CN107140623B - A method of preparing graphene - Google Patents
A method of preparing graphene Download PDFInfo
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- CN107140623B CN107140623B CN201710372817.5A CN201710372817A CN107140623B CN 107140623 B CN107140623 B CN 107140623B CN 201710372817 A CN201710372817 A CN 201710372817A CN 107140623 B CN107140623 B CN 107140623B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- 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
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- 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
Abstract
The present invention relates to a kind of methods for preparing graphene, it includes the following steps: 1) by carbohydrate and metal nitrate hydrate dissolution in deionized water solvent, then in 150-300 DEG C of hydro-thermal reaction 0.1-3 h, reaction terminates to obtain fluffy solid product, it is rolled into powder and obtains template carbon material, wherein, carbohydrate and the mass ratio of metal nitrate salt hydrate are 0.1-2:0.5-3；2) by template carbon material under atmosphere of inert gases in 300-1000 DEG C of carbonization 1-6 h, obtain grapheme material, then with acid solution impregnate remove template, washed, drying to obtain graphene.The method of the present invention carbon source selects the carbohydrates such as lactose, maltose, galactolipin, sucrose for the first time；Preparation step is simple and convenient to operate, environmentally friendly, is conducive to industrialized production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of preparation of graphene is mainly used for synthesizing
Graphene.
Background technique
Graphene is since 2004 are found, due to its excellent thermal property, mechanical property, electric property, machinery
Performance and other performances get more and more people's extensive concerning, and wherein the theoretical specific surface area of single-layer graphene reaches 2650 m2/ g, leads
Hot coefficient reaches 5300 W/mK, and electron mobility reaches 15000 cm at room temperature2/ VS, by global researcher
Research extensively, grapheme material be used in transistor, lithium battery, supercapacitor, sensor, photoelectric device, at water pollution
Reason, flexible display etc. all have huge potential research and application value.
With going deep into for people's research, various preparation methods also developed by people therewith, wherein comparing tool
It is representational to have micromechanics removing, oxidation-reduction method, chemical vapour deposition technique, epitaxial growth method, chemical synthesis etc..Wherein
Micromechanics stripping method is to be bonded repeatedly with adhesive tape, remove high orientation pyrolytic graphite, is then transferred on substrate material surface, this
Method is complicated for operation, and yield is extremely low, is unfavorable for promotion and application；Oxidation-reduction method graphene be easy fault of construction, time-consuming,
Organic solvent toxicity used is big, safety is low；Chemical vapour deposition technique the high requirements on the equipment, complex process and be difficult to control, at
Ben Taigao；Epitaxial growth method monocrystal SiC is expensive, and preparation condition is just carved, and needs to carry out under high temperature high vacuum, turns from substrate
It moves difficult；In contrast, chemical synthesis reaction step is complicated, laborious time-consuming, the graphite that catalyst pollutes the environment, and synthesizes
Alkene has been easy fault of construction, is unfavorable for being mass produced.However, people have been devoted to find it is a kind of it is easy to operate, without environment
Pollution, production cost is low, the method that can be mass-produced, to realize the industrialized production and application of graphene.
Science and 2004 year 666-669 pages of 306 phase reported the field effect of single layer C film, reported for the first time in article
This material now highly visible of road graphene, preparation method are bond with adhesive tape repeatedly, remove high orientation and be pyrolyzed stone
Ink is then transferred on substrate material surface, has obtained single-layer graphene for the first time.104386684 B of Chinese invention patent CN is proposed
A kind of new method preparing graphene, i.e., by one or more of agriculture and forestry organic waste material, tealeaves and seaweed plant biomass
It carries out pretreatment to clean up, metallic catalyst, solvent metal supported catalyst in biomass is then added, adds pore-creating
Agent high temperature cabonization obtains graphene.The graphene that this method obtains is since raw material mix is uncertain and raw material is different, product
It changes greatly, the graphene for determining structure and property cannot be obtained.102701193 B of Chinese invention patent CN proposes use
Carbon materials, magnetic steel needle abrasive body and solvent are put into grinding container by two methods of wet process preparation and dry process, close
It closes；Container merging is had in the space in transformation magnetic field, is removed, the mixed of graphite nano micro-flake-graphene is made after removing
Close object, isolated graphene.The impure separation of the graphene that this method obtains is inconvenient, and preparation process takes a long time, right
Equipment requirement is higher.
In conclusion the method for preparing graphene is seldom, what is be able to produce is just more rare, finds easy to operate, performance
Stablize, the method that can be mass graphene is still huge challenge.
Summary of the invention
Present invention aims to overcome that prior art defect, provides and a kind of new prepare grapheme material in a mild condition
Method, this method step is simple, easy to operate, environmentally friendly, is conducive to industrialized production.
To achieve the above object, the present invention adopts the following technical scheme:
A method of graphene being prepared, this method comprises the following steps:
1) by carbohydrate and metal nitrate hydrate dissolution in deionized water solvent, then in 150-300 DEG C of hydro-thermal
React 0.1-3 h, reaction terminate obtain fluffy solid product, be rolled into powder and obtain template carbon material, wherein carbohydrate and
The mass ratio of metal nitrate salt hydrate is 0.1-2:0.5-3；
2) by template carbon material in atmosphere of inert gases (such as N2Environment) under in 300-1000 DEG C of carbonization 1-6 h, obtain
Then grapheme material is impregnated with acid solution and removes template, washed, drying to obtain graphene.
Specifically, the carbohydrate is one or more of lactose, maltose, galactolipin and sucrose in step 1)
Mixture.
Specifically, the metal nitrate salt hydrate is zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, six water in step 1)
Close the mixture of one or more of cobalt nitrate and magnesium nitrate hexahydrate.
Further, in step 2, when immersion, acid solution used was preferably the dilute hydrochloric acid of concentration 5-15%, dilute sulfuric acid and dilute
Any one in nitric acid or two or more mixtures, soaking time are 2-8 h.
Compared to the prior art, beneficial achievement of the invention is as follows:
1) carbon source that graphene is prepared in the present invention selects the carbohydrates such as lactose, maltose, galactolipin, sucrose for the first time；
2) present invention prepare graphene technique it is relatively simple, repeatability is strong, obtains that product is more, reaction condition is easy
Reach, it is low for equipment requirements, largely reduce production cost；
3) preparing resulting graphene using the method for the present invention is a kind of three-dimensional lamella multiple hole grapheme material, and is had
Preferable thermal stability and water solubility, yield is higher, is easy industrialized mass production.
Detailed description of the invention:
Fig. 1 is the photo of solution and obtained final product before 1 hydro-thermal reaction of embodiment；
Fig. 2 is the Fourier transform infrared spectroscopy figure for the graphene that embodiment 1 is prepared；
Fig. 3 is the Raman spectrogram for the graphene that embodiment 1 is prepared；
Fig. 4 is the scanning electron microscope (SEM) photograph for the graphene that embodiment 1 is prepared.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
A method of graphene is prepared, specifically: by 0.5 g lactose and 1.0 g zinc nitrate hexahydrates 100 ml's
It is evenly spread under ultrasound condition in beaker in the deionized water solvent of 5 mL, guarantees to be completely dissolved, solution clear；It will burn
Cup is transferred in baking oven in 220 DEG C of 0.5 h of hydro-thermal reaction, and reaction terminates to obtain fluffy solid product, is rolled into powder and is obtained
Template carbon material.By template carbon material in N2Environment 2 h of lower 600 DEG C of carbonizations obtain grapheme material, then are soaked with 10% dilute hydrochloric acid
6 h are steeped to remove template, is cleaned, is collected by centrifugation with ethyl alcohol, deionized water respectively, dry 12 h to get 0.1 final g stone is arrived
Black alkene.
Fig. 1 is that photo is compared before and after embodiment 1 hydro-thermal reaction, in figure this it appears that: product is solid powder sample, sample
Product homogeneity is good, and sample size is larger.
Fig. 2 is the Fourier transform infrared spectroscopy figure for the graphene that embodiment 1 is prepared, 3430 cm in figure-1It is corresponding
It is the resonance absorbing peak of-NH- key, 1614 cm-1Corresponding bands of a spectrum are the coabsorption peak of C-N, 1400 cm-1With 1264 cm-1It is right
The bands of a spectrum answered are the resonance absorbing peaks of aromatic rings, and Spectrum Analysis illustrates to prepare the carbon material that resulting sample is N doping.
The graphite Raman spectrogram that Fig. 3 embodiment 1 is prepared, mainly there are three peak, the peaks G 1584.58 for Raman spectrum
cm-1With 2 peak D, 2800 cm-1The characteristics of showing material graphene-structured, the peak D are 1352.59 cm-1Show that how scarce sample be
Sunken graphene, ID / IG=0.921 also demonstrates this point.Raman shows that sample is the grapheme material of more defects.
Fig. 4 is the scanning sample for the grapheme material that embodiment 1 is prepared, it can be seen that sample structure is three-dimensional porous
Layer material.
Embodiment 2
A method of graphene is prepared, specifically: by 0.5 g maltose and 1.5 g zinc nitrate hexahydrates in 100 mL
Beaker in evenly spread in the deionized water solvent of 5 mL under ultrasound condition, guarantee to be completely dissolved, solution clear；It will
Beaker is transferred to 220 DEG C of 0.5 h of hydro-thermal reaction in baking oven, and reaction terminates to obtain fluffy solid product, is rolled into powder and obtains
Template carbon material.By template carbon material in N2Environment 2 h of lower 600 DEG C of carbonizations obtain grapheme material, then are soaked with 10% dilute sulfuric acid
6 h are steeped, cleaned, be collected by centrifugation with ethyl alcohol, deionized water respectively, drying 12 h to get 0.1 final g graphene is arrived.
Embodiment 3
A method of graphene is prepared, specifically: by 1.2 g galactolipins and 1.8 g Nickelous nitrate hexahydrates in 500 mL
Beaker in evenly spread in the deionized water solvent of 20mL under ultrasound condition, guarantee to be completely dissolved, solution clear；It will
Beaker is transferred to 260 DEG C of 1 h of hydro-thermal reaction in baking oven, and reaction terminates to obtain fluffy solid product, is rolled into powder and obtains mould
Plate carbon material.By template carbon material in N2Environment 1 h of lower 800 DEG C of carbonizations obtains grapheme material, then is impregnated with 15% dust technology
8 h are cleaned with ethyl alcohol, deionized water respectively, are collected by centrifugation, drying 18 h to get 0.24 final g graphene is arrived.
Embodiment 4
A method of preparing graphene, specifically: by 2 g sucrose and 2.5 g cabaltous nitrate hexahydrates 500 mL burning
It is evenly spread in the deionized water solvent of 20 mL under ultrasound condition in cup, guarantees to be completely dissolved, solution clear；It will burn
Cup is transferred to 280 DEG C of 3 h of hydro-thermal reaction in baking oven, and reaction terminates to obtain fluffy solid product, is rolled into powder and obtains template
Carbon material.By template carbon material in N2Environment 4 h of lower 400 DEG C of carbonizations obtain grapheme material, then impregnate 3 with 15% dust technology
H is cleaned with ethyl alcohol, deionized water respectively, is collected by centrifugation, drying 8 h to get 0.4 final g graphene is arrived.
Embodiment 5
A method of preparing graphene, specifically: by 0.2g lactose and 0.8 g magnesium nitrate hexahydrate 100 mL burning
It is evenly spread in the deionized water solvent of 5 mL under ultrasound condition in cup, guarantees to be completely dissolved, solution clear；By beaker
240 DEG C of 2 h of hydro-thermal reaction in baking oven are transferred to, reaction terminates to obtain fluffy solid product, is rolled into powder and obtains template carbon
Material.By template carbon material in N2Environment 3 h of lower 600 DEG C of carbonizations obtain grapheme material, then impregnate 6 h with 15% dilute hydrochloric acid,
It cleaned, be collected by centrifugation with ethyl alcohol, deionized water respectively, drying 12 h to get 0.04 final g graphene is arrived.
Embodiment 6
A method of preparing graphene, specifically: by 1.0 g lactose and 3 g zinc nitrate hexahydrates 200 mL burning
It is evenly spread in the deionized water solvent of 10 mL under ultrasound condition in cup, guarantees to be completely dissolved, solution clear；It will burn
Cup is transferred to 240 DEG C of 1 h of hydro-thermal reaction in baking oven, and reaction terminates to obtain fluffy solid product, is rolled into powder and obtains template
Carbon material.By template carbon material in N2Environment 31 h of lower 600 DEG C of carbonizations obtain grapheme material, then impregnate 6 with 15% dust technology
H is cleaned with ethyl alcohol, deionized water respectively, is collected by centrifugation, drying 12 h to get 0.2 final g graphene is arrived.
Claims (3)
1. a kind of method for preparing graphene, which is characterized in that this method comprises the following steps:
1) by carbohydrate and metal nitrate hydrate dissolution in deionized water solvent, then in 150-300 DEG C of hydro-thermal reaction
0.1-3 h, reaction terminate to obtain fluffy solid product, are rolled into powder and obtain template carbon material, wherein carbohydrate and metal
The mass ratio of nitrate hydrate is 0.1-2:0.5-3；
2) by template carbon material under atmosphere of inert gases in 300-1000 DEG C of carbonization 1-6 h, obtain grapheme material, so
It is impregnated afterwards with acid solution and removes template, washed, drying to obtain graphene, structure is three-dimensional porous sheet layer material；
The carbohydrate is the mixture of one or more of lactose, maltose and galactolipin.
2. preparing the method for graphene according to claim 1, which is characterized in that in step 1), the metal nitrate salt water
Conjunction object is one or more of zinc nitrate hexahydrate, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and magnesium nitrate hexahydrate
Mixture.
3. preparing the method for graphene according to claim 1, which is characterized in that in step 2, when immersion acid solution used
It is for any one or two or more mixtures, the soaking time in the dilute hydrochloric acid, dilute sulfuric acid and dust technology of concentration 5-15%
2-8 h.
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| CN108428557B (en) * | 2018-04-09 | 2019-11-08 | 青岛科技大学 | A kind of preparation method of two-dimensional layer carbon material |
| CN112225203B (en) * | 2020-10-19 | 2022-03-22 | 中南大学 | Method for preparing thin-layer graphene negative active material by using antibiotic fungi residues |
| CN112599358B (en) * | 2020-12-18 | 2022-06-14 | 郑州大学 | Porous carbon nano-chip embedded gold nanocrystalline composite material and preparation method thereof |
| CN113401894A (en) * | 2021-05-26 | 2021-09-17 | 武汉理工大学 | Method for preparing graphene by taking heavy aromatic hydrocarbon as raw material |
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| CN104340978A (en) * | 2014-10-22 | 2015-02-11 | 苏州正业昌智能科技有限公司 | Preparation method of graphene-based composite material |
| CN106115802A (en) * | 2016-06-28 | 2016-11-16 | 苏州宽温电子科技有限公司 | A kind of preparation method of graphene composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104340978A (en) * | 2014-10-22 | 2015-02-11 | 苏州正业昌智能科技有限公司 | Preparation method of graphene-based composite material |
| CN106115802A (en) * | 2016-06-28 | 2016-11-16 | 苏州宽温电子科技有限公司 | A kind of preparation method of graphene composite material |
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| 葡萄糖催化热解制备晶态碳纳米材料研究;展艳珊等;《郑州师范教育》;20160725;第5卷(第4期);37-41页 * |
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