CN106517155A - Environment friendly method of preparing graphene - Google Patents
Environment friendly method of preparing graphene Download PDFInfo
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- CN106517155A CN106517155A CN201610884096.1A CN201610884096A CN106517155A CN 106517155 A CN106517155 A CN 106517155A CN 201610884096 A CN201610884096 A CN 201610884096A CN 106517155 A CN106517155 A CN 106517155A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
Abstract
The invention relates to an environment friendly method of preparing graphene, the method comprises the implementation steps of preparing oxidation graphene dispersion liquid, preparing thiourea dioxide reducing agent and preparing graphene powder. The method adopts the reducing agent thiourea dioxide to conduct revivification to the oxidation graphene, and obtains graphene, the method has the characteristics of being simple in preparation, green and environmentally friendly, high in reductivity and being controllable and the like, and solves very well the problems of high reaction temperature, large energy consumption, severe environment pollution, and high price occurred in the process of preparing graphene using the traditional oxidation-reduction method. The prepared graphene has excellent dispersibility and stability, has the potential of high conductivity, meanwhile, the method reduces cost greatly, facilitates the achieving of large area industrialized production, and provides certain references and lessons for the industrialization and application of subsequent graphene and graphene compound material. The method has huge potential application value in the fields of graphene super electric power, flexible display and health physiotherapy, car component and the like.
Description
Technical field
The invention belongs to technical field of new material preparation, is related to a kind of environmentally friendly method for preparing Graphene.
Background technology
Since 2004, strong K seas nurse (Andre K.Geim) of peace moral of Univ Manchester UK and Constant
Ding Nuowoxiaoluo (Konstantin Novoselov) professors laboratory be by mechanically pulling off method successfully obtain it is a kind of new
Graphene material, Graphene and graphene composite material are prepared and its application study, are worldwide caused wide
General concern.Graphene is a kind of two-dimension plane structure by monolayer carbon atomic building, due to excellent conduction, heat conduction, good
Specific surface area and high intensity of good light transmission and super large etc., be widely used in nesa coating, Flexible Displays,
The various fields such as ultracapacitor, lithium ion battery, solar cell, biology sensor, car body materials, space flight military project.Therefore,
Favorite of the Graphene as New Times material circle, it may be said that the application of Graphene is would be possible in semiconductor, electronic component information
Cause a new revolution etc. industry.On March 18th, 2016, China News Service's latest report, Graphene tyre performance improve and
It is surprisingly found that in terms of extending the life-span, China will build up first Graphene Tire experiment room, and this will further expand Graphene
Application.
For at present, the technology of preparing of Graphene is concentrated mainly on mechanical stripping method, epitaxial growth method, chemical vapor deposition
And chemistry redox method etc..In these technologies of preparing, chemistry redox method is due to low cost, easy to operate, work
The features such as skill is simple, it is considered to be Graphene prepare and application study in widest method and receive much concern.Chemical oxidation
The essential core mechanism of reducing process is to carry out intercalation oxidation processes by strong acid to natural flake graphite to obtain graphene oxide, so
Carry out oxygen-containing functional group (hydroxyl-OH, the carboxylic of strong reduction removal surface of graphene oxide afterwards in the presence of suitable reducing agent
Base-COOH, carbonyl-C=O etc.) after obtain Graphene.Common reducing agent has borohydride sodium, hydration hydrazine and its derivative, highly concentrated
Hydrogen iodide of degree etc..In these reducing agents, hydration hydrazine and its derivative is not as with severe toxicity, environmental pollution greatly, is inconsistent
The target being fated for environmentally friendly development and the strategy of sustainable development；And the reaction of sodium borohydride reduction graphene oxide needs
Heating, energy consumption are big, and increase considerably the fault of construction of Graphene；The hydrogen iodide of high concentration has extremely strong corrosion simultaneously
Property, the cost of oxidation-reduction method along with these reducing agents are expensive, is considerably increased, the extensive application of the method is limited
Further develop.Therefore, develop a kind of with high efficiency, nontoxic pollution-free, low cost, the reduction of efficient graphene oxide
Method is extremely important.
The content of the invention
It is an object of the invention to provide a kind of environmentally friendly method for preparing Graphene, solves existing Graphene and prepares
Low, the of poor quality and big for environment pollution problem of method high cost, efficiency.
The technical solution adopted in the present invention is：
A kind of environmentally friendly method for preparing Graphene, including following implementation steps：
(1) prepare graphene oxide dispersion；
(2) prepare thiourea dioxide reducing agent：Thiourea dioxide and NaOH are added in deionized water and stirs molten
Solution, wherein thiourea dioxide are 1 with the mass ratio of NaOH：3-9, thiourea dioxide with the mass volume ratio of deionized water is
10-30g/ml；
(3) prepare graphene powder：In graphene oxide dispersion prepared by step (), add step (two) to prepare
Thiourea dioxide reducing agent, stirring reaction, controlling reaction temperature be 30-80 DEG C, react 0.5-2.0 hours, that is, obtain graphite
Alkene mixed solution；Finally Graphene mixed solution is carried out washing, vacuum freeze drying, that is, obtain described Graphene；
The concentration of the graphene oxide of described graphene oxide dispersion is 0.4-0.5mg/ml；
Described thiourea dioxide reducing agent is 1 with the volume ratio of graphene oxide dispersion：10-1000.
Further, described step () prepares graphene oxide dispersion and comprises the following steps：
1. first graphite, the concentrated sulfuric acid and sodium nitrate are sequentially added in reaction vessel, by reaction vessel be placed in ice bath with
Rotating speed is continuously stirred (mixing speed can not be too high, easily makes liquid splash) for 80-100r/min, keeps system temperature to be less than 3
DEG C reaction 27-33 minutes；Then potassium permanganate is slowly added to several times, keeps temperature of reaction system to continue reaction less than 15 DEG C
2-3 hours, then raise temperature to 30-40 DEG C, react 2.5-3 hours；
Reaction is added to several times abundant, the strict control of temperature is easy for each reactant in this temperature range
Give full play to its respective strong oxidation performance.Primarily to obtaining graphite oxide.
2. 78-82 DEG C and plus deionized water reaction 25-35 minutes are warming up to and then by the reactant liquor that 1. step obtains；Afterwards
It is slowly added to hydrogen peroxide and persistently stirs in being maintained at 28-38 DEG C of water-bath, until solution becomes glassy yellow, the not no gas of solution surface
Till bubble or number of bubbles are little；The volume of described deionized water is 2.5-3 with concentrated sulfuric acid volume ratio:1.5-1, described are double
Containing the hydrogen peroxide that mass fraction is 25%-30% in oxygen water；
Hydrogen peroxide is that, in order to eliminate excessive strong oxidizer, hydrogen peroxide is excessively to fully react.
3. after removal step 2. gained reactant liquor in metal ion, then by residual reaction liquid vacuum filtration and centrifugation
Wash to neutrality, vacuum drying afterwards obtains graphene oxide powder；
Vacuum filtration can improve cleaning efficiency with reference to centrifuge washing, while vacuum filtration can control graphene oxide
Size range.
4. the graphene oxide powder for finally 3. obtaining step adds ultrasonic disperse in deionized water, that is, obtain aoxidizing stone
Black alkene dispersion liquid；
Ultrasonic disperse is, for the reunion for preventing graphene oxide, to be easy to preferably storage.
Above step, for comparing current existing technology, maximum advantage is to increase homemade before centrifuge washing
Vacuum filtration, controls the size of graphene oxide by the aluminum oxide miillpore filter size of vacuum filtration.
Graphite is graphite with the mass ratio of potassium permanganate, sodium nitrate：Potassium permanganate：Sodium nitrate=1：6-30：0.5-2.5,
Graphite is 1 with the mass volume ratio of the concentrated sulfuric acid：30-150g/ml.
Further, the H containing mass fraction 98% in the described concentrated sulfuric acid2SO4。
Further, described graphite is the natural scale structure of 200 mesh.
Further, when step (three) is reacted, using ultraviolet (UV) cure lamp to Graphene mixed solution ultraviolet irradiation 30-
120 minutes, for improving the reducing degree of graphene oxide, while increasing the dispersion stabilization being dispersed in water of Graphene.
Further, when step (three) is washed：Adopt low-speed centrifugal washing and high speed centrifugation washing alternately washing 15 times with
On, described low-speed centrifugal centrifugal speed is 1500-2000rmp, and described high speed centrifugation speed is 10000-12000rmp.
Further, when step (three) is washed, cleaning solution used is deionized water or watery hydrochloric acid that mass fraction is 3%.
Further, in step 2, vacuum freeze drying temperature is not less than -45 DEG C, and pressure is 40-50Pa, and drying time is
40-50h。
Than prior art, the invention has the beneficial effects as follows：
1. the present invention carries out reduction using reducing agent thiourea dioxide and obtains Graphene to graphene oxide, with preparation side
Method is simple, environmental protection and the features such as high and controllable reducing degree, solves traditional oxidation-reduction method well and prepares graphite
Alkene reaction temperature is high, energy consumption is big, environmental pollution is serious, expensive problem.
2. the Graphene for obtaining has good dispersiveness and stability, with the potentiality that height is led, while greatly reducing
Cost, is advantageously implemented large area industrialized production, the industrialization and application of Graphene and graphene composite material after being
Certain reference and reference are provided.
3. huge potential application valency is had in the field such as the super electric, Flexible Displays of Graphene and health physical therapy, automobile component
Value.
Description of the drawings
Fig. 1 is the process chart of the inventive method；
Fig. 2 is the schematic diagram that the present invention prepares Graphene；
Fig. 3 is the XPS figures of Graphene prepared by the inventive method；
Fig. 4 is the microscopic appearance of Graphene prepared by the inventive method.
Specific embodiment
Below in conjunction with the accompanying drawings, the present invention is described in detail for specific embodiment and specific embodiment.
(1) specific embodiment
The invention provides a kind of environmentally friendly method for preparing Graphene, its flow process as shown in figure 1, specifically include with
Lower step is implemented：
(1) prepare graphene oxide dispersion；
(2) prepare thiourea dioxide reducing agent：By NaOH, (described NaOH can also be sodium acid carbonate, carbon
Sour sodium or ammoniacal liquor or NaOH, sodium acid carbonate, sodium carbonate or ammoniacal liquor mix according to arbitrary proportion) and thiourea dioxide
(CH4N2O2S) stirring and dissolving in deionized water, wherein thiourea dioxide are 1 with the mass ratio of NaOH：3-9, titanium dioxide
Thiocarbamide is 10-30g/ml with the mass volume ratio of deionized water；
(3) prepare graphene powder：In graphene oxide dispersion prepared by step (), add step (two) to prepare
Thiourea dioxide reducing agent, stirring reaction, controlling reaction temperature be 30-80 DEG C, react 0.5-2.0 hours, that is, obtain graphite
Alkene mixed solution；Finally Graphene mixed solution is carried out washing, vacuum freeze drying, that is, obtain described Graphene；
The concentration of the middle graphene oxide of described graphene oxide dispersion is 0.4-0.5mg/ml；
Described thiourea dioxide reducing agent is 1 with the volume ratio of graphene oxide dispersion：10-1000.
Further, described step () prepares graphene oxide dispersion and comprises the following steps：
1. first graphite, the concentrated sulfuric acid and sodium nitrate are sequentially added in reaction vessel, by reaction vessel be placed in ice bath with
Rotating speed is continuously stirred (mixing speed can not be too high, easily makes liquid splash) for 80-100r/min, keeps system temperature to be less than 3
DEG C reaction 27-33 minutes；Then potassium permanganate is slowly added to several times, keeps temperature of reaction system to continue reaction less than 15 DEG C
2-3 hours, then raise temperature to 30-40 DEG C, react 2.5-3 hours；
Reaction is added to several times abundant, the strict control of temperature is easy for each reactant in this temperature range
Give full play to its respective strong oxidation performance.Primarily to obtaining graphite oxide.
2. 78-82 DEG C and plus deionized water reaction 25-35 minutes are warming up to and then by the reactant liquor that 1. step obtains；Afterwards
It is slowly added to hydrogen peroxide and persistently stirs in being maintained at 28-38 DEG C of water-bath, until solution becomes glassy yellow, the not no gas of solution surface
Till bubble or number of bubbles are little；The volume of described deionized water is 2.5-3 with concentrated sulfuric acid volume ratio:1.5-1, described are double
Containing the hydrogen peroxide that mass fraction is 25%-30% in oxygen water；
Hydrogen peroxide is that, in order to eliminate excessive strong oxidizer, hydrogen peroxide is excessively to fully react.
3. after removal step 2. gained reactant liquor in metal ion, then by residual reaction liquid vacuum filtration and centrifugation
Wash to neutrality, vacuum drying afterwards obtains graphene oxide powder；
Vacuum filtration can improve cleaning efficiency with reference to centrifuge washing, while vacuum filtration can control graphene oxide
Size range.
4. the graphene oxide powder for finally 3. obtaining step adds ultrasonic disperse in deionized water, that is, obtain aoxidizing stone
Black alkene dispersion liquid；
Ultrasonic disperse is, for the reunion for preventing graphene oxide, to be easy to preferably storage.
Above step, for comparing current existing technology, maximum advantage is to increase homemade before centrifuge washing
Vacuum filtration, controls the size of graphene oxide by the aluminum oxide miillpore filter size of vacuum filtration.
Graphite is graphite with the mass ratio of potassium permanganate, sodium nitrate：Potassium permanganate：Sodium nitrate=1：6-30：0.5-2.5,
Graphite is 1 with the mass volume ratio of the concentrated sulfuric acid：30-150g/ml.
Further, the H containing mass fraction 98% in the described concentrated sulfuric acid2SO4。
Further, described graphite is the natural scale structure of 200 mesh.
Further, when step (three) is reacted, using ultraviolet (UV) cure lamp to Graphene mixed solution ultraviolet irradiation 30-
120 minutes, for improving the reducing degree of graphene oxide, while increasing the dispersion stabilization being dispersed in water of Graphene.
Further, when step (three) is washed：Adopt low-speed centrifugal washing and high speed centrifugation washing alternately washing 15 times with
On, described low-speed centrifugal centrifugal speed is 1500-2000rmp, and described high speed centrifugation speed is 10000-12000rmp.
Further, when step (three) is washed, cleaning solution used is deionized water or watery hydrochloric acid that mass fraction is 3%.
Further, in step 2, vacuum freeze drying temperature is not less than -45 DEG C, and pressure is 40-50Pa, and drying time is
40-50h。
The present invention carries out reduction using environmentally friendly reducing agent thiourea dioxide and obtains Graphene to graphene oxide.Also
Former mechanism figure is as shown in Figure 2.Thiourea dioxide itself does not have reproducibility and oxidisability.But under alkalescence and suitable temperature
With very high reduction potential, therefore have that reproducibility is strong, heat endurance is good, it is the features such as storage convenient transportation, especially nontoxic
Environmentally safe, low price.So, thiourea dioxide is in hydroxyl (OH-) in the presence of alkalescence condition under, occur chemistry
Reaction generates the sulfinic acid (general structure R-S (=O)-OH) with reproducibility, and subsequently at a certain temperature, sulfinic acid can divide
Solution produces HSO3 -And H+, HSO3 -Can remove with the functional group reactionses of graphene oxide paripheral zone with very strong reproducibility, secondly H+Presence also there is extremely strong ring opening, both combine the functional group of graphene oxide is removed more completely, from
And obtain the few Graphene of high-quality, fault of construction.In addition, instant invention overcomes existing reducing agent chemical reaction temperature is high, energy
Consumption is big, environmental pollution is serious, expensive shortcoming.It is mainly manifested in and is made using a kind of environmentally friendly reducing agent at room temperature
For high performance Graphene is gone out, while graphite can simply be controlled by controlling reaction temperature, time and reductant concentration
Alkene quality.The Graphene that the present invention is prepared has good dispersiveness and stability, with the potentiality that height is led, substantially reduces
Cost, is advantageously implemented large area industrialized production.
(2) specific embodiment
Embodiment 1
It is prepared by step 1, graphene oxide
(1) by 30ml dense H2SO4、0.5g NaNO3, 1g Graphite sequentially add in 500ml beakers, connect in ice bath
Continuous high degree of agitation, keeps system temperature to be 0 DEG C of reaction 30min；(2) by 6g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 2h is reacted, keeps temperature of reaction system to be 10 DEG C；(3) 35 DEG C are warming up to, 2.5h is reacted；(4) 80 DEG C are warming up to and are added
90ml deionized waters react 30min；(5) it is slowly added to the H that mass fraction is 30%2O2And kept for 33 DEG C persistently stir in a water bath
Mix, until solution becomes glassy yellow, till solution surface does not have bubble or number of bubbles little.(6) vacuum for-
Under 0.04MPa, vacuum filtration and rotating speed are centrifuge washing 10 times under 10000rmp, by PH meter detections after cleaning solution PH is 6,
Last is -0.8MPa in vacuum, and temperature is to be dried 40h in 40 DEG C of vacuum drying chamber to obtain graphene oxide about 0.5g.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 0.4g being vacuum dried in weighing step 1 is placed in beaker, at the same add 1000ml go from
Sub- water, ultrasonic disperse 30min obtain 0.4mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 1g:3g:10ml matches somebody with somebody
Put reductant solution.And the reducing agent of 1ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.4mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 30 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and be stirred continuously by 80r/min of rotating speed, sustained response 30min, subsequently obtain Graphene mixing molten
Liquid.The Graphene mixed solution for obtaining is placed under uviol lamp and irradiates 30min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 2000rmp is washed 5 times, outwells supernatant liquid, then by under
Layer sediment high speed 10000rmp centrifuge washing 15 times, counts detection after cleaning solution PH is 6 by PH, takes bottom sediment thing dry
Dry temperature is -45 DEG C, is dried 40h in the vacuum freeze drier of pressure 40Pa, you can obtain Graphene powder 0.25g.
Embodiment 2
It is prepared by step 1, graphene oxide
(1) by 80ml dense H2SO4、1.5g NaNO3, 2.5g Graphite are sequentially added in 500ml beakers, in ice bath
Continuous high degree of agitation, keeps system temperature to be 2 DEG C of reaction 32min；(2) by 20g KMnO4Divide 3 times and be slowly added to, every 10min
Plus once, 2.5h is reacted, keep temperature of reaction system to be 12 DEG C；(3) 37 DEG C are warming up to, 3h is reacted；(4) 81 DEG C are warming up to and are added
240ml deionized waters react 32min；(5) it is slowly added to the H that mass fraction is 25%2O2And kept for 35 DEG C persistently stir in a water bath
Mix, until solution becomes glassy yellow, till solution surface does not have bubble or number of bubbles little.(6) vacuum for-
Under 0.05MPa, vacuum filtration and rotating speed are centrifuge washing 16 times under 10000rmp, by PH meter detections after cleaning solution PH is 6,
Last is -0.9MPa in vacuum, and temperature is to be dried 45h in 45 DEG C of vacuum drying chamber and obtain graphene oxide to be about 1.25g
Left and right.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 1.25g being vacuum dried in weighing step 1 is placed in beaker, at the same add 2500ml go from
Sub- water, ultrasonic disperse 50min obtain 0.5mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 1g:4g:15ml matches somebody with somebody
Put reductant solution.And the reducing agent of 3ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.5mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 55 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and rotating speed is stirred continuously for 100r/min, sustained response 1.5h, subsequently obtains Graphene mixing molten
Liquid.The Graphene mixed solution for obtaining is placed under uviol lamp and irradiates 40min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 2000rmp is washed 10 times, is outwelled supernatant liquid, then will
Lower sediment thing high speed 11000rmp centrifuge washing 15 times, counts detection after cleaning solution PH is 6 by PH, takes bottom sediment thing and exist
Baking temperature is -42 DEG C, is dried 45h in the vacuum freeze drier of pressure 45Pa, you can obtain Graphene powder 0.6g.
Embodiment 3
It is prepared by step 1, graphene oxide
(1) by 300ml dense H2SO4、4g NaNO3, 6g Graphite sequentially add in 1000ml beakers, connect in ice bath
Continuous high degree of agitation, keeps system temperature to be 3 DEG C of reaction 33min；(2) by 50g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 3h is reacted, keeps temperature of reaction system to be 15 DEG C；(3) 40 DEG C are warming up to, 3h is reacted；(4) 82 DEG C are warming up to and are added
900ml deionized waters react 35min；(5) it is slowly added to the H that mass fraction is 30%2O2And kept for 38 DEG C persistently stir in a water bath
Mix, until solution becomes glassy yellow, till solution surface does not have bubble or number of bubbles little.(6) vacuum for-
Under 0.06MPa, vacuum filtration and rotating speed are centrifuge washing 14 times under 9000rmp, by PH meter detections after cleaning solution PH is 6.5,
Last is -1MPa in vacuum, and temperature is to be dried 50h in 50 DEG C of vacuum drying chamber and obtain graphene oxide to be about 3g or so.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 3g being vacuum dried in weighing step 1 is placed in beaker, while adding 6000ml deionizations
Water, ultrasonic disperse 60min obtain 0.5mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 1g:5g:20ml matches somebody with somebody
Put reductant solution.And the reducing agent of 15ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.5mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 80 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and be stirred continuously, sustained response 2h, subsequently obtain Graphene mixed solution.By the Graphene for obtaining
Mixed solution is placed under uviol lamp and irradiates 60min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 5000rmp is washed 17 times, is outwelled supernatant liquid, then will
Lower sediment thing high speed 12000rmp centrifuge washing 20 times, counts detection after cleaning solution PH is 6.8 by PH, takes bottom sediment thing
It is -40 DEG C in baking temperature, in the vacuum freeze drier of pressure 50Pa, is dried 50h, you can obtains Graphene powder 1.5g.
Embodiment 4
It is prepared by step 1, graphene oxide
(1) by 75ml dense H2SO4、0.5g NaNO3, 0.5g Graphite are sequentially added in 500ml beakers, in ice bath
Continuous high degree of agitation, keeps system temperature to be 1 DEG C of reaction 33min；(2) by 15g KMnO4Divide 3 times and be slowly added to, every 10min
Plus once, 2.2h is reacted, keep temperature of reaction system to be 12 DEG C；(3) 30 DEG C are warming up to, 3h is reacted；(4) 78 DEG C are warming up to and are added
225ml deionized waters react 25min；(5) it is slowly added to the 30%H that mass fraction is 30%2O2And kept for 33 DEG C hold in a water bath
Continuous stirring, until solution becomes glassy yellow, till solution surface does not have bubble or number of bubbles little.(6) vacuum for-
Under 0.04MPa, vacuum filtration and rotating speed are centrifuge washing 14 times under 10000rmp, by PH meter detections after cleaning solution PH is 6,
Last is -0.8MPa in vacuum, and temperature is to be dried 50h in 50 DEG C of vacuum drying chamber to obtain graphene oxide about 0.25g.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 0.25g being vacuum dried in weighing step 1 is placed in beaker, at the same add 500ml go from
Sub- water, ultrasonic disperse 30min obtain 0.5mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 3g:18g:66ml matches somebody with somebody
Put reductant solution.And the reducing agent of 50ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.5mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 40 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and be stirred continuously, sustained response 30min, subsequently obtain Graphene mixed solution.By the graphite for obtaining
Alkene mixed solution is placed under uviol lamp and irradiates 80min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 2000rmp is washed 5 times, outwells supernatant liquid, then by under
Layer sediment high speed 11000rmp centrifuge washing 15 times, counts detection after cleaning solution PH is 6 by PH, takes bottom sediment thing dry
Dry temperature is -45 DEG C, is dried 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 0.1g.
Embodiment 5
It is prepared by step 1, graphene oxide
(1) by 500ml dense H2SO4、12.5g NaNO3, 5g Graphite sequentially add in reaction vessel, connect in ice bath
Continuous high degree of agitation, keeps system temperature to be 2.5 DEG C of reaction 27min；(2) by 100g KMnO4Divide 3 times and be slowly added to, every
10min adds once, reacts 2.5h, keeps temperature of reaction system to be 12 DEG C；(3) 30 DEG C are warming up to, 3h is reacted；(4) 78 are warming up to
DEG C and plus 1500ml deionized waters reaction 30min；(5) it is slowly added to the H that mass fraction is 30%2O2And kept for 28 DEG C in water-bath
In persistently stir, until solution becomes glassy yellow, till solution surface does not have bubble or number of bubbles little.(6) in vacuum
Be vacuum filtration under -0.04MPa and rotating speed be centrifuge washing 14 times under 10000rmp, detection is counted by PH and treats that cleaning solution PH is 6
Afterwards, it is finally -0.8MPa in vacuum, temperature is to be dried 50h in 50 DEG C of vacuum drying chamber and obtain graphene oxide to be about
2.5g left and right.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 2.5g being vacuum dried in weighing step 1 is placed in beaker, while 5L deionized waters are added,
Ultrasonic disperse 45min, obtains 0.5mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 4g:28g:100ml
Configuration reductant solution.And the reducing agent of 100ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.5mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 60 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and be stirred continuously, sustained response 1.5h, subsequently obtain Graphene mixed solution.By the graphite for obtaining
Alkene mixed solution is placed under uviol lamp and irradiates 100min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 2000rmp is washed 7 times, outwells supernatant liquid, then by under
Layer sediment high speed 11000rmp centrifuge washing 18 times, counts detection after cleaning solution PH is 6 by PH, takes bottom sediment thing dry
Dry temperature is -45 DEG C, is dried 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 1.3g.
Embodiment 6
It is prepared by step 1, graphene oxide
(1) by 7L dense H2SO4、200g NaNO3, 100g Graphite sequentially add in reaction vessel, it is continuous in ice bath
High degree of agitation, keeps system temperature to be 3 DEG C of reaction 30min；(2) by 1500g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 2h is reacted, keeps temperature of reaction system to be 12 DEG C；(3) 35 DEG C are warming up to, 3h is reacted；(4) 80 DEG C and plus 21L are warming up to
Deionized water reacts 30min；(5) it is slowly added to 30%H2O2And kept for 33 DEG C persistently stir in a water bath, until solution becomes bright
Yellow, till solution surface does not have bubble or number of bubbles little.(6) vacuum be -0.04MPa under vacuum filtration and rotating speed
For centrifuge washing under 10000rmp 14 times, detection is counted after cleaning solution PH is 6 by PH, be finally -0.8MPa in vacuum, temperature
Spend.
It is prepared by step 2, graphene oxide dispersion
The graphene oxide 50g being vacuum dried in weighing step 1 is placed in beaker, while adding 100L deionizations
Water, ultrasonic disperse 60min obtain 0.5mg/ml graphene oxide dispersions.
It is prepared by step 3, reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of NaOH (NaOH) and deionized water is 10g:90g:300ml
Configuration reductant solution.And the reducing agent of 300ml is weighed with graduated cylinder.
Step 4, ultraviolet irradiation
Graphene oxide dispersion of the concentration obtained in step 2 for 0.5mg/ml is placed in magnetic stirring apparatus,
Treat that temperature is increased to 80 DEG C, then the titanium dioxide for being slowly added to measure in step 3 in graphene oxide dispersion with glue head dropper
Thiocarbamide reductant solution, and be stirred continuously, sustained response 2h, obtain Graphene mixed solution.The Graphene for obtaining is mixed
Solution is placed under uviol lamp and irradiates 120min.
It is prepared by step 5, Graphene powder
By the mixed liquor in step 4, in centrifuge, first low speed 2000rmp is washed 10 times, is outwelled supernatant liquid, then will
Lower sediment thing high speed 11000rmp centrifuge washing 20 times, counts detection after cleaning solution PH is 6 by PH, takes bottom sediment thing and exist
Baking temperature is -45 DEG C, is dried 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 25g.
Fig. 3 and Fig. 4 be the inventive method prepare Graphene XPS figure and microscopic appearance, as can be seen from the figure this
Bright obtained Graphene oxygen-containing functional group (C-O, C=O, COOH) is reduced in a large number, and Graphene is distributed and is had in flaky texture
There is pleated structure.Contrast the inventive method prepares the cost of Graphene, such as following table with conventional method：
The Cost comparisons of 1 present invention of table and conventional method
It can be seen that, the present invention successfully prepares high-quality, high connductivity using the thiourea dioxide of nontoxic pollution-free, low cost
Graphene, with preparation method is simple, environmental protection and the features such as high and controllable reducing degree, solves traditional oxygen well
Change the shortcoming that reducing process prepares Graphene, the industrialization of Graphene and graphene composite material and application for after provides certain
With reference to and use for reference, have huge potential application valency in the field such as the super electric, Flexible Displays of Graphene and health physical therapy, automobile component
Value.
Claims (8)
1. a kind of environmentally friendly method for preparing Graphene, it is characterised in that：Including following implementation steps：
(1) prepare graphene oxide dispersion；
(2) prepare thiourea dioxide reducing agent：Thiourea dioxide and NaOH are added into stirring and dissolving in deionized water, its
Middle thiourea dioxide is 1 with the mass ratio of NaOH：3-9, thiourea dioxide are 10- with the mass volume ratio of deionized water
30g/ml；
(3) prepare graphene powder：Addition step (two) is prepared in graphene oxide dispersion prepared by step () two
Aminoiminomethanesulfonic acid reducing agent, stirring reaction, controlling reaction temperature are 30-80 DEG C, react 0.5-2.0 hours, obtain Graphene mixing
Solution；Finally Graphene mixed solution is carried out washing, vacuum freeze drying, that is, obtain described Graphene；
In described graphene oxide dispersion, the concentration of graphene oxide is 0.4-0.5mg/ml；
Described thiourea dioxide reducing agent is 1 with the volume ratio of graphene oxide dispersion：10-1000.
2. a kind of environmentally friendly method for preparing Graphene according to claim 1, it is characterised in that：
Described step () prepares graphene oxide dispersion and comprises the following steps：
1. first graphite, the concentrated sulfuric acid and sodium nitrate are sequentially added in reaction vessel, reaction vessel is placed in ice bath with rotating speed
Continuously stir for 80-100r/min, system temperature is kept less than 3 DEG C of reaction 27-33 minutes；Then Gao Meng is slowly added to several times
Sour potassium, keeps temperature of reaction system to continue reaction 2-3 hours less than 15 DEG C, then raises temperature to 30-40 DEG C, and 2.5-3 is little for reaction
When；
2. 78-82 DEG C and plus deionized water reaction 25-35 minutes are warming up to and then by the reactant liquor that 1. step obtains；It is slow afterwards
Add hydrogen peroxide and persistently stir in being maintained at 28-38 DEG C of water-bath, until solution becomes glassy yellow, solution surface do not have bubble or
Till number of bubbles is little；The volume of described deionized water is 2.5～3 with concentrated sulfuric acid volume ratio:1.5～1, described dioxygen
Containing the hydrogen peroxide that mass fraction is 25%～30% in water；
3. after removal step 2. gained reactant liquor in metal ion, then by residual reaction liquid vacuum filtration and centrifuge washing
To neutral, it is vacuum dried afterwards and obtains graphene oxide powder；
4. the graphene oxide powder for finally 3. obtaining step adds ultrasonic disperse in deionized water, that is, obtain graphene oxide
Dispersion liquid；
Graphite is graphite with the mass ratio of potassium permanganate, sodium nitrate：Potassium permanganate：Sodium nitrate=1：6-30：0.5-2.5, graphite
Mass volume ratio with the concentrated sulfuric acid is 1：30-150g/ml.
3. a kind of environmentally friendly method for preparing Graphene according to claim 2, it is characterised in that：Described dense sulphur
H containing mass fraction 98% in acid2SO4。
4. a kind of environmentally friendly method for preparing Graphene according to claim 2, it is characterised in that：Described graphite
For the natural scale structure of 200 mesh.
5. a kind of environmentally friendly method for preparing Graphene according to claim 1, it is characterised in that：It is true in step 2
Vacuum freecing-dry temperature is not less than -45 DEG C, and pressure is 40-50Pa, and drying time is 40-50 hours.
6. a kind of environmentally friendly method for preparing Graphene according to claim 1, it is characterised in that：Step (three) is anti-
At once, using ultraviolet (UV) cure lamp to Graphene mixed solution ultraviolet irradiation 30-120 minutes.
7. a kind of environmentally friendly method for preparing Graphene according to claim 1, it is characterised in that：Step (three) wash
When washing：Using low-speed centrifugal washing and high speed centrifugation washing alternately washing more than 15 times, described low-speed centrifugal speed is 1500-
2000rmp, described high speed centrifugation speed are 10000-12000rmp.
8. a kind of environmentally friendly method for preparing Graphene according to claim 1 or 7, it is characterised in that：Step
(3) when washing, cleaning solution used is deionized water or watery hydrochloric acid that mass fraction is 3%.
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