CN104828801B - A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus - Google Patents
A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus Download PDFInfo
- Publication number
- CN104828801B CN104828801B CN201510228997.0A CN201510228997A CN104828801B CN 104828801 B CN104828801 B CN 104828801B CN 201510228997 A CN201510228997 A CN 201510228997A CN 104828801 B CN104828801 B CN 104828801B
- Authority
- CN
- China
- Prior art keywords
- brucite
- precipitate
- kinds
- powder
- dimension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses the preparation method of a kind of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus, specifically comprise the following steps that and brucite is added in appropriate sodium butyrate solution, stirring, aging, add acetone and parathion-methyl, 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, it is heated to 400～600 DEG C under vacuum, calcining 2～4h, it is then added in hydrochloric acid solution, by precipitate and separate the most under vacuum, it is heated to 2000～2500 DEG C, thermally treated 3～6h, i.e. obtain two dimension three kinds of element doping Graphenes of nitrogen sulfur phosphorus 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 nitrogen sulfur phosphorus three
Plant the preparation method of element doping 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 nitrogen three kinds of element doping Graphenes of sulfur phosphorus.
To this end, the invention provides techniques below scheme, a kind of two dimension three kinds of elements of nitrogen sulfur phosphorus are mixed
The preparation method of miscellaneous Graphene, in turn includes the following steps:
1) according to the amount of the corresponding 0.5～1mmol sodium butyrate of every gram of brucite, by 20-50 mesh
The brucite of sieve joins in the sodium butyrate 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 the neatly that butanoic acid is modified
Stone suspension；
2) according still further to the acetone and 1.5～3 that every gram of brucite corresponding amount is 0.5～1.5mmol
The parathion-methyl of mmol, brucite acetone and parathion-methyl being added to butanoic acid modified hangs
In turbid liquid, 60～70 DEG C of waters bath with thermostatic control are stirred 6～8h, precipitate are separated from liquid,
It is washed with deionized water precipitate 2～3 times, dries, grind, cross 20～40 mesh sieves and obtain modified water
Talcum 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 three kinds of element doping Graphenes of nitrogen sulfur phosphorus 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
Sodium butyrate, exchanges to hydrotalcite layers by anion exchange effect by sodium butyrate, and recycling has
Distributional effects between machine thing, is adsorbed onto hydrotalcite layers by acetone and parathion-methyl, and
Nitrogen phosphorus sulphur atom can compare and is evenly distributed between Organic substance, through 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 three kinds of element doping Graphenes of nitrogen sulfur phosphorus after heat treatment still can keep former
Some layer thickness.
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 sodium butyrate, the commercially available of 20 mesh sieves will be crossed
Magnesium aluminum-hydrotalcite joins in the sodium butyrate solution that mass percent concentration is 0.1%, at 60 DEG C
Water bath with thermostatic control is stirred 5h, aging 12h, obtains the brucite suspension that butanoic acid is modified；Again
According to acetone and the parathion-methyl of 3mmol that every gram of brucite corresponding amount is 0.5mmol,
Acetone and parathion-methyl are added in the brucite suspension that butanoic acid is modified, at 60 DEG C of constant temperature
Stirred in water bath 6h, separates this precipitate from liquid, is washed with deionized water precipitate 2
Time, dry, grind, cross 20 mesh sieves and obtain modified hydrotalcite powder；The modified water that will obtain
Talcum powder is put in vacuum tube furnace, is heated to 400 DEG C under vacuum, vacuum calcining
2h, is cooled to room temperature；Powder after calcining is joined mass percent concentration is 20%
In hydrochloric acid solution, every gram of corresponding 5 milliliters of hydrochloric acid solutions of powder, stir 3h under nitrogen protection,
Precipitate and separate, dries；By the product that obtains under vacuum, it is heated to 2000 DEG C, warp
Heat treatment 3h, i.e. obtains two dimension three kinds of element doping Graphenes of nitrogen sulfur phosphorus after cooling.
Embodiment 2
According to the amount of every gram of brucite correspondence 1mmol sodium butyrate, the commercially available nickel of 50 mesh sieves will be crossed
Aluminum hydrotalcite joins in the sodium butyrate solution that mass percent concentration is 1%, at 70 DEG C of constant temperature
Stirred in water bath 6h, aging 24h, obtain the brucite suspension that butanoic acid is modified；According still further to
Every gram of brucite corresponding amount is acetone and the parathion-methyl of 1.5mmol of 1.5mmol, will
Acetone and parathion-methyl are added in the brucite suspension that butanoic acid is modified, at 70 DEG C of thermostatted waters
Bath is stirred 8h, this precipitate is separated from liquid, is washed with deionized water precipitate 3 times,
Dry, grind, cross 40 mesh sieves and obtain modified hydrotalcite powder；The modified hydrotalcite that will obtain
Powder is put in vacuum tube furnace, is heated to 600 DEG C under vacuum, vacuum calcining 4h,
It is cooled to room temperature；Powder after calcining is joined the hydrochloric acid that mass percent concentration is 40% molten
In liquid, every gram of corresponding 10 milliliters of hydrochloric acid solutions of powder, stir 4h, precipitation under nitrogen protection
Separate, dry；By the product that obtains under vacuum, it is heated to 2500 DEG C, at heat
Reason 6h, i.e. obtains two dimension three kinds of element doping Graphenes of nitrogen sulfur phosphorus after cooling.
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 sodium butyrate, the neatly of 20 mesh sieves will be crossed
Stone joins in the sodium butyrate solution that mass percent concentration is 0.5%, 60 DEG C of waters bath with thermostatic control
Middle stirring 6h, aging 24h, obtain the brucite suspension that butanoic acid is modified；According still further to every gram
Brucite corresponding amount is acetone and the parathion-methyl of 1.5mmol of 0.75mmol, by third
Ketone and parathion-methyl are added in the brucite suspension that butanoic acid is modified, 70 DEG C of waters bath with thermostatic control
Middle stirring 8h, separates this precipitate from liquid, is washed with deionized water precipitate 3 times,
Dry, grind, cross 40 mesh sieves and obtain modified hydrotalcite powder；The modified hydrotalcite that will obtain
Powder is put in vacuum tube furnace, is heated to 500 DEG C under vacuum, vacuum calcining 4h,
It is cooled to room temperature；Powder after calcining is joined the hydrochloric acid that mass percent concentration is 40% molten
In liquid, every gram of corresponding 10 milliliters of hydrochloric acid solutions of powder, stir 4h, precipitation under nitrogen protection
Separate, dry；By the product that obtains under vacuum, it is heated to 2500 DEG C, at heat
Reason 5h, i.e. obtains two dimension three kinds of element doping Graphenes of nitrogen sulfur phosphorus after cooling.
Claims (1)
1. the preparation method of two-dimentional nitrogen three kinds of element doping Graphenes of sulfur phosphorus, it is characterised in that: include successively
Following steps:
1) according to the amount of the corresponding 0.5～1mmol sodium butyrate of every gram of brucite, the neatly of 20-50 mesh sieve will be crossed
Stone joins in the sodium butyrate solution that mass percent concentration is 0.1%～1%, in 60～70 DEG C of waters bath with thermostatic control
Stirring 5～6h, aging 12～24h, obtain the brucite suspension that butanoic acid is modified；
2) according still further to acetone and the methyl of 1.5～3mmol that every gram of brucite corresponding amount is 0.5～1.5mmol
Parathion, is added to acetone and parathion-methyl in the brucite suspension that butanoic acid is modified, 60～70 DEG C of perseverances
Tepidarium is stirred 6～8h, precipitate is separated from liquid, be 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 three kinds of element doping Graphenes of nitrogen sulfur phosphorus are i.e. obtained after cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510228997.0A CN104828801B (en) | 2015-05-07 | 2015-05-07 | A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510228997.0A CN104828801B (en) | 2015-05-07 | 2015-05-07 | A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104828801A CN104828801A (en) | 2015-08-12 |
| CN104828801B true CN104828801B (en) | 2016-11-09 |
Family
ID=53807066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510228997.0A Active CN104828801B (en) | 2015-05-07 | 2015-05-07 | A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104828801B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502593B (en) * | 2011-10-11 | 2013-07-10 | 中国石油大学(北京) | Preparation method of grapheme or doped graphene or graphene complex |
| CN102910622B (en) * | 2012-10-25 | 2014-10-29 | 常州大学 | Preparation method of two-dimensional nano-graphene |
-
2015
- 2015-05-07 CN CN201510228997.0A patent/CN104828801B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104828801A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104817063B (en) | A kind of preparation method of two dimension nitrogen phosphorus doping Graphene | |
| CN104817080B (en) | A kind of preparation method of nitrogen sulfur phosphorus doping graphene film | |
| CN102910622B (en) | Preparation method of two-dimensional nano-graphene | |
| CN104817077B (en) | A kind of preparation method of nitrogen phosphorus doping graphene film | |
| Yang et al. | Crystal defect-mediated {0 1 0} facets of Bi2MoO6 nanosheets for removal of TC: enhanced mechanism and degradation pathway | |
| Xiao et al. | Controlled synthesis and characterization of CuO nanostructures through a facile hydrothermal route in the presence of sodium citrate | |
| Liu et al. | Large-scale synthesis of single-crystalline CuO nanoplatelets by a hydrothermal process | |
| Jang et al. | Synthesis of porous and nonporous ZnO nanobelt, multipod, and hierarchical nanostructure from Zn-HDS | |
| Zhang et al. | Effect of doping 3d transition metal (Fe, Co, and Ni) on the electronic, magnetic and optical properties of pentagonal ZnO2 monolayer | |
| CN104828812B (en) | A kind of preparation method of two dimension sulfur phosphorus doping Graphene | |
| Jang et al. | Dynamic transition between Zn-HDS and ZnO; growth and dissolving mechanism of dumbbell-like ZnO bipod crystal | |
| Korobochkin et al. | Thermal preparation and characterization of nanodispersed copper-containing powders produced by non-equilibrium electrochemical oxidation of metals | |
| CN104817060B (en) | A kind of preparation method of two dimension lithium doping Graphene | |
| CN104828801B (en) | A kind of preparation method of two dimension nitrogen three kinds of element doping Graphenes of sulfur phosphorus | |
| CN104817062B (en) | A kind of preparation method of two dimension nitrogen-doped graphene | |
| CN104828800B (en) | A kind of preparation method of sulfur doping graphene film | |
| CN104843693A (en) | Preparation method of N-doped graphene sheet | |
| CN104843692A (en) | Preparation method of two-dimensional sulfur nitrogen doped graphene | |
| CN104860292A (en) | Preparation method of two-dimensional nitrogen-sulfur phosphate doped with graphene | |
| CN104817079A (en) | Preparation method of two-dimension phosphorus-doped graphene | |
| Yang et al. | Designated‐Tailoring on {100} Facets of Cu2O Nanostructures: From Octahedral to Its Different Truncated Forms | |
| CN104828813A (en) | Preparation method of two-dimensional iron doped graphene | |
| CN104817078B (en) | Preparation method of a sulfur- and nitrogen-doped graphene sheet | |
| CN106365143A (en) | Production method of boron doped carbon quantum dots | |
| CN106398689A (en) | A preparing method of a boron nitrogen doped carbon quantum dot |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201203 Address after: 272000 room 2211, Jinchen international building, Linghua South Road, Liuhang street, high tech Zone, Jining City, Shandong Province Patentee after: Jining xinruida Information Technology Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |