CN105347340A - Preparation method of graphene oxide - Google Patents
Preparation method of graphene oxide Download PDFInfo
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- CN105347340A CN105347340A CN201510924233.5A CN201510924233A CN105347340A CN 105347340 A CN105347340 A CN 105347340A CN 201510924233 A CN201510924233 A CN 201510924233A CN 105347340 A CN105347340 A CN 105347340A
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Abstract
The invention relates to a preparation method of graphene oxide. The method comprises the steps of adding a graphite raw material and a pro-oxidant into aqueous alkali and placing in a sealed container, wherein 1 to 50g of graphite raw material and 1 to 30g of pro-oxidant are added into every 100ml of aqueous alkali; displacing gas in the container with oxygen and charging the oxygen till the pressure is 1 to 20 Mpa, reacting at the temperature of 101 DEG C to 650 DEG C, taking a reacted product out after the reaction is finished, performing solid-liquid separation, washing an obtained solid phase and drying, so as to obtain a graphene oxide solid product, and a liquid phase is recycled and is reused after being treated. By adopting the preparation method, the large dosages of strong acid and strong oxidant can be avoided in the reaction, waste acid and waste liquid are reduced, the extent of the reaction can be adjusted by controlling the reaction temperature and the oxygenating pressure, the structural damage loss of the graphene oxide prepared in a strong acidic condition is effectively avoided, and the tedious separation and washing processes for preparing the graphene oxide are simplified. The aqueous alkali is recyclable, so that the production cost is effectively reduced, the process is simple, the flow is short, and the cost is low.
Description
Technical field
The present invention relates to a kind of method preparing graphene oxide.
Background technology
Graphene oxide (GO) is the important intermediate that oxidation reduction process prepares Graphene.Univ Manchester UK physicist An Deliegaimu and Constantine Nuo Woxiaoluofu in 2004, success isolates single-layer graphene from graphite, confirm that it can Individual existence found the quantum hall effect under integer quantum Hall effect and normal temperature condition respectively, obtain the research of having ignited after Nobel Prize in physics for 2010 Graphene in double harness.The breaking tenacity of Graphene is steel 200 times, and have good elasticity, stretch range can reach 20% of own dimensions simultaneously.Graphene has the substitute that great potentiality become silicon, manufactures superminiature transistor, and be used for producing following supercomputer, the travelling speed of computer processor will promote hundreds of times.The structure of the transmittance that Graphene is high and densification makes it be suitable as very much the raw material of transparent electron product, as transparent touch display screen, luminescent screen and solar panel.The surface tissue of its uniqueness is also had to have the application of good antibacterial effect in medical treatment and space material to have great prospect.As the thinnest, the hardest, a kind of novel nano-material that electrical and thermal conductivity performance is the strongest that find at present, because unique physicochemical property of Graphene has very consequence on the materials application of hard-core technology.
Preparing the common method of Graphene is at present mechanically peel method, oxidation reduction process, SiC epitaxial growth method and chemical Vapor deposition process (CVD).But all there is obvious disadvantage in four kinds of methods, mechanically peel method production capacity is low, oxidation reduction process uses strong acid strong oxidizer to be oxidized, and pollutes comparatively large but output is high, and the common fault of SiC epitaxial growth method and chemical Vapor deposition process be high to the requirement of equipment, cost is high and production capacity is low.
Present stage oxidation reduction process operation easier minimum and with low cost be scale operation technical grade Graphene the best way.The concrete grammar of oxidation reduction process is, with natural flake graphite or expanded graphite as starting material, this one-phase of graphene oxide that after the oxidation of strong acid strong oxidizer prepared by (strong acid and strong oxidizer are the vitriol oil, concentrated hydrochloric acid, perchloric acid, potassium permanganate etc.) is called oxidation stage, then is prepared into Graphene through reductive agent reduction (reductive agent is hydrazine hydrate, sodium borohydride etc.).But traditional oxidation stage can produce a large amount of spent acid, and need dilution heat release to be oxidized further at separation phase to make concentrated acid also be difficult to reclaim, and in waste liquid, also have a large amount of separation of heavy metal ions intractability very large; Be oxidized under concentrated acid condition, the oxidized degree of graphite is difficult to control, and is easy to destroy to graphite-structure the Graphene causing preparing of low quality.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of degree of oxidation controlled, destroys little, and avoid the preparation method of the graphene oxide of the use of strong acid in preparation process to graphite-structure.
For solving above technical problem, the preparation method of a kind of graphene oxide provided by the invention, that graphite raw material, pro-oxidant are added alkaline solution and be placed in encloses container, wherein, 1 ~ 50g graphite raw material and 1 ~ 30g pro-oxidant is added in every 100ml alkaline solution, with replacement of oxygen gas in container and to be filled with oxygen to pressure be 1 ~ 20Mpa, react temperature 101 DEG C ~ 650 DEG C, reaction terminates rear taking-up reaction product solid-liquid separation, the washing of gained solid phase is also dry, obtain graphene oxide solid product, liquid phase reclaims and recycles after treatment.
Design of the present invention is graphite raw material at the oxygen of alkaline solution and certain pressure, and heated oxide prepares graphene oxide under the effect of pro-oxidant, thus overcome oxidation reduction process prepare Graphene oxidation stage exist defect, the method degree of oxidation is controlled, destroy little to graphite-structure, and be a kind of environmentally friendly synthetic route, the alkali lye produced is treated can be recycled, cost is low, method is simple, effectively prevent in strong acid oxidizing process and produces the problem such as spent acid and separation difficulty.
Under above reaction conditions, in container, in-situ reaction pressure is at 10Mpa ~ 60Mpa.Solid-liquid separating method comprises suction filtration, centrifugal; The described solid product dilute hydrochloric acid of 5% ~ 10% washs; Described solid product drying means is for comprising oven dry, seasoning, lyophilize.Liquid phase is recyclable, and treatment process is: according to paper mill wastewater before seal pot to after the adjustment of solution paper mill wastewater, recycle as alkaline solution.
As preferred technical scheme, the time of carrying out reacting is 10 ~ 72 hours, and on this basis, preferred scheme is dissolved in the water by the graphene oxide solid product obtained, and ultrasonic disperse, obtains graphite oxide dispersion soln.
As the preferred technical scheme of another kind, the solute of described alkaline solution is potassium hydroxide or sodium hydroxide.On this basis, the solvent of described alkaline solution is the one in water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol and butanols.Preferably, with the substance withdrawl syndrome of alkaline solution of above-mentioned solute and solvent preparation for 5 ~ 20mol/L.
As the preferred technical scheme of another kind, described pro-oxidant is the one in saltpetre, potassium nitrite, SODIUMNITRATE or Sodium Nitrite.
As the preferred technical scheme of another kind, described graphite raw material is natural flake graphite or expanded graphite.The grain graininess of preferred graphite raw material is 30 ~ 500 orders.
As the preferred technical scheme of another kind, be react temperature 350 DEG C ~ 500 DEG C.
The present invention proposes the beneficial effect that alkali oxidation prepares graphene oxide method and is: (1) this reaction can avoid a large amount of strong acid and the use of strong oxidizer, reduces a large amount of spent acid waste liquids, reduces costs environmental protection.(2) to be oxidized with the use of alkaline solution at oxygen and pro-oxidant and to prepare graphene oxide, the problems such as level of response controls by the control to temperature of reaction and oxygenate pressure, the graphene oxide structural damage disappearance prepared under effectively prevent strong acidic condition.(3) with simple to operate, be separated easily, simplify acid and prepare the loaded down with trivial details separating, washing process of graphite oxide.(4) alkaline solution recycles, and effectively reduces production cost, and technique is simple, and flow process is short, and cost is low.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of sample prepared by the present invention.
Embodiment
Embodiment 1
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
Get 3g325 order natural flake graphite, 12gKOH, 3gKNO
3, insert in reactor, add in 25ml deionized water, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then fill oxygen to 5Mpa, reactor is heated to 450 DEG C, stirring reaction 36 hours.Be cooled to room temperature after reaction terminates, solid product, through solid-liquid separation, first washs through dilute hydrochloric acid with 5%, then is washed till neutrality with deionized water, dry and obtain graphene oxide solid 2.752g at 100 DEG C by reactant.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 2
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
By the alkali lye 13mL reclaimed in embodiment 1, add 6.25gKOH and 17mL deionized water according to the concentration of the KOH recorded before the sealing of embodiment 1 reactor and adjust to same concentrations, get 3g325 order natural flake graphite, 3gKNO
3, insert in reactor, add 25ml circulation alkali liquor, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 3Mpa that fills oxygen is by reactor heat temperature raising 600 DEG C, stirring reaction 36 hours.Be cooled to room temperature after reaction terminates, reactant is through solid-liquid separation, and solid product washs through 5% dilute hydrochloric acid, then is washed till neutrality with deionized water, dries and obtain graphene oxide solid 2.804g at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 3
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is NaOH, and pro-oxidant is NaNO
3reaction process and result.
Get 5g325 order natural flake graphite, 12gNaOH, 3gNaNO
3, insert in reactor, add in 25ml deionized water, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 5Mpa that fills oxygen is by reactor heat temperature raising 450 DEG C, 36 hours stirring reaction time.Be cooled to room temperature after reaction terminates, reactant is through solid-liquid separation, and solid washs through 10% dilute hydrochloric acid, then is washed till neutrality with deionized water, dries and obtain graphene oxide solid 4.763g at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of NaOH solution before reaction to solution paper mill wastewater.
Embodiment 4
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
Get 3g325 order natural flake graphite, 25gKOH, 5gKNO
3, insert in reactor, add in 25ml deionized water, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 5Mpa that fills oxygen, by reactor heat temperature raising 450 DEG C, stirring reaction 72 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, solid washs through 10% dilute hydrochloric acid, then is washed till neutrality with deionized water, dries and obtain graphene oxide solid 2.733g at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 5
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
2reaction process and result.
Get 3g325 order natural flake graphite, 12gKOH, 3gKNO
2, insert in reactor, add in 25ml ethanol, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 5Mpa that fills oxygen is by reactor heat temperature raising 450 DEG C, stirring reaction 36 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, solid washs through 10% dilute hydrochloric acid, dries and obtain graphene oxide solid 2.767g at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 6
It is natural flake graphite 200 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
Get 3g200 order natural flake graphite, 20gKOH, 6gKNO
3, insert in reactor, add in 25ml deionized water, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 6Mpa that fills oxygen, by reactor heat temperature raising 450 DEG C, stirring reaction 50 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, solid washs through 10% dilute hydrochloric acid, then is washed till neutrality with deionized water, dries and obtain graphene oxide solid 2.624g at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 7
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
Get 3g325 order natural flake graphite, 12gKOH, 3gKNO
3, insert in reactor, add in 25ml deionized water, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 7Mpa that fills oxygen is by reactor heat temperature raising 450 DEG C, stirring reaction 36 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, by solid first through 10% salt acid elution, then be washed till neutrality with deionized water, at 100 DEG C, dry and obtain graphene oxide solid 2.749g.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.By the graphene oxide solid of gained, get 0.3g and be dissolved in 50ml distilled water, namely 100W supersound process 20min obtains graphite oxide dispersion soln.
Embodiment 8
It is expanded graphite 30 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
2reaction process and result.
Get 0.25g30 order expanded graphite, 12gKOH, 0.25gKNO
2, insert in reactor, add in 25ml glycerol, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then fill oxygen to 1Mpa, reactor is heated to 650 DEG C, stirring reaction 10 hours.Be cooled to room temperature after reaction terminates, solid product, through solid-liquid separation, first washs through dilute hydrochloric acid with 5%, then is washed till neutrality with deionized water, dry and obtain graphene oxide solid at 100 DEG C by reactant.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 9
It is natural flake graphite 500 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
3reaction process and result.
Get 12.5g500 order natural flake graphite, 20gKOH, 7.5gKNO
3, insert in reactor, add in 25ml ethylene glycol, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 20Mpa that fills oxygen, by reactor heat temperature raising 101 DEG C, stirring reaction 72 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, solid washs through 10% dilute hydrochloric acid, then is washed till neutrality with deionized water, dries and obtain graphene oxide solid at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 10
It is expanded graphite 325 order that the present embodiment illustrates at graphite, and alkali is KOH, and pro-oxidant is KNO
2reaction process and result.
Get 3g325 order expanded graphite, 7gKOH, 3gKNO
2, insert in reactor, add in 25ml propyl alcohol, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 3Mpa that fills oxygen is by reactor heat temperature raising 350 DEG C, stirring reaction 48 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, solid washs through 10% dilute hydrochloric acid, dries and obtain graphene oxide solid at 100 DEG C.Liquid phase reclaims, and after adjusting, recycles as alkaline solution according to the concentration of KOH solution before reaction to solution paper mill wastewater.
Embodiment 11
It is natural flake graphite 325 order that the present embodiment illustrates at graphite, and alkali is NaOH, and pro-oxidant is NaNO
3reaction process and result.
Get 3g325 order natural flake graphite, 20gNaOH, 3gNaNO
3, insert in reactor, add in 25ml methyl alcohol, stir 10min.The airtight rear replacement of oxygen gas reactor of reactor three times, then the 10Mpa that fills oxygen is by reactor heat temperature raising 500 DEG C, stirring reaction 48 hours.Be cooled to room temperature, solid-liquid separation after reaction terminates, by solid first through 10% salt acid elution, then be washed till neutrality with deionized water, dry at 100 DEG C and obtain graphene oxide solid.By the graphene oxide solid of gained, get 0.3g and be dissolved in 50ml distilled water, namely 100W supersound process 20min obtains graphite oxide dispersion soln.
Claims (10)
1. the preparation method of a graphene oxide, it is characterized in that: graphite raw material, pro-oxidant add alkaline solution and be placed in encloses container, wherein, 1 ~ 50g graphite raw material and 1 ~ 30g pro-oxidant is added in every 100ml alkaline solution, with replacement of oxygen gas in container and to be filled with oxygen to pressure be 1 ~ 20Mpa, react temperature 101 DEG C ~ 650 DEG C, reaction terminates rear taking-up reaction product solid-liquid separation, the washing of gained solid phase is also dry, obtain graphene oxide solid product, liquid phase reclaims and recycles after treatment.
2. method according to claim 1, is characterized in that: the time of carrying out reacting is 10 ~ 72 hours.
3. method according to claim 2, is characterized in that: the graphene oxide solid product obtained is dissolved in the water, and ultrasonic disperse obtains graphite oxide dispersion soln.
4. the method according to claim 1,2 or 3, is characterized in that: the solute of described alkaline solution is potassium hydroxide or sodium hydroxide.
5. method according to claim 4, is characterized in that: the solvent of described alkaline solution is the one in water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol and butanols.
6. method according to claim 5, is characterized in that: the substance withdrawl syndrome of described alkaline solution is 5 ~ 20mol/L.
7. the method according to claim 1,2,3,5 or 6, is characterized in that: described pro-oxidant is the one in saltpetre, potassium nitrite, SODIUMNITRATE or Sodium Nitrite.
8. method according to claim 7, is characterized in that: described graphite raw material is natural flake graphite or expanded graphite.
9. method according to claim 8, is characterized in that: the grain graininess of graphite raw material is 30 ~ 500 orders.
10. method according to claim 1, is characterized in that: wherein said liquid phase recovery and treatment method is, after adjusting solution paper mill wastewater according to paper mill wastewater before seal pot, recycle as alkaline solution.
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Cited By (6)
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| CN106276874A (en) * | 2016-08-10 | 2017-01-04 | 安徽省宁国天成电工有限公司 | A kind of preparation method of heater Graphene |
| CN106542529A (en) * | 2016-12-06 | 2017-03-29 | 江苏悦达新材料科技有限公司 | A kind of method that green prepares high-quality graphene |
| CN107777683A (en) * | 2017-11-20 | 2018-03-09 | 浙江海虹控股集团有限公司 | A kind of new method for producing graphene oxide |
| CN108975323A (en) * | 2018-09-05 | 2018-12-11 | 七台河宝泰隆石墨烯新材料有限公司 | graphene oxide cleaning method |
| CN113782837A (en) * | 2021-08-03 | 2021-12-10 | 东风悦达起亚汽车有限公司 | Preparation method of high-quality graphene battery |
| CN114229969A (en) * | 2021-12-30 | 2022-03-25 | 山西诺沃科技有限公司 | Electronic control ionic membrane material for separating phosphate ions in water and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106276874A (en) * | 2016-08-10 | 2017-01-04 | 安徽省宁国天成电工有限公司 | A kind of preparation method of heater Graphene |
| CN106542529A (en) * | 2016-12-06 | 2017-03-29 | 江苏悦达新材料科技有限公司 | A kind of method that green prepares high-quality graphene |
| CN107777683A (en) * | 2017-11-20 | 2018-03-09 | 浙江海虹控股集团有限公司 | A kind of new method for producing graphene oxide |
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| CN113782837A (en) * | 2021-08-03 | 2021-12-10 | 东风悦达起亚汽车有限公司 | Preparation method of high-quality graphene battery |
| CN114229969A (en) * | 2021-12-30 | 2022-03-25 | 山西诺沃科技有限公司 | Electronic control ionic membrane material for separating phosphate ions in water and preparation method thereof |
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