CN104817079A - Preparation method of two-dimension phosphorus-doped graphene - Google Patents
Preparation method of two-dimension phosphorus-doped graphene Download PDFInfo
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- CN104817079A CN104817079A CN201510229625.XA CN201510229625A CN104817079A CN 104817079 A CN104817079 A CN 104817079A CN 201510229625 A CN201510229625 A CN 201510229625A CN 104817079 A CN104817079 A CN 104817079A
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Abstract
The invention discloses a preparation method of two-dimension phosphorus-doped graphene. The preparation method particularly includes following steps: adding hydrotalcite to a proper amount of a sodium butyrate solution, stirring the mixture, aging the mixture, adding n-butyl phosphate, stirring the mixture in a constant-temperature water bath at 60-70 DEG C for 6-8 h, separating a precipitation from liquid, washing the precipitation with deionized water for 2-3 times, drying and grinding the precipitation, sieving the precipitation through a sieve being 20-40 in meshes to obtain modified hydrotalcite powder, heating the powder in a vacuum tubular furnace to 400-600 DEG C under a vacuum condition for calcining the powder for 2-4 h, adding the calcined powder to a hydrochloric acid solution, separating the precipitation, heating the precipitation to 2000-2500 DEG C under the vacuum condition to perform heat treatment for 3-6 h, and cooling a product to obtain the two-dimension phosphorus-doped graphene. The preparation method is simple in raw materials and is mild in conditions.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly relate to a kind of preparation method of two-dimentional phosphorus doping Graphene.
Background technology
In the R&D process of novel material, dimension has become an important parameter of modulating substance structure and characteristics.When material changes to two dimension, a peacekeeping zero dimension by three-dimensional structure, will there is significant change in its geometry and physics-chem characteristic.Two-dimension nano materials is widely used in the various fields such as solid nano device, sensing and function film because having the photoelectric properties of anisotropy and uniqueness.Particularly high starch breeding carbon 001 is in the face of the resistivity of radioactive rays uniqueness, be expected the radiation resistance material for medical low energy neutron radiation resistance material, X-Ray monochromator radiation resistance material and nuclear fusion device, the novel radiation resistance material of one that it will become advanced science and technology field.
As two-dimensional material, general thickness direction is monoatomic layer or diatomic layer carbon atom.The theoretical implications that two-dimension single layer atomic crystal can not exist has been broken in the discovery of Graphene, has caused the research boom of current people to two-dimentional monoatomic layer material.This not only becomes one of important source producing new knowledge in nano science field, and is that development performance function nano material and device provide opportunity.One of the study hotspot in this field current carries out functional modification to monoatomic layer material.Along with going deep into of research, the demand of two-dimension nano materials is also progressively increased, is badly in need of simple synthetic method.
But because two-dimension nano materials surface free energy is higher, unconventional method is often adopted in preparation process, such as can prepare the large-area Graphene two-dimension nano materials of high quality by CVD, but the expensive of desirable substrate material monocrystalline nickel, this is the important factor affecting Graphene suitability for industrialized production, also have cost higher in addition, complex process.Also has oxidation-reduction method in addition, its shortcoming is that preparation in macroscopic quantity easily brings the Graphene of waste liquor contamination and preparation to there is certain defect, such as, the textural defect of the topological defect such as five-ring, seven-membered ring or existence-OH group, these will cause Graphene part electrical property loss of energy, and the application of Graphene is restricted.
One of study hotspot of current field of graphene carries out functional modification to monoatomic layer material.People dream of always can in these monoatomic layer materials regular and discretely introduce atoms metal to form novel monoatomic layer magneticsubstance, catalytic material and gas adsorption material, but because transition metal atoms is easily assembled, this dream fails to realize in Graphene and monoatomic layer always.
Semi-conductor can be doped, and the semiconductor energy gap after doping can change to some extent.According to the difference of hotchpotch, between the energy gap of proper semiconductor, there will be different energy rank.Donor atom can produce new energy rank in the place near conduction band, acceptor atom is then producing new energy rank near the place of valence band.Hotchpotch is the position changing fermi level for another great effect of energy band structure.Under thermally equilibrated state, fermi level still can keep definite value, and this characteristic can draw other useful electrical characteristic a lot.
Layered di-hydroxyl composite metal oxidate (Layered Double Hydroxides, be called for short LDH), also known as hydrotalcite, is the important inorganic functional material of a class.The adjustable sex change of the laminate structure of its uniqueness and laminate element and interlayer anion gets more and more people's extensive concerning, introducing new object negatively charged ion through ion-exchange to interlayer can make laminate structure and composition produce corresponding change, thus can prepare the functional materials that a large class has special property.Hydrotalcite material belongs to anion type laminated compound.Lamellar compound refer to there is laminate structure, a compounds that interlayer ion has interchangeability, some functional guest species are introduced bedding void and laminate distance are strutted thus form layer-pillared compound by the intercalation utilizing lamellar compound main body to have under strong polar molecule effect and the interchangeability of interlayer ion.
Hydrotalcite chemical structure of general formula is: [M
2+ 1-xm
3+x (OH)
2]
x+[(A
n-)
x/nmH
2o], wherein M
2+for Mg
2+, Ni
2+, Mn
2+, Zn
2+, Ca
2+, Fe
2+, Cu
2+deng divalent metal; M
3+for Al
3+, Cr
3+, Fe
3+, Co
3+deng trivalent metal cation; A
n-for negatively charged ion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6h
4(COO)
2 2-etc. inorganic and organic ion and complexing ion, when interlevel inorganic negatively charged ion is different, the interlamellar spacing of hydrotalcite is different.
Summary of the invention
The object of the invention is, for overcoming complicated process of preparation in prior art, expensive etc. deficiency, to provide a kind of preparation method of two-dimentional phosphorus doping Graphene.
For this reason, the invention provides following technical scheme, a kind of preparation method of two-dimentional phosphorus doping Graphene, in turn includes the following steps:
1) according to the amount of every gram of hydrotalcite correspondence 0.5 ~ 1mmol Sodium propanecarboxylate, it is in the Sodium propanecarboxylate solution of 0.1% ~ 1% that the hydrotalcite crossing 20-50 mesh sieve is joined mass percent concentration, 5 ~ 6h is stirred in 60 ~ 70 DEG C of waters bath with thermostatic control, aging 12 ~ 24h, obtains the hydrotalcite suspension liquid of Sodium propanecarboxylate modification;
2) be the phosphate n-butyl of 2 ~ 4mmol according to every gram of hydrotalcite corresponding amount again, phosphate n-butyl is added in the hydrotalcite suspension liquid of Sodium propanecarboxylate modification, 6 ~ 8h is stirred in 60 ~ 70 DEG C of waters bath with thermostatic control, throw out is separated from liquid, throw out is washed 2 ~ 3 times with deionized water, dry, grinding, cross 20 ~ 40 mesh sieves and obtain modified hydrotalcite powder;
3) the modified hydrotalcite powder obtained is put into vacuum tube furnace, be heated to 400 ~ 600 DEG C under vacuum, vacuum calcining 2 ~ 4h, is cooled to room temperature;
4) powder after calcining being joined mass percent concentration is in the hydrochloric acid soln of 20% ~ 40%, and every gram of powder correspondence 5 ~ 10 milliliters of hydrochloric acid solns, stir 3 ~ 4h, precipitate and separate under nitrogen protection, dries;
5) by the product that obtains under vacuum, be heated to 2000 ~ 2500 DEG C, through thermal treatment 3 ~ 6h, after cooling, namely obtain two-dimentional phosphorus doping Graphene.
Compared with prior art, the present invention has following useful technique effect:
1. prepare this nano material source simple, utilize common anion surfactant Sodium propanecarboxylate, by anionresin effect, butyric acid root is exchanged to hydrotalcite layers, distributional effects between recycling organism, phosphate n-butyl is adsorbed onto hydrotalcite layers, and phosphorus atom can compare and is evenly distributed between organism, the lamella carbon material with nanoscale can be obtained through oven dry, carbonization, stripping.
2. utilizing the special construction of hydrotalcite, guaranteeing that interlayer organism is being monomolecular dispersion with one deck or two layers, forms two-dimentional polymerizable aromatic carbon structure after 400 ~ 600 DEG C of carbonizations.
3. the material after carbonization is after overpickling, and hydrotalcite itself destructurized, metal oxide is by acid dissolve, and the carbonaceous material of interlayer is peeled off naturally, and process is simple, gentle.
4. the two-dimentional phosphorus doping Graphene after thermal treatment still can keep original layer thickness.
Embodiment
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
According to the amount of the corresponding 1mmol Sodium propanecarboxylate of every gram of hydrotalcite, it is in the Sodium propanecarboxylate solution of 0.1% that the commercially available magnesium aluminum-hydrotalcite crossing 50 mesh sieves is joined mass percent concentration, in 70 DEG C of waters bath with thermostatic control, stir 6h, aging 24h, obtain the hydrotalcite suspension liquid of Sodium propanecarboxylate modification; Be the phosphate n-butyl of 4mmol according to every gram of hydrotalcite corresponding amount again, phosphate n-butyl is added in the hydrotalcite suspension liquid of Sodium propanecarboxylate modification, 8h is stirred in 70 DEG C of waters bath with thermostatic control, throw out is separated from liquid, throw out is washed 3 times with deionized water, dry, grinding, cross 40 mesh sieves and obtain modified hydrotalcite powder; The modified hydrotalcite powder obtained is put into vacuum tube furnace, is heated to 600 DEG C under vacuum, vacuum calcining 4h, is cooled to room temperature; It is in the hydrochloric acid soln of 40% that powder after calcining is joined mass percent concentration, and every gram of corresponding 10 milliliters of hydrochloric acid solns of powder, stir 4h under nitrogen protection, precipitate and separate, dry; By the product that obtains under vacuum, be heated to 2500 DEG C, through thermal treatment 6h, after cooling, namely obtain two-dimentional phosphorus doping Graphene.
Embodiment 2
According to the amount of the corresponding 0.5mmol Sodium propanecarboxylate of every gram of hydrotalcite, it is in the Sodium propanecarboxylate solution of 1% that the commercially available nickel aluminum hydrotalcite crossing 20 mesh sieves is joined mass percent concentration, in 60 DEG C of waters bath with thermostatic control, stir 5h, aging 12h, obtain the hydrotalcite suspension liquid of Sodium propanecarboxylate modification; Be the phosphate n-butyl of 2mmol according to every gram of hydrotalcite corresponding amount again, phosphate n-butyl is added in the hydrotalcite suspension liquid of Sodium propanecarboxylate modification, 6h is stirred in 60 DEG C of waters bath with thermostatic control, throw out is separated from liquid, throw out is washed 2 times with deionized water, dry, grinding, cross 20 mesh sieves and obtain modified hydrotalcite powder; The modified hydrotalcite powder obtained is put into vacuum tube furnace, is heated to 400 DEG C under vacuum, vacuum calcining 2h, is cooled to room temperature; It is in the hydrochloric acid soln of 20% that powder after calcining is joined mass percent concentration, and every gram of corresponding 5 milliliters of hydrochloric acid solns of powder, stir 3h under nitrogen protection, precipitate and separate, dry; By the product that obtains under vacuum, be heated to 2000 DEG C, through thermal treatment 3h, after cooling, namely obtain two-dimentional phosphorus doping Graphene.
Embodiment 3
First according to the obtained magnalium type hydrotalcite of document (Hydrotalcite by Hydrothermal Method synthesizes, applied chemistry, 2001,18,70-72) synthesis; Hydrotalcite is crossed 40 mesh sieves, for subsequent use.
According to the amount of the corresponding 0.8mmol Sodium propanecarboxylate of every gram of hydrotalcite, it is in the Sodium propanecarboxylate solution of 0.5% that the hydrotalcite crossing 50 mesh sieves is joined mass percent concentration, stirs 6h, aging 24h, obtain the hydrotalcite suspension liquid of Sodium propanecarboxylate modification in 70 DEG C of waters bath with thermostatic control; Be the phosphate n-butyl of 4mmol according to every gram of hydrotalcite corresponding amount again, phosphate n-butyl is added in the hydrotalcite suspension liquid of Sodium propanecarboxylate modification, 8h is stirred in 70 DEG C of waters bath with thermostatic control, throw out is separated from liquid, throw out is washed 3 times with deionized water, dry, grinding, cross 40 mesh sieves and obtain modified hydrotalcite powder; The modified hydrotalcite powder obtained is put into vacuum tube furnace, is heated to 600 DEG C under vacuum, vacuum calcining 4h, is cooled to room temperature; It is in the hydrochloric acid soln of 40% that powder after calcining is joined mass percent concentration, and every gram of corresponding 10 milliliters of hydrochloric acid solns of powder, stir 4h under nitrogen protection, precipitate and separate, dry; By the product that obtains under vacuum, be heated to 2500 DEG C, through thermal treatment 4h, after cooling, namely obtain two-dimentional phosphorus doping Graphene.
Claims (1)
1. a preparation method for two-dimentional phosphorus doping Graphene, is characterized in that: in turn include the following steps:
1) according to the amount of every gram of hydrotalcite correspondence 0.5 ~ 1mmol Sodium propanecarboxylate, it is in the Sodium propanecarboxylate solution of 0.1% ~ 1% that the hydrotalcite crossing 20-50 mesh sieve is joined mass percent concentration, 5 ~ 6h is stirred in 60 ~ 70 DEG C of waters bath with thermostatic control, aging 12 ~ 24h, obtains the hydrotalcite suspension liquid of Sodium propanecarboxylate modification;
2) be the phosphate n-butyl of 2 ~ 4mmol according to every gram of hydrotalcite corresponding amount again, phosphate n-butyl is added in the hydrotalcite suspension liquid of Sodium propanecarboxylate modification, 6 ~ 8h is stirred in 60 ~ 70 DEG C of waters bath with thermostatic control, throw out is separated from liquid, throw out is washed 2 ~ 3 times with deionized water, dry, grinding, cross 20 ~ 40 mesh sieves and obtain modified hydrotalcite powder;
3) the modified hydrotalcite powder obtained is put into vacuum tube furnace, be heated to 400 ~ 600 DEG C under vacuum, vacuum calcining 2 ~ 4h, is cooled to room temperature;
4) powder after calcining being joined mass percent concentration is in the hydrochloric acid soln of 20% ~ 40%, and every gram of powder correspondence 5 ~ 10 milliliters of hydrochloric acid solns, stir 3 ~ 4h, precipitate and separate under nitrogen protection, dries;
5) by the product that obtains under vacuum, be heated to 2000 ~ 2500 DEG C, through thermal treatment 3 ~ 6h, after cooling, namely obtain two-dimentional phosphorus doping Graphene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
| 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 |
| KR20150020156A (en) * | 2014-12-29 | 2015-02-25 | 성균관대학교산학협력단 | Preparing method of doped reduced graphene oxide using ionic liquid, and doped reduced graphene oxide prepared by the same |
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| US20130098768A1 (en) * | 2011-07-12 | 2013-04-25 | Research & Business Foundation Sungkyunkwan University | Electrodeposition of graphene layer from doped graphite |
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Application publication date: 20150805 |