CN108658060A - A kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap - Google Patents
A kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap Download PDFInfo
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- CN108658060A CN108658060A CN201810673572.4A CN201810673572A CN108658060A CN 108658060 A CN108658060 A CN 108658060A CN 201810673572 A CN201810673572 A CN 201810673572A CN 108658060 A CN108658060 A CN 108658060A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of preparation methods of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap, and this method is using phosphate, carboxylate and carbonate as raw material.Include the following steps (1) by phosphate, the two of which of carboxylate and carbonate compound is 0.01 in molar ratio:20~40:20 or three kind in molar ratio be 0.01:0.01:20~40:40:20 mixed grindings are uniform；(2) by the mixture obtained in step (1) under an argon atmosphere in calcining；(3) product dilute hydrochloric acid, distilled water and the ethyl alcohol of gained in step (2) are washed for several times, to remove extra salt, then, product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping.The present invention outstanding advantages be：Raw material is cheap and easy to get, environmentally protective, and synthesis step is simple and easy to do, and product obtained has adjustable optical property, with catalysis photodissociation aquatic products hydrogen activity and with preferable stability, has potential application in terms of opto-electronic device and the energy.
Description
Technical field
The invention belongs to the synthesis technical fields of the graphene of two-dimensional functional material Heteroatom doping, and in particular to Yi Zhongdan
The preparation method of the graphene nanometer sheet of layer phosphorus doping, controllable adjusting is carried out by the doping of phosphorus to the band gap of material.
Background technology
The application of optical device is the hot issue of researcher, and the band gap for adjusting material plays to pass weight device performance
The effect wanted.Excellent device should have high efficiency, and high stability, low cost is low, is readily synthesized.Graphene is a kind of very special
The different two-dimensional nano sheet material being made of carbon atom, have honeycomb and some unique performances such as its optics, calorifics,
Electrical and mechanical performance is all very excellent, these become the excellent candidate material of photoelectric device.In addition, graphene has height
Thermal conductivity (about 5000W m-1K-1), excellent carrier mobility (200000cm2V-1s-1) and high specific surface area is (about
2600m2g-1), therefore it is highly suitable to be applied in device.However, graphene is zero band gap semi-metal, this is applied to it
Device is unfavorable.It is the major obstacle for limiting grapheme material and using in the devices to lack suitable band gap, therefore is based on stone
The development of the photoelectric device of black alkene depends on whether to realize the controllable adjustment of graphene band gap.Currently, many methods are available
In the band gap for adjusting graphene, such as field effect, Water Molecular Adsorption, chemical functionalization, graphene, metal are deposited on substrate
Electrode contacts and adulterates hetero atom with graphene.However, adjusting stone using field effect and the method for substrate deposition graphene
The band gap of black alkene is very complicated, and in addition the absorption of hydrone and chemical functionalization method condition are harsh, are contacted with graphene
Metal electrode (such as Co, Ni, Pd, Al, Cu, Ag, Pt and Au) in method is harmful to environment.In comparison, with the miscellaneous original of doping
Sub- method regulation and control graphene band gap is simple and easy to do, and condition is controllable.
Based on factors above, adulterates hetero atom with graphene and cause people regulating and controlling band gap and greatly pay close attention to, therefore seek
The graphene of green and effective Heteroatom doping is asked to be very important to improve the performance of device.Hetero atom (such as N, P, S or
B) there is electron deficient or electron rich property, they can change the photoelectric property of grapheme material by opening band gap.Each
In kind of material, phosphorus is one of element most abundant on the earth, and there are three kinds of forms：Red, the allotrope of white and black.
In particular, the gap tunable of black phosphorus ranging from 0.3eV to 2.0eV.Phosphorus doping graphene can be by adjusting phosphorus in graphene
Content makes it have suitable band gap, therefore manufactures high performance device, so as to improve its performance.Compared with other materials, phosphorus
The advantages that doped graphene semiconductor has band gap adjustable, and charge carrier mobility is high, and specific surface area is high, and thermal conductivity is high, can
To improve its efficiency and stability.
Invention content
The technical issues of being not easy to adjust present invention aim to address single-layer graphene band gap provides a kind of simple system
It is standby go out the adjustable single layer phosphorus doping graphene nanometer sheet of band gap one-step method for synthesizing.The preparation method uses a kind of new raw material
Proportioning, preparation method is simple and easy to do, and product has adjustable optical property, has catalysis photodissociation aquatic products hydrogen activity.
The purpose of the present invention can be realized by following scheme：
A kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap, includes the following steps:
(1) it is 0.01 in molar ratio by the two of which of phosphate compounds, carboxylate compounds and carbonate compound:
20~40:20 or three kind in molar ratio be 0.01:0.01:20~40:40:20 mixed grindings are uniform；
(2) mixture obtained in step (1) is added in corundum porcelain boat and is put into tube furnace, mixture is in argon gas gas
5~600min is calcined in 500~3000 DEG C under atmosphere, heating rate is 0.1~10 DEG C/min, after calcining, in argon gas atmosphere
Lower cooled to room temperature；
(3) product of gained in step (2) is washed for several times with 0.1~2mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, to remove
Extra salt is removed, then, product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping.
Above-described phosphate compounds is disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium hypophosphite, metaphosphoric acid
Sodium, sodium pyrophosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, calcium monohydrogen phosphate, calcium phosphate, calcium pyrophosphate, diammonium hydrogen phosphate,
Ammonium dihydrogen phosphate, one kind in ammonium phosphate；Carboxylate compounds are sodium gluconate, K-IAO, calcium gluconate, lemon
One kind in sour sodium, potassium citrate, calcium citrate, ammonium citrate, enuatrol, potassium oleate；Carbonate compound is sodium carbonate, carbon
One kind in sour potassium, magnesium carbonate, zinc carbonate, ammonium carbonate, sodium bicarbonate, saleratus, ammonium hydrogen carbonate.
The present invention outstanding advantages be：Raw material is cheap and easy to get, environmentally protective, and synthesis step is simple and easy to do, product obtained
With adjustable optical property, with catalysis photodissociation aquatic products hydrogen activity and with preferable stability.
Description of the drawings
Fig. 1 is the field emission scanning electron microscope and element point of the graphene nanometer sheet of the single layer phosphorus doping prepared by embodiment 4
Butut.
Fig. 2 is the transmission electron microscope and atomic force microscope of the graphene nanometer sheet of the single layer phosphorus doping prepared by embodiment 4
Figure.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but the present invention is not limited merely to following embodiment.
Embodiment 1
(1) 0.1640g sodium phosphates and 21.1980g sodium carbonate mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
5min is calcined under atmosphere in 500 DEG C, heating rate is 0.1 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 0.1mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by extra salt.
Embodiment 2
(1) 2.1227g potassium phosphates and 27.6420g potassium carbonate mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
600min is calcined under atmosphere in 3000 DEG C, heating rate is 10 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 2mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
Embodiment 3
(1) 10.1565g ammonium phosphate and 16.8020g sodium bicarbonate mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
50min is calcined under atmosphere in 800 DEG C, heating rate is 0.5 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 0.5mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by extra salt.
Embodiment 4
(1) 16.3940g sodium phosphates and 43.6280g sodium gluconate mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
100min is calcined under atmosphere in 1300 DEG C, heating rate is 1 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 1mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
Fig. 1 is the field emission scanning electron microscope and element point of the graphene nanometer sheet of the single layer phosphorus doping prepared by the present embodiment
Butut, from figure can the product there is very thin lamellar structure, and sample contains carbon and P elements, both elements are uniform
It must be distributed in lamellar structure；Fig. 2 be the present embodiment prepared by single layer phosphorus doping graphene nanometer sheet transmission electron microscope and
Atomic force microscopy diagram, for the lamella close to transparent, atomic force microscopy diagram shows that the nanometer sheet of the sample is thick as can be seen from Figure
Degree is 0.58nm, illustrates the graphene nanometer sheet for being successfully prepared single layer phosphorus doping.
Embodiment 5
(1) 2.1227g potassium phosphates and 64.8820g potassium citrate mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
200min is calcined under atmosphere in 1600 DEG C, heating rate is 2 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 1.5mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by extra salt.
Embodiment 6
(1) 10.1565g ammonium phosphate and 60.8880g enuatrol mixed grindings is uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
300min is calcined under atmosphere in 1800 DEG C, heating rate is 5 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 2mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
Embodiment 7
(1) by 1.6394g sodium phosphates, 2.1814g sodium gluconates and 21.1980g sodium carbonate mixed grindings are uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
400min is calcined under atmosphere in 2000 DEG C, heating rate is 8 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 1mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
Embodiment 8
(1) by 10.1565g potassium carbonate, 16.2205g potassium citrates and 27.6420g potassium carbonate mixed grindings are uniform.
(2) mixture obtained in step (1) is added in corundum magnetic boat and is put into tube furnace, mixture is in argon gas gas
500min is calcined under atmosphere in 2500 DEG C, heating rate is 10 DEG C/min, after calcining, naturally cools to room under an argon atmosphere
Temperature.
(3) product of gained in step (2) is washed for several times with 2mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
Claims (5)
1. a kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap, it is characterised in that：
(1) by phosphate compounds, the two of which of carboxylate compounds and carbonate compound is 0.01 in molar ratio:20~
40:20 or three kind in molar ratio be 0.01:0.01:20~40:40:20 mixed grindings are uniform；
(2) mixture obtained in step (1) is added in corundum porcelain boat and is put into tube furnace, mixture is under an argon atmosphere
5~600min is calcined in 500~3000 DEG C, heating rate is 0.1~10 DEG C/min, after calcining, under an argon atmosphere certainly
So it is cooled to room temperature；
(3) product of gained in step (2) is washed for several times with 0.1~2mol/L dilute hydrochloric acid, distilled water and ethyl alcohol, it is more to remove
Then product is dried in vacuo 10h at 80 DEG C and obtains the graphene nanometer sheet of single layer phosphorus doping by remaining salt.
2. preparation method according to claim 1, it is characterised in that：The phosphate compounds is disodium hydrogen phosphate,
Sodium dihydrogen phosphate, sodium phosphate, sodium hypophosphite, sodium metaphosphate, sodium pyrophosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, phosphorus
Sour hydrogen calcium, calcium phosphate, calcium pyrophosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, one kind in ammonium phosphate.
3. preparation method according to claim 1, it is characterised in that：The carboxylate compounds be sodium gluconate,
One in K-IAO, calcium gluconate, sodium citrate, potassium citrate, calcium citrate, ammonium citrate, enuatrol, potassium oleate
Kind.
4. preparation method according to claim 1, it is characterised in that：The carbonate compound is sodium carbonate, carbonic acid
One kind in potassium, magnesium carbonate, zinc carbonate, ammonium carbonate, sodium bicarbonate, saleratus, ammonium hydrogen carbonate.
5. preparation method according to claim 1, it is characterised in that：Mole of phosphate compounds and carboxylate compounds
Than being 0.01:20~40:20, the molar ratio of phosphate compounds and carbonate compound is 0.01:20~40:20, phosphate
The molar ratio of compound, carboxylate compounds and carbonate compound is 0.01:0.01:20~40:40:20.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451487A (en) * | 2019-07-04 | 2019-11-15 | 北京理工大学 | A kind of preparation method of the boron doped graphene nanometer sheet of the adjustable single p-type of band gap |
| CN113582165A (en) * | 2021-07-21 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus atom doped graphene nanocomposite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140097A (en) * | 2014-07-25 | 2014-11-12 | 深圳新宙邦科技股份有限公司 | Phosphor doped grapheme and preparing method thereof |
| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
-
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- 2018-06-26 CN CN201810673572.4A patent/CN108658060A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140097A (en) * | 2014-07-25 | 2014-11-12 | 深圳新宙邦科技股份有限公司 | Phosphor doped grapheme and preparing method thereof |
| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451487A (en) * | 2019-07-04 | 2019-11-15 | 北京理工大学 | A kind of preparation method of the boron doped graphene nanometer sheet of the adjustable single p-type of band gap |
| CN113582165A (en) * | 2021-07-21 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus atom doped graphene nanocomposite |
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Application publication date: 20181016 |