CN103787317B - A kind of preparation method of graphene oxide dispersion - Google Patents
A kind of preparation method of graphene oxide dispersion Download PDFInfo
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- CN103787317B CN103787317B CN201410001555.8A CN201410001555A CN103787317B CN 103787317 B CN103787317 B CN 103787317B CN 201410001555 A CN201410001555 A CN 201410001555A CN 103787317 B CN103787317 B CN 103787317B
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Abstract
The present invention discloses a kind of preparation method of graphene oxide dispersion.Namely first supersound process obtains the graphite/sulfuric acid mixture of sulfate radical intercalation, in the graphite/sulfuric acid mixture of gained sulfate radical intercalation, add potassium permanganate carry out middle temperature oxidizing reaction and obtain preliminary graphite oxide, then carrying out high-temperature hydrolysis must with the graphite oxide of hydrophilic radical, add hydrogen peroxide continuation oxidizing reaction and obtain glassy yellow graphite oxide turbid solution, centrifugal or filter, the brown color pureed obtained or the mixing solutions process of cake hydrogen peroxide and the vitriol oil, obtain the graphite oxide with a large amount of hydrophilic radical, washing, vacuum-drying joins ultrasonic graphene oxide dispersion in solvent after obtaining pure graphite oxide.Graphene oxide good dispersity in gained graphene oxide dispersion, good stability, lamella is larger.This preparation method simplifies processing step, and reduce production cost and energy consumption, reaction process is without NO
2/ N
2o
4toxic gas is released, environmental friendliness.
Description
Technical field
The invention belongs to technical field of preparation of graphene oxide, particularly relate to a kind of preparation method of graphene oxide dispersion.
Background technology
It is generally acknowledged, graphite oxide is as the criterion two-dimensional layered structure, in oxidising process, and the graphene sheet layer keyed jointing oxygen-containing functional groups such as a large amount of hydroxyls, carboxyl and epoxy group(ing).Due to the supporting role of the water between these functional groups and lamella; the lattice parameter of original graphite is expanded to the 0.6-1.1nm (Lerf of graphite oxide by 0.335nm; A. etc. solid-state physics chemistry 67; 1106 (2006)) monolithic, being more conducive to realize graphene oxide is peeled off and serialization preparation; Simultaneously, functional group also gives the excellent chemically reactive of graphene oxide sheet and wetting property, and make negative electricity on its surface band, in water, (or in alkali lye) nano-scale dispersion can be formed, thus lay a good foundation for the Application of composite of graphene oxide or nano ordered assembling.
The method of conventional synthesis graphene oxide is that graphite oxide peels off into graphene oxide by supersound process through Hummers method synthesis graphite oxide.First, owing to using SODIUMNITRATE in the reaction process of its synthesis graphite oxide, can give off poisonous gas NO
2/ N
2o
4, contaminate environment.Low-temp reaction needs temperature to control below 0 DEG C, suitability for industrialized production difficulty.In addition, the graphite oxide of gained peels off into graphene oxide by supersound process merely needs the longer time, be generally 2-5h, and the difficulty realizing peeling off into single-layer graphene is larger, the single-layer graphene size of gained is less, for 0.1-10 μm, productive rate is also lower, is 10-20% relative to multilayer (2-10 layer) graphene oxide.
Summary of the invention
Object of the present invention provides a kind of without toxic gas NO to solve above-mentioned technical problem
2/ N
2o
4release, short period of time higher without low-temp reaction process, productive rate ultrasonic the preparation method of larger-size single-layer graphene oxide dispersion liquid.Graphene oxide good dispersity in prepared graphene oxide dispersion, good stability, containing a large amount of oxy radicals, has potential using value at graphene oxide composite material, catalysis, photoelectric field.
Technical scheme of the present invention
1, a preparation method for graphene oxide dispersion, specifically comprises the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, graphite is mixed with the ratio of the vitriol oil in 1g:20mL, ultrasonic 0.5h ~ 1.5h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is natural graphite powder or natural flake graphite or micro crystal graphite or expanded graphite;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add potassium permanganate, ultrasonic 5 ~ 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:6 ~ 10;
It is 200-300r/min that the graphite/sulfuric acid of the sulfate radical intercalation of gained/potassium permanganate mixture is controlled mixing speed, and temperature is carry out oxidizing reaction 1 ~ 3h at 25 ~ 40 DEG C, obtains graphite oxide tentatively;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as its volume 1-5 deionized water doubly, then control temperature is 90 ~ 100 DEG C of reaction 10 ~ 20min that are hydrolyzed, and forms the graphite oxide with hydrophilic radical;
In the solution of the graphite oxide with hydrophilic radical of gained, be incorporated as the mixing solutions that its volume 2-5 aqueous hydrogen peroxide solution being 30% by deionized water and mass percent concentration is doubly mixed to form, obtain the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
Add in the brown color pureed or cake of gained by
the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the ultrasonic rear centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical;
The mixing solutions of described hydrogen peroxide and vitriol oil mixing gained, calculates by volume, is hydrogen peroxide: the vitriol oil is 1:3 ~ 7;
(4) preparation of, pure graphene oxide
The purees of the aqueous hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is preferably until effluent liquid is for neutral successively with mass percent concentration, centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are that 60-80 DEG C of vacuum-drying obtains graphite oxide;
Calculating in mass ratio, i.e. graphite oxide: solvent is 1:1, joins in solvent by the graphite oxide of gained, is then carry out ultrasonic 15-60min in the ultrasonoscope of 100W namely to obtain graphene oxide dispersion at room temperature power;
Described solvent is water, ethanol, acetone or tetrahydrofuran (THF) etc.
Beneficial effect of the present invention
The preparation method of a kind of graphene oxide dispersion of the present invention, due to without low-temp reaction step, thus simplifies processing step, reduce production cost and energy consumption, and reaction process does not add SODIUMNITRATE, therefore without NO
2/ N
2o
4toxic gas is released, environmentally friendly.
Further, the preparation method of a kind of graphene oxide dispersion of the present invention, the graphene oxide that can obtain the larger individual layer of lamella because the short period of time is ultrasonic, thus effectively solve existing graphene oxide produce in dispersed bad, poor stability and the ultrasonic problem causing lamella less for a long time.Graphene oxide good dispersity in the graphene oxide dispersion of i.e. final gained, good stability, size is comparatively large, and be 0.1-10 μm, its productive rate is 80-90% relative to multilayer (2-10 layer) graphene oxide.
Further, the preparation method of a kind of graphene oxide dispersion of the present invention, because the graphene oxide in prepared graphene oxide contains a large amount of oxygen-containing functional groups, therefore in the covalent modification, fire-retardant, photoelectric field of other material and graphene oxide, there is potential using value.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of graphite oxide prepared in Fig. 1, embodiment 1;
The Raman spectrum of the natural flake graphite used in Fig. 2, embodiment 2;
The Raman spectrum of the graphene oxide in Fig. 3, embodiment 1 gained graphene oxide dispersion;
The Raman spectrum of the graphene oxide in Fig. 4, embodiment 2 gained graphene oxide dispersion;
The AFM figure of the graphene oxide in Fig. 5 a, embodiment 1 gained graphene oxide dispersion;
The thickness chart of the graphene oxide in Fig. 5 b, embodiment 1 gained graphene oxide dispersion;
The AFM figure of the graphene oxide in Fig. 6 a, embodiment 2 gained graphene oxide dispersion;
The thickness chart of the graphene oxide in Fig. 6 b, embodiment 2 in gained graphene oxide dispersion;
The partial enlarged drawing of the Blocked portion in Fig. 7, Fig. 6 a.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
In the embodiment of the present invention, Raman spectrum test uses the silent Raman spectrometer (model DXRRamanMacroscope) flying your production of generation of U.S.'s match.
Scanning electron microscope used in the embodiment of the present invention is the S-3400N scanning electronic microscope that Hitachi produces.
Atomic force microscope used in the embodiment of the present invention is the Agilent5500SPM that Agilent company of the U.S. produces.
The ultrasonic equipment used of the present invention is the BG-02C Ultrasonic Cleaners that Guangzhou Bang Jie Electronics Co., Ltd. produces.
embodiment 1
A preparation method for graphene oxide dispersion, specifically comprises the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, the vitriol oil being 98% by 1.5g graphite and 30ml concentration mixes in the ratio of 1g:20mL, ultrasonic 1h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is natural graphite powder;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add 6g potassium permanganate, ultrasonic 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:4;
Then by the graphite/sulfuric acid/potassium permanganate mixture of the sulfate radical intercalation of gained under rotating speed is 250r/min, control temperature is 35 DEG C and carries out oxidizing reaction 2h, obtained preliminary graphite oxide;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as its volume 1-1.5 deionized water 100ml doubly, be hydrolyzed reaction 15min under constant temperature 98 DEG C of conditions, obtains the graphite oxide with hydrophilic radical;
The mixing solutions that the aqueous hydrogen peroxide solution being 30% by 300ml deionized water and 25ml mass percent concentration being incorporated as its volume 2 times in the solution of the graphite oxide with hydrophilic radical of gained is mixed to form, obtains the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
Add in the brown color pureed or cake of gained 50ml by
the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical after ultrasonic 10min;
The mixing solutions of described hydrogen peroxide and vitriol oil mixing gained, calculates by volume, is hydrogen peroxide: the vitriol oil is 1:5;
(4) preparation of, pure graphene oxide
Be that the purees of the dilute hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is until effluent liquid is for neutral with mass percent concentration successively, centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are that 60 DEG C of vacuum-drying 12h obtain pure graphite oxide;
The graphite oxide surface sweeping Electronic Speculum of above-mentioned gained scanned, as shown in Figure 1, as can be seen from Figure 1, the graphite oxide of gained is orderly laminate structure to the scanning electron microscope (SEM) photograph of gained, easily peels off the graphene oxide for individual layer;
By mass, graphite oxide: solvent is the ratio of 1:1, is distributed to 0.01g by the 0.01g graphite oxide of gained
solventin, then under room temperature, be carry out ultrasonic 40min in the ultrasonic apparatus of 100W namely to obtain graphene oxide dispersion at power;
Described solvent is water.
embodiment 2
A preparation method for graphene oxide dispersion, specifically comprises the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, the vitriol oil being 98% by 1.5g graphite and 30ml concentration mixes in the ratio of 1g:20mL, ultrasonic 1h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is natural flake graphite;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add 6g potassium permanganate, ultrasonic 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:4;
By the graphite/sulfuric acid/potassium permanganate mixture of the sulfate radical intercalation of gained under rotating speed is 250r/min, control temperature is 35 DEG C and carries out oxidizing reaction 2h, obtained preliminary graphite oxide;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as its volume 1-1.5 deionized water 100ml doubly, be hydrolyzed reaction 15min under constant temperature 98 DEG C of conditions, obtains the graphite oxide with hydrophilic radical;
The mixing solutions that the aqueous hydrogen peroxide solution being 30% by 300ml deionized water and 25ml mass percent concentration being incorporated as its volume 2 times in the solution of the graphite oxide with hydrophilic radical of gained is mixed to form, obtains the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
Add in the brown color pureed or cake of gained 50ml by
the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical after ultrasonic 10min;
Described hydrogen peroxide and the mixing solutions of the vitriol oil, calculate by volume, be hydrogen peroxide: the vitriol oil is 1:5;
(4) preparation of, pure graphene oxide
Be that the purees of the dilute hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is until effluent liquid is for neutral with mass percent concentration successively, centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are that 60 DEG C of vacuum-drying 12h obtain pure graphite oxide;
The graphite oxide surface sweeping Electronic Speculum of above-mentioned gained scanned, as shown in Figure 1, as can be seen from Figure 1, the graphite oxide of gained is orderly laminate structure to the scanning electron microscope (SEM) photograph of gained, easily peels off the graphite oxide for individual layer;
By mass, graphite oxide: solvent is the ratio of 1:1, is distributed to 0.01g by the 0.01g graphite oxide of gained
solventin, then under room temperature, be carry out ultrasonic 40min in the ultrasonic apparatus of 100W namely to obtain graphene oxide dispersion at power;
Described solvent is deionized water.
Adopt Raman spectrometer respectively to the Raman spectrum of the natural flake graphite used in embodiment 2, the Raman spectrum of the graphene oxide in the graphene oxide dispersion of embodiment 1 gained, graphene oxide in the graphene oxide dispersion of embodiment 2 gained carries out Raman spectrometry, result is as Fig. 2, Fig. 3, shown in Fig. 4, from Fig. 2, the contrast of Fig. 3 and Fig. 4 can be found out, graphene oxide there occurs obvious change relative to the D peak of natural flaky graphite and the intensity at G peak, natural flake graphite raw material and embodiment 1 as we can see from the figure, in embodiment 2, the graphene oxide layer of preparation all has three place's characteristic peaks, the G peak being positioned at 1580cm-1 respectively, be positioned at the D peak near 1350cm-1, and the 2D peak be positioned near 2700cm-1, but the D peak intensity of flaky graphite is starkly lower than the G peak intensity of flaky graphite, and the D peak of graphene oxide is close with G peak intensity, the ordered structure indicating flaky graphite graphite in oxidising process is thus destroyed, graphite flake layer is stripped and becomes graphene oxide.
In the Raman spectrogram of embodiment 1, embodiment 2, D peak is close with G peak intensity, and the D peak intensity of raw material natural flake graphite is starkly lower than G peak intensity, and this is the main difference of graphene oxide and graphite; In the Raman spectrogram of embodiment 1, embodiment 2, D peak is far above the D peak of raw material natural flake graphite, and this is because the ordered structure of graphite in oxidising process is destroyed, and shows that graphite flake layer is stripped.
Atomic force microscope is adopted to carry out pattern and thickness measurement to the graphene oxide in the graphene oxide dispersion of preparation in the graphene oxide in the graphene oxide dispersion of preparation in embodiment 1, embodiment 2 respectively, the AFM figure of the graphene oxide of gained and thickness chart are shown in Fig. 5 a, Fig. 5 b, Fig. 6 a, Fig. 6 b respectively;
Fig. 5 a is the AFM figure that AFM schemes, Fig. 6 a is the graphene oxide in the graphene oxide dispersion of gained in embodiment 2 of the graphene oxide in the graphene oxide dispersion of gained in embodiment 1.Carry out contrast by Fig. 5 b, Fig. 6 b can find out, in the preparation method of a kind of graphene oxide dispersion of the present invention gained graphene oxide dispersion in graphene oxide lamella densely distributed, lamella size is about 4um.
Fig. 7 is the partial enlarged drawing of the Blocked portion of Fig. 6 a, from Fig. 7, can find out that the graphene oxide lamella size in graphene oxide dispersion prepared by the present invention is about 4um further, lamella can fold and be not easy to reunite, the graphene oxide snappiness indicated thus in the graphene oxide dispersion of gained in the preparation method of a kind of graphene oxide dispersion of the present invention is good, is not easy to reunite.
Fig. 5 b is the thickness chart of the graphene oxide in the graphene oxide dispersion of gained in embodiment 1, Fig. 6 b is the thickness chart of the graphene oxide in the graphene oxide dispersion of embodiment 2 gained, from Fig. 5 b, Fig. 6 b can find out that the lamellar spacing of the graphene oxide in graphene oxide dispersion is about 1nm, this and the thickness of document single-layer graphene oxide are the consistent (Lerf of 0.6-1.1nm report, A. etc. solid-state physics chemistry 67, 1106 (2006)), show thus, in the preparation method of a kind of graphene oxide dispersion of the present invention gained graphene oxide dispersion in graphene oxide be individual layer.
embodiment 3
A preparation method for graphene oxide dispersion, specifically comprises the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, the vitriol oil being 98% by 1.5g graphite and 30ml mass percent concentration mixes in the ratio of 1g:20mL, ultrasonic 1h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is micro crystal graphite;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add 6g potassium permanganate, ultrasonic 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:4;
Then by the graphite/sulfuric acid/potassium permanganate mixture of the sulfate radical intercalation of gained under rotating speed is 250r/min, control temperature is 35 DEG C and carries out oxidizing reaction 2h, obtained preliminary graphite oxide;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as the deionized water 100ml of its volume 2 times, be hydrolyzed reaction 10 ~ 20min under constant temperature 98 DEG C of conditions, forms the graphite oxide with hydrophilic radical;
The mixing solutions that the aqueous hydrogen peroxide solution being 30% by 300ml deionized water and 25ml mass percent concentration being incorporated as its volume 2 times in the solution of the graphite oxide with hydrophilic radical of gained is mixed to form, obtains the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
Add in the brown color pureed or cake of gained 50ml by
the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical after ultrasonic 10min;
The mixing solutions of described hydrogen peroxide and vitriol oil mixing gained, calculates by volume, is hydrogen peroxide: the vitriol oil is 1:5;
(4) preparation of, pure graphene oxide
Be that the pureed of the dilute hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is until effluent liquid is for neutral with mass percent concentration successively, after centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are that 60 DEG C of vacuum-drying 12h obtain pure graphite oxide;
By mass, graphite oxide: solvent is the ratio of 1:1, is distributed to 0.01g by the 0.01g graphite oxide of gained
solventin, then under room temperature, be carry out ultrasonic 40min in the ultrasonic apparatus of 100W namely to obtain graphene oxide dispersion at power;
Described solvent is deionized water.
Graphene oxide in the graphene oxide solution dispersion liquid of above-mentioned gained, the Agilent5500SPM atomic force microscope instrument produced through Agilent company of the U.S. measures, and its size is comparatively large, and be 1-10um, its productive rate is 90% relative to multilayer graphene oxide.
embodiment 4
A preparation method for graphene oxide dispersion, specifically comprises the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, the vitriol oil being 98% by 1.5g graphite and 30ml mass percent concentration mixes in the ratio of 1g:20mL, ultrasonic 1h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is expanded graphite;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add 6g potassium permanganate, ultrasonic 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:4;
Then by the graphite/sulfuric acid/potassium permanganate mixture of the sulfate radical intercalation of gained under rotating speed is 250r/min, control temperature is 35 DEG C and carries out oxidizing reaction 2h, obtained preliminary graphite oxide;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as its volume 2 times, i.e. 100ml deionized water, be hydrolyzed reaction 15min under constant temperature 98 DEG C of conditions, forms the solution of the graphite oxide with hydrophilic radical;
What in the solution of the graphite oxide with hydrophilic radical of gained, be incorporated as its volume 2 times is that 30% aqueous hydrogen peroxide solution mixes the mixing solutions formed by 300mL deionized water and 25ml mass percent concentration, obtains the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
In the brown color pureed or cake of gained, be incorporated as its volume 5 times, namely 50ml is by the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical after ultrasonic 10min;
The mixing solutions of described hydrogen peroxide and vitriol oil mixing gained, calculates, i.e. hydrogen peroxide by volume: the vitriol oil is 1:5;
(4) preparation of, pure graphene oxide
Be that the purees of the aqueous hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is until effluent liquid is for neutral with mass percent concentration successively, centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are 60 DEG C and carry out vacuum-drying 12h, namely obtain pure graphite oxide;
Calculating in mass ratio, i.e. graphite oxide: solvent is the ratio of 1:1, is distributed in solvent by the graphite oxide of gained, then under room temperature, is carry out ultrasonic 30min in the ultrasonic apparatus of 100W namely to obtain graphene oxide dispersion at power;
Described solvent is deionized water.
Graphene oxide in the graphene oxide solution dispersion liquid of above-mentioned gained, the Agilent5500SPM atomic force microscope of producing through Agilent company of the U.S. measures, its size is comparatively large, and be 0.1-10um, its productive rate is 90% relative to multilayer (2-10 layer) graphene oxide.
In sum, the preparation method of a kind of graphene oxide dispersion of the present invention, successfully can prepare the dispersion liquid of single-layer graphene oxide, graphene oxide good dispersity lamella in gained graphene oxide dispersion is intensive, stability and snappiness good, be not easy reunite, lamella is 0.1-10um more greatly, productive rate is higher, and its productive rate is 80%-90% relative to multilayer (2-10 layer) graphene oxide.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (1)
1. a preparation method for graphene oxide dispersion, is characterized in that specifically comprising the following steps:
(1), the preparation of the graphite/sulfuric acid mixture of sulfate radical intercalation
At normal temperatures, graphite is mixed with the ratio of the vitriol oil in 1g:20mL, ultrasonic 0.5 ~ 1.5h, the graphite/sulfuric acid mixture of obtained sulfate radical intercalation;
Described graphite is that particle diameter is 80 order-500 object natural graphite powders, natural flake graphite, micro crystal graphite or expanded graphite;
(2) preparation of, preliminary graphite oxide:
Disposablely in the graphite/sulfuric acid mixture of the sulfate radical intercalation of step (1) gained at normal temperatures add potassium permanganate, ultrasonic 5 ~ 10s obtains the graphite/sulfuric acid/potassium permanganate mixture of sulfate radical intercalation;
The addition of potassium permanganate calculates in mass ratio, i.e. graphite: potassium permanganate is 1:6 ~ 10;
Then by the graphite/sulfuric acid/potassium permanganate mixture of the sulfate radical intercalation of gained under agitation, control temperature is 25 ~ 40 DEG C and carries out oxidizing reaction 1 ~ 3h, obtains graphite oxide tentatively;
(3), with the preparation of the graphite oxide of hydrophilic radical
In the solution of the preliminary graphite oxide of step (2) gained, be incorporated as its volume 1-5 deionized water doubly, be hydrolyzed reaction 10 ~ 20min under constant temperature 90 ~ 100 DEG C of conditions, forms the solution of the graphite oxide with hydrophilic radical;
In the solution of the graphite oxide with hydrophilic radical of gained, be incorporated as its volume 2-5 aqueous hydrogen peroxide solution being 30% by deionized water and mass percent concentration doubly mix the mixing solutions formed, obtain the jonquilleous graphite oxide aqueous solution;
By centrifugal for the jonquilleous graphite oxide aqueous solution of gained or filtration, obtain brown color pureed or cake;
Be incorporated as in the brown color pureed or cake of gained its volume 2-10 doubly by the mixing solutions of hydrogen peroxide and vitriol oil mixing gained, the ultrasonic rear centrifugal purees obtaining graphite oxide with a large amount of hydrophilic radical;
The mixing solutions of described hydrogen peroxide and vitriol oil mixing gained, calculates, i.e. hydrogen peroxide by volume: the vitriol oil is 1:3-7;
(4) preparation of, pure graphene oxide
Be that the purees of the aqueous hydrochloric acid of 10% and the graphite oxide with a large amount of hydrophilic radical of deionized water wash step (3) gained is until effluent liquid is for neutral with mass percent concentration successively, centrifugal or suction filtration, the precipitation of gained or filter cake control temperature are 60-80 DEG C and carry out vacuum-drying, namely obtain graphite oxide;
Calculating in mass ratio, i.e. graphite oxide: solvent is 1:1, joins in solvent by the graphite oxide of gained, then under room temperature, is carry out ultrasonic 15-60min in the ultrasonic apparatus of 100W namely to obtain graphene oxide dispersion at power;
Described solvent is water, ethanol, acetone or tetrahydrofuran (THF).
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