CN102491318A - Method for preparing graphene oxide - Google Patents
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- CN102491318A CN102491318A CN2011104143157A CN201110414315A CN102491318A CN 102491318 A CN102491318 A CN 102491318A CN 2011104143157 A CN2011104143157 A CN 2011104143157A CN 201110414315 A CN201110414315 A CN 201110414315A CN 102491318 A CN102491318 A CN 102491318A
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Abstract
The invention discloses a method for preparing a graphene oxide. The method comprises the following steps of: a) adding concentrated inorganic acid into a sealed reactor, adding graphite powder with stirring, reducing the temperature to the temperature of between 0 and 4 DEG C, and adding potassium permanganate to react for 0.5 to 2 hours; b) heating the obtained reaction system to the temperature of between 60 and 70 DEG C, and standing for 12 to 24 hours; c) adding hydrogen peroxide into distilled water in a volume ratio of 1:10, freezing to obtain ice, transferring the graphite oxide to the distilled water containing the hydrogen peroxide until the ice is completely dissolved, uniformly stirring, performing suction filtration, washing and drying to obtain the graphene oxide. The graphite powder, the concentrated acid and the potassium permanganate serve as raw materials, and the raw materials are low in cost and readily available; NO, NO2 and other toxic gases are prevented from being produced; the reaction temperature is as low as 60-70 DEG C; and the product has high dye adsorption capacity and high industrial application value.
Description
Technical field
The present invention relates to a kind of method that adopts solvent-thermal method to prepare graphene oxide at low temperatures, belong to the functional materials preparing technical field.
Background technology
Graphene is a kind of carbonaceous novel material of the cellular crystalline network of individual layer of the tightly packed one-tenth of carbon atom, is a kind of two dimensional crystal, is the elementary cell that makes up other dimension blackings (like zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).The history in existing more than 60 year of the theoretical investigation of Graphene, but all the time, people generally believe that the two dimensional crystal structure of this strictness is owing to thermodynamic phase is difficult to independent stable existence.Up to 2004, the study group of Univ Manchester UK utilized the method for the high oriented graphite of tape stripping to obtain self-existent two-dimentional Graphene crystal, for the experimental study of two-dimensional system provides wide space.
At present preparation method of graphene has mechanically peel method, chemical Vapor deposition process (CVD), epitaxial growth method, electrochemical process, graphite oxide reduction method etc., and wherein the graphene film amount that obtains of mechanically peel method is few, and randomness is big; CVD method and epitaxial growth method mostly with SiC as substrate, cost is high, poor controllability; The Graphene amount that electrochemical method obtains is less, wayward.The graphite oxide reduction method is through introducing oxygen-containing functional group at graphite surface, increase interlamellar spacing, thereby reduce the Van der Waals force between the layer, through its hybridization state of method change such as ultrasonic, obtains Graphene through reduction more then.The graphite oxide reduction method with its cheaply advantage become one of present most popular method; The preparation method of graphene oxide mainly is Hummers method (Hummers at present; W.S.&Offeman; R.E.Preparation of graphitic oxide.J.Am.Chem.Soc.80,1339 (1958)).This method need adopt cooling earlier, the three-step approach that heats up in two steps again in the process of preparation graphene oxide in the system of opening wide; And utility appliance such as condensing reflux; Need accurate control reaction temperature and temperature up to 98 ℃ in the process, the graphene oxide for preparing also needs ultrasonic for a long time, complex steps; The concentration of product is lower, is not suitable for mass production.Chinese patent CN102225754A discloses a kind of method that adopts seal pot to prepare graphene oxide, has adopted nitrate salt in the raw material, and temperature of reaction is 80-130 ℃, can produce NO and NO in the reaction process
2Deng toxic gas, reduced the security of reaction process, be not suitable for industrial production.
The present invention adopts solvent-thermal method to prepare graphene oxide at low temperatures, and sample can be used for the absorption of organic dye, also can directly reduce, and obtains Graphene.Sample contains abundant oxygen-containing functional group, and output is bigger.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts solvent-thermal method to prepare graphene oxide, this method temperature is lower, easy and simple to handle, save energy, and the graphene oxide of preparation has the characteristics of equal solvent soluble in water, and output is bigger.Mild condition of the present invention, synthesis device is simple, favorable reproducibility, for the mass production of graphene oxide provides maybe.
For achieving the above object, it is raw material that the present invention adopts Graphite Powder 99, and the mixing acid of the vitriol oil or the vitriol oil and SPA is intercalator, and potassium permanganate is oxygenant.Experimental technique obtains the graphene oxide material of different degree of oxidations through changing the ratio and the reaction times of oxygenant and Graphite Powder 99.
Technical scheme of the present invention is:
A kind of method for preparing graphene oxide may further comprise the steps:
A) dense mineral acid is added in the sealed reactor, under agitation, add Graphite Powder 99, be cooled to 0～4 ℃ then, add potassium permanganate again, reaction 0.5～2h;
Wherein, material proportion is the dense mineral acid of 23ml/1g Graphite Powder 99, and quality is than Graphite Powder 99: potassium permanganate=1: 4～6;
B) reaction system that obtains above the general is heated to 60～70 ℃, and 12～24h is placed in sealing;
C) by volume in the zero(ppm) water: the ratio of ydrogen peroxide 50=10: 1 adds ydrogen peroxide 50 in zero(ppm) water, freeze to the ice cube shape, graphite oxide is transferred in the zero(ppm) water that contains ydrogen peroxide 50; The zero(ppm) water of the corresponding 100ml of 1g graphite dissolves to ice cube fully, and the back suction filtration stirs; Use 5% HCl, zero(ppm) water, washing with alcohol graphene oxide to sulfate radical-free respectively; And be neutral, with product dry 6h under 50 ℃, obtain graphene oxide at last.
Described dense mineral acid is one or both in the vitriol oil and the SPA.
Described ydrogen peroxide 50 is the ydrogen peroxide 50 of mass percent 30%.
Advantage of the present invention:
1, adopting Graphite Powder 99, the vitriol oil and potassium permanganate is raw material, and raw materials cost is cheap to be easy to get.
2, adopt seal pot to prepare at present adopting nitrate salt in the method for graphene oxide is oxygenant, does not adopt nitrate salt in the raw material of the present invention, has prevented NO, NO
2Generation Deng toxic gas.
3, in seal pot, prepare graphene oxide, the preparation method is simple, and is easy to operate, can be through ratio of regulating oxygenant and the degree of oxidation that oxidization time is regulated graphene oxide.Increase with oxidant ratio; The growth of oxidization time, the interlamellar spacing maximum of graphene oxide can be to
4, temperature of reaction is lower; Just can obtain the graphene oxide of interlamellar spacing under 60～70 ℃ the condition for
; Be far smaller than 80-130 ℃ that present patent adopts; Save energy; The graphene oxide that obtains contains abundant oxygen-containing functional group, and is fit to the preparation of a large amount of graphene oxides.
5, the graphene oxide of preparation has good dye adsorption ability, and the maximal absorptive capacity to the 20mg/l methylene blue solution can reach 199.2mg/g at normal temperatures, has industrial application value.
Description of drawings
Fig. 1 is the XRD figure of the graphene oxide of embodiment 1,2,3,4,5 preparations
Fig. 2 (a) is the not dry graphene oxide solid of embodiment 1 microphotograph; (b) be the photo of the colloidal solution of the water-soluble formation of embodiment 1 undried graphene oxide;
Fig. 3 is the SEM figure of embodiment 1 dry rear oxidation Graphene.
Embodiment
Embodiment 1: measure the 23ml vitriol oil (massfraction is 98%); Join in the polytetrafluoroethyllining lining of stainless steel cauldron of 50ml, after mixing under the magneton stirring condition, add the 1g Graphite Powder 99; Under the condition of ice-water bath, be cooled to 0～4 ℃; Add 6g potassium permanganate, the time is controlled at 1h, and sample is stirred.After the still sealing, put into 70 ℃ of thermostat containers, place 24h, accomplish graphite oxidation, sample is lavender.
Press the ydrogen peroxide 50 that adds 10ml mass percent 30% in the 100ml zero(ppm) water, cooling is frozen to the ice cube shape.Graphite oxide is transferred in the zero(ppm) water mixture that contains ydrogen peroxide 50 that is frozen into ice cube, treated that it dissolves back (sample is glassy yellow) fully, the sand core funnel suction filtration is used in the back that stirs.HCl with 5%, zero(ppm) water, ethanol wash graphite oxide successively and extremely detect sulfate radical-free with barium chloride solution, and are neutral.Sample is put into 50 ℃ of dry 6h of air dry oven.Obtain the 1.2g graphene oxide.(Fig. 1 curve a) is respectively 2 θ=26.55 ° (002) and 2 θ=54.70 ° (004) to the X ray characteristic diffraction peak of Graphite Powder 99 (Graphite); The interlamellar spacing of representing Graphite Powder 99 for
along with the effect of oxygenant; The characteristic diffraction peak of Graphite Powder 99 is more and more not obvious; And the characteristic diffraction peak of graphene oxide is more and more obvious; And diffraction angle is more and more littler, and in the X ray diffracting spectrum of Fig. 1 sample, curve b represents the spectrogram of embodiment 1 sample; Can know that by figure the characteristic peak of graphite disappears, the crystalline structure of this explanation Graphite Powder 99 is destroyed.The diffraction peak grow of graphene oxide explain that body shape graphite has become less, the thin carbon-coating (Nano grade) of size, and percent crystallinity reduces.At this moment (Daniela C.Marcano et.al.Improved synthesis of graphene oxide ACS Nano.20104 (8): 4806-14) its interlamellar spacing also has obvious increase to the interlamellar spacing of graphene oxide, explains that the degree of oxidation of the graphene oxide that seal pot prepares is higher than the graphite oxide
of Hummers method preparation for
.Like Fig. 2 a is the microphotograph of undried graphene oxide, shows that the graphene oxide that obtains is the glassy yellow solid, and with T Chen, Baoqing Zeng etc. are to consistent (the Journal of physics of the description of graphene oxide; 2009,188:012051).Photo when the colloidal solution of the water-soluble formation of undried graphene oxide that Fig. 2 b obtains for embodiment 1 is diluted to concentration and is 0.05mg/l.Like Fig. 3 is the SEM figure of dried graphene oxide, on scheming, can find out that graphene oxide becomes laminated structure, looser, in its edge section obvious fold is arranged.
This sample is 199.2mg/g to the maximal absorptive capacity of the methylene blue solution of 20mg/l.
Embodiment 2: other experimental procedures are with embodiment 1; Only change the amount of potassium permanganate; The quality that adds potassium permanganate is 5g; The mass ratio of Graphite Powder 99 and potassium permanganate is 1: 5, and curve c is the X ray diffracting spectrum of this sample among Fig. 1, can know that by figure the characteristic diffraction peak of Graphite Powder 99 is not obvious; The interlamellar spacing of calculating the gained sample shows that for
the oxygenant consumption reduces, and its reactive force in graphite layers reduces.
Embodiment 3: other experimental procedures are with embodiment 1; Only through changing the amount of putting into of potassium permanganate; The quality that adds potassium permanganate is 4g; The mass ratio of Graphite Powder 99 and potassium permanganate is 1: 4, and curve d is the X ray diffracting spectrum of this sample among Fig. 1, and the characteristic diffraction peak of Graphite Powder 99 begins not obvious; The interlamellar spacing of calculating the gained sample shows that for
the oxygenant consumption further reduces, and its reactive force in graphite layers also reduces.
Embodiment 4: other experimental procedures are with embodiment 1; Only through changing the reaction times; Reaction times is 12h; Curve e is the X ray diffracting spectrum of this sample among Fig. 1; The characteristic diffraction peak of Graphite Powder 99 is not obvious, and the interlamellar spacing of calculating the gained sample shows the reaction times minimizing for
, and its reactive force in graphite layers reduces.This possibly be because in time minimizing, and the liquid evaporation amount in the seal pot reduces, and the pressure that seal pot is produced also reduces, the layer of graphite oxide with layer the variation of arrangement become not obvious.
Embodiment 5: other experimental procedures are with embodiment 3; Only through changing the composition of concentrated acid; The concentrated acid that adds is the mixture of the vitriol oil (massfraction is 98%) and SPA (massfraction is 85%); Volume ratio is 9: 1; Curve f is the X ray diffracting spectrum of this sample among Fig. 1; The characteristic diffraction peak of Graphite Powder 99 is not obvious, and it is similar with the sample of embodiment 3 for
interlamellar spacing that the characteristic diffraction peak of graphene oxide is that 2 θ=11.20 ° calculate the interlamellar spacing of sample, but the characteristic diffraction peak of graphene oxide is more obvious.This possibly be because the functional group on SPA that adds and graphene oxide surface interacts, and makes the molecule that inserts graphite layers more, and interlamellar spacing is more stable.
Can find out from top embodiment; Through changing the add-on and the oxidization time of oxygenant, can change the degree of oxidation of graphene oxide, when quality than Graphite Powder 99: during potassium permanganate=1: 6; Under 70 ℃, oxidization time is that the degree of oxidation of the graphene oxide that obtains of 24h is the highest.
Claims (3)
1. method for preparing graphene oxide is characterized by and may further comprise the steps:
A) dense mineral acid is added in the sealed reactor, under agitation, add Graphite Powder 99, be cooled to 0～4 ℃ then, add potassium permanganate again, reaction 0.5～2h;
Wherein, material proportion is the dense mineral acid of 23ml/1g Graphite Powder 99, and quality is than Graphite Powder 99: potassium permanganate=1:4～6;
B) reaction system that obtains above the general is heated to 60～70 ℃, and 12～24h is placed in sealing;
C) ratio of zero(ppm) water: ydrogen peroxide 50=10:1 adds ydrogen peroxide 50 in zero(ppm) water by volume, freezes to the ice cube shape, graphite oxide is transferred in the zero(ppm) water that contains ydrogen peroxide 50; The zero(ppm) water of the corresponding 100ml of 1g graphite dissolves to ice cube fully, and the back suction filtration stirs; The HCl, zero(ppm) water, washing with alcohol graphite oxide that use massfraction 5% respectively are to sulfate radical-free; And be neutral, with product dry 6h under 50 ℃, obtain graphene oxide at last.
2. the method for preparing graphene oxide as claimed in claim 1 is characterized by described dense mineral acid and is in the vitriol oil and the SPA one or both.
3. the method for preparing graphene oxide as claimed in claim 1 is characterized by the ydrogen peroxide 50 that described ydrogen peroxide 50 is a mass percent 30%.
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