CN104828812B - A kind of preparation method of two dimension sulfur phosphorus doping Graphene - Google Patents
A kind of preparation method of two dimension sulfur phosphorus doping Graphene Download PDFInfo
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Abstract
The present invention discloses the preparation method of a kind of two dimension sulfur phosphorus doping Graphene, specifically comprise the following steps that and brucite is added in appropriate dodecylbenzene sodium sulfonate solution, stirring, aging, add acetone and phosphate n-butyl, 60～70 DEG C of waters bath with thermostatic control are stirred 6～8h, precipitate is separated from liquid, it is washed with deionized water precipitate 2～3 times, dry, grind, cross 20～40 mesh sieves and obtain modified hydrotalcite powder；Powder will be obtained and put in vacuum tube furnace, be heated to 400～600 DEG C under vacuum, calcine 2～4h, it is then added in hydrochloric acid solution, by precipitate and separate the most under vacuum, is heated to 2000～2500 DEG C, thermally treated 3～6h, i.e. obtain two dimension sulfur phosphorus doping Graphene after cooling.The method material is simple, mild condition.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly relate to a kind of two dimension sulfur phosphorus doping
The preparation method of Graphene.
Background technology
In the R&D process of new material, dimension has become a weight of modulating substance structure and characteristic
Want parameter.When material is changed to two dimension, a peacekeeping zero dimension by three dimensional structure, its geometry and thing
Physical chemistry characteristic will occur significant change.Two-dimension nano materials is because having anisotropy and uniqueness
Photoelectric properties and be widely used in numerous necks such as solid nano device, sensing and function film
Territory.Particularly high starch breeding carbon 001 is in the face of the resistivity of lonizing radiation uniqueness, it is expected to be used for
Medical low energy neutron radiation resistance material, X-Ray monochromator radiation resistance material and nuclear fusion
The radiation resistance material of device, it is by the one becoming advanced science and technology field novel radioprotective material
Material.
As two-dimensional material, general thickness direction is monoatomic layer or diatomic layer carbon atom.Graphite
The theoretical implications that two-dimension single layer atomic crystal can not exist has been broken in the discovery of alkene, has caused at present
People's research boom to two dimension monoatomic layer material.This not only becomes generation in nano science field
One of important source of new knowledge, and provide for developing performance function nano material and device
Opportunity.One of the study hotspot in this field is that monoatomic layer material is carried out functional modification at present.
Along with going deep into of research, the demand of two-dimension nano materials is also stepped up, is badly in need of simple
Synthetic method.
But owing to two-dimension nano materials surface free energy is higher, often use in preparation process
Unconventional method, such as can prepare the large-area Graphene of high-quality two by CVD
Dimension nano material, but the expensive of preferable substrate material monocrystalline nickel, this is to affect stone
The key factor of ink alkene industrialized production, the most relatively costly, complex process.Additionally also
Having oxidation-reduction method, its shortcoming is the graphite that magnanimity preparation easily brings waste liquor contamination and preparation
There is certain defect, such as, the topological defect such as five-membered ring, heptatomic ring or existence-OH base in alkene
The fault of construction of group, these will cause Graphene part electrical property loss of energy, make Graphene
Application is restricted.
One of study hotspot of field of graphene is that monoatomic layer material is carried out functionalization at present
Modify.People dream of always can be regular and introduce gold discretely in these monoatomic layer materials
Belong to atom to constitute novel monoatomic layer magnetic material, catalysis material and gas adsorption material,
But owing to transition metal atoms is easily assembled, this dream fails at Graphene and monatomic always
Realize in Ceng.
Quasiconductor can be doped, and the semiconductor energy gap after doping can change.Depend on
According to the difference of alloy, between the energy gap of intrinsic semiconductor, there will be different energy rank.Execute
Body atom can produce new energy rank near the local of conduction band, and acceptor atom is then
New energy rank are being produced near the place of valence band.Alloy is for another of band structure
Significant impact is the position changing fermi level.Fermi level under thermally equilibrated state
Still can keep definite value, this characteristic can draw a lot of other useful electrical characteristics.
(Layered Double Hydroxides is called for short layered di-hydroxyl composite metal oxidate
LDH), also known as brucite, it is the important inorganic functional material of a class.The stratiform knot of its uniqueness
The adjustable degeneration of structure and laminate element and interlayer anion gets more and more people's extensive concerning, through ion
Exchange and layer structure and composition can be made to produce corresponding change to the new object anion of interlayer introducing
Change, thus a big class can be prepared there is the functional material of special nature.Hydrotalcite material belongs to
Anion type laminated compound.Lamellar compound refers to have layer structure, interlayer ion has
One compounds of interchangeability, utilizes lamellar compound main body institute under highly polar molecular action
The intercalation having and the interchangeability of interlayer ion, introduce some functional guest species
Laminate distance is also strutted thus forms layer-pillared compound by bedding void.
Brucite chemical structure of general formula is: [M2+ 1-xM3+x(OH)2]x+[(An-)x/n·mH2O],
Wherein M2+For Mg2+、Ni2+、Mn2+、Zn2+、Ca2+、Fe2+、Cu2+Etc. bivalence gold
Belong to cation；M3+For Al3+、Cr3+、Fe3+、Co3+Deng trivalent metal cation；An-
For anion, such as CO3 2-、NO3 -、Cl-、OH-、SO4 2-、PO4 3-、C6H4(COO)2 2-
Etc. inorganic and organic ion and complex ion, when interlevel inorganic anion is different, neatly
The interlamellar spacing of stone is different.
Summary of the invention
It is an object of the invention to as overcoming complicated process of preparation in prior art, expensive etc.
Not enough, it is provided that the preparation method of a kind of two dimension sulfur phosphorus doping Graphene.
To this end, the invention provides techniques below scheme, a kind of two dimension sulfur phosphorus doping Graphene
Preparation method, in turn includes the following steps:
1) according to the amount of the corresponding 0.5～1mmol dodecylbenzene sodium sulfonate of every gram of brucite, will
The brucite crossing 20-50 mesh sieve joins the dodecane that mass percent concentration is 0.1%～1%
In base benzene sulfonic acid sodium salt solution, stirring 5～6h in 60～70 DEG C of waters bath with thermostatic control, aging 12～24h,
Obtain the brucite suspension that DBSA is modified；
2) according still further to the acetone and 1～5mmol that every gram of brucite corresponding amount is 0.1～0.5mmol
Phosphate n-butyl, is added to the brucite that DBSA is modified by acetone and phosphate n-butyl
In suspension, 60～70 DEG C of waters bath with thermostatic control are stirred 6～8h, precipitate is divided from liquid
From, it is washed with deionized water precipitate 2～3 times, dries, grind, cross 20～40 mesh sieves and changed
Property brucite powder；
3) the modified hydrotalcite powder obtained is put in vacuum tube furnace, under vacuum
It is heated to 400～600 DEG C, vacuum calcining 2～4h, it is cooled to room temperature；
4) powder after calcining is joined the hydrochloric acid that mass percent concentration is 20%～40% molten
In liquid, every gram of corresponding 5～10 milliliters of hydrochloric acid solutions of powder, stirring 3～4h under nitrogen protection,
Precipitate and separate, dries；
5) by the product that obtains under vacuum, it is heated to 2000～2500 DEG C, at heat
Reason 3～6h, i.e. obtains two dimension sulfur phosphorus doping Graphene after cooling.
Compared with prior art, the present invention has a following useful technique effect:
1. prepare this nano material source simple, utilize common anion surfactant
Dodecylbenzene sodium sulfonate, is exchanged to dodecylbenzene sodium sulfonate by anion exchange effect
Hydrotalcite layers, the distributional effects between recycling Organic substance, acetone and phosphate n-butyl are inhaled
It is attached to hydrotalcite layers, and sulphur atom can compare and is evenly distributed between Organic substance, warp
Cross drying, carbonization, stripping can prepare the lamella material with carbon element with nanoscale.
2. utilize the special construction of brucite, it is ensured that interlayer Organic substance is being with one layer or two
The monomolecular dispersion of layer, forms two dimension polymerizable aromatic carbon structure after 400～600 DEG C of carbonizations.
3. the material after carbonization is after overpickling, and the structure of brucite itself is broken
Bad, metal-oxide is dissolved by acid, and the carbonaceous material of interlayer is peeled off naturally, process is simple,
Gentle.
4. the two-dimentional sulfur phosphorus doping Graphene after heat treatment still can keep original interlayer thick
Degree.
Detailed description of the invention
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 every gram of brucite correspondence 0.5mmol dodecylbenzene sodium sulfonate, incited somebody to action 20
The commercially available magnesium aluminum-hydrotalcite of mesh sieve joins the detergent alkylate that mass percent concentration is 0.1%
In sodium sulfonate solution, 60 DEG C of waters bath with thermostatic control are stirred 5h, aging 12h, obtains dodecane
The brucite suspension that base benzenesulfonic acid is modified；It is 0.1mmol according still further to every gram of brucite corresponding amount
Acetone and 5mmol phosphate n-butyl, acetone and phosphate n-butyl are added to detergent alkylate
In the brucite suspension of sulfonic acid modified, 60 DEG C of waters bath with thermostatic control are stirred 6h, by this precipitation
Thing separates from liquid, is washed with deionized water precipitate 2 times, dries, and grinds, and crosses 20 mesh
Sieve obtains modified hydrotalcite powder；The modified hydrotalcite powder obtained is put into vacuum tube furnace
In, it is heated to 400 DEG C under vacuum, vacuum calcining 2h, it is cooled to room temperature；To forge
Powder after burning joins in the hydrochloric acid solution that mass percent concentration is 20%, every gram of powder pair
Answer 5 milliliters of hydrochloric acid solutions, stir 3h, precipitate and separate under nitrogen protection, dry；Will
The product arrived under vacuum, is heated to 2000 DEG C, thermally treated 3h, after cooling and get final product
To two dimension sulfur phosphorus doping Graphene.
Embodiment 2
According to the amount of every gram of brucite correspondence 1mmol dodecylbenzene sodium sulfonate, incited somebody to action 50
The commercially available nickel aluminum hydrotalcite of mesh sieve joins the detergent alkylate sulphur that mass percent concentration is 1%
In acid sodium solution, 70 DEG C of waters bath with thermostatic control are stirred 6h, aging 24h, obtains dodecyl
The brucite suspension that benzenesulfonic acid is modified；It is 0.5mmol according still further to every gram of brucite corresponding amount
Acetone and 1mmol phosphate n-butyl, acetone and phosphate n-butyl are added to detergent alkylate
In the brucite suspension of sulfonic acid modified, 70 DEG C of waters bath with thermostatic control are stirred 8h, by this precipitation
Thing separates from liquid, is washed with deionized water precipitate 3 times, dries, and grinds, and crosses 40 mesh
Sieve obtains modified hydrotalcite powder；The modified hydrotalcite powder obtained is put into vacuum tube furnace
In, it is heated to 600 DEG C under vacuum, vacuum calcining 4h, it is cooled to room temperature；To forge
Powder after burning joins in the hydrochloric acid solution that mass percent concentration is 40%, every gram of powder pair
Answer 10 milliliters of hydrochloric acid solutions, stir 4h, precipitate and separate under nitrogen protection, dry；Will
The product arrived under vacuum, is heated to 2500 DEG C, thermally treated 6h, after cooling and get final product
To two dimension sulfur phosphorus doping Graphene.
Embodiment 3
Be first according to document (Hydrotalcite by Hydrothermal Method synthesize, applied chemistry, 2001,18,
70-72) synthesis prepares magnalium type brucite；Brucite is crossed 40 mesh sieves, standby.
According to the amount of every gram of brucite correspondence 0.8mmol dodecylbenzene sodium sulfonate, incited somebody to action 20
It is molten that the brucite of mesh sieve joins the dodecylbenzene sodium sulfonate that mass percent concentration is 0.5%
In liquid, 60 DEG C of waters bath with thermostatic control are stirred 6h, aging 24h, obtains DBSA
Modified brucite suspension；It is the acetone of 0.4mmol according still further to every gram of brucite corresponding amount
With 5mmol phosphate n-butyl, acetone and phosphate n-butyl are added to DBSA and change
Property brucite suspension in, in 70 DEG C of waters bath with thermostatic control stir 8h, by this precipitate from liquid
Body separates, is washed with deionized water precipitate 3 times, dry, grind, cross 40 mesh sieves and obtain
Modified hydrotalcite powder；The modified hydrotalcite powder obtained is put in vacuum tube furnace, very
500 DEG C it are heated under empty condition, vacuum calcining 4h, it is cooled to room temperature；By the powder after calcining
End joins in the hydrochloric acid solution that mass percent concentration is 40%, every gram of corresponding 10 millis of powder
Rise hydrochloric acid solution, stir 4h, precipitate and separate under nitrogen protection, dry；The product that will obtain
Product under vacuum, are heated to 2500 DEG C, and thermally treated 5h i.e. obtains two dimension after cooling
Sulfur phosphorus doping Graphene.
Claims (1)
1. the preparation method of a two-dimentional sulfur phosphorus doping Graphene, it is characterised in that: in turn include the following steps:
1) according to the amount of the corresponding 0.5～1mmol dodecylbenzene sodium sulfonate of every gram of brucite, by 20-50
The brucite of mesh sieve joins in the dodecylbenzene sodium sulfonate solution that mass percent concentration is 0.1%～1%,
Stirring 5～6h, aging 12～24h in 60～70 DEG C of waters bath with thermostatic control, obtain DBSA modification
Brucite suspension；
2) according still further to the acetone that every gram of brucite corresponding amount is 0.1～0.5mmol and 1～5mmol phosphoric acid just
Butyl ester, is added to acetone and phosphate n-butyl in the brucite suspension that DBSA is modified,
60～70 DEG C of waters bath with thermostatic control are stirred 6～8h, precipitate is separated from liquid, is washed with deionized water precipitate
2～3 times, dry, grind, cross 20～40 mesh sieves and obtain modified hydrotalcite powder；
3) the modified hydrotalcite powder obtained is put in vacuum tube furnace, be heated under vacuum
400～600 DEG C, vacuum calcining 2～4h, it is cooled to room temperature；
4) powder after calcining is joined in the hydrochloric acid solution that mass percent concentration is 20%～40%, often
The corresponding 5～10 milliliters of hydrochloric acid solutions of gram powder, stirring 3～4h under nitrogen protection, precipitate and separate, dry；
5) by the product that obtains under vacuum, it is heated to 2000～2500 DEG C, thermally treated 3～6h,
Two dimension sulfur phosphorus doping Graphene is i.e. obtained after cooling.
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| CN102910622B (en) * | 2012-10-25 | 2014-10-29 | 常州大学 | Preparation method of two-dimensional nano-graphene |
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