CN103864057A - Phosphor-doped graphene, its preparation method and its application - Google Patents
Phosphor-doped graphene, its preparation method and its application Download PDFInfo
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- CN103864057A CN103864057A CN201210526363.XA CN201210526363A CN103864057A CN 103864057 A CN103864057 A CN 103864057A CN 201210526363 A CN201210526363 A CN 201210526363A CN 103864057 A CN103864057 A CN 103864057A
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Abstract
The invention provides phosphor-doped graphene, its preparation method and its application. According to the phosphor-doped graphene, oxygen atom content in phosphor-doped graphene accounts for 2-5% of total atomicity. The preparation method comprises the following steps: dispersing graphite oxide and an organic phosphine compound in a volatile organic solvent and then volatilizing the solvent, acquiring a mixture of the graphite oxide and the organic phosphine compound; heating the mixture of the graphite oxide and the organic phosphine compound to the temperature of 600-1100 DEG C under protective atmosphere, and insulating for 0.5-2 hours. The protective atmosphere can be used for a catalyst of an oxygen reduction reaction, and appears good performance.
Description
Technical field
The present invention relates to a kind of phosphorus doping Graphene and its preparation method and application, belong to the synthetic field of materials chemistry.
Background technology
Graphene is by individual layer sp
2the hexagonal lattice that the carbon atom of hydridization forms, since 2004 find, because its unique character has caused global concern, has obtained research widely in various fields such as electronics, mechanics, nano-catalytics.The important prerequisite that Graphene is applied to microelectronic device is that its band gap, carrier concentration, carrier polarity etc. are adjustable, is the important way that realizes this regulation and control and Graphene is carried out to modification by chemical doping.Research finds, effectively the doping of p-/n-type Graphene can substitute the carbon atom realization in Graphene lattice by heteroatoms, shows that chemical doping is that one does not affect Graphene satisfactory electrical conductivity and adjusts the practicable method of its some performances simultaneously.About the chemical doping method of Graphene mainly can comprise element doping, compound doped and carbonaceous material doping etc.For example, utilize element doping to make Graphene generation chemical modification, strengthen its physical and chemical performance, be applied in semiconductor material, proved a kind of very effective method, meanwhile, this grapheme material through element doping modification also starts to be concerned in the application of catalyst field.
Studies show that, Graphene is carried out to nonmetal doping, such as nitrogen doping, boron doping etc. form transfer transport or electron hole on graphene-based, and then the semiconductor material that provides performance to improve; Graphene is carried out to doped with metal elements, repeatedly the inlaying and deintercalation in Graphene carrier by metal nanoparticle, by the large specific surface characteristic of Graphene, show good catalytic performance, from the angle of catalytic performance research, what receive publicity is mainly the doped products of the precious metals such as Au, Pt, Pd.
At present, the research of nonmetal doping Graphene be mainly for doped element be the modified graphene of nitrogen, boron, sulphur, Graphene after these doping is in electron device and electricity material field, for example in semiconductor material, electrical condenser, the application of sensor technology, all show excellent performance, and, they are also concerned in the application of catalytic field, and especially attempting being applied in the Cathodic oxygen reduction of fuel cell with the alternative traditional platinum base of cheap non-metal catalyst and other precious metal materials is study hotspot in recent years.
About non-metallic element nitrogen, sulphur, the catalytic performance research of boron doped graphene also starts to have some reports in recent years, for example Qu, L. wait and disclose nitrogen-doped graphene (ACS Nano 2010, 4, 1321-1326), Yang, Z. wait and disclose sulfur doping Graphene (ACS Nano 2012, 6, 205-211), Sheng, Z.-H. wait and disclose boron doped graphene (J. Mater.Chem.2012, 22, 390-395), more than study in obtaining described nonmetal doping Graphene and also proved these catalytic performances that had through the Graphene of doping vario-property in oxygen reduction reaction.
In catalyst field, adulterate and can promote the catalytic performance to some reaction by phosphoric, be proved, the carbon material of phosphorus doping starts to cause increasing concern.For example, Liu, the people such as Z.-W are reacted and have been obtained phosphorus doping graphite linings by high temperature pyrolysis, the doping of phosphorus is 0.26%, show good performance (Angew.Chem.Iht.Ed.2011,50,3257-3261) as the catalyzer of fuel battery negative pole oxygen reduction reaction; Yang, people's designs such as D.-S have obtained the order mesoporous carbon structure of phosphorus doping, and the doping of phosphorus is 1.36%, is applied to equally the Cathodic oxygen reduction of fuel cell, shows good catalytic performance (J .Am.Chem.Soc.2012,134,16127-16130).Phosphorus is than the non-metallic element such as nitrogen, sulphur, and its electronegativity is closer to carbon, and its difficulty that replaces carbon in carbon material is relatively larger.How to realize the phosphorus doping to Graphene and a kind of phosphorus doping grapheme material of the substrate as performance boost is provided, there is no concrete report.
On the other hand, the above-mentioned nonmetal doping Graphene that has had report is mainly the method preparation by chemical vapour deposition, is subject to raw material and preparation technology's restriction, and cost is higher, be unfavorable for realizing scale operation, therefore also just limited the popularization of practical application.
So, still do not have at present a kind of method that can low cost and be easy to realize scale operation to obtain the technology of phosphorus doping Graphene.
Summary of the invention
The invention provides a kind of phosphorus doping Graphene, when thering is phosphorus doping in this modified graphene, also there is the oxygen of certain content, thereby be beneficial to as composite substrate materials and good catalytic performance is provided.
The present invention also provides a kind of method of preparing described phosphorus doping Graphene, by the control to raw material and technique, can realize when phosphoric is introduced to Graphene, and the oxygen level in controlled doping product, and preparation cost is low, is beneficial to and realizes scale operation.
The present invention also provides the application of described phosphorus doping Graphene as oxygen reduction catalyst.
The invention provides a kind of phosphorus doping Graphene, the oxygen atomicity content in described phosphorus doping Graphene accounts for the 2-5% of total atom number.
Phosphorus doping Graphene provided by the invention has suitable oxygen level, adulterates the performance that provides simultaneously realizing phosphoric, in application, is also beneficial to and provides and adjust well-oxygenated environment.
Phosphorus doping Graphene provided by the invention can be to utilize graphite oxide to prepare with reacting of organic phosphine compound.
The present invention also provides a kind of preparation method of above-mentioned phosphorus doping Graphene, and the method comprises:
Graphite oxide and organic phosphine compound are scattered in to volatile organic solvent, become the mixed solution of organic phosphine and graphite oxide, the mass ratio of described graphite oxide and organic phosphine compound is 1:5-20;
Described mixed solution, not higher than 60 DEG C of solvent flashings, is obtained to the mixture of graphite oxide and organic phosphine compound;
The mixture of described graphite oxide and organic phosphine compound is warming up to 600-1100 DEG C in protective atmosphere, and is incubated 0.5-2 hour.
Preparation in accordance with the present invention, adopts organic phosphine compound as phosphorus source, adopts graphite oxide as carbon source, in controlled thermal response system, when graphite oxide is converted into Graphene, realize the Effective Doping of phosphoric, thereby obtain described phosphorus doping grapheme material.
In concrete scheme of the present invention, in described temperature range, can decompose and provide the organic phosphine compound of phosphoric all to can be used as phosphorus source, for example, can be selected from triphenylphosphine, three naphthyl phosphines or tetraphenylphosphonibromide bromide etc.Wherein, because triphenylphosphine raw material is easy to get, degradation production is at high temperature entirely gas, can not pollute product, be beneficial to control product purity, and cost is lower, in the embodiment of the present invention, uses triphenylphosphine to provide phosphoric as phosphorus source, and use other organic phosphine compounds also can obtain the phosphorus doping Graphene in the present invention.
In concrete scheme of the present invention, in selective oxidation graphite, oxygen atomicity content accounts for the 20-40% of total atom number, in realizing phosphorus doping, is conducive to control the oxygen level of product.The acquisition of graphite oxide can the oxidising process by graphite realize, and by the change to oxidizing condition and the selection of oxygenant, obtain the having needed oxygen level oxidation products of (oxygen atomicity content).The graphite oxide adopting in the embodiment of the present invention is use liquid phase oxidation (Hummers method) preparation, that is, and and the method that uses the vitriol oil, SODIUMNITRATE and potassium permanganate in ice-water bath, graphite to be oxidized.Those skilled in the art can know, any method that can obtain above-mentioned graphite oxide all can be used, and the present invention does not limit this.
Preparation in accordance with the present invention, utilize volatile organic solvent realize organic phosphine source and graphene oxide fully mix with disperse after also need organic solvent to remove, for the stable organic phosphine obtaining and the mixture system of graphite oxide, require solvent flashing under not higher than 60 DEG C of conditions, be more preferred from the volatilization of carrying out solvent at 40-55 DEG C.This process can maintain stirring, obtains the mixture of graphite oxide and organic phosphine compound.The temperature of solvent evaporates there are differences because of the difference of selected volatile solvent, rising temperature is conducive to the quick volatilization of volatile solvent, but too high temperature can cause too fast solvent evaporates speed, be unfavorable for dispersion system stable of organic phosphine and graphite oxide, generally can be at not higher than 60 DEG C, for example 40-55 DEG C, maintains and stirs 6-12 hour, completes the volatilization of solvent.
Preparation in accordance with the present invention is warming up to 600-1100 DEG C by the mixture of described graphite oxide and organic phosphine compound in protective atmosphere, is more preferred from 700-1050 DEG C, and is incubated 0.5-2 hour.In this process, by high-temperature calcination, there is doping and reduction reaction in graphite oxide and organic phosphine compound, form phosphorus doping Graphene, and this hot environment is also beneficial to the oxygen level reducing in product simultaneously under the hot conditions that graphite oxide exists at organic phosphine.Contriver studies have shown that, selects above-mentioned temperature of reaction and time, is beneficial to the content control to phosphorus and oxygen element in the Graphene of preparation.Too low or the too short meeting of time of temperature causes the phosphorus doping Graphene oxygen level that obtains higher, and excess Temperature or overlong time can cause the reduction of phosphorus doping amount even can not obtain the Graphene of phosphorus doping.In the embodiment of the present invention, soaking time is about 1-1.5 hour.Phosphorus atom number in product can account for the 0.5-2% left and right of total atom number.
Preparation in accordance with the present invention, volatile organic solvent, as realizing fully mixing and the carrier of dispersion of organic phosphine source and graphene oxide, does not have special restriction, is beneficial to disperse or dissolve reaction raw materials, and be beneficial to volatilization as primary condition, such as ethanol, toluene or tetrahydrofuran (THF) etc.Consider from cost of material and the low angle of toxicity, in the embodiment of the present invention, use dehydrated alcohol as volatile organic solvent.
The preparation method of the mixed solution of described organic phosphine and graphite oxide is for to be scattered in respectively or simultaneously volatile organic solvent by graphite oxide and organic phosphine compound, the present invention does not limit, adopt volatile organic solvent first to dissolve after organic phosphine compound but be more preferred from, graphite oxide is added in formed organic phosphine solution again, and make it to be dispersed.As mentioned above, also can first make graphite oxide be scattered in volatile organic solvent, then add organo phosphorous compounds, further disperse to obtain the mixed solution of described organic phosphine and graphite oxide.
Preparation in accordance with the present invention, the dispersing method of use, for using ultrasonic wave to disperse or magnetic stirring, also can adopt other conventional dispersing method and device.And be convenient to comparison for the result obtaining in experimentation, and in the embodiment of the present invention, adopting ultrasonic wave dispersion method, those skilled in the art can know, and any dispersing method that can reach dispersed effect all can use, and the present invention is not restricted this.In one embodiment of the invention, graphite oxide and organic phosphine compound are scattered in to volatile organic solvent simultaneously, ultrasonic dispersion 30-60 minute, can obtain the mixed solution of homodisperse organic phosphine and graphite oxide.In another embodiment of the present invention, adopt volatile organic solvent first to dissolve after organic phosphine compound, gained solution is carried out to ultrasonic dispersion 10-20 minute, again graphite oxide is added in formed organic phosphine solution, and further carry out ultrasonic dispersion 30-60 minute, can obtain the mixed solution of homodisperse organic phosphine and graphite oxide.
Preparation in accordance with the present invention, makes the mixture of described graphite oxide and organic phosphine compound that thermal response occur in protective atmosphere, wherein protects gas can use the non-oxidized gas such as rare gas element (such as helium, argon gas etc.) or nitrogen.Reaction unit can use tube furnace etc., uses airtight silica tube as reaction unit in the embodiment of the present invention.
The present invention also provides the application of a kind of phosphorus doping Graphene as oxygen reduction catalyst.For example can use it in fuel battery negative pole oxygen reduction reaction, also can be for the applied hydrogen reduction system of any phosphorus-containing catalyst.
The present invention program's enforcement, at least has the following advantages:
1, adopting graphite oxide and organic phosphine is raw material, when organic phosphine is decomposed release phosphoric, graphite oxide is realized and is adulterated and be reduced into graphene-structured, and than the chemical Vapor deposition process that has report, preparation cost significantly reduces and is easy to realize scale operation;
2, the organo phosphorous compounds of selecting at high temperature degradation production is entirely gas, can not pollute product;
3, in realizing Graphene phosphorus doping, control the content that the environment of high temperature effectively reduces oxygen in product (preparation method of the present invention can control oxygen level in product lower than 5%), improve phosphorus doping Graphene and be applied to the electroconductibility in electrode materials, be also beneficial to the well-oxygenated environment of regulation and control use procedure;
4, prepared phosphorus doping Graphene is applied in fuel battery negative pole oxygen reduction reaction, shows good catalytic performance.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the phosphorus doping Graphene prepared of one embodiment of the present of invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the phosphorus doping Graphene prepared of one embodiment of the present of invention.
Fig. 3 is the Raman spectrogram of the phosphorus doping Graphene prepared of one embodiment of the present of invention.
Fig. 4 is the x-ray photoelectron energy spectrogram of the phosphorus doping Graphene prepared of one embodiment of the present of invention.
Fig. 5 is the x-ray photoelectron energy spectrogram of phosphoric in the phosphorus doping Graphene prepared of one embodiment of the present of invention.
Fig. 6 is the cyclic voltammetry curve of the phosphorus doping Graphene catalytic oxidation-reduction reaction prepared of one embodiment of the present of invention.
Embodiment
Below in conjunction with specific embodiment and relevant drawings, embodiment of the present invention and technique effect are described more fully.But the present invention can many multi-form embodiments, should not be construed as and be limited to the embodiment of statement herein.
Embodiment 1
1, the preparation of graphite oxide:
In 250mL round-bottomed flask, add 1 gram of crystalline flake graphite and 23 milliliters of vitriol oils, under room temperature, stir 24 hours.Afterwards, in formed suspension liquid, add 500 milligrams of SODIUMNITRATE, continue to maintain to stir and dissolve for 5 minutes.
Round-bottomed flask is placed in to ice-water bath, and high degree of agitation, slowly adds 3 grams of potassium permanganate.After reinforced, remove ice-water bath, maintain under stirring and temperature is strict controlled within the scope of 35 ± 3 ° of C and heats 30 minutes, subsequently, in reactant, slowly add 3 ml deionized water by syringe, maintain to stir after 5 minutes and add again 3 milliliters of deionized waters, after 5 minutes, add again 40 milliliters of deionized waters, maintain 15 minutes.Finally add 140 ml deionized water to dilute, then add 10 milliliter of 30% hydrogen peroxide to finish reaction, obtain graphite oxide.
Obtained graphite oxide (suspension liquid) is moved in several centrifuge tubes, add deionized water to clean (fully mixing with graphite oxide), carry out centrifugal most solutions is sucked with dropper afterwards, in centrifuge tube, continue to add deionized water, supersound process is cleaned graphite oxide, and recentrifuge sucks and graphite oxide sticky lower floor put into 60 ° of C vacuum drying ovens after supernatant liquid and dry with dropper, collect graphite oxide product, as the raw material of subsequent embodiment.
2, the preparation of phosphorus doping Graphene:
Take 30 milligrams of graphite oxides of being prepared by aforesaid method and 150 milligrams of triphenylphosphines add in 80 milliliters of dehydrated alcohols, use ultrasonic method to disperse 50 minutes, the mixture of formation is heated and stirred at 45 DEG C, approximately 8 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 700 DEG C of insulations 1 hour, obtain phosphorus doping Graphene.
Use transmission electron microscope (Transmission Electron Microscopy, TEM) and scanning electronic microscope (Scanning Electron Microscopy, SEM) phosphorus doping Graphene prepared by the present embodiment carry out the sign of microscopic appearance.As shown in Figure 1, can clearly find out by TEM photo the lamella of preparing Graphene, the SEM photo in Fig. 2 shows that prepared Graphene is multilayered structure.
Fig. 3 is the Raman spectrogram of the phosphorus doping Graphene prepared of the present embodiment.Can see, at displacement 1300cm
-1there is D peak, displacement 1600cm in left and right
-1there is G peak and at 2500-3000cm in left and right
-1the 2D peak occurring, product prepared by proved embodiment has graphene-structured.
Fig. 4 is the x-ray photoelectron energy spectrogram of the phosphorus doping Graphene prepared of the present embodiment.Can see, in product prepared by the present embodiment, contain and only contain carbon, oxygen and phosphoric, hardly containing other impurity.By can draw the relative percentage composition of each pantogen subnumber to the conversion of peak intensity, wherein phosphorus atom number accounts for 1.6% of total atom number, and oxygen atomicity accounts for 4.2% of total atom number.
Fig. 5 is the amplification demonstration figure at P2p peak in Fig. 4, the x-ray photoelectron energy spectrogram of the phosphorus doping Graphene phosphoric that prepared by the present embodiment.As shown in Figure 5, can see the peak of obvious P-C key and the peak of P-O key, in the phosphorus doping Graphene that further confirmation obtains, contain phosphoric, also show that phosphoric is to be present in the phosphorus doping Graphene being obtained with the form of P-C key and P-O key.
Embodiment 2
Use the graphite oxide of preparation in embodiment 1 to carry out the preparation of phosphorus doping Graphene, following embodiment is identical.
Taking 600 milligrams of triphenylphosphines adds in 80 milliliters of dehydrated alcohols, use ultrasonic method to disperse 15 minutes, in this triphenylphosphine solution, add 30 milligrams of graphite oxides afterwards, use ultrasonic method to disperse 60 minutes, the mixture heated and stirred at 55 DEG C forming, approximately 6.5 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 1050 DEG C of insulations 70 minutes, obtain phosphorus doping Graphene product.
Utilize TEM and SEM to characterize to obtained phosphorus doping Graphene, result is identical with embodiment 1.Further shown by X-ray photoelectron spectroscopic analysis, (phosphorus atom number accounts for the per-cent of total atom number to the phosphorus doping amount of the phosphorus doping Graphene preparing, implication is identical in the following embodiments for it) be 0.8%, (oxygen atomicity accounts for the per-cent of total atom number to oxygen level, implication is identical in the following embodiments for it) be 2.1%, and as the catalystic material of oxygen reduction reaction, show good performance.
Embodiment 3
Taking 30 milligrams of graphite oxides (being prepared by the method in embodiment 1) is added in 180 milliliters of dehydrated alcohols, use ultrasonic method to disperse 20 minutes, in gained mixed solution, add 600 milligrams of triphenylphosphines afterwards, use ultrasonic method to disperse 40 minutes, the mixture heated and stirred at 45 DEG C forming, approximately 10 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 650 DEG C of insulations 90 minutes, obtain phosphorus doping Graphene product.
Utilize TEM and SEM to characterize to obtained phosphorus doping Graphene, result is identical with embodiment 1.Further shown by X-ray photoelectron spectroscopic analysis, the phosphorus doping Graphene phosphorus doping amount preparing is 1.8%, and oxygen level is 4.4%, and as the catalystic material of oxygen reduction reaction, shows good performance.
Embodiment 4
Taking 150 milligrams of triphenylphosphines adds in 80 milliliters of dehydrated alcohols, use ultrasonic method to disperse 15 minutes, in this triphenylphosphine solution, add 30 milligrams of graphite oxides (being prepared by method in embodiment 1) afterwards, use ultrasonic method to disperse 60 minutes, the mixture heated and stirred at 55 DEG C forming, approximately 6 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.。The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 1050 DEG C of insulations 55 minutes, obtain phosphorus doping Graphene product.
Utilize TEM and SEM to characterize to obtained phosphorus doping Graphene, result is identical with embodiment 1.Further shown by X-ray photoelectron spectroscopic analysis, the phosphorus doping Graphene phosphorus doping amount preparing is 0.6%, and oxygen level is 2.3%, and as the catalystic material of oxygen reduction reaction, shows good performance.
Embodiment 5
Taking 150 milligrams of triphenylphosphines adds in 80 milliliters of dehydrated alcohols, use ultrasonic method to disperse 15 minutes, in this triphenylphosphine solution, add 30 milligrams of graphite oxides (being prepared by method in embodiment 1) afterwards, use ultrasonic method to disperse 60 minutes, the mixture heated and stirred at 55 DEG C forming, approximately 6 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 700 DEG C of insulations 60 minutes, obtain phosphorus doping Graphene product.
Utilize TEM and SEM to characterize to obtained phosphorus doping Graphene, result is identical with embodiment 1.Shown by X-ray photoelectron spectroscopic analysis, the phosphorus doping Graphene phosphorus doping amount preparing is 1.4%, and oxygen level is 4%, and as the catalystic material of oxygen reduction reaction, shows good performance.
Embodiment 6
Taking 450 milligrams of triphenylphosphines adds in 100 milliliters of dehydrated alcohols, use ultrasonic method to disperse 15 minutes, in this triphenylphosphine solution, add 30 milligrams of graphite oxides (being prepared by method in embodiment 1) afterwards, use ultrasonic method to disperse 60 minutes, the mixture heated and stirred at 55 DEG C forming, approximately 6.5 hours, make absolute ethanol volatilizes, obtain the mixture of graphite oxide and triphenylphosphine.The mixture of graphite oxide and triphenylphosphine is placed on to silica tube center, passes into argon gas and form protective atmosphere, be warming up to 1100 DEG C of insulations 60 minutes, obtain phosphorus doping Graphene product.
Utilize TEM and SEM to characterize to obtained phosphorus doping Graphene, result is identical with embodiment 1.Further shown by X-ray photoelectron spectroscopic analysis, the phosphorus doping Graphene phosphorus doping amount preparing is 0.7%, and oxygen level is 2.2%, and as the catalystic material of oxygen reduction reaction, shows good performance.
Embodiment 7
Phosphorus doping Graphene prepared by the embodiment of the present invention can be applied in the oxygen reduction reaction of fuel battery negative pole, is described in detail in the present embodiment.
Use the oxygen reduction reaction of the phosphorus doping Graphene catalytic fuel cell cathode of preparation in embodiment 1.Under alkaline condition (the 0.1M KOH aqueous solution), use cyclic voltammetry to study the effect of phosphorus doping Graphene catalytic oxidation-reduction reaction, scanning speed is 100mVs
-1.
The reaction formula of above-mentioned oxygen reduction reaction is:
O
2+4e
-+2H
2O->4OH
-。
Fig. 6 is the cyclic voltammetry curve of the phosphorus doping Graphene catalytic oxidation-reduction reaction prepared of the present invention.As shown in Figure 6, in comparison solution, be full of N
2and O
2time curve, can see clearly near-0.4V in curve, having obvious reduction peak to occur, shown the hydrogen reduction catalytic performance that this phosphorus doping Graphene has.
Finally it should be noted that: above each embodiment, only in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or some or all of technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (11)
1. a phosphorus doping Graphene, the oxygen atomicity content in this phosphorus doping Graphene accounts for the 2-5% of total atom number.
2. phosphorus doping Graphene according to claim 1, it is to utilize graphite oxide to prepare with reacting of organic phosphine compound.
3. the preparation method of the phosphorus doping Graphene described in claim 1 or 2, the method comprises:
Graphite oxide and organic phosphine compound are scattered in to volatile organic solvent, become the mixed solution of organic phosphine and graphite oxide, the mass ratio of described graphite oxide and organic phosphine compound is 1:5-20;
Described mixed solution, not higher than 60 DEG C of solvent flashings, is obtained to the mixture of graphite oxide and organic phosphine compound;
The mixture of described graphite oxide and organic phosphine compound is warming up to 600-1100 DEG C in protective atmosphere, and is incubated 0.5-2 hour.
4. preparation method according to claim 3, wherein, described organic phosphine is selected from triphenylphosphine, three naphthyl phosphine or tetraphenylphosphonibromide bromide.
5. according to the preparation method described in claim 3 or 4, wherein, in described graphite oxide, oxygen atomicity content accounts for the 20-40% of total atom number.
6. preparation method according to claim 3, wherein, at 40-55 DEG C of solvent flashing, obtains the mixture of graphite oxide and organic phosphine compound by described mixed solution.
7. preparation method according to claim 3 wherein, is warming up to 700-1050 DEG C by the mixture of described graphite oxide and organic phosphine compound, and is incubated 0.5-2 hour in protective atmosphere.
8. preparation method according to claim 3, wherein, described volatile organic solvent is the solvent that can dissolve organic phosphine, the preparation method of the mixed solution of described organic phosphine and graphite oxide is: adopt volatile organic solvent to dissolve organic phosphine compound, graphite oxide is added in formed organic phosphine solution, and make it to be dispersed.
9. according to the preparation method described in any one in claim 3,4,6 or 8, wherein, described volatile organic solvent comprises ethanol, toluene or tetrahydrofuran (THF).
10. according to the preparation method described in claim 3 or 8, wherein, described in be separated into and use ultrasonic wave to disperse or magnetic stirring.
Phosphorus doping Graphene described in 11. claims 1 or 2 is as the application of oxygen reduction reaction catalyzer.
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