CN103641108A - Method for preparing graphene oxide by using N-methyl-N-morpholine oxide - Google Patents
Method for preparing graphene oxide by using N-methyl-N-morpholine oxide Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene oxide by using an N-methyl-N-morpholine oxide. The method comprises the following steps: firstly, preparing an N-methyl-N-morpholine oxide solution, adding graphite powder, performing ultrasonic oscillation treatment so as to uniformly mixing the graphite powder in the N-methyl-N-morpholine oxide solution; secondly, adding acid and potassium permanganate in the mixed solution, performing ultrasonic oscillation and heat preservation, introducing oxygen, heating and stirring, then centrifuging to obtain a precipitate, and performing washing and vacuum freeze drying on the precipitate to obtain the graphene oxide; meanwhile, recycling the N-methyl-N-morpholine oxide solution for reuse. The method has the advantages that the obtained graphene is good in dispersibility and excellent in mass transfer effect by using an N-methyl-N-morpholine oxide-potassium permanganate acid solution as a solvent system of dispersing the graphite and matching with the ultrasonic wave; the preparation process is environment-friendly and the requirement on equipment is low, the continuous operation can be realized, and the solvent system can be recycled after being used.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, relate in particular to a kind of method of preparing graphene oxide with N-methyl-N-morpholine oxide, belong to biochemical industry and field of chemical engineering.
Background technology
N-methyl-N-morpholine oxide (N-methylmorpholine-N-oxide compound) is a kind of heterocycle tertiary amino oxides, be widely used in Insecticides (tech) & Herbicides (tech), metal antirusting agent, fibre finish and solvent, toxicity is less, recyclable than ethanol, being considered to the most promising organic solvent at present, is also at present really can realize the solvent that suitability for industrialized production and prospect are considerable.
Graphene is as a kind of type material, the scholar of Univ Manchester UK in 2004 utilizes tape stripping highly oriented pyrolytic graphite to obtain high-quality graphene, and proposed to characterize the optical means of Graphene, its electric property has been carried out to systematic study, find that Graphene has the ballistic transport characteristic of very high carrier concentration, mobility and submicron-scale, thereby started the upsurge of Graphene research.Graphene is the bi-dimensional cellular shape structure by the tightly packed one-tenth of monolayer carbon atom, the thickness of this Graphene crystal film only has 0.335nm, be 200,000 of hair diameter/, be the current known the highest material of intensity in the world, be the basic structural unit that forms other dimension carbon materials.Due to unique two-dirnentional structure feature and splendid crystallography quality, the current carrier of Graphene shows the behavior that is similar to photon, for research relativistic quantum mechanics phenomenon provides desirable experiment porch, in addition Graphene also has the characteristics such as excellent electricity, optics, calorifics, mechanics, so the aspect such as being on the scene effect transistor, unicircuit, single-molecule detection device, transparent conductive film, functional composite material, energy storage material, support of the catalyst has broad application prospects.
Although there has been the multiple method of preparing Graphene at present, the output of Graphene and quality have had lifting significantly, greatly promoted the research to Graphene intrinsic physical property and application, but the magnanimity that how realizes Graphene for different application is controlled preparation, its quality, structure is regulated and controled to be still to the significant challenge of current Graphene research field.At present, the preparation means of Graphene can be divided into 2 types conventionally, i.e. chemical process and physical method.Physical method is to obtain from having graphite or the similar material of the perfect type of high lattice, and the Graphene yardstick of acquisition is all more than 80nm, and physical method comprises mechanically peel method, epitaxy method, heating SiC method, explosion method etc.And chemical process is to prepare by micromolecular method synthetic or solution separating, obtain Graphene yardstick below 10nm, chemical process comprises graphite graft process, thermal expansion stripping method, electrochemical process, chemical Vapor deposition process, ball milled, graphite oxide reduction method etc., and these methods more or less exist that preparation efficiency is low, highly toxic substance, contaminate environment or be difficult for the shortcomings such as recovery.
Therefore, the efficient callable Graphene production medium of developing green and technique are problems in the urgent need to address.The environmental protection of N-methyl-N-morpholine oxide, does not also utilize N-methyl-N-morpholine oxide to prepare the method for Graphene at present.
Summary of the invention
Goal of the invention: the object of this invention is to provide and a kind ofly prepare that dispersion coefficient is high, mass transfer effect good and the method for graphene oxide with low cost with N-methyl-N-morpholine oxide.
Technical scheme: the method for preparing graphene oxide with N-methyl-N-morpholine oxide of the present invention, comprise the steps: first, preparation N-methyl-N-morpholine oxide solution, add Graphite Powder 99, and process with ultrasonic oscillation, Graphite Powder 99 is blended in N-methyl-N-morpholine oxide solution equably; Secondly, add acid and potassium permanganate, then use ultrasonic oscillation in above-mentioned mixed solution, this process is carried out under keeping warm mode; Then pass into wherein oxygen, centrifugal acquisition precipitation after heated and stirred, precipitation obtains graphene oxide after washing, vacuum lyophilization, reclaims N-methyl-N-morpholine oxide solution simultaneously and reuses.
Described N-methyl-N-morpholine oxide solution is the aqueous solution of N-methyl-N-morpholine oxide or the dimethyl sulphoxide solution of N-methyl-N-morpholine oxide.
The concentration of aqueous solution of described N-methyl-N-morpholine oxide is 88%-93% (w%), and the dimethyl sulphoxide solution of described N-methyl-N-morpholine oxide is 80%-93% (w%).
The Graphite Powder 99 adding be the 1-3%(w% of N-methyl-N-morpholine oxide solution weight).
The potassium permanganate adding is the 2%-6% of N-methyl-N-morpholine oxide solution quality.
The acid adding is the 1-3% (w%) of N-methyl-N-morpholine oxide solution weight.
The acid adding is the mixture of sulfuric acid or sulfuric acid and nitric acid.
Described ultrasonic oscillation is treated to the ultrasonication 20min-30min that adopts 90w-100w.
By dilute hydrochloric acid solution and deionized water wash precipitation.
Described recovery N-methyl-N-morpholine oxide solution is that the liquid that centrifugation is obtained obtains 140-150 ℃ of underpressure distillation
The temperature of described insulation is 90-120 ℃, and soaking time is 30-50min.
Reaction mechanism: the present invention adopts solvent assisting ultrasonic stripping method to prepare Graphene, a small amount of graphite is scattered in solvent N-methyl-N-morpholine oxide-potassium permanganate acidic solution, form the dispersion liquid of lower concentration, wherein, N-methyl-N-morpholine oxide and potassium permanganate and acid can actings in conjunction, strengthened the effect of the oxidized and limellar stripping of Graphene, utilize hyperacoustic effect to destroy the Van der Waals force of graphite layers simultaneously, now solvent can insert graphite layers, peel off layer by layer, prepare Graphene, then pass into oxygen, strengthened the degree of oxidation of graphene sheet layer, thereby make the better effects if of peeling off of Graphene, finally obtain the good graphene oxide of a large amount of limellar strippings.
Beneficial effect: compared with prior art, its remarkable advantage is in the present invention: 1, adopt the solvent system that N-methyl-N-morpholine oxide-potassium permanganate acidic solution is dispersed graphite, be equipped with ultrasonic wave, the graphene oxide good dispersity and the mass transfer effect that obtain are good; 2, preparation process environmental protection of the present invention, pollution-free, and lower to equipment requirements, can operate continuously, realizes scale operation; 3, solvent system is used rear recyclable recycling, and energy-saving and emission-reduction, realize distributing rationally of resource, possess good application prospect.
Accompanying drawing explanation
Fig. 1 is that graphite of the present invention is dispersed in the schematic diagram that obtains suspension liquid in N-methyl-N-morpholine oxide-potassium permanganate acidic solution.
Fig. 2 is the schematic diagram that the present invention makes graphene oxide powder.
Embodiment
Below technical scheme of the present invention is elaborated.
Embodiment 1: first, compound concentration is the aqueous solution of N-methyl-N-morpholine oxide of 93%, gets in the aqueous solution that 1g Graphite Powder 99 adds 100g N-methyl-N-morpholine oxide, and 90w ultrasonic oscillation is processed 30min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, to adding 5g concentration in above-mentioned mixed solution, be 5% sulfuric acid and 2g potassium permanganate, use again 90w ultrasonic oscillation 30min, graphite linings is peeled off layer by layer and obtained Graphene, referring to as Fig. 1, what now obtain is that graphite is dispersed in the suspension liquid in above-mentioned solvent, and this process is reaction vessel to be put into water-bath be incubated, temperature is 90 ℃, and the time is 50min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 ℃ of heated and stirred 30min, precipitation with 5% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, Fig. 2 is the schematic diagram of graphene oxide powder, and the 150 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and reused.
Embodiment 2: first, compound concentration is the aqueous solution 100g of N-methyl-N-morpholine oxide of 88%, gets in the aqueous solution that 3g Graphite Powder 99 adds N-methyl-N-morpholine oxide, and 100w ultrasonic oscillation is processed 20min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, to adding 6g concentration in above-mentioned mixed solution, be 5% sulfuric acid and 6g potassium permanganate, then use 100w ultrasonic oscillation 20min, graphite linings is peeled off layer by layer and obtained Graphene, this process is reaction vessel to be put into water-bath be incubated, and temperature is 120 ℃, and soaking time is 30min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 ℃ of heated and stirred 40min, precipitation with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, the 140 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 3: first, compound concentration is the aqueous solution 100g of N-methyl-N-morpholine oxide of 92%, gets in the aqueous solution that 2g Graphite Powder 99 adds N-methyl-N-morpholine oxide, and 95w ultrasonic oscillation is processed 25min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, to adding 3g concentration in above-mentioned mixed solution, be 5% sulfuric acid and 3g potassium permanganate, then use 95w ultrasonic oscillation 25min, graphite linings is peeled off layer by layer and obtained Graphene, this process is reaction vessel to be put into water-bath be incubated, and temperature is 100 ℃, and the time is 40min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 95 ℃ of heated and stirred 45min, precipitation with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, the 145 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 4: first, compound concentration is the aqueous solution 100g of N-methyl-N-morpholine oxide of 80%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, and 100w ultrasonic oscillation is processed 20min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, to adding 1g concentration in above-mentioned mixed solution, be 5% sulfuric acid, nitric acid and the 5g potassium permanganate that 2g concentration is 5%, then use 100w ultrasonic oscillation 20min, graphite linings is peeled off layer by layer and obtained Graphene, this process is reaction vessel to be put into water-bath be incubated, and temperature is 110 ℃, and the time is 40min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 ℃ of heated and stirred 40min, precipitation with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, the 140 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 5: first, compound concentration is the dimethyl sulphoxide solution 100g of N-methyl-N-morpholine oxide of 93%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, and 90w ultrasonic oscillation is processed 30min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, be 5% sulfuric acid and 4g potassium permanganate, then use 90w ultrasonic oscillation 30min to adding 5g concentration in above-mentioned mixed solution, graphite linings is peeled off layer by layer and obtained Graphene, this process is reaction vessel to be put into water-bath be incubated, and temperature is 90 ℃, and the time is 30min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 120 ℃ of heated and stirred 30min, precipitation with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, the 140 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 6: first, the dimethyl sulphoxide solution of N-methyl-N-morpholine oxide that preparation 100g concentration is 90%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, and 97w ultrasonic oscillation is processed 28min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, to adding 1g concentration in above-mentioned mixed solution, be 5% sulfuric acid and 4g potassium permanganate, then use 97w ultrasonic oscillation 28min, graphite linings is peeled off layer by layer and obtained Graphene, this process is reaction vessel to be put into water-bath be incubated, and temperature is 100 ℃, and the time is 45min.Then from container bottom, pass into oxygen, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 120 ℃ of heated and stirred 30min, precipitation with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then will after washed precipitation vacuum lyophilization, obtain graphene oxide, the 140 ℃ of underpressure distillation of liquid that simultaneously centrifugation obtained are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Claims (10)
1. a method of preparing graphene oxide with N-methyl-N-morpholine oxide, it is characterized in that comprising the steps: first, preparation N-methyl-N-morpholine oxide solution, adds Graphite Powder 99, and process with ultrasonic oscillation, Graphite Powder 99 is blended in N-methyl-N-morpholine oxide solution equably; Secondly, add acid and potassium permanganate, then use ultrasonic oscillation in above-mentioned mixed solution, this process is carried out under keeping warm mode; Then pass into wherein oxygen, centrifugal acquisition precipitation after heated and stirred, precipitation obtains graphene oxide after washing, vacuum lyophilization, reclaims N-methyl-N-morpholine oxide solution simultaneously and reuses.
2. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: described N-methyl-N-morpholine oxide solution is the aqueous solution of N-methyl-N-morpholine oxide or the dimethyl sulphoxide solution of N-methyl-N-morpholine oxide.
3. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 2, it is characterized in that: the aqueous solution mass concentration of described N-methyl-N-morpholine oxide is 88%-93%, the dimethyl sulphoxide solution of described N-methyl-N-morpholine oxide is 80%-93%.
4. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: the Graphite Powder 99 adding is the 1-3% of N-methyl-N-morpholine oxide solution weight.
5. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: the potassium permanganate adding is the 2%-6% of N-methyl-N-morpholine oxide solution quality.
6. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: the acid adding is the 1-6% of N-methyl-N-morpholine oxide solution weight.
7. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: the acid adding is the mixture of sulfuric acid or sulfuric acid and nitric acid.
8. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: described ultrasonic oscillation is treated to the ultrasonication 20min-30min that adopts 90w-100w.
9. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, it is characterized in that: by dilute hydrochloric acid solution and deionized water wash precipitation, described recovery N-methyl-N-morpholine oxide solution is that the liquid that centrifugation is obtained obtains 140-150 ℃ of underpressure distillation.
10. the method for preparing graphene oxide with N-methyl-N-morpholine oxide according to claim 1, is characterized in that: the temperature of described insulation is 90-120 ℃, and soaking time is 30-50min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| TWI588089B (en) * | 2015-10-20 | 2017-06-21 | Acelon Chem & Fiber Corp | Method of preparing of graphene-natural cellulose blended meltblown nonwoven fabric |
| TWI596245B (en) * | 2015-10-20 | 2017-08-21 | 聚隆纖維股份有限公司 | Method of preparing graphene-natural cellulose blended fiber |
| TWI621744B (en) * | 2015-10-20 | 2018-04-21 | 聚泰環保材料科技股份有限公司 | Method of preparing of natural graphene cellulose blended spunbond nonwoven fabric |
| CN109292766A (en) * | 2018-12-12 | 2019-02-01 | 天津市职业大学 | A kind of clean preparation method of Activated Graphite alkene |
| CN109694056A (en) * | 2019-01-28 | 2019-04-30 | 天津理工大学 | A kind of method that liquid phase removing graphite oxide prepares graphene |
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| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
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| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
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| CHAN-JUN KIM ET AL.: "Graphene oxide/cellulose composite using NMMO monohydrate", 《CARBOHYDRATE POLYMERS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI588089B (en) * | 2015-10-20 | 2017-06-21 | Acelon Chem & Fiber Corp | Method of preparing of graphene-natural cellulose blended meltblown nonwoven fabric |
| TWI596245B (en) * | 2015-10-20 | 2017-08-21 | 聚隆纖維股份有限公司 | Method of preparing graphene-natural cellulose blended fiber |
| TWI621744B (en) * | 2015-10-20 | 2018-04-21 | 聚泰環保材料科技股份有限公司 | Method of preparing of natural graphene cellulose blended spunbond nonwoven fabric |
| 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 |
| CN109292766A (en) * | 2018-12-12 | 2019-02-01 | 天津市职业大学 | A kind of clean preparation method of Activated Graphite alkene |
| CN109292766B (en) * | 2018-12-12 | 2021-09-28 | 天津市职业大学 | Clean production method of active graphene |
| CN109694056A (en) * | 2019-01-28 | 2019-04-30 | 天津理工大学 | A kind of method that liquid phase removing graphite oxide prepares graphene |
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