CN103382028A - Preparation of graphene oxide and post-processing method for waste liquor - Google Patents
Preparation of graphene oxide and post-processing method for waste liquor Download PDFInfo
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Abstract
The invention relates to a preparation method for graphene oxide. The preparation method comprises the following steps: a. mixing a graphite powder and concentrated sulfuric acid at the low temperature; b. adding potassium permanganate, and heating to carry out an intermediate temperate reaction; c. adding water for a high temperature reaction, d. adding hydrogen peroxide aqueous solution for a reaction, and after finishing the reaction, filtering the obtained bright yellow solution; e. washing the filter cake with HCl aqueous solution; f. after drying the obtained solid, putting into water for stirring, and dialyzing; and g. removing a substrate by a centrifugal way to obtain a stable dispersion liquid of graphene oxide.
Description
Technical field
The present invention relates to graphene oxide preparation and waste liquid post-treating method.
Background technology
Graphene is by sp
2The hydridization carbon atom is interconnected to form the new carbon of monolayers thick bi-dimensional cellular shape structure.Graphene has started huge research boom due to the specific surface area of its superelevation, unusual electroconductibility and excellent mechanical property at aspects such as novel energy-storing material, catalyzer, polymer carriers.
The eco-friendly magnanimity of Graphene is synthetic is its prerequisite that realizes many application.Graphene is the graphite of individual layer.What we need to do peels off out from graphite with it exactly, can complete by physics or chemical process and peel off.The Graphene excellent performance of physical method gained is prepared but be difficult to magnanimity.Chemical method is opened interlamellar spacing and is generated oxygen-containing functional group by the graphite oxide powder, and further ultrasonic or stirring can get mono-layer graphite oxide alkene.The individual layer redox graphene that follow-up reduction process can obtain disperseing.But this method preparation in macroscopic quantity, preparation method's first-selection when being the Graphene extensive application.
Yet due to the natural inertia of graphite, the process of graphene oxide preparation must be completed in very harsh chemical environment.The method for preparing graphene oxide is also in improving gradually.As far back as 1859, Englishize scholar B.C.Brodie is by the chemical structure of the chemically reactive research graphite of graphite, he joins Potcrate in mixing of graphite and nitrosonitric acid, obtained a kind of material that can disperse in neutral and alkaline water, if carry out repeatedly oxidation, the content of C, H, O can reach a limit, wherein C accounts for 60.74%, H accounts for 1.85%, O and accounts for 37.41%, and carbon-to-oxygen ratio is about 2.16:1.This method is used nitrosonitric acid, danger and contaminate environment; 4 days reaction times, very large impact preparation efficiency.L.Staudenmaier has carried out some improvement to the method for B.C.Brodie, he has added a certain proportion of vitriol oil to improve the acidity of system in system, add Potcrate in graphite-sulfuric acid-nitrosonitric acid mixed system in batches, rather than as the method for B.C.Brodie disposable adding, multistep oxidation again, this has simplified experimental procedure to a certain extent, degree of oxidation for evaluating graphite, can adopt carbon-to-oxygen ratio (amount of carbon species is divided by the amount of oxygen species), although because the graphite oxide of preparation can contain some water, different drying meanss, can affect measurement result, but can roughly understand by carbon-to-oxygen ratio the degree of oxidation of graphite.The carbon-to-oxygen ratio value of the product of Staudenmaier method and Brodie's is close, is about 2.89:1.Certainly, it is now know that raising acidity is not only in sulfuric acid the effect here for we, also is inserted into the lamella of graphite as intercalation reagent, and direct enlargement layer spacing is for the attack of oxygenant provides certain space.U. Hofmann further improves forefathers' method, his operation steps is constant, just original nitrosonitric acid is replaced the concentrated nitric acid for 68%, and the danger coefficient of whole system further reduces, and oxidation is more abundant, and carbon-to-oxygen ratio is compared low with the Staudenmaier method.These methods have all been used concentrated nitric acid, its degradation production nitrogen oxides pollution environment; In addition, the generation that the use of oxygenant chloric acid potassium has brought the dioxide peroxide that explosion hazard is arranged is not suitable for scale operation.
From between 100 years of B.C.Brodie graphite oxide, scientist be all adopted Potcrate as oxygenant with graphite oxidation, until 1958, Hummers has successfully adopted potassium permanganate to prepare graphite oxide as oxygenant first.Experimental procedure is divided into three parts, at first be the intercalation of low temperature in the solution of SODIUMNITRATE-potassium permanganate-vitriol oil (ice bath), form single order sulfuric acid-graphite intercalation compound, the deep oxidation reaction of middle temperature (40 degrees centigrade) subsequently, forming the oxy radical attack, form manganate, is the hydrolysis reaction of high temperature at last, simultaneously large water gaging enters aluminum oxide/graphite layer enlargement layer spacing, and the carbon-to-oxygen ratio of product is about 2.25:1.The Hummers method reaction times only needs approximately 3 hours, and additive method needs 3 days, compares the reaction times with other method shorter; Do not need to use nitrosonitric acid, reaction hazardness is less; Degree of oxidation is compared also more abundant with additive method, thus the Hummers method be at present with chemical oxidization method prepare graphite oxide the most frequently used one of method.The descendant also is studied the Hummers method, thereby has derived a lot of Innovative methods, and for example SODIUMNITRATE has been removed by the James of Rice University M. Tour seminar, with the H of 9:1
2SO
4/ H
3PO
4Be solvent, increased the amount of potassium permanganate, the degree of oxidation of the graphite oxide that obtains is higher.Although SODIUMNITRATE has been removed in such improvement, double sulfuric acid and potassium permanganate, and introduced the difficult phosphoric acid of removing, well a lot of unlike the Hummers method in fact.
To sum up, but a kind of more eco-friendly and method preparation in macroscopic quantity graphene oxide of development is the important prerequisite that Graphene is used.
Summary of the invention
The purpose of this invention is to provide a kind of eco-friendly preparation in macroscopic quantity graphene oxide method and follow-up method for treating waste liquid.
the method for preparing graphene oxide provided by the invention, comprise the steps: the mixing in ice-water bath with Graphite Powder 99 and the vitriol oil, after adding potassium permanganate and stirring certain hour, middle temperature reaction is carried out in intensification, adding certain water gaging to carry out pyroreaction stirred 15 minutes again, the aqueous solution that adds at last hydrogen peroxide, react that the gained bright yellow solution to be filtered and use 250 mL volume ratios after complete be the HCl solution washing of 1:10, with the gained solid after air drying, stir certain hour in water, dialysis one Zhou Houzai is after centrifugal removal substrate under the rotating speed of 4000rpm in water, obtain the stable dispersions of graphene oxide.
Wherein, the particle diameter of described Graphite Powder 99 is the 50-12000 order, preferred 325 orders; The mass percentage concentration of the described vitriol oil is 68-98%, preferred 98%; The mass percentage concentration of described aqueous hydrogen peroxide solution is 10 30%, preferred 30%; The amount ratio of the aqueous solution of described Graphite Powder 99, the vitriol oil, potassium permanganate and hydrogen peroxide is 1 5g:50 100 mL:3 20g:5 40mL, preferred 3g:70mL:9g:20mL; In described reactions steps, the time that low temperature mixes is at 5 minutes to 1 hour, preferred 10 minutes; 30 50 ℃ of middle temperature temperature of reaction, preferred 40 ℃; Time is 15 300 minutes, preferred 30 minutes; The pyrohydrolysis amount of water is at 0.5 5 times of sulfuric acid volumes, preferred 2 times of sulfuric acid volumes; 80 100 ℃ of pyroreaction temperature, preferred 95 ℃; 5 minutes to 300 minutes pyroreaction time, preferred 15 minutes.
The method of follow-up liquid waste disposal provided by the invention, the filtrate when comprising the steps: the preparation graphite oxide is filtered is collected, and after the waste liquid dilution, stirs and slowly drips neutralization reagent, and the pH of regulator solution reaches 10.Solution obtains brown precipitation through after ageing, will be deposited in supernatant liquor and separate, and obtains the precipitation of manganese.The concentration of supernatant liquor mn ion is lower than 0.4 mg/L at this moment.
Wherein, extension rate is at 2 10 times, preferred 4 times; Aftertreatment neutralization reagent used can be potassium hydroxide or its solution, salt of wormwood or its solution, ammonia or its solution, preferred potassium hydroxide solution; Neutralization reagent is as selecting potassium hydroxide solution, its concentration between 0.05 0.5 g/mL, preferred 0.2 g/mL.
Take above-mentioned graphene oxide provided by the invention as raw material, carry out the product that follow-up reduction, chemically modified make and also belong to protection scope of the present invention.
The preparation method of graphene oxide of the present invention has the following advantages:
1) preparation method is quick, effective, simple and easy to do, produces without waste gas and explosive substance.
2) graphene oxide of preparation, AFM and SEM characterization result show whole individual layers, the lamella size is between between hundreds of nanometer to tens micron; XRD shows that interlamellar spacing is opened fully, and oxidation is abundant.
3) the graphene oxide oxygen-containing functional group content of preparation belongs to normal range.XPS C 1s characterization result shows that the oxygen-containing functional group peak intensity obviously strengthens, and full spectrum scans C/O than 2.38, enough oxygen content; The Raman characterization result shows I
D/ I
GPeak intensity is than the obvious increase of Graphite Powder 99; Ultraviolet characterizes obvious n π * transition, shows that oxygen-containing functional group is sufficient.
4) preparation method does not use SODIUMNITRATE, has avoided the nitrogen oxides pollution gas purging, has simplified simultaneously liquid waste disposal.
5) method for subsequent processing is controlled at the concentration of (heavy metal ion) mn ion below 0.12mg/L, has reached the regulation of the World Health Organization to Manganese in Drinking Water content.
Description of drawings
Fig. 1 is photo and the ultraviolet spectrogram of graphene oxide dispersion liquid.
Fig. 2 is the XPS collection of illustrative plates of graphene oxide.
Fig. 3 is scanning electron microscope (SEM) picture of graphene oxide.
Fig. 4 is atomic force microscope (AFM) picture of graphene oxide.
Fig. 5 is X-ray diffraction (XRD) spectrogram of graphene oxide.
Fig. 6 is the Raman spectrum of graphene oxide.
Fig. 7 is the infrared spectrum of graphene oxide.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but protection scope of the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.
Preparation method of the present invention has improved the Hummers method, does not add SODIUMNITRATE fully.Concrete implementation step is: 3.0 g natural graphite powders (325 order) are mixed in ice-water bath with the vitriol oil of 70 mL 98wt %, the rear 9.0g potassium permanganate that slowly adds stirs, the whole speed control that adds is in the 20min left and right, continue to stir subsequently 10 minutes, with reaction mixture stirring reaction 30 minutes under 40 ° of C conditions.Add 140 mL deionized waters in reaction solution, after being warming up to 95 ° of C, continued stirring reaction 15 minutes.
Mixed solution is poured in the 500ml deionized water, added 20mL 30wt% H in stirring
2O
2The aqueous solution.Resulting bright yellow solution is filtered use again 250 ml 1:10 HCl solution washings (divide and wash for three times).Resulting filter cake is dissolved in the 200mL deionized water, stirs 12 hours, and the solution solution that dialysis obtained dialysis in 10 days in 8,000 14000 dialysis tubing of packing into is poured in beaker, stirs after 12 hours, ultrasonic 30 minutes, peels off graphite oxide.The solution that obtains carries out centrifugation, at first turns lower 40 minutes 3000 and removes precipitation, then turn lower 40 minutes 10000 and obtain lower floor's adopting dark liquid, and freeze-drying obtains product.
Adopt UV spectrum to characterize, have obvious 232nm carbon-carbon double bond π π in spectrogram (Fig. 1)
*Absorption peak, and the two key n π of 300nm carbon oxygen
*Absorption peak shows and has introduced oxygen-containing functional group.Fig. 4 is the picture of the aqueous solution of the graphene oxide of 0.5 mg/mL, shows that the large π key of graphite is effectively destroyed.
Adopt XPS to characterize, acquired results as shown in Figure 2.As seen from the figure, the peak area of carbon and oxygen functional group accounts for 29.8%, and unoxidized carbon carbon functional group accounts for 70.2%, proves that further Graphite Powder 99 fully is oxidized into graphene oxide.
Adopt the SEM means that the graphene oxide that this embodiment prepares gained is characterized, result as shown in Figure 3.As seen from the figure, the graphene oxide size is between hundreds of nanometer to tens micron.
Adopt the AFM means that the thickness of graphite oxide Xi is characterized, as can be seen from Figure 4, the height of graphene oxide lamella is lower than 1 nanometer, and the graphene oxide that this surperficial present method makes is single layer structure.
Adopt the XRD means to characterize the packed structures of graphite oxide, Fig. 5 has showed graphite oxide (001) characteristic peak, at the peak of unique position of 2 θ=10.9 graphite oxide, graphite peaks do not occur at 2 θ=26.4 places, show that degree of oxidation is higher, the interlamellar spacing by calculating graphite oxide approximately 8.
Adopt Raman spectrum means to characterize, acquired results as shown in Figure 6.1360 cm in figure
-1Near scattering peak is the graphite peaks (D peak) with textural defect, at 1600 cm
-1Near peak is kish peak (G).As can be seen from the figure the strength ratio at peak, the D of the graphene oxide after peroxidation peak/G obviously increases, and shows that the degree of oxidation of graphene oxide is higher.
Adopt the infrared spectra means to characterize, acquired results as shown in Figure 7.O H stretching vibration (3,600 3300 cm in figure
1), C=O stretching vibration (1,740 1720 cm
1), C=C stretching vibration (~ 1620 cm
1), O H flexural vibration (1420cm
-1), C O stretching vibration (1230 cm
1), aromatics or vinyl=C O C stretching vibration (~ 1000 cm
1) graphene oxide that shows present method preparation has traditional method and prepare the same functional group's kind of graphene oxide.
Filtrate when the preparation graphite oxide is filtered is collected, after 3-4 times of waste liquid dilution, stir and slowly drip the potassium hydroxide aqueous solution of 0.2 g/ml, the pH of regulator solution reaches 10, the purpose of dilution is to prevent from that vitriolate of tartar is saturated to separate out, and affects separating effect with mn ion generation co-precipitation.Solution through ageing in 24 hours after, obtain brown precipitation, will be deposited in supernatant liquor and separate, obtain the precipitation of manganese.This moment, the concentration of supernatant liquor mn ion was 0.12 mg/L.
Claims (10)
1. the preparation method of a graphene oxide, comprise the steps:
A. with Graphite Powder 99 and vitriol oil low-temperature mixed,
B. add potassium permanganate, heat up and carry out middle temperature reaction,
C. add water and carry out pyroreaction,
D. add aqueous hydrogen peroxide solution to react, react and the gained bright yellow solution is filtered after complete,
E. use HCl solution washing filter cake,
F. with after the gained solid drying, put into water and stir, dialysis,
G. remove substrate by centrifugation, obtain the stable dispersions of graphene oxide.
2. the preparation method of graphene oxide according to claim 1, the particle diameter that it is characterized in that described Graphite Powder 99 is the 50-12000 order, the mass percentage concentration of the described vitriol oil is 68-98%, the mass percentage concentration of described aqueous hydrogen peroxide solution is 10 30%, and the amount ratio of described Graphite Powder 99, the vitriol oil, potassium permanganate and aqueous hydrogen peroxide solution is 1 5g:50 100mL:3 20g:5 40mL.
3. the preparation method of claim 1 or 2 described graphene oxide, is characterized in that low-temperature mixed described in step a 5 minutes-1 hour; Graphite Powder 99 or other carbon materials are as raw material, the mass percentage concentration of the described vitriol oil is 98%, the mass percentage concentration of described aqueous hydrogen peroxide solution is 30%, and the amount ratio of described Graphite Powder 99, the vitriol oil, potassium permanganate and aqueous hydrogen peroxide solution is 3g:70mL:9g:20mL.
4. the preparation method of described graphene oxide according to claim 1 and 2, it is characterized in that, low-temperature mixed described in step a 5 minutes-1 hour, in described in step b, warm temperature of reaction is 30 50 ℃, 15 300 minutes described reaction times, amount of water described in step c is 0.5 5 times of sulfuric acid volumes, 80 100 ℃ of described pyroreaction temperature, 5 minutes-300 minutes described pyroreaction time.
5. the preparation method of described graphene oxide according to claim 1 and 2, it is characterized in that, low-temperature mixed described in step a 10 minutes, in described in step b, warm temperature of reaction is 40 ℃, 30 minutes described reaction times, amount of water described in step c is 2 times of sulfuric acid volumes, 95 ℃ of described pyroreaction temperature, 15 minutes described pyroreaction time.
6. the preparation method of described graphene oxide according to claim 1 and 2, is characterized in that, the aqueous solution of HCl described in step e is the volume ratio of HCl and the water of 1:10, and in step f, dialysis time is 7 days, and centrifugation described in step g is chosen the rotating speed of 4000rpm.
7. the waste liquid post-treating method of a graphene oxide, comprise the steps:
A. will prepare the filtrate dilution in the graphene oxide method,
B. the dilution filtrate of regulating step a is to PH=10,
C. with step b gained ageing of solution, precipitate,
D. the supernatant liquor in step c is separated, obtain the throw out of manganese.
8. the waste liquid post-treating method of graphene oxide according to claim 7, is characterized in that, in step a, extension rate is 2 10 times, regulates PH in step b and use potassium hydroxide or its solution, salt of wormwood or its solution, ammonia or its solution.
9. the preparation method of according to claim 7 or 8 described graphene oxides, is characterized in that, in step a, extension rate is chosen 4 times, regulates PH in step b and use potassium hydroxide solution, and its concentration is 0.05 0.5 g/mL.
10. the preparation method of graphene oxide according to claim 9, is characterized in that, the concentration of described potassium hydroxide solution is 0.2 g/mL.
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| CN112500584A (en) * | 2020-12-18 | 2021-03-16 | 青岛科技大学 | Graphene/cellulose aqueous dispersion and preparation method thereof |
| CN112645317A (en) * | 2020-12-30 | 2021-04-13 | 南通第六元素材料科技有限公司 | Preparation method and equipment of graphene oxide or graphite oxide |
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