CN105776197B - A kind of porous surface grapheme material and preparation method thereof - Google Patents
A kind of porous surface grapheme material and preparation method thereof Download PDFInfo
- Publication number
- CN105776197B CN105776197B CN201610257353.9A CN201610257353A CN105776197B CN 105776197 B CN105776197 B CN 105776197B CN 201610257353 A CN201610257353 A CN 201610257353A CN 105776197 B CN105776197 B CN 105776197B
- Authority
- CN
- China
- Prior art keywords
- grapheme material
- porous surface
- graphene
- solution
- surface grapheme
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of porous surface grapheme material and preparation method thereof, the preparation method comprises the following steps：(1) grapheme material is dispersed in the fulvescent that ultrasound is uniformly dispersed and is translucent to solution in cosolvent；(2) metal nitrate is added in the solution obtained to step (1), stirring to metal nitrate is completely dissolved；(3) solid carbon dioxide is added in the solution obtained to step (2)；(4) solution for obtaining step (3) carries out heating response, reacted solution cooling, centrifugation, dry, collection solid product in closed container；(5) step (4) is collected to obtained solid product to calcine in an inert atmosphere, porous surface grapheme material is produced.Preparation method of the present invention is simple, raw material is easy to get, and low for equipment requirements, simple to operate, reaction speed is fast, preparation time is short, pollution-free, energy-conserving and environment-protective, and the grapheme material surface pore prepared is evenly distributed, controllable, easily realizes industrialized production.
Description
Technical field
The present invention relates to a kind of technical field of nano material, and in particular to a kind of porous surface grapheme material and its preparation
Method.
Background technology
2004, the Andre Geim professor research teams of graceful Chester university were obtained using a kind of method of mechanical stripping
The graphene of monoatomic layer thickness, and measure their physical property-Hall effect.Therefore, they obtain 2010
Year Nobel Prize in physics.The good performance of graphene and application prospect cause scientific research field and the height of application field is closed
Note.Graphene-supported composite oxides are one of numerous research fields in graphene composite material, in above-mentioned compound, stone
Black alkene is due to high electric conductivity, specific surface area and good chemical stability and mechanical performance, so as to get composite wood
Expect that overall electric conductivity, machining property are greatly improved.At present, on preparing graphene oxide composite
Research report it is a lot, above-mentioned composite has all been shown in fields such as ultracapacitor, lithium ion battery, photocatalysis
Good application prospect.
But, graphene is lamellar structure, and lithium ion, sodium ion etc. can not penetrate graphenic surface.It is former due to more than
Cause, this grapheme material, ion can only be migrated in the plane parallel to graphene, and in the ion in its plane
Migration velocity is relatively low, and disadvantages mentioned above have impact on the raising of graphene composite material performance.Surface has porose grapheme material not
It is only capable of overcoming disadvantages mentioned above, and adds the ratio of graphene edge so that obtains larger in the ability of fixed oxide
Improve.
The preparation method portalled in graphenic surface corrosion developed at present mainly has three kinds：First method is concentrated nitric acid
And the oxidizing method such as potassium permanganate, the shortcoming of this kind of method is the use of concentrated acid, the washing of a large amount of water or dialysis, table
The size of face and distribution density are uncontrollable；Second method is needed in graphite in oxide surface ablation, this method
Alkene surface deposition oxide nano particle.The technology of ex situ deposition nano particle causes the size and load efficiency of nano particle
It is uncontrollable, therefore cause the size and density controllable degree in the hole that ablation goes out not high.In addition, in-situ deposition oxide nano particles
Technology inevitably causes the irregular of nano-particle to grow up also due to precipitation reaction is carried out in aqueous, therefore,
The controllability of the size of nano-pore and surface distributed density is not high.In addition, precipitating reagent is needed to use in precipitation reaction, therefore,
Cumbersome washing step is needed in follow-up processing procedure.The third method be by aryl-aryl coupling react under
And on chemical method and high-energy technical method, be typically all to be prepared in substrate, yield is relatively low.For example apply
Porous graphene ultrasound in concentrated nitric acid solution is obtained in patent CN104959134A, CN104934574A, is being prepared
Substantial amounts of concentrated acid is used in journey, it is therefore desirable to cumbersome centrifugation, washing step.One kind described in patent CN102107868A is more
In the preparation method of hole grapheme material, nano particle is deposited in graphenic surface using ex situ technology, due to nano particle
Size and load efficiency it is uncontrollable, therefore cause the size and density degree of controllability in the hole that ablation goes out not high.
The content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides a kind of method for preparing porous graphene material, this method
Cost of material is low, technique is simple, and the grapheme material surface pore prepared is evenly distributed, controllable.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of method for preparing porous surface grapheme material, comprises the following steps：
(1) grapheme material is dispersed in the fulvescent that ultrasound is uniformly dispersed and is translucent to solution in cosolvent；
(2) metal nitrate is added in the solution obtained to step (1), stirring to metal nitrate is completely dissolved；
(3) solid carbon dioxide (dry ice) is added in the solution obtained to step (2)；
(4) solution for obtaining step (3) carries out heating response in closed container, reacted solution cooling, centrifugation,
Dry, collect solid product；
(5) step (4) is collected to obtained solid product to calcine in an inert atmosphere, porous surface graphene material is produced
Material.
It is preferred that, the grapheme material is reduced graphene, graphene oxide or graphite oxide；
It is preferred that, the cosolvent is methanol, ethanol, propyl alcohol or acetonitrile；
It is preferred that, the metal nitrate is any one or more of nickel nitrate, copper nitrate, cobalt nitrate and ferric nitrate；
It is preferred that, the mass volume ratio of the grapheme material and the cosolvent is 1:0.2-5, the mass volume ratio
Unit be mg/mL；The mass ratio of the graphene and the metal nitrate is 1:0.5-4；The dry ice with it is described closed
The mass volume ratio of container is 1:20-40, the unit of the mass volume ratio is g/mL；
It is preferred that, the closed container is autoclave, the condition of the heating response：Reaction temperature is 150-200
DEG C, the reaction time is 0.5-1 hours；
It is preferred that, the inert atmosphere is argon gas or nitrogen；
It is preferred that, 600-900 DEG C of the calcining heat of the calcining, calcination time is 0.5-1 hours；
Present invention also offers the porous surface grapheme material prepared by any of the above-described method.
The porous surface grapheme material of the present invention can be widely applied in photocatalysis field, photoelectromagnetic field and adsorption material
Material field.
Preparation method reaction mechanism of the present invention：The present invention, as swelling agent, after being heated in closed container, is done using dry ice
Ice expands rapidly cosolvent, and forms in closed container high pressure, the carbon that carbon dioxide solubility is formed in a small amount of crystallization water
Acid ion take part in the formation of presoma, and obtained presoma is impalpable structure, limits and loads oxygen in graphenic surface
The crystallization of compound particle and the increase of particle diameter so that area load oxide evenly, while avoiding free receive
The formation of rice grain so that the corrosion in graphenic surface hole is evenly.Due to the difference of the different oxide temperature of carbon thermal reduction, with
And different oxides obtain the of different sizes of metal nanoparticle after carbon thermal reduction, by adjust add nitrate species,
The size and distribution density of realizing nano surface hole of the mass ratio and calcining heat of graphene and nitrate are controllable.
Beneficial effects of the present invention are：
1. the invention provides a kind of porous surface grapheme material and preparation method thereof.It is initiative in preparation method
Use solid carbon dioxide (dry ice) as swelling agent, without additional complexity equipment；
2. preparation method of the present invention is simple, raw material is easy to get, low for equipment requirements, simple to operate, reaction speed is fast, when preparing
Between it is short, while without using with precipitating reagents such as corrosivity, explosivity, the ammoniacal liquor of human toxicity, sodium hydroxide, potassium hydroxide or
For dispersed surfactant, and the oxidant, the safe nothing of preparation method such as the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate
Pollution, energy-conserving and environment-protective；And the post-processing step complicated without washing etc., technological process is greatly simplify, chemistry is easily produced dirty
Dye, easily realizes industrialized production；
3. the porous surface grapheme material even pore distribution that the present invention is prepared, while adding nitric acid by adjusting
Salt species, graphene and the mass ratio of nitrate and the size for realizing nano surface hole of calcining heat and be distributed close
Degree is controllable.The porous surface grapheme material that the present invention is prepared can be widely applied in photocatalysis field, photoelectromagnetic field
With sorbing material field, have a good application prospect.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only embodiments of the invention, for this area
For those of ordinary skill, on the premise of not paying creative work, it can also be obtained according to the accompanying drawing of offer other attached
Figure.
Fig. 1 is obtained porous surface grapheme material electron scanning micrograph prepared by embodiment 1.
Embodiment
The invention will be further described for shown embodiment below in conjunction with the accompanying drawings.
Embodiment 1
2 milligrams of graphene oxides are dispersed in 10 milliliters of ethanol, ultrasound is uniformly dispersed and is translucent to solution
Fulvescent, add the stirring of 8 milligrams of nickel nitrates and be allowed to be completely dissolved.5 grams of solid carbon dioxides are added in above-mentioned solution (dry
Ice), said mixture is placed in 100 milliliters of autoclaves, in 200 DEG C of heating responses 0.5 hour, stirred simultaneously；Will be anti-
Should after solution cooling, centrifugation, dry, in inert atmosphere (nitrogen) at 800 DEG C calcine 1 hour, obtain surface have receive
The graphene of metre hole.As shown in figure 1, the porous graphene material surface hole is uniformly distributed, nano-pore aperture integrated distribution exists
In the range of 80-150nm.
Embodiment 2
30 milligrams of graphene oxides are dispersed in 20 ml methanols, ultrasound is uniformly dispersed and is translucent to solution
Fulvescent, add the stirring of 60 milligrams of copper nitrates.4 grams of solid carbon dioxides (dry ice) are added in above-mentioned solution, will be above-mentioned
Mixture is placed in 100 milliliters of autoclaves, in 170 DEG C of heating responses 0.8 hour, is stirred simultaneously；By reacted solution
Cool down, centrifuge, dry, calcine 1h at 600 DEG C in inert atmosphere (argon gas), obtaining surface has the graphene of nano-pore,
The porous graphene material surface hole is uniformly distributed, and nano-pore aperture integrated distribution is in the range of 100-200nm.
Embodiment 3
200 milligrams of graphene oxides are dispersed in 40 milliliters of acetonitriles, ultrasound is uniformly dispersed to solution and in semi-transparent
Bright fulvescent, adds 100 milligrams of ferric nitrate stirrings and is allowed to be completely dissolved.5 grams of solid-state titanium dioxides are added in above-mentioned solution
Carbon (dry ice), said mixture is placed in 200 milliliters of autoclaves, in 180 DEG C of heating responses 1 hour, is stirred simultaneously；Will
The cooling of reacted solution, centrifugation, dry, 0.5h is calcined at 900 DEG C in inert atmosphere (argon gas), obtain surface and have to receive
The graphene of metre hole, the porous graphene material surface hole is uniformly distributed, and nano-pore aperture integrated distribution is in 50-100nm models
In enclosing.
Embodiment 4
50 milligrams of reduced graphenes are dispersed in 100 milliliters of propyl alcohol, ultrasound is uniformly dispersed and is translucent to solution
Fulvescent, add the stirring of 40 milligrams of cobalt nitrates.10 grams of solid carbon dioxides (dry ice) are added in above-mentioned solution, will be above-mentioned
Mixture is placed in 400 milliliters of autoclaves, in 150 DEG C of heating responses 1 hour, is stirred simultaneously；Reacted solution is cold
But, centrifuge, dry, calcine 0.5h at 800 DEG C in inert atmosphere (nitrogen), obtaining surface has the graphene of nano-pore,
The porous graphene material surface hole is uniformly distributed, and nano-pore aperture integrated distribution is in the range of 60-120nm.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, not to present invention protection model
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deform still within protection scope of the present invention that creative work can make.
Claims (10)
1. a kind of method for preparing porous surface grapheme material, it is characterised in that comprise the following steps：
（1）Grapheme material is dispersed in the fulvescent that ultrasound is uniformly dispersed and is translucent to solution in cosolvent；
（2）To step（1）Metal nitrate is added in obtained solution, stirring to metal nitrate is completely dissolved；
（3）To step（2）Solid carbon dioxide is added in obtained solution；
（4）By step（3）Obtained solution carries out heating response in closed container, and reacted solution is cooled down, centrifuges, done
It is dry, collect solid product；
（5）By step（4）Collect obtained solid product to calcine in an inert atmosphere, produce porous surface grapheme material；
Wherein, the condition of the heating response：Reaction temperature is 150-200 DEG C, and the reaction time is 0.5-1 hours；
The calcining heat of the calcining is 600-900 DEG C, and calcination time is 0.5-1 hours.
2. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the graphene
Material is reduced graphene or graphene oxide.
3. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the graphene
Material is replaced with graphite oxide.
4. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the cosolvent
For methanol, ethanol, propyl alcohol or acetonitrile.
5. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the metal nitre
Hydrochlorate is any one or more of nickel nitrate, copper nitrate, cobalt nitrate and ferric nitrate.
6. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the graphene
The mass volume ratio of material and the cosolvent is 1:0.2-5, the unit of the mass volume ratio is mg/mL；The graphene
Mass ratio with the metal nitrate is 1:0.5~ 4；The mass volume ratio of the dry ice and the closed container is 1:20-
40, the unit of the mass volume ratio is g/mL.
7. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the closed appearance
Device is autoclave.
8. a kind of method for preparing porous surface grapheme material as claimed in claim 1, it is characterised in that the indifferent gas
Atmosphere is argon gas or nitrogen.
9. a kind of porous surface grapheme material that claim 1-8 any one methods describeds are prepared.
10. the porous surface grapheme material described in claim 9 is in photocatalysis field, photoelectromagnetic field and sorbing material field
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610257353.9A CN105776197B (en) | 2016-04-22 | 2016-04-22 | A kind of porous surface grapheme material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610257353.9A CN105776197B (en) | 2016-04-22 | 2016-04-22 | A kind of porous surface grapheme material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776197A CN105776197A (en) | 2016-07-20 |
| CN105776197B true CN105776197B (en) | 2017-09-15 |
Family
ID=56399319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610257353.9A Expired - Fee Related CN105776197B (en) | 2016-04-22 | 2016-04-22 | A kind of porous surface grapheme material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776197B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089655A (en) * | 2017-06-16 | 2017-08-25 | 青岛大学 | A kind of method that utilization Mechanical Method prepares single-layer graphene |
| CN107335443B (en) * | 2017-07-12 | 2018-08-21 | 太原理工大学 | The method that explosion method quickly prepares graphene-supported multimetal reforming catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2984365B1 (en) * | 2011-12-20 | 2014-01-17 | Toulouse Inst Nat Polytech | METHOD FOR MANUFACTURING GRAPHENE AND GRAPHENE OBTAINED BY THIS METHOD |
| CN102849734B (en) * | 2012-09-28 | 2014-12-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method of porous graphene |
| CN103466604A (en) * | 2013-08-13 | 2013-12-25 | 华东理工大学 | Preparation method of porous graphene |
| CN105293476B (en) * | 2015-11-16 | 2018-07-10 | 复旦大学 | A kind of preparation method of large scale graphene oxide or graphene |
-
2016
- 2016-04-22 CN CN201610257353.9A patent/CN105776197B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776197A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jia et al. | One-pot template-free synthesis and highly ethanol sensing properties of ZnSnO3 hollow microspheres | |
| Yang et al. | Facile dicyandiamide-mediated fabrication of well-defined CuO hollow microspheres and their catalytic application | |
| CN102614871B (en) | Method for preparing grapheme/silver nanoparticles composite material by using liquid phase method | |
| CN105397103A (en) | Nano-silver/graphene composite material and preparation method thereof | |
| CN102698666B (en) | Based on the preparation method of the graphene/nanometer particle composite material of infrared irridiation | |
| CN102745675A (en) | Preparation method of spinel-type magnetic MFe2O4/graphene composite material | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN102633307A (en) | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles | |
| CN104785266B (en) | A kind of preparation method of nano-cobaltic-cobaltous oxide/graphene composite material | |
| CN104174422A (en) | High nitrogen doped graphene and fullerene-like molybdenum selenide hollow-ball nanocomposite and preparation method thereof | |
| CN105923625B (en) | A kind of preparation method of graphene-supported uniform single oxide quantum dot | |
| Shahmiri et al. | Effect of pH on the synthesis of CuO nanosheets by quick precipitation method | |
| CN102133645B (en) | Preparation method of environment-friendly micron-size triangular silver sheet | |
| CN102718209B (en) | Method for preparing graphene based on reduction of divalent iron ion | |
| Liang et al. | Controlled synthesis of Co3O4 nanopolyhedrons and nanosheets at low temperature | |
| Fan et al. | Spontaneous growth of CuO nanoflakes and microflowers on copper in alkaline solutions | |
| Motlagh et al. | Structural properties of nickel hydroxide/oxyhydroxide and oxide nanoparticles obtained by microwave-assisted oxidation technique | |
| CN108339562B (en) | Preparation method of iron ion doped carbon nitride nanotube and obtained product | |
| CN108394935B (en) | A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet | |
| CN105776197B (en) | A kind of porous surface grapheme material and preparation method thereof | |
| CN105800604A (en) | Preparation method of graphene-loaded cobalt ferrite quantum dot | |
| CN106215968B (en) | A kind of carbon coating CuO composite material and preparation methods of doping nitrogen | |
| CN108855217B (en) | Preparation method and application of copper-based metal organic framework nano sheet | |
| CN105329932A (en) | Method for large-scale preparation of carbon-doped mixed transition metal oxide porous microspheres | |
| Yang et al. | Progress on two-dimensional binary oxide materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170915 Termination date: 20180422 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |