CN103496690B - A kind of preparation method of graphene oxide - Google Patents
A kind of preparation method of graphene oxide Download PDFInfo
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- CN103496690B CN103496690B CN201310416137.0A CN201310416137A CN103496690B CN 103496690 B CN103496690 B CN 103496690B CN 201310416137 A CN201310416137 A CN 201310416137A CN 103496690 B CN103496690 B CN 103496690B
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Abstract
The invention discloses a kind of preparation method of graphene oxide; It comprises, sulfuric acid is used to carry out preliminary oxidation as oxygenant to graphite raw material as solvent, nitrosonitric acid or nitrate, then add potassium permanganate in batches, complete deep oxidation and the stripping of graphite at a certain temperature, re-use water and preliminary cancellation is carried out to reaction, finally add 30% aqueous hydrogen peroxide solution and carry out degree of depth cancellation to reaction, drying obtains graphene oxide; Beneficial effect of the present invention: preparation process is simple, and preparation temperature is low, reaction conditions is easy to control, and the advantage such as can to prepare in a large number.Can obtain constant product quality, not have dirt settling, sheet footpath size is homogeneous, has consistence, the graphene oxide of easily dispersion.
Description
Technical field
The present invention relates to graphene oxide technical field, particularly relate to a kind of preparation method of graphene oxide.
Background technology
Graphene oxide is the oxide compound of Graphene, and its color is brown color.Graphene oxide thin slice is that powdered graphite is through chemical oxidation and the product after peeling off.Graphene oxide is single atomic shell, can expand to some tens of pm at any time on lateral dimension, therefore, and its construct trans typical size of general chemistry and Materials science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, has polymkeric substance, colloid, film, and amphiphilic characteristic.
Chemical method prepares that graphene oxide is with low cost and production efficiency is higher, ready-madely prepares the best approach of graphene oxide for industrial production.But current method is in production quality control, reaction conditions also exists all weak points on controlling.The present invention solves these problems at present, provides a reaction controlling condition simply, constant product quality and the method that can prepare in a large number for preparing high-quality graphene oxide.
Summary of the invention
Object of the present invention is exactly to solve the problem, and provides a kind of preparation method of graphene oxide, and it is simple that it has preparation process, and preparation temperature is low, and reaction conditions is easy to control, and is suitable for the advantages such as suitability for industrialized production.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for graphene oxide, using 98% sulfuric acid as solvent, 86% nitrosonitric acid or nitrate as oxygenant, the mass ratio of graphite and sulfuric acid is 1:75-2:225, and the mass ratio of graphite and nitrate is 3:1-1:2, carries out preliminary oxidation to graphite; Then divide and add potassium permanganate 6-24 times, the mass ratio of graphite and potassium permanganate is 5:1-1:3, completes deep oxidation and the stripping of graphite at 20-45 DEG C; Carry out preliminary cancellation with water to reaction again, the mass ratio of graphite and water is 1:50-1:87; Finally adding massfraction is that 30% aqueous hydrogen peroxide solution carries out degree of depth cancellation to reaction, and aqueous hydrogen peroxide solution and graphite quality, than being 3:4-9:2, obtain graphene oxide.
Described nitrate is SODIUMNITRATE or saltpetre.
Described graphite is the graphite of granularity 48-10000 object natural flake graphite or synthetic form rule.
Described graphite preliminary oxidation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and after reinforced, isothermal reaction temperature is 30-35 DEG C, and the reaction times is 2-8 hours.
Described graphite deep oxidation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding potassium permanganate, control temperature is less than 15 DEG C, and after reinforced, isothermal reaction temperature is 20-45 DEG C, and the reaction times is 70-160 hours.
The preliminary cancellation of described reaction, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding water, control temperature is less than 60 DEG C, and after reinforced, isothermal reaction temperature is 70-90 DEG C, and the reaction times is 2-6 hours.
Described reaction depth cancellation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding aqueous hydrogen peroxide solution, control temperature is less than 60 DEG C, and after reinforced, isothermal reaction temperature is 50-60 DEG C, and the reaction times is 4-14 hours.
The present invention also provides a kind of graphene oxide prepared according to aforesaid method.
Beneficial effect of the present invention: the inventive method preparation process is simple, preparation temperature is low, reaction conditions is easy to control, and is suitable for the advantages such as suitability for industrialized production, the graphene oxide constant product quality of preparation, homogeneous without dirt settling, sheet footpath size, easily disperse in multiple organic reagent.
Accompanying drawing explanation
Fig. 1 is graphene oxide and the ethanol colloid mixture of the embodiment of the present invention 1 preparation;
Fig. 2 is the electron scanning micrograph of graphene oxide prepared by the embodiment of the present invention 1.
Fig. 3 is X ray diffracting spectrum prepared by the embodiment of the present invention 1.
Wherein, in Fig. 3, the 1. graphite X ray diffracting spectrum of synthetic form rule, the graphite X ray diffracting spectrum of the graphene oxide of the 2. embodiment of the present invention 1 preparation.
Embodiment.
Embodiment 1:
5L tetra-mouthfuls of round-bottomed flasks install mechanical stirring, air set pipe, glass stopper, drying tube, thermometer additional.Add the graphite 40g of synthetic form rule, SODIUMNITRATE 15g, 98% sulfuric acid 3Kg, isothermal reaction temperature is 30 DEG C, and mechanical stirring revolution is adjusted to 80rpm, reacts 2 hours; Add in batches potassium permanganate 60g(often criticize reinforced quality must not more than 5g, feeding interval must not be less than 3 minutes), control temperature of reaction between charge period and be less than 10 DEG C, after feeding intake, naturally 25 DEG C are risen to, isothermal reaction 144 hours, due to reaction solution thickness gradually, needing adjusting rotary speed constant is 80-85rpm; Constant pressure funnel is used to drip 2.5Kg distilled water in reaction solution, adjusting rotary speed is 100-105rpm, strict control rate of addition, control reacting liquid temperature between charge period and be no more than 60 DEG C, outer bath starts heating, control reacting liquid temperature and rise to 80 DEG C, adjusting rotary speed is 100-105rpm, constant temperature 4 hours; Drip 30% hydrogen peroxide 100g, control rate of addition, between charge period, reacting liquid temperature must not more than 60 DEG C, and adjusting rotary speed is 100-105rpm, after feeding intake, 50 DEG C of constant temperature stir 14 hours, stop stirring, centrifugation, adds 3Kg distilled water, centrifugal 2 times of repetitive scrubbing, drying obtains graphene oxide.
As shown in drawings, Fig. 1 is the colloid mixture of graphene oxide and ethanol prepared by the embodiment of the present invention 1 to result, shows the graphene oxide favorable dispersity in organic solvent of preparation, and can stable existence; As can be seen from Figure 2, the graphene oxide of the embodiment of the present invention 1 preparation is homogeneous without dirt settling, sheet footpath size.As shown in Figure 3, disappear in the X ray diffracting spectrum of the graphene oxide that the strong diffraction peak of graphite is prepared in the embodiment of the present invention 1, illustrate that graphene oxide prepared by the embodiment of the present invention 1 is fully peeled off and obtain individual layer.
Embodiment 2:
5L tetra-mouthfuls of round-bottomed flasks install mechanical stirring, air set pipe, glass stopper, drying tube, thermometer additional.Add natural flake graphite graphite 40g, concentrated nitric acid 27g, 98% sulfuric acid 4Kg.Constant temperature answers temperature to be 30 DEG C, and mechanical stirring revolution is adjusted to 80rpm, reacts 6 hours; Add in batches potassium permanganate 30g(often criticize reinforced quality must not more than 5g, feeding interval must not be less than 3 minutes), control temperature of reaction between charge period and be less than 10 DEG C, after feeding intake, naturally 30 DEG C are risen to, isothermal reaction 72 hours, due to reaction solution thickness gradually, needing adjusting rotary speed constant is 80-85rpm; Constant pressure funnel is used to drip 2Kg distilled water in reaction solution, adjusting rotary speed is 100-105rpm, strict control rate of addition, control reacting liquid temperature between charge period and be no more than 60 DEG C, outer bath starts heating, control reacting liquid temperature and rise to 90 DEG C, adjusting rotary speed is 100-105rpm, constant temperature 2 hours; Temperature fall to 60 DEG C, adjusting rotary speed is 100-105rpm, drips 30% hydrogen peroxide 30g, control rate of addition, between charge period, reacting liquid temperature more than 60 DEG C, must not stop indirect heating, adjusting rotary speed is 100-105rpm, after feeding intake, 50 DEG C of constant temperature stir 4 hours, stop stirring, centrifugation, add 3Kg distilled water, centrifugal 2 times of repetitive scrubbing, drying obtains graphene oxide.
Embodiment 3:
5L tetra-mouthfuls of round-bottomed flasks install mechanical stirring, air set pipe, glass stopper, drying tube, thermometer additional.Add natural flake graphite graphite 40g, concentrated nitric acid 80g, 98% sulfuric acid 4.5Kg.Isothermal reaction temperature is 30 DEG C, and mechanical stirring revolution is adjusted to 80rpm, reacts 6 hours; Add in batches potassium permanganate 120g(often criticize reinforced quality must not more than 5g, feeding interval must not be less than 3 minutes), control temperature of reaction between charge period and be less than 10 DEG C, after feeding intake, naturally 30 DEG C are risen to, isothermal reaction 72 hours, due to reaction solution thickness gradually, needing adjusting rotary speed constant is 80-85rpm; Use constant pressure funnel to drip 3.4Kg distilled water in reaction solution, adjusting rotary speed is 100-105rpm, strictly controls rate of addition, between charge period, reacting liquid temperature is no more than 60 DEG C, and outer bath starts heating, controls reacting liquid temperature and rises to 90 DEG C, adjusting rotary speed is 100-105rpm, constant temperature 6 hours; Temperature fall to 60 DEG C, adjusting rotary speed is 100-105rpm, drips 30% hydrogen peroxide 180g, control rate of addition, reacting liquid temperature more than 60 DEG C, must not stop indirect heating, adjusting rotary speed is 100-105rpm, after feeding intake, 60 DEG C of constant temperature stir 12 hours, stop stirring, centrifugation, add 3Kg distilled water, centrifugal 2 times of repetitive scrubbing, drying obtains graphene oxide.
Embodiment 4:
5L tetra-mouthfuls of round-bottomed flasks install mechanical stirring, air set pipe, glass stopper, drying tube, thermometer additional.Add the graphite 40g of synthetic form rule, saltpetre 27g, 98% sulfuric acid 4Kg.Isothermal reaction temperature is 30 DEG C, and mechanical stirring revolution is adjusted to 80rpm, reacts 6 hours; Control temperature of reaction and be less than 10 DEG C, add potassium permanganate 120g, (often criticizing reinforced quality must not more than 5g in batches, feeding interval must not be less than 3 minutes) feed intake after, naturally rise to 30 DEG C, isothermal reaction 96 hours, due to reaction solution thickness gradually, needing adjusting rotary speed constant is 80-85rpm; Constant pressure funnel is used to drip 2.5Kg distilled water in reaction solution, adjusting rotary speed is 100-105rpm, strict control rate of addition, control reacting liquid temperature between charge period and be no more than 60 DEG C, outer bath starts heating, control reacting liquid temperature and rise to 70 DEG C, adjusting rotary speed is 100-105rpm, constant temperature 4 hours; Temperature fall to 60 DEG C, adjusting rotary speed is 100-105rpm, drips 30% hydrogen peroxide 50g, control rate of addition, reacting liquid temperature more than 60 DEG C, must not stop indirect heating, adjusting rotary speed is 100-105rpm, after feeding intake, 60 DEG C of constant temperature stir 8 hours, stop stirring, centrifugation, add 3Kg distilled water, centrifugal 2 times of repetitive scrubbing, drying obtains graphene oxide.
Embodiment 5:
In 100L single-glass reactor, put into the graphite 500g of synthetic form rule, SODIUMNITRATE 377g, 98% sulfuric acid 36Kg.Isothermal reaction temperature is 30 DEG C, and mechanical stirring revolution is adjusted to 80rpm, under this condition, reacts 14 hours; Control temperature of reaction and be less than 10 DEG C, add in batches potassium permanganate 2.25Kg(often criticize reinforced quality must not more than 100g, feeding interval must not be less than 5 minutes), after feeding intake, naturally 30 DEG C are risen to, isothermal reaction 144 hours, due to reaction solution thickness gradually, needing adjusting rotary speed constant is 80-85rpm; Constant pressure funnel is used to drip 28Kg distilled water in reaction solution, adjusting rotary speed is 100-105rpm, strict control rate of addition, control reacting liquid temperature between charge period and be no more than 70 DEG C, reactor is bathed outward and is started heating, control reacting liquid temperature and rise to 90 DEG C, adjusting rotary speed is 100-105rpm, constant temperature 2.5 hours; Temperature fall to 60 DEG C, adjusting rotary speed is 100-105rpm, drips 30% hydrogen peroxide 1.6Kg, and control rate of addition, reacting liquid temperature must not more than 60 DEG C.Stop indirect heating, adjusting rotary speed is 100-105rpm, and after feeding intake, 60 DEG C of constant temperature stir 12 hours, stops stirring, and centrifugation, adds 30Kg distilled water, and centrifugal 2 times of repetitive scrubbing, drying obtains graphene oxide.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (2)
1. the preparation method of a graphene oxide, it is characterized in that, using 98% sulfuric acid as solvent, 86% nitrosonitric acid or nitrate as oxygenant, the mass ratio of graphite and sulfuric acid is 1:75-2:225, the mass ratio of graphite and nitrate is 3:1-1:2, carries out preliminary oxidation to graphite; Then divide and add potassium permanganate 6-24 times, the mass ratio of graphite and potassium permanganate is 5:1-1:3, completes deep oxidation and the stripping of graphite at 20-45 DEG C; Carry out preliminary cancellation with water to reaction again, the mass ratio of graphite and water is 1:50-1:87; Finally adding massfraction is that 30% aqueous hydrogen peroxide solution carries out degree of depth cancellation to reaction, and aqueous hydrogen peroxide solution and graphite quality, than being 3:4-9:2, obtain graphene oxide;
Described nitrate is SODIUMNITRATE or saltpetre;
Described graphite is the graphite of granularity 48-10000 object natural flake graphite or synthetic form rule;
Described graphite preliminary oxidation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and temperature of reaction is 15-30 DEG C, and the reaction times is 2-8 hours;
Described graphite deep oxidation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding potassium permanganate, control temperature is less than 15 DEG C, and after reinforced, isothermal reaction temperature is 20-45 DEG C, and the reaction times is 70-160 hours;
The preliminary cancellation of described reaction, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding water, control temperature is less than 60 DEG C, and after reinforced, isothermal reaction temperature is 70-90 DEG C, and the reaction times is 2-6 hours;
Described reaction depth cancellation, its reaction conditions is, mechanical stirring rotating speed is 60-200rpm, and during adding aqueous hydrogen peroxide solution, control temperature is less than 60 DEG C, and after reinforced, isothermal reaction temperature is 50-60 DEG C, and the reaction times is 4-14 hours.
2. the graphene oxide prepared of the method for claim 1.
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| TWI552956B (en) * | 2015-05-29 | 2016-10-11 | 國立臺灣科技大學 | Producing method of graphene and applications thereof |
| CN106238060B (en) * | 2016-09-29 | 2019-04-26 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite material |
| CN112374493A (en) * | 2020-12-28 | 2021-02-19 | 中国科学技术大学先进技术研究院 | Method for preparing monolayer graphene oxide with controllable sheet diameter size |
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