphines of addition, ultrasonic 10 points
Clock dispersion mixing is uniform, is dried to obtain solid mixture；By solid mixture in inert gas shielding
Under, power is radiation treatment 10 minutes in 350 watts of microwave reactors, is cooled to room temperature, i.e. makes
Obtaining phosphorus doping Graphene, wherein the atomic percentage conc of phosphorus is 1.77%.
Prepare phosphorus doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electron microscope
(SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS)
Scheme similar to [embodiment 1].
[embodiment 3]
The ultrasonic stripping in 100 milliliters of ethanol of 500 milligrams of graphite oxides is prepared 5 in 2 hours
Mg/ml graphene oxide solution, the most wherein 0.5 gram of triphenylphosphine of addition, ultrasonic 10 points
Clock dispersion mixing is uniform, is dried to obtain solid mixture；By solid mixture in inert gas shielding
Under, power is radiation treatment 3 minutes in 1200 watts of microwave reactors, is cooled to room temperature, i.e. makes
Obtaining phosphorus doping Graphene, wherein the atomic percentage conc of phosphorus is 1.05%.
Prepare phosphorus doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electron microscope
(SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS)
Scheme similar to [embodiment 1].
[embodiment 4]
The ultrasonic stripping in 100 milliliters of isopropanols of 200 milligrams of graphite oxides is prepared for 1.5 hours
2 mg/ml graphene oxide solution, the most wherein 4 grams of tricyclohexyl phosphines of addition, ultrasonic 25
Minute dispersion mixing is uniform, is dried to obtain solid mixture；Solid mixture is protected at noble gas
Protecting down, power is radiation treatment 5 minutes in 1000 watts of microwave reactors, is cooled to room temperature, i.e.
Preparing phosphorus doping Graphene, wherein the atomic percentage conc of phosphorus is 1.11%.
Prepare phosphorus doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electron microscope
(SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS)
Scheme similar to [embodiment 1].
Claims (10)
1. the method producing phosphorus doping Graphene, comprises the following steps:
A) by the most ultrasonic for graphite oxide stripping, graphene oxide solution is obtained；
B) described graphene oxide solution and phosphorus-containing matter being mixed, supersound process makes it disperse to mix
Close uniformly, obtain liquid mixture；It is dried described liquid mixture, obtains solid mixture；
C) described solid mixture microwave exposure under inert gas shielding is processed, is cooled to room temperature,
Obtain described phosphorus doping Graphene.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that step
A) ultrasonic splitting time is 0.5～2 hour, and step b) sonication treatment time is 5～30 minutes.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that described
The concentration of graphene oxide solution is 0.1～7 mg/ml.
The method producing phosphorus doping Graphene the most according to claim 3, it is characterised in that described
The concentration of graphene oxide solution is 0.5～5 mg/ml.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that described
Solvent is water, ethanol, isopropanol, hexamethylene, benzene, acetone, oxolane, crassitude
Ketone, ethyl pyrrolidone, dimethylformamide or dimethyl acetylamide.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that described
Phosphorus-containing matter be triphenylphosphine, triphenylphosphine oxide, three (o-tolyl) phosphine, to methyl triphenyl
Phosphine, tert-butyl diphenyl phosphine, allyldiphenylphosphine, ethyldiphenylphosphine, diphenyl ethyoxyl
Phosphine, benzyldiphenylphosphine, diphenylcyclohexyl phosphine, isopropyl biphenyl phosphine, diamyl Phenylphosphine,
Phenyldicyclohexylphosphine, tricyclohexyl phosphine, thricyclohexyl phosphine oxide, tert-butyl group dicyclohexylphosphontetrafluoroborate or three
At least one in benzyl phosphine.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that microwave
Radiation treatment is carried out in microwave reactor.
The method producing phosphorus doping Graphene the most according to claim 7, it is characterised in that described
The power of microwave reactor is 350～1200 watts, and exposure time is 30 seconds～10 minutes.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that described
Phosphorus-containing matter is 1～50 with the weight ratio of graphene oxide in graphene oxide solution.
The method producing phosphorus doping Graphene the most according to claim 1, it is characterised in that institute
Stating noble gas is at least one in nitrogen, argon or helium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111099578A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped three-dimensional graphene material |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
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| CN103508444A (en) * | 2012-06-21 | 2014-01-15 | 海洋王照明科技股份有限公司 | Phosphorus doped graphene and preparation method thereof |
| CN103840160A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene composite material and preparation method thereof |
| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099578A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped three-dimensional graphene material |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
| CN113912051B (en) * | 2021-11-22 | 2022-11-29 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
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Application publication date: 20170104 |