CN103641108B - A kind of N-methyl-N-morpholine oxide prepares the method for graphene oxide - Google Patents
A kind of N-methyl-N-morpholine oxide prepares the method for graphene oxide Download PDFInfo
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Abstract
The invention discloses a kind of method that N-methyl-N-morpholine oxide prepares graphene oxide, comprise the steps: first, preparation N-methyl-N-morpholine oxide solution, adds Graphite Powder 99, and use ultrasonic oscillation process, make Graphite Powder 99 be blended in N-methyl-N-morpholine oxide solution equably; Secondly, in above-mentioned mixed solution, add acid and potassium permanganate, then use ultrasonic oscillation, and be incubated; Then pass into oxygen, after heated and stirred, centrifugal acquisition precipitation, precipitates and obtain graphene oxide after washing, vacuum lyophilization, reclaims N-methyl-N-morpholine oxide solution simultaneously and reuses.Advantage of the present invention is adopt N-methyl-N-morpholine oxide-potassium permanganate acidic solution to be the solvent system of dispersed graphite, is equipped with ultrasonic wave, the graphene oxide good dispersity obtained and mass transfer effect is excellent; Preparation process environmental protection and lower to equipment requirements, can operate continuously; Recyclable recycling after solvent system uses.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, particularly relate to a kind of method that N-methyl-N-morpholine oxide prepares graphene 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 heterocyclic tertiary amines oxide compound, be widely used in Insecticides (tech) & Herbicides (tech), metal antirusting agent, fibre finish and solvent, toxicity ratio ethanol is little, recyclable, being considered at present the most promising organic solvent, is also really can realize suitability for industrialized production at present and the considerable solvent of prospect.
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 propose the optical means characterizing Graphene, systematic study has been carried out to its electric property, find that Graphene has the ballistic transport characteristic of very high carrier concentration, mobility and submicron-scale, thus started the upsurge of Graphene research.Graphene is by the bi-dimensional cellular shape structure of the tightly packed one-tenth of monolayer carbon atom, the thickness of this Graphene crystal film only has 0.335nm, be hair diameter 200,000/, being the material that intensity is the highest in the world known at present, is form the basic structural unit of other dimension carbon materials.Due to two dimension structure feature and the splendid crystallography quality of uniqueness, the current carrier of Graphene shows the behavior being similar to photon, for research relativistic quantum mechanics phenomenon provides desirable experiment porch, in addition Graphene also has the excellent characteristic such as electricity, optics, calorifics, mechanics, and therefore the aspect such as 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 had the multiple method preparing Graphene at present, the seed output and quality of Graphene has had and has promoted significantly, greatly facilitate the research to Graphene intrinsic physical property and application, but the magnanimity how realizing Graphene for different application controls preparation, its quality, structure are 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 usually, i.e. chemical process and physical method.Physical method obtains from the graphite or similar material with the perfect type of high lattice, and the Graphene yardstick of acquisition is all at more than 80nm, and physical method comprises mechanically peel method, epitaxy method, heating SiC method, explosion method etc.And chemical process is the method preparation by micromolecular synthesis or solution separating, obtain Graphene yardstick at below 10nm, chemical process comprises graphite intercalation method, thermal expansion stripping method, electrochemical process, chemical Vapor deposition process, ball milled, graphite oxide reduction method etc., and these methods more or less also exist that preparation efficiency is low, highly toxic substance, contaminate environment or the not easily shortcoming 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 a kind of N-methyl-N-morpholine oxide and prepare that dispersion coefficient is high, mass transfer effect good and the method for graphene oxide with low cost.
Technical scheme: N-methyl-N-morpholine oxide of the present invention prepares the method for graphene oxide, comprise the steps: first, preparation N-methyl-N-morpholine oxide solution, add Graphite Powder 99, and use ultrasonic oscillation process, make Graphite Powder 99 be blended in N-methyl-N-morpholine oxide solution equably; Secondly, in above-mentioned mixed solution, add acid and potassium permanganate, then use ultrasonic oscillation, this process is carried out under keeping warm mode; Then pass into oxygen wherein, after heated and stirred, centrifugal acquisition precipitation, precipitates and obtain 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 added and the 1-3%(w% for N-methyl-N-morpholine oxide solution weight).
The potassium permanganate added is the 2%-6% of N-methyl-N-morpholine oxide solution quality.
The acid added is the 1-3% (w%) of N-methyl-N-morpholine oxide solution weight.
The acid added is the mixture of sulfuric acid or sulfuric acid and nitric acid.
Described ultrasonic oscillation is treated to the ultrasonication 20min-30min adopting 90w-100w.
By dilute hydrochloric acid solution and deionized water wash precipitation.
Described recovery N-methyl-N-morpholine oxide solution is that liquid centrifugation obtained obtains 140-150 DEG C of underpressure distillation
The temperature of described insulation is 90-120 DEG C, and soaking time is 30-50min.
Reaction mechanism: the present invention adopts solvent assisting ultrasonic stripping method to prepare Graphene, by a small amount of graphite dispersion in Solvents 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, enhance the effect of the oxidized and limellar stripping of Graphene, utilize the Van der Waals force of hyperacoustic action breaks down graphite layers simultaneously, now solvent can insert graphite layers, peel off layer by layer, prepare Graphene, then oxygen is passed into, strengthen the degree of oxidation of graphene sheet layer, thus make the peeling effect of Graphene better, 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 N-methyl-N-morpholine oxide-potassium permanganate acidic solution to be the solvent system of dispersed graphite, be equipped with ultrasonic wave, the graphene oxide good dispersity obtained and mass transfer effect is excellent; 2, preparation process environmental protection of the present invention, pollution-free, and lower to equipment requirements, can operate continuously, realize scale operation; 3, solvent system uses rear recyclable recycling, and energy-saving and emission-reduction, realize distributing rationally of resource, possess good application prospect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that graphite dispersion of the present invention obtains suspension liquid in N-methyl-N-morpholine oxide-potassium permanganate acidic solution.
Fig. 2 is the schematic diagram that the present invention obtains graphene oxide powder.
Embodiment
Below technical scheme of the present invention is elaborated.
Embodiment 1: first, compound concentration is the aqueous solution of the N-methyl-N-morpholine oxide of 93%, gets 1g Graphite Powder 99 and adds in the aqueous solution of 100gN-methyl-N-morpholine oxide, 90w ultrasonic oscillation process 30min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, sulfuric acid and 2g potassium permanganate that 5g concentration is 5% is added in above-mentioned mixed solution, use 90w ultrasonic oscillation 30min again, graphite linings is peeled off layer by layer and obtains Graphene, see such as Fig. 1, what now obtain is the suspension liquid of graphite dispersion in above-mentioned solvent, and this process reaction vessel is put into water-bath be incubated, temperature is 90 DEG C, and the time is 50min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 DEG C of heated and stirred 30min, precipitate with 5% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then graphene oxide is obtained by after washed precipitation vacuum lyophilization, Fig. 2 is the schematic diagram of graphene oxide powder, and the liquid simultaneously centrifugation obtained 150 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and reused.
Embodiment 2: first, compound concentration is the aqueous solution 100g of the N-methyl-N-morpholine oxide of 88%, gets 3g Graphite Powder 99 and adds in the aqueous solution of N-methyl-N-morpholine oxide, 100w ultrasonic oscillation process 20min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, in above-mentioned mixed solution, add sulfuric acid and 6g potassium permanganate that 6g concentration is 5%, then use 100w ultrasonic oscillation 20min, graphite linings is peeled off layer by layer and obtains Graphene, this process reaction vessel is put into water-bath be incubated, and temperature is 120 DEG C, and soaking time is 30min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 DEG C of heated and stirred 40min, precipitate with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then obtain graphene oxide by after washed precipitation vacuum lyophilization, the liquid simultaneously centrifugation obtained 140 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 3: first, compound concentration is the aqueous solution 100g of the N-methyl-N-morpholine oxide of 92%, gets 2g Graphite Powder 99 and adds in the aqueous solution of N-methyl-N-morpholine oxide, 95w ultrasonic oscillation process 25min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, in above-mentioned mixed solution, add sulfuric acid and 3g potassium permanganate that 3g concentration is 5%, then use 95w ultrasonic oscillation 25min, graphite linings is peeled off layer by layer and obtains Graphene, this process reaction vessel is put into water-bath be incubated, and temperature is 100 DEG C, and the time is 40min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 95 DEG C of heated and stirred 45min, precipitate with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical in filtrate, then obtain graphene oxide by after washed precipitation vacuum lyophilization, the liquid simultaneously centrifugation obtained 145 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 4: first, compound concentration is the aqueous solution 100g of the N-methyl-N-morpholine oxide of 80%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, 100w ultrasonic oscillation process 20min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, add in above-mentioned mixed solution 1g concentration be 5% sulfuric acid, 2g concentration be 5% nitric acid and 5g potassium permanganate, then use 100w ultrasonic oscillation 20min, graphite linings is peeled off layer by layer and obtains Graphene, this process reaction vessel is put into water-bath be incubated, and temperature is 110 DEG C, and the time is 40min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 100 DEG C of heated and stirred 40min, precipitate with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then obtain graphene oxide by after washed precipitation vacuum lyophilization, the liquid simultaneously centrifugation obtained 140 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 5: first, compound concentration is the dimethyl sulphoxide solution 100g of the N-methyl-N-morpholine oxide of 93%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, 90w ultrasonic oscillation process 30min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, in above-mentioned mixed solution, add sulfuric acid and 4g potassium permanganate that 5g concentration is 5%, then use 90w ultrasonic oscillation 30min, graphite linings is peeled off layer by layer and obtains Graphene, this process reaction vessel is put into water-bath be incubated, and temperature is 90 DEG C, and the time is 30min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 120 DEG C of heated and stirred 30min, precipitate with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then obtain graphene oxide by after washed precipitation vacuum lyophilization, the liquid simultaneously centrifugation obtained 140 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Embodiment 6: first, preparation 100g concentration is the dimethyl sulphoxide solution of the N-methyl-N-morpholine oxide of 90%, gets the dimethyl sulphoxide solution that 1g Graphite Powder 99 adds N-methyl-N-morpholine oxide, 97w ultrasonic oscillation process 28min, make Graphite Powder 99 dispersed, obtain the mixed solution of lower concentration.Secondly, in above-mentioned mixed solution, add sulfuric acid and 4g potassium permanganate that 1g concentration is 5%, then use 97w ultrasonic oscillation 28min, graphite linings is peeled off layer by layer and obtains Graphene, this process reaction vessel is put into water-bath be incubated, and temperature is 100 DEG C, and the time is 45min.Then oxygen is passed into from container bottom, make N-methyl-N-morpholine oxide saturated absorption oxygen, centrifugal acquisition precipitation after 120 DEG C of heated and stirred 30min, precipitate with 6% dilute hydrochloric acid solution and deionized water wash until can't detect sulfate radical and nitrate radical in filtrate, then obtain graphene oxide by after washed precipitation vacuum lyophilization, the liquid simultaneously centrifugation obtained 140 DEG C of underpressure distillation are reclaimed N-methyl-N-morpholine oxide solution and are reused.
Claims (7)
1. prepare the method for graphene oxide with N-methyl-N-morpholine oxide for one kind, it is characterized in that comprising the steps: first, preparation N-methyl-N-morpholine oxide solution, adds Graphite Powder 99, and use ultrasonic oscillation process, make Graphite Powder 99 be blended in N-methyl-N-morpholine oxide solution equably; Secondly, in above-mentioned mixed solution, add acid and potassium permanganate, then use ultrasonic oscillation, this process is carried out under keeping warm mode; Then pass into oxygen wherein, after heated and stirred, centrifugal acquisition precipitation, precipitates and obtain graphene oxide after washing, vacuum lyophilization, reclaims N-methyl-N-morpholine oxide solution simultaneously and reuses; Wherein, the Graphite Powder 99 added is the 1-3% of N-methyl-N-morpholine oxide solution weight, the potassium permanganate added is the 2%-6% of N-methyl-N-morpholine oxide solution quality, and the acid added is the 1-6% of N-methyl-N-morpholine oxide solution weight, described acid to be concentration be 5% sulfuric acid or nitric acid.
2. N-methyl-N-morpholine oxide according to claim 1 prepares the method for graphene oxide, it 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. N-methyl-N-morpholine oxide according to claim 2 prepares the method for graphene oxide, 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. N-methyl-N-morpholine oxide according to claim 1 prepares the method for graphene oxide, it is characterized in that: the acid added is the mixture of sulfuric acid or sulfuric acid and nitric acid.
5. N-methyl-N-morpholine oxide according to claim 1 prepares the method for graphene oxide, it is characterized in that: described ultrasonic oscillation is treated to the ultrasonication 20min-30min adopting 90w-100w.
6. N-methyl-N-morpholine oxide according to claim 1 prepares the method for graphene oxide, 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 liquid centrifugation obtained obtains 140-150 DEG C of underpressure distillation.
7. N-methyl-N-morpholine oxide according to claim 1 prepares the method for graphene oxide, it is characterized in that: the temperature of described insulation is 90-120 DEG C, and soaking time is 30-50min.
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| 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 |
| TWI588089B (en) * | 2015-10-20 | 2017-06-21 | Acelon Chem & Fiber Corp | Method of preparing of graphene-natural cellulose blended meltblown 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 |
| 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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| Graphene oxide/cellulose composite using NMMO monohydrate;Chan-Jun Kim et al.;《Carbohydrate Polymers》;20110531;第86卷;第903-909页 * |
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