CN103508444B - Phosphorus doped graphene and preparation method thereof - Google Patents
Phosphorus doped graphene and preparation method thereof Download PDFInfo
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- CN103508444B CN103508444B CN201210206949.8A CN201210206949A CN103508444B CN 103508444 B CN103508444 B CN 103508444B CN 201210206949 A CN201210206949 A CN 201210206949A CN 103508444 B CN103508444 B CN 103508444B
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Abstract
The invention provides a preparation method for phosphorus doped graphene. The preparation method comprises the following steps: uniformly mixing graphite oxide and phosphorus pentoxide in a mass ratio of 1: 0.5-3 and placing an obtained mixture in a reactor; introducing protective gas into the reactor, wherein introduction flow velocity of the protective gas is 200 to 400 ml/min; heating the interior of the reactor to a temperature of 800 to 900 DEG C at a heating speed of 15 to 20 DEG C/min and maintaining the temperature for 30 min to 2 h; and cooling the reactor to room temperature in the protective gas with flow velocity of 200 to 400 ml/min so as to prepare the phosphorus doped graphene. According to the method, phosphorus pentoxide is used as a phosphorus source, the maximum doping amount of elemental phosphorus can approach 10%, so the adjustable range of phosphorus is wide; and the method has the advantages of simple process, convenient operation, no special requirements on equipment and easy realization of large scale industrial production. The invention further provides the phosphorus doped graphene prepared by using the preparation method.
Description
Technical field
The present invention relates to materials synthesis field, more particularly to a kind of phosphorus doping Graphene and preparation method thereof.
Background technology
Graphene is the discoveries such as peace moral strong K sea nurse (Andre K.Geim) of Univ Manchester UK in 2004
A kind of Two-dimensional Carbon atomic crystal, is the very thin material with carbon element of single or multiple lift.Single-layer graphene has excellent conduction, heat conductivity
Can be with low thermal coefficient of expansion, and its theoretical specific surface area is up to 2630m2/ g (A Peigney, Ch Laurent, et
Al.Carbon, 2001,39,507), can be used for effect transistor, electrode material, composite, liquid crystal display material, sensor
Deng.
The method preparing Graphene at present mainly has graphite breakaway (Novoselov K S, Geim A K, et al.
Science 2004,306,666), chemistry redox method [D A Dikin, et al.Nature 2007,448,457；
Sasha Stankovich, Dmitriy A Dikin, Richard D Piner, et al.Carbon 2007,45,1558],
Ultrasonic stripping method (Guohua Chen, Wengui Weng, Dajun Wu, et al.Carbon.2004,42,753), chemical gas
Phase sedimentation (Alexander N, Obraztsov.Nature nanotechnology.2009,4,212) etc..Generally, these
The Graphene of method preparation is all intrinsic Graphene.
Research carries out the big focus that element doping modification is current field of nanometer material technology to Graphene.Theoretical research table
Bright, Graphene band structure after element doping has adjustment, thus Graphene can greatly be expanded in optics, electricity and magnetics
Application in field.At present, the research of doped graphene preparation method is not very abundant, and focuses mostly in nitrogen-doped graphene
Research and boron-doped graphite alkene research on, phosphorus doping Graphene is more rare, and in the phosphorus doping Graphene reported phosphorus unit
Cellulose content is relatively low, and the adjustable extent of phosphorus content is narrower.Because phosphorus is lower than nitrogen electronegativity, the electronics to Graphene therefore after phosphorus doping
Characteristic impact is different, and therefore, the exploitation of phosphorus doping Graphene is significant.
Content of the invention
For solving the above problems, the present invention is intended to provide a kind of preparation method of phosphorus doping Graphene, this preparation method with
Phosphorus pentoxide prepares phosphorus doping Graphene as phosphorus source, the highest doping accessible 10% of P elements, therefore phosphorus content
Adjustable extent width.Meanwhile, the invention provides passing through the phosphorus doping Graphene that this preparation method is obtained.
The invention provides a kind of preparation method of phosphorus doping Graphene, comprise the following steps：
First, the ratio for 1: 0.5～3 takes graphite oxide and phosphorus pentoxide mix homogeneously to be placed in reactor in mass ratio
In；Then, it is passed through protective gas toward in reactor, the flow velocity that is passed through of described protective gas is 200～400ml/min；Connect
, with the programming rate of 15～20 DEG C/min, the temperature in reactor is warming up to 800～900 DEG C, and keeps 30min～2h；
Finally, flow velocity be 200～400ml/min protective gas in be cooled to room temperature, prepared phosphorus doping Graphene.
Preferably, described protective gas is at least one in argon, nitrogen and helium.
Preferably, described reactor is tube furnace.
Preferably, the mass ratio of described graphite oxide and phosphorus pentoxide is 1: 1～2.
Preferably, described graphite oxide adopts following steps to be obtained：
Graphite is added in concentrated sulphuric acid and the mix acid liquor of concentrated nitric acid composition and forms mixed liquor, the temperature of mixed liquor is kept
Stir 10～30min at -2～2 DEG C；It is slowly added potassium permanganate in mixed liquor, continue to be maintained at the temperature of mixed liquor-
2～2 DEG C of stirring 1h；Mixed liquor is warming up to 80～90 DEG C and keeps 0.5～2h；Add deionized water in mixed liquor, continue
It is incubated 0.5～2h at 80～90 DEG C；And add hydrogen peroxide to remove potassium permanganate, sucking filtration in mixed liquor, use dilute hydrochloric acid successively
With deionized water, solidss are washed, after dried solidss, obtain graphite oxide；Described graphite and described concentrated sulphuric acid and dense
The solid-to-liquid ratio of nitric acid is 1g: 80～110ml: 15～35ml；Described graphite is 1: 1～10 with the mass ratio of described potassium permanganate；
Potassium permanganate is 1g: 1～3ml with the solid-to-liquid ratio of hydrogen peroxide.
Preferably, the purity of described graphite is 90%～99.9%.
The preparation method of phosphorus doping Graphene of the present invention prepares phosphorus doping Graphene, phosphorus unit using phosphorus pentoxide as phosphorus source
The highest doping of element accessible 10%, the therefore adjustable extent width of phosphorus content, the width adjusting wide ranges between energy level, so
The phosphorus doping Graphene of suitable phosphorus element content can be prepared according to the requirement of device performance.In addition this preparation method technique letter
Single, it is easy to operate, to equipment no particular/special requirement, it is easy to accomplish large-scale industrial production.
Present invention also offers a kind of phosphorus doping Graphene, it is prepared that described phosphorus doping Graphene is prepared as described above method.
Preferably, in described phosphorus doping Graphene, the doping of P elements is 5%～10%.
It is mixed with P elements, because phosphorus is lower than nitrogen electronegativity, therefore to Graphene after phosphorus doping in this phosphorus doping Graphene
Characteristic electron impact different.Phosphorus doping belongs to p-type doping, and the impurity energy level that phosphorus impurities produce can be distributed in fermi level two
Side, one close to conduction band, one close to valence band, and be spaced between two energy levels relatively N doping will width, be therefore thus obtained
Phosphorus doping Graphene be applied to some specific component structures, such as sensor.Additionally, the doping of P elements does not affect
The conjugated structure of Graphene itself, that is, do not destroy the electron transmission between big π key, remains the excellent conductance of Graphene itself
Rate.
A kind of phosphorus doping Graphene that the present invention provides and preparation method thereof, has the advantages that：
This preparation method, using phosphorus pentoxide as phosphorus source, the adjustable extent width of phosphorus content, process is simple, is easy to operate,
To equipment no particular/special requirement, it is easy to accomplish large-scale industrial production；
It is mixed with P elements, it is applied to some specific units device in the phosphorus doping Graphene being obtained by this preparation method
Part structure, such as sensor, additionally, the doping of P elements does not affect the conjugated structure of Graphene itself, remain Graphene
The excellent electrical conductivity of itself.
Specific embodiment
The invention provides a kind of preparation method of phosphorus doping Graphene, comprise the following steps：
First, the ratio for 1: 0.5～3 takes graphite oxide and phosphorus pentoxide mix homogeneously to be placed in reactor in mass ratio
In；Then, it is passed through protective gas toward in reactor, the flow velocity that is passed through of described protective gas is 200～400ml/min；Connect
, with the programming rate of 15～20 DEG C/min, the temperature in reactor is warming up to 800～900 DEG C, and keeps 30min～2h；
Finally, flow velocity be 200～400ml/min protective gas in be cooled to room temperature, prepared phosphorus doping Graphene.
Described protective gas is at least one in argon, nitrogen and helium.
Described reactor is tube furnace.
The mass ratio of described graphite oxide and phosphorus pentoxide is 1: 1～2.
Described graphite oxide adopts following steps to be obtained：
Graphite is added in concentrated sulphuric acid and the mix acid liquor of concentrated nitric acid composition and forms mixed liquor, the temperature of mixed liquor is kept
Stir 10～30min at -2～2 DEG C；It is slowly added potassium permanganate in mixed liquor, continue to be maintained at the temperature of mixed liquor-
2～2 DEG C of stirring 1h；Mixed liquor is warming up to 80～90 DEG C and keeps 0.5～2h；Add deionized water in mixed liquor, continue
It is incubated 0.5～2h at 80～90 DEG C；And add hydrogen peroxide to remove potassium permanganate, sucking filtration in mixed liquor, use dilute hydrochloric acid successively
With deionized water, solidss are washed, after dried solidss, obtain graphite oxide；Described graphite and described concentrated sulphuric acid and dense
The solid-to-liquid ratio of nitric acid is 1g: 80～110ml: 15～35ml；Described graphite is 1: 1～10 with the mass ratio of described potassium permanganate；
Potassium permanganate is 1g: 1～3ml with the solid-to-liquid ratio of hydrogen peroxide.
The purity of described graphite is 90%～99.9%.
The preparation method of phosphorus doping Graphene of the present invention prepares phosphorus doping Graphene, phosphorus unit using phosphorus pentoxide as phosphorus source
The highest doping of element accessible 10%, the therefore adjustable extent width of phosphorus content, the width adjusting wide ranges between energy level, so
The phosphorus doping Graphene of suitable phosphorus element content can be prepared according to the requirement of device performance.In addition this preparation method technique letter
Single, it is easy to operate, to equipment no particular/special requirement, it is easy to accomplish large-scale industrial production.
Present invention also offers a kind of phosphorus doping Graphene, it is prepared that described phosphorus doping Graphene is prepared as described above method.
In described phosphorus doping Graphene, the doping of P elements is 5%～10%.
It is mixed with P elements, because phosphorus is lower than nitrogen electronegativity, therefore to Graphene after phosphorus doping in this phosphorus doping Graphene
Characteristic electron impact different.Phosphorus doping belongs to p-type doping, and the impurity energy level that phosphorus impurities produce can be distributed in fermi level two
Side, one close to conduction band, one close to valence band, and be spaced between two energy levels relatively N doping will width, be therefore thus obtained
Phosphorus doping Graphene be applied to some specific component structures, such as sensor.Additionally, the doping of P elements does not affect
The conjugated structure of Graphene itself, that is, do not destroy the electron transmission between big π key, remains the excellent conductance of Graphene itself
Rate.
A kind of phosphorus doping Graphene that the present invention provides and preparation method thereof, has the advantages that：
This preparation method, using phosphorus pentoxide as phosphorus source, the adjustable extent width of phosphorus content, process is simple, is easy to operate,
To equipment no particular/special requirement, it is easy to accomplish large-scale industrial production；
It is mixed with P elements, it is applied to some specific units device in the phosphorus doping Graphene being obtained by this preparation method
Part structure, such as sensor, additionally, the doping of P elements does not affect the conjugated structure of Graphene itself, remain Graphene
The excellent electrical conductivity of itself.
Described below is the preferred embodiment of the present invention it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Embodiment one
A kind of preparation method of phosphorus doping Graphene, comprises the following steps：
It is that 65% concentrated nitric acid is with 90ml mass fraction that the graphite that 1g purity is 95% adds 24ml mass fraction
Mix in 98% concentrated sulphuric acid, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, more at leisure toward mixing
Potassium permanganate is added, potassium permanganate is 5: 1 with the mass ratio of graphite, stirs 1 hour, then heats the mixture to 85 DEG C in thing
Lower holding 30min, adds deionized water to continue to keep 30min at 85 DEG C, deionized water with the liquid-solid ratio of graphite is afterwards
90ml: 1g, it is eventually adding the hydrogenperoxide steam generator that mass fraction is 30%, hydrogenperoxide steam generator is 10ml with the liquid-solid ratio of graphite
: 1g, stir 10min, sucking filtration is carried out to mixture, then with dilute hydrochloric acid and deionized water, solidss is washed respectively successively,
The solid-to-liquid ratio of dilute hydrochloric acid, deionized water and graphite is 100ml: 150ml: 1g, washs 3 times altogether, and last solid matter is true at 60 DEG C
In empty baking oven, drying obtains graphite oxide in 12 hours.
Ratio for 1: 3 takes graphite oxide and phosphorus pentoxide mix homogeneously in mass ratio, and being placed in flow velocity is 300ml/min
Argon atmosphere in, be warming up to 900 DEG C with the programming rate of 15 DEG C/min, keep 2h, the subsequently argon for 300ml/min in flow velocity
Atmosphere is down to room temperature in enclosing, prepared phosphorus doping Graphene.
Embodiment two
A kind of preparation method of phosphorus doping Graphene, comprises the following steps：
It is that 68% concentrated nitric acid is with 350ml mass fraction that the graphite that 5g purity is 90% adds 100ml mass fraction
Mix in 80% concentrated sulphuric acid, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, more at leisure toward mixing
Potassium permanganate is added, potassium permanganate is 4: 1 with the mass ratio of graphite, stirs 1 hour, then heats the mixture to 85 DEG C in thing
Lower holding 30min, adds deionized water to continue to keep 30min at 85 DEG C, deionized water with the liquid-solid ratio of graphite is afterwards
60ml: 1g, it is eventually adding the hydrogenperoxide steam generator that mass fraction is 30%, hydrogenperoxide steam generator is 5ml with the liquid-solid ratio of graphite:
1g, stirs 10min, carries out sucking filtration to mixture, then with dilute hydrochloric acid and deionized water, solidss are washed respectively successively, dilute
The solid-to-liquid ratio of hydrochloric acid, deionized water and graphite is 90ml: 60ml: 1g, washs 3 times altogether, last solid matter dries in 60 DEG C of vacuum
In case, drying obtains graphite oxide in 12 hours.
Ratio for 1: 2 takes graphite oxide and phosphorus pentoxide mix homogeneously in mass ratio, and being placed in flow velocity is 200ml/min
Nitrogen atmosphere in, be warming up to 850 DEG C with the programming rate of 20 DEG C/min, keep 1h, the subsequently nitrogen for 200ml/min in flow velocity
Atmosphere is down to room temperature in enclosing, prepared phosphorus doping Graphene.
Embodiment three
A kind of preparation method of phosphorus doping Graphene, comprises the following steps：
It is that 50% concentrated nitric acid is with 180ml mass fraction that the graphite that 2g purity is 99.9% adds 48ml mass fraction
Mix in 98% concentrated sulphuric acid, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, more at leisure toward mixing
Potassium permanganate is added, potassium permanganate is 4: 1 with the mass ratio of graphite, stirs 1 hour, then heats the mixture to 85 DEG C in thing
Lower holding 30min, adds deionized water to continue to keep 30min at 85 DEG C, deionized water with the liquid-solid ratio of graphite is afterwards
90ml: 1g, it is eventually adding the hydrogenperoxide steam generator that mass fraction is 30%, hydrogenperoxide steam generator with the liquid-solid ratio of graphite is
7.5ml: 1g, stir 10min, sucking filtration is carried out to mixture, then with dilute hydrochloric acid and deionized water, solidss is carried out respectively successively
Washing, the solid-to-liquid ratio of dilute hydrochloric acid, deionized water and graphite is 100ml: 150ml: 1g, washs 3 times altogether, and last solid matter is 60
In DEG C vacuum drying oven, drying obtains graphite oxide in 12 hours.
Ratio for 1: 1 takes graphite oxide and phosphorus pentoxide mix homogeneously in mass ratio, and being placed in flow velocity is 400ml/min
Helium atmosphere in, be warming up to 900 DEG C with the programming rate of 20 DEG C/min, keep 1h, the subsequently helium for 400ml/min in flow velocity
Atmosphere is down to room temperature in enclosing, prepared phosphorus doping Graphene.
Example IV
A kind of preparation method of phosphorus doping Graphene, comprises the following steps：
It is that 65% concentrated nitric acid is with 95ml mass fraction that the graphite that 1g purity is 95% adds 25ml mass fraction
Mix in 90% concentrated sulphuric acid, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, more at leisure toward mixing
Potassium permanganate is added, potassium permanganate is 3: 1 with the mass ratio of graphite, stirs 1 hour, then heats the mixture to 85 DEG C in thing
Lower holding 30min, adds deionized water to continue to keep 30min at 85 DEG C, deionized water with the liquid-solid ratio of graphite is afterwards
100ml: 1g, it is eventually adding the hydrogenperoxide steam generator that mass fraction is 30%, hydrogenperoxide steam generator is 8ml with the liquid-solid ratio of graphite
: 1g, stir 10min, sucking filtration is carried out to mixture, then with dilute hydrochloric acid and deionized water, solidss is washed respectively successively,
The solid-to-liquid ratio of dilute hydrochloric acid, deionized water and graphite is 100ml: 150ml: 1g, washs 3 times altogether, and last solid matter is true at 60 DEG C
In empty baking oven, drying obtains graphite oxide in 12 hours.
Ratio for 2: 1 takes graphite oxide and phosphorus pentoxide mix homogeneously in mass ratio, and being placed in flow velocity is 200ml/min
Argon atmosphere in, be warming up to 800 DEG C with the programming rate of 15 DEG C/min, keep 30min, be subsequently 200ml/min in flow velocity
Argon atmosphere in be down to room temperature, prepared phosphorus doping Graphene.
Effect example
Phosphorus doping Graphene obtained by embodiment one～tetra- is passed through containing of the wherein each essential element of XPS measurements determination
Amount, test result such as table 1 below.
Phosphorus doping Graphene each essential element content in table 1 embodiment one～example IV
| Carbon (%) | P elements (%) | Oxygen element (%) | |
| Embodiment one | 80.2 | 9.2 | 10.6 |
| Embodiment two | 81.3 | 8.6 | 10.1 |
| Embodiment three | 81.4 | 7.2 | 11.4 |
| Example IV | 83.2 | 5.9 | 10.9 |
As can be seen from Table 1, the phosphorus content of the phosphorus doping Graphene that the embodiment of the present invention is obtained can reach
9.2%, there is higher phosphorus content, and the content of phosphorus can be adjusted in wider scope.
Phosphorus doping Graphene electrical conductivity performance test in table 2 embodiment one～example IV
| Electrical conductivity (S/m) | |
| Embodiment one | 1783 |
| Embodiment two | 1742 |
| Embodiment three | 1623 |
| Example IV | 1522 |
As can be seen from Table 2, test through four probe instrument, the phosphorus doping Graphene that the embodiment of the present invention is obtained
Electrical conductivity higher, up to 1783S/m.
Claims (7)
1. a kind of preparation method of phosphorus doping Graphene is it is characterised in that comprise the following steps：First, in mass ratio for 1: 0.5
～3 ratio takes graphite oxide and phosphorus pentoxide mix homogeneously to be placed in reactor；Then, it is passed through protectiveness toward in reactor
Gas, the flow velocity that is passed through of described protective gas is 200～400ml/min；Then, will with the programming rate of 15～20 DEG C/min
Temperature in reactor is warming up to 800～900 DEG C, and keeps 30min～2h；Finally, it is 200～400ml/min's in flow velocity
It is cooled to room temperature, prepared phosphorus doping Graphene in protective gas.
2. as claimed in claim 1 a kind of preparation method of phosphorus doping Graphene it is characterised in that described protective gas is
At least one in argon, nitrogen and helium.
3. as claimed in claim 1 a kind of preparation method of phosphorus doping Graphene it is characterised in that described reactor be tubular type
Stove.
4. as claimed in claim 1 a kind of preparation method of phosphorus doping Graphene it is characterised in that described graphite oxide and five
The mass ratio aoxidizing two phosphorus is 1: 1～2.
5. as claimed in claim 1 a kind of preparation method of phosphorus doping Graphene it is characterised in that described graphite oxide adopt
Following steps are obtained：
Graphite is added in concentrated sulphuric acid and the mix acid liquor of concentrated nitric acid composition and forms mixed liquor, the temperature of mixed liquor is maintained at -2
～2 DEG C of stirring 10～30min；It is slowly added potassium permanganate in mixed liquor, continue for the temperature of mixed liquor to be maintained at -2～2
DEG C stirring 1h；Mixed liquor is warming up to 80～90 DEG C and keeps 0.5～2h；Add deionized water in mixed liquor, continue 80
～90 DEG C of insulation 0.5～2h；And adding hydrogen peroxide to remove potassium permanganate in mixed liquor, sucking filtration, successively with dilute hydrochloric acid and going
Ionized water washs to solidss, obtains graphite oxide after dried solidss；Described graphite and described concentrated sulphuric acid and concentrated nitric acid
Solid-to-liquid ratio be 1g: 80～110ml: 15～35ml；Described graphite is 1: 1～10 with the mass ratio of described potassium permanganate；Gao Meng
Sour potassium is 1g: 1～3ml with the solid-to-liquid ratio of hydrogen peroxide.
6. as claimed in claim 5 a kind of preparation method of phosphorus doping Graphene it is characterised in that the purity of described graphite is
90%～99.9%.
7. a kind of phosphorus doping Graphene is it is characterised in that described phosphorus doping Graphene will by right arbitrary in claim 1～6
The preparation method asking described is obtained, and in described phosphorus doping Graphene, the doping of P elements is 5%～10%.
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| CN104140097B (en) * | 2014-07-25 | 2016-06-08 | 深圳新宙邦科技股份有限公司 | A kind of phosphorus doping Graphene and preparation method thereof |
| CN106276866A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | The production method of phosphorus doping Graphene |
| CN106276865A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | The method producing phosphorus doping Graphene |
| CN106335890B (en) * | 2015-07-16 | 2019-02-19 | 中国石油化工股份有限公司 | The preparation method of phosphorus doping graphene |
| WO2017063434A1 (en) | 2015-10-15 | 2017-04-20 | 济南圣泉集团股份有限公司 | Carbon-containing nanostructure composite, polymer material using same and preparation method |
| EP3202848B1 (en) | 2015-10-27 | 2021-03-17 | Jinan Shengquan Group Share Holding Co., Ltd. | Composite polyester material, composite polyester fibre, preparation method therefor and use thereof |
| WO2017071359A1 (en) | 2015-10-27 | 2017-05-04 | 济南圣泉集团股份有限公司 | Composite polyurethane foam containing graphene, and preparation method and use |
| CN105504199B (en) * | 2015-11-27 | 2019-01-08 | 济南圣泉集团股份有限公司 | A kind of composite polyurethane foam containing graphene, preparation method and purposes |
| WO2017084507A1 (en) | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | Graphene-containing modified latex as well as preparation method therefor and application thereof |
| CN105525377B (en) | 2015-11-26 | 2018-08-17 | 济南圣泉集团股份有限公司 | A kind of functional regenerated cellulose fibre and its preparation method and application |
| JP6663991B2 (en) * | 2015-11-20 | 2020-03-13 | 済南聖泉集団股▲ふん▼有限公司Ｊｉｎａｎ Ｓｈｅｎｇｑｕａｎ Ｇｒｏｕｐ Ｓｈａｒｅ Ｈｏｌｄｉｎｇ Ｃｏ．， Ｌｔｄ | Functional regenerated cellulose fiber and its preparation method and use |
| CN112366316B (en) * | 2020-09-27 | 2022-03-01 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
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