CN106517155B - A kind of environmentally friendly method for preparing graphene - Google Patents
A kind of environmentally friendly method for preparing graphene Download PDFInfo
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- CN106517155B CN106517155B CN201610884096.1A CN201610884096A CN106517155B CN 106517155 B CN106517155 B CN 106517155B CN 201610884096 A CN201610884096 A CN 201610884096A CN 106517155 B CN106517155 B CN 106517155B
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- 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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- 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 present invention relates to a kind of environmentally friendly methods for preparing graphene, including following implementation steps：Graphene oxide dispersion is prepared, thiourea dioxide reducing agent is prepared and prepares graphene powder.The present invention carries out reduction to graphene oxide using reducing agent thiourea dioxide and obtains graphene, have the characteristics that preparation method is simple, environmentally protective and reducing degree is high and controllable, has well solved traditional oxidation-reduction method and prepared the problem that graphene reaction temperature is high, energy consumption is big, environmental pollution is serious, expensive.Obtained graphene has good dispersibility and stability, the potentiality led with height, cost is greatly reduced simultaneously, is advantageously implemented large area industrialized production, certain reference and reference are provided for the industrialization and application of later graphene and graphene composite material.There is huge potential application value in the fields such as the super electric, Flexible Displays of graphene and health physical therapy, automobile component.
Description
Technical field
The invention belongs to technical field of new material preparation, are related to a kind of environmentally friendly method for preparing graphene.
Background technology
Since 2004, the strong seas the K nurse of peace moral (Andre K.Geim) and Constant of Univ Manchester UK
Ding Nuowoxiaoluo (Konstantin Novoselov) professors laboratory be by mechanically pulling off method successfully obtain it is a kind of novel
Carbon material --- graphene, graphene and graphene composite material prepare and its application study, worldwide causes wide
General concern.Graphene is a kind of two-dimension plane structure being made of single layer of carbon atom, due to excellent conduction, heat conduction, good
Specific surface area and the high intensity etc. of good light transmission and super large, be widely used in transparent conductive film, Flexible Displays,
The various fields such as ultracapacitor, lithium ion battery, solar cell, biosensor, car body materials, space flight military project.Therefore,
Favorite of the graphene as new era material circle, it may be said that the application of graphene would be possible in semiconductor, electronic component information
Etc. industries cause a new revolution.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 service life, China will build up first graphene Tire experiment room, this will further expand graphene
Application field.
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 at 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 be concerned.Chemical oxidation
The essential core mechanism of reduction method is to carry out intercalation oxidation processes to natural flake graphite by strong acid to obtain graphene oxide, so
Oxygen-containing functional group (hydroxyl-OH, the carboxylic of strong reduction removal surface of graphene oxide are carried out under the action of suitable reducing agent afterwards
Base-COOH, carbonyl-C=O etc.) after obtain graphene.Common reducing agent has borohydride sodium, is hydrated hydrazine and its derivative, is highly concentrated
The hydrogen iodide etc. of degree.In these reducing agents, for hydration hydrazine and its derivative due to having severe toxicity, environmental pollution is very big, is not 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 is big, and increases considerably the fault of construction of graphene；The hydrogen iodide of high concentration has extremely strong corrosion simultaneously
Property, along with these reducing agents are expensive, the cost of oxidation-reduction method is considerably increased, the extensive use of this method is limited
With further development.Therefore, exploitation is a kind of having high efficiency, nontoxic and pollution-free, inexpensive, efficient graphene oxide reduction
Method is extremely important.
Invention content
The object of the present invention is to provide a kind of environmentally friendly methods for preparing graphene, solve existing graphene and prepare
Method is of high cost, efficiency is low, of poor quality and the problem of cause serious pollution to the environment.
The technical solution adopted in the present invention is：
A kind of environmentally friendly method for preparing graphene, including following implementation steps：
(1) graphene oxide dispersion is prepared；
(2) thiourea dioxide reducing agent is prepared：It is molten by being stirred in thiourea dioxide and sodium hydroxide addition deionized water
Solution, the wherein mass ratio of thiourea dioxide and sodium hydroxide are 1：The mass volume ratio of 3-9, thiourea dioxide and deionized water is
10-30g/ml；
(3) graphene powder is prepared：Step (2) is added in graphene oxide dispersion prepared by step (1) to prepare
Thiourea dioxide reducing agent, be stirred to react, controlling reaction temperature is 30-80 DEG C, and reaction 0.5-2.0 hours is to get to graphite
Alkene mixed solution；Finally graphene mixed solution is washed, vacuum freeze drying is to get to the graphene；
A concentration of 0.4-0.5mg/ml of the graphene oxide of the graphene oxide dispersion；
The volume ratio of the thiourea dioxide reducing agent and graphene oxide dispersion is 1：10-1000.
Further, the step (one) prepares graphene oxide dispersion and includes the following steps：
1. graphite, the concentrated sulfuric acid and sodium nitrate are sequentially added in reaction vessel first, by reaction vessel be placed in ice bath with
Rotating speed is that 80-100r/min is continuously stirred (mixing speed cannot be too high, is easy to make liquid splash), and system temperature is kept to be less than 3
DEG C reaction 27-33 minutes；Then it is slowly added to potassium permanganate several times, keeping temperature of reaction system to be no more than 15 DEG C, the reaction was continued
2-3 hours, 30-40 DEG C is then raised temperature to, is reacted 2.5-3 hours；
It is added to reaction several times fully, the stringent 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. 1. reaction solution that step obtains then is warming up to 78-82 DEG C and deionized water is added to react 25-35 minutes；Later
It is slowly added to hydrogen peroxide and is maintained in 28-38 DEG C of water-bath persistently stir, until solution becomes glassy yellow, solution surface does not have gas
Until bubble or number of bubbles are seldom；The volume of the deionized water is 2.5-3 with concentrated sulfuric acid volume ratio:1.5-1, described is double
Contain the hydrogen peroxide that mass fraction is 25%-30% in oxygen water；
Hydrogen peroxide is to eliminate excessive strong oxidizer, and hydrogen peroxide is excessively to fully react.
3. after removal step 2. gained reaction solution in metal ion, then by residual reaction liquid be filtered by vacuum and centrifuge
Washing to neutrality, later vacuum drying obtains graphene oxide powder；
Vacuum filtration can improve the cleaning efficiency in conjunction with centrifuge washing, while vacuum filtration can control graphene oxide
Size range.
4. ultrasonic disperse is added in deionized water to get to oxidation stone in the graphene oxide powder for finally 3. obtaining step
Black alkene dispersion liquid；
Ultrasonic disperse is the reunion of graphene oxide in order to prevent, convenient for preferably storage.
Above step, for current existing technology, biggest advantage be increase before centrifuge washing it is homemade
Vacuum filtration, the size of graphene oxide is controlled by the aluminium oxide miillpore filter size of vacuum filtration.
The mass ratio of graphite and potassium permanganate, sodium nitrate is graphite：Potassium permanganate：Sodium nitrate=1：6-30：0.5-2.5,
The mass volume ratio of graphite and the concentrated sulfuric acid is 1：30-150g/ml.
Further, the H containing mass fraction 98% in the concentrated sulfuric acid2SO4。
Further, the graphite is the natural scale structure of 200 mesh.
Further, when step (3) 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 of graphene being dispersed in water.
Further, when step (3) is washed：Use low-speed centrifugal washing and high speed centrifugation washing alternately washing 15 times with
On, the low-speed centrifugal centrifugal speed is 1500-2000rmp, and the high speed centrifugation speed is 10000-12000rmp.
Further, the dilute hydrochloric acid that cleaning solution used is deionized water when step (3) is washed or mass fraction is 3%.
Further, vacuum freeze drying temperature is not less than -45 DEG C, pressure 40-50Pa in step 2, and drying time is
40-50h。
Compared with the prior art, the beneficial effects of the invention are as follows：
1. the present invention carries out reduction to graphene oxide using reducing agent thiourea dioxide and obtains graphene, there is preparation side
The features such as method is simple, environmentally protective and reducing degree is high and controllable has well solved traditional oxidation-reduction method and has prepared graphite
The problem that alkene reaction temperature is high, energy consumption is big, environmental pollution is serious, expensive.
2. obtained graphene has good dispersibility and stability, there are the high potentiality led, greatly reduce simultaneously
Cost is advantageously implemented large area industrialized production, is the industrialization and application of later graphene and graphene composite material
Certain reference and reference are provided.
3. having in the fields such as the super electric, Flexible Displays of graphene and health physical therapy, automobile component huge potential using valence
Value.
Description of the drawings
Fig. 1 is the process flow chart of the method for the present invention；
Fig. 2 is the schematic diagram that the present invention prepares graphene；
Fig. 3 is the XPS figures of graphene prepared by the method for the present invention；
Fig. 4 is the microscopic appearance of graphene prepared by the method for the present invention.
Specific implementation mode
Below in conjunction with the accompanying drawings, the present invention is described in detail for specific implementation mode and specific embodiment.
(1) specific implementation mode
The present invention provides a kind of environmentally friendly method for preparing graphene, flow as shown in Figure 1, specifically include with
Lower step is implemented：
(1) graphene oxide dispersion is prepared；
(2) thiourea dioxide reducing agent is prepared：By sodium hydroxide, (sodium hydroxide can also be sodium bicarbonate, carbon
Either ammonium hydroxide or sodium hydroxide, sodium bicarbonate, sodium carbonate or ammonium hydroxide mix sour sodium according to arbitrary proportion) and thiourea dioxide
(CH4N2O2S) stirring and dissolving in deionized water, the wherein mass ratio of thiourea dioxide and sodium hydroxide are 1：3-9, titanium dioxide
Thiocarbamide and the mass volume ratio of deionized water are 10-30g/ml；
(3) graphene powder is prepared：Step (2) is added in graphene oxide dispersion prepared by step (1) to prepare
Thiourea dioxide reducing agent, be stirred to react, controlling reaction temperature is 30-80 DEG C, and reaction 0.5-2.0 hours is to get to graphite
Alkene mixed solution；Finally graphene mixed solution is washed, vacuum freeze drying is to get to the graphene；
A concentration of 0.4-0.5mg/ml of the middle graphene oxide of the graphene oxide dispersion；
The volume ratio of the thiourea dioxide reducing agent and graphene oxide dispersion is 1：10-1000.
Further, the step (one) prepares graphene oxide dispersion and includes the following steps：
1. graphite, the concentrated sulfuric acid and sodium nitrate are sequentially added in reaction vessel first, by reaction vessel be placed in ice bath with
Rotating speed is that 80-100r/min is continuously stirred (mixing speed cannot be too high, is easy to make liquid splash), and system temperature is kept to be less than 3
DEG C reaction 27-33 minutes；Then it is slowly added to potassium permanganate several times, keeping temperature of reaction system to be no more than 15 DEG C, the reaction was continued
2-3 hours, 30-40 DEG C is then raised temperature to, is reacted 2.5-3 hours；
It is added to reaction several times fully, the stringent 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. 1. reaction solution that step obtains then is warming up to 78-82 DEG C and deionized water is added to react 25-35 minutes；Later
It is slowly added to hydrogen peroxide and is maintained in 28-38 DEG C of water-bath persistently stir, until solution becomes glassy yellow, solution surface does not have gas
Until bubble or number of bubbles are seldom；The volume of the deionized water is 2.5-3 with concentrated sulfuric acid volume ratio:1.5-1, described is double
Contain the hydrogen peroxide that mass fraction is 25%-30% in oxygen water；
Hydrogen peroxide is to eliminate excessive strong oxidizer, and hydrogen peroxide is excessively to fully react.
3. after removal step 2. gained reaction solution in metal ion, then by residual reaction liquid be filtered by vacuum and centrifuge
Washing to neutrality, later vacuum drying obtains graphene oxide powder；
Vacuum filtration can improve the cleaning efficiency in conjunction with centrifuge washing, while vacuum filtration can control graphene oxide
Size range.
4. ultrasonic disperse is added in deionized water to get to oxidation stone in the graphene oxide powder for finally 3. obtaining step
Black alkene dispersion liquid；
Ultrasonic disperse is the reunion of graphene oxide in order to prevent, convenient for preferably storage.
Above step, for current existing technology, biggest advantage be increase before centrifuge washing it is homemade
Vacuum filtration, the size of graphene oxide is controlled by the aluminium oxide miillpore filter size of vacuum filtration.
The mass ratio of graphite and potassium permanganate, sodium nitrate is graphite：Potassium permanganate：Sodium nitrate=1：6-30：0.5-2.5,
The mass volume ratio of graphite and the concentrated sulfuric acid is 1：30-150g/ml.
Further, the H containing mass fraction 98% in the concentrated sulfuric acid2SO4。
Further, the graphite is the natural scale structure of 200 mesh.
Further, when step (3) 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 of graphene being dispersed in water.
Further, when step (3) is washed：Use low-speed centrifugal washing and high speed centrifugation washing alternately washing 15 times with
On, the low-speed centrifugal centrifugal speed is 1500-2000rmp, and the high speed centrifugation speed is 10000-12000rmp.
Further, the dilute hydrochloric acid that cleaning solution used is deionized water when step (3) is washed or mass fraction is 3%.
Further, vacuum freeze drying temperature is not less than -45 DEG C, pressure 40-50Pa in step 2, and drying time is
40-50h。
The present invention carries out reduction to graphene oxide using environmentally friendly reducing agent thiourea dioxide and obtains graphene.Also
Original machine reason figure is as shown in Figure 2.Thiourea dioxide itself does not have reproducibility and oxidisability.But under alkalinity and suitable temperature
With very high reduction potential, thus with reproducibility it is strong, thermal stability is good, store convenient transportation the features such as, it is especially nontoxic
It is environmentally safe, it is cheap.So thiourea dioxide is in hydroxyl (OH-) in the presence of alkaline condition under, occur chemistry
Reaction generates the sulfinic acid (general structure R-S (=O)-OH) with reproducibility, and then at a certain temperature, sulfinic acid can divide
Solution generates HSO3 -And H+, HSO3 -It can be removed with the functional group reactions of graphene oxide paripheral zone with very strong reproducibility, secondly H+Presence also have extremely strong ring opening, the two be combined so that graphene oxide functional group removal more completely, from
And obtain the few graphene of high quality, fault of construction.In addition, the present invention overcomes existing reducing agent chemical reaction temperature height, energy
The disadvantage that consumption is big, environmental pollution is serious, expensive.It is mainly manifested in and is made at room temperature using a kind of environmentally friendly reducing agent
It is standby go out high performance graphene, while simply can control graphite by controlling reaction temperature, time and reductant concentration
Alkene quality.The graphene that the present invention is prepared has good dispersibility and stability, has the high potentiality led, substantially reduces
Cost, is advantageously implemented large area industrialized production.
(2) specific embodiment
Embodiment 1
Step 1, prepared by graphene oxide
(1) by the dense H of 30ml2SO4、0.5g NaNO3, 1g Graphite sequentially add in 500ml beakers, connect in ice bath
Continuous high degree of agitation, it is 0 DEG C of reaction 30min to keep system temperature；(2) by 6g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 2h is reacted, it is 10 DEG C to keep temperature of reaction system；(3) 35 DEG C are warming up to, 2.5h is reacted；(4) 80 DEG C are warming up to and is added
90ml deionized waters react 30min；(5) it is slowly added to the H that mass fraction is 30%2O2And it is kept for 33 DEG C and persistently stirred in a water bath
Mix, until solution becomes glassy yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) vacuum degree be-
Vacuum filtration and rotating speed are centrifuge washing 10 times under 10000rmp under 0.04MPa, by PH meter detections after cleaning solution PH is 6,
It is finally -0.8MPa in vacuum degree, temperature obtains graphene oxide about 0.5g for dry 40h in 40 DEG C of vacuum drying chamber.
Step 2, prepared by graphene oxide dispersion
The graphene oxide 0.4g being dried in vacuo in step 1 is weighed to be placed in beaker, at the same be added 1000ml go from
Sub- water, ultrasonic disperse 30min obtain 0.4mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 1g:3g:10ml matches
Set reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 1ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.4mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 30 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and be stirred continuously for 80r/min with rotating speed, sustained response 30min, it is molten then to obtain graphene mixing
Liquid.Obtained graphene mixed solution is placed under ultraviolet lamp and irradiates 30min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 2000rmp is washed 5 times in centrifuge, outwells supernatant liquid, then will under
Layer sediment high speed 10000rmp centrifuge washings 15 times take bottom sediment object dry by PH meter detections after cleaning solution PH is 6
Dry temperature is -45 DEG C, dry 40h in the vacuum freeze drier of pressure 40Pa, you can obtain Graphene powder 0.25g.
Embodiment 2
Step 1, prepared by graphene oxide
(1) by the dense H of 80ml2SO4、1.5g NaNO3, 2.5g Graphite sequentially add in 500ml beakers, in ice bath
Continuous high degree of agitation, it is 2 DEG C of reaction 32min to keep system temperature；(2) by 20g KMnO4Divide 3 times and be slowly added to, every 10min
Add once, react 2.5h, it is 12 DEG C to keep temperature of reaction system；(3) 37 DEG C are warming up to, 3h is reacted；(4) 81 DEG C are warming up to and is added
240ml deionized waters react 32min；(5) it is slowly added to the H that mass fraction is 25%2O2And it is kept for 35 DEG C and persistently stirred in a water bath
Mix, until solution becomes glassy yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) vacuum degree be-
Vacuum filtration and rotating speed are centrifuge washing 16 times under 10000rmp under 0.05MPa, by PH meter detections after cleaning solution PH is 6,
It is finally -0.9MPa in vacuum degree, temperature is about 1.25g for dry 45h obtains graphene oxide in 45 DEG C of vacuum drying chamber
Left and right.
Step 2, prepared by graphene oxide dispersion
The graphene oxide 1.25g being dried in vacuo in step 1 is weighed to be placed in beaker, at the same be added 2500ml go from
Sub- water, ultrasonic disperse 50min obtain 0.5mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 1g:4g:15ml matches
Set reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 3ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.5mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 55 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and rotating speed is stirred continuously for 100r/min, sustained response 1.5h, and it is molten then to obtain graphene mixing
Liquid.Obtained graphene mixed solution is placed under ultraviolet lamp and irradiates 40min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 2000rmp is washed 10 times in centrifuge, is outwelled supernatant liquid, then will
Lower sediment thing high speed 11000rmp centrifuge washings 15 times take bottom sediment object to exist by PH meter detections after cleaning solution PH is 6
Drying temperature is -42 DEG C, dry 45h in the vacuum freeze drier of pressure 45Pa, you can obtain Graphene powder 0.6g.
Embodiment 3
Step 1, prepared by graphene oxide
(1) by the dense H of 300ml2SO4、4g NaNO3, 6g Graphite sequentially add in 1000ml beakers, connect in ice bath
Continuous high degree of agitation, it is 3 DEG C of reaction 33min to keep system temperature；(2) by 50g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 3h is reacted, it is 15 DEG C to keep temperature of reaction system；(3) 40 DEG C are warming up to, 3h is reacted；(4) 82 DEG C are warming up to and is added
900ml deionized waters react 35min；(5) it is slowly added to the H that mass fraction is 30%2O2And it is kept for 38 DEG C and persistently stirred in a water bath
Mix, until solution becomes glassy yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) vacuum degree be-
Vacuum filtration and rotating speed are centrifuge washing 14 times under 9000rmp under 0.06MPa, by PH meter detections after cleaning solution PH is 6.5,
It is finally -1MPa in vacuum degree, temperature is about 3g or so for dry 50h obtains graphene oxide in 50 DEG C of vacuum drying chamber.
Step 2, prepared by graphene oxide dispersion
It weighs the graphene oxide 3g being dried in vacuo in step 1 to be placed in beaker, while 6000ml deionizations is added
Water, ultrasonic disperse 60min obtain 0.5mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 1g:5g:20ml matches
Set reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 15ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.5mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 80 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and be stirred continuously, sustained response 2h then obtains graphene mixed solution.The graphene that will be obtained
Mixed solution, which is placed under ultraviolet lamp, irradiates 60min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 5000rmp is washed 17 times in centrifuge, is outwelled supernatant liquid, then will
Lower sediment thing high speed 12000rmp centrifuge washings 20 times take bottom sediment object by PH meter detections after cleaning solution PH is 6.8
It is -40 DEG C in drying temperature, dry 50h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 1.5g.
Embodiment 4
Step 1, prepared by graphene oxide
(1) by the dense H of 75ml2SO4、0.5g NaNO3, 0.5g Graphite sequentially add in 500ml beakers, in ice bath
Continuous high degree of agitation, it is 1 DEG C of reaction 33min to keep system temperature；(2) by 15g KMnO4Divide 3 times and be slowly added to, every 10min
Add once, react 2.2h, it is 12 DEG C to keep temperature of reaction system；(3) 30 DEG C are warming up to, 3h is reacted；(4) 78 DEG C are warming up to and is added
225ml deionized waters react 25min；(5) it is slowly added to the 30%H that mass fraction is 30%2O2And it is kept for 33 DEG C and held in a water bath
Continuous stirring, until solution becomes glassy yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) vacuum degree be-
Vacuum filtration and rotating speed are centrifuge washing 14 times under 10000rmp under 0.04MPa, by PH meter detections after cleaning solution PH is 6,
It is finally -0.8MPa in vacuum degree, temperature obtains graphene oxide about 0.25g for dry 50h in 50 DEG C of vacuum drying chamber.
Step 2, prepared by graphene oxide dispersion
The graphene oxide 0.25g being dried in vacuo in step 1 is weighed to be placed in beaker, at the same be added 500ml go from
Sub- water, ultrasonic disperse 30min obtain 0.5mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 3g:18g:66ml matches
Set reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 50ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.5mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 40 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and be stirred continuously, sustained response 30min then obtains graphene mixed solution.The graphite that will be obtained
Alkene mixed solution, which is placed under ultraviolet lamp, irradiates 80min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 2000rmp is washed 5 times in centrifuge, outwells supernatant liquid, then will under
Layer sediment high speed 11000rmp centrifuge washings 15 times take bottom sediment object dry by PH meter detections after cleaning solution PH is 6
Dry temperature is -45 DEG C, dry 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 0.1g.
Embodiment 5
Step 1, prepared by graphene oxide
(1) by the dense H of 500ml2SO4、12.5g NaNO3, 5g Graphite sequentially add in reaction vessel, connect in ice bath
Continuous high degree of agitation, it is 2.5 DEG C of reaction 27min to keep system temperature；(2) by 100g KMnO4Divide 3 times and is slowly added to, every
10min adds once, reacts 2.5h, and it is 12 DEG C to keep temperature of reaction system；(3) 30 DEG C are warming up to, 3h is reacted；(4) 78 are warming up to
DEG C and add 1500ml deionized waters react 30min；(5) it is slowly added to the H that mass fraction is 30%2O2And 28 DEG C of holding is in water-bath
In persistently stir, until solution becomes glassy yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) in vacuum degree
It is centrifuge washing 14 times under 10000rmp for vacuum filtration and rotating speed under -0.04MPa, waits for that cleaning solution PH is 6 by PH meter detections
Afterwards, in vacuum degree it is finally -0.8MPa, temperature is that dry 50h obtains graphene oxide and is about in 50 DEG C of vacuum drying chamber
2.5g left and right.
Step 2, prepared by graphene oxide dispersion
It weighs the graphene oxide 2.5g being dried in vacuo in step 1 to be placed in beaker, while 5L deionized waters is added,
Ultrasonic disperse 45min obtains 0.5mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 4g:28g:100ml
Configure reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 100ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.5mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 60 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and be stirred continuously, sustained response 1.5h then obtains graphene mixed solution.The graphite that will be obtained
Alkene mixed solution, which is placed under ultraviolet lamp, irradiates 100min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 2000rmp is washed 7 times in centrifuge, outwells supernatant liquid, then will under
Layer sediment high speed 11000rmp centrifuge washings 18 times take bottom sediment object dry by PH meter detections after cleaning solution PH is 6
Dry temperature is -45 DEG C, dry 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 1.3g.
Embodiment 6
Step 1, prepared by graphene oxide
(1) by the dense H of 7L2SO4、200g NaNO3, 100g Graphite sequentially add in reaction vessel, it is continuous in ice bath
High degree of agitation, it is 3 DEG C of reaction 30min to keep system temperature；(2) by 1500g KMnO4Be slowly added to points for 3 times, every 10min plus
Once, 2h is reacted, it is 12 DEG C to keep temperature of reaction system；(3) 35 DEG C are warming up to, 3h is reacted；(4) 80 DEG C are warming up to and adds 21L
Deionized water reacts 30min；(5) it is slowly added to 30%H2O2And kept for 33 DEG C and persistently stirred in a water bath, until solution becomes bright
Yellow, solution surface do not have bubble or number of bubbles it is seldom until.(6) vacuum filtration and rotating speed in the case where vacuum degree is -0.04MPa
By PH meter detections after cleaning solution PH is 6 it is finally -0.8MPa, temperature in vacuum degree for centrifuge washing under 10000rmp 14 times
Degree obtains graphene oxide about 50g for dry 50h in 50 DEG C of vacuum drying chamber.
Step 2, prepared by graphene oxide dispersion
It weighs the graphene oxide 50g being dried in vacuo in step 1 to be placed in beaker, while 100L deionizations is added
Water, ultrasonic disperse 60min obtain 0.5mg/ml graphene oxide dispersions.
Step 3, prepared by reducing agent
According to thiourea dioxide (CH4N2O2S), the ratio of sodium hydroxide (NaOH) and deionized water is 10g:90g:300ml
Configure reducing agent solution.It is used in combination graduated cylinder to weigh the reducing agent of 300ml.
Step 4, ultraviolet irradiation
The graphene oxide dispersion of a concentration of 0.5mg/ml obtained in step 2 is placed in magnetic stirring apparatus,
It waits for that temperature is increased to 80 DEG C, then the titanium dioxide measured in step 3 is slowly added into graphene oxide dispersion with rubber head dropper
Thiocarbamide reducing agent solution, and be stirred continuously, sustained response 2h obtains graphene mixed solution.Obtained graphene is mixed
Solution, which is placed under ultraviolet lamp, irradiates 120min.
Step 5, prepared by Graphene powder
By the mixed liquor in step 4, first low speed 2000rmp is washed 10 times in centrifuge, is outwelled supernatant liquid, then will
Lower sediment thing high speed 11000rmp centrifuge washings 20 times take bottom sediment object to exist by PH meter detections after cleaning solution PH is 6
Drying temperature is -45 DEG C, dry 48h in the vacuum freeze drier of pressure 50Pa, you can obtain Graphene powder 25g.
Fig. 3 and Fig. 4 is the XPS figures and microscopic appearance of graphene prepared by the method for the present invention, as can be seen from the figure this hair
Bright graphene oxygen-containing functional group (C-O, C=O, COOH) obtained largely reduces, the flaky structure distribution of graphene and tool
There is pleated structure.Comparison the method for the present invention prepares the cost of graphene, such as following table with conventional method：
The Cost comparisons of table 1 present invention and conventional method
As it can be seen that the present invention successfully prepares high quality, highly conductive using nontoxic and pollution-free, inexpensive thiourea dioxide
Graphene has the characteristics that preparation method is simple, environmentally protective and reducing degree is high and controllable, has well solved traditional oxygen
Change reduction method the shortcomings that preparing graphene, for later graphene and graphene composite material industrialization and applying provide it is certain
With reference to and use for reference, have in the fields such as the super electric, Flexible Displays of graphene and health physical therapy, automobile component huge potential using valence
Value.
Claims (6)
1. a kind of environmentally friendly method for preparing graphene, it is characterised in that：Including following implementation steps：
(1) graphene oxide dispersion is prepared；
(2) thiourea dioxide reducing agent is prepared：Stirring and dissolving in deionized water is added in thiourea dioxide and sodium hydroxide,
The mass ratio of middle thiourea dioxide and sodium hydroxide is 1：The mass volume ratio of 3-9, thiourea dioxide and deionized water is 10-
30g/ml；
(3) graphene powder is prepared：Step (2) is prepared two are added in graphene oxide dispersion prepared by step (1)
Aminoiminomethanesulfonic acid reducing agent, is stirred to react, and controlling reaction temperature is 30-80 DEG C, is reacted 0.5-2.0 hours, obtains graphene mixing
Solution；Finally graphene mixed solution is washed, vacuum freeze drying is to get to the graphene；
A concentration of 0.4-0.5mg/ml of graphene oxide in the graphene oxide dispersion；
The volume ratio of the thiourea dioxide reducing agent and graphene oxide dispersion is 1：10-1000；
The step (one) prepares graphene oxide dispersion and includes the following steps：
1. first sequentially adding graphite, the concentrated sulfuric acid and sodium nitrate in reaction vessel, reaction vessel is placed in ice bath with rotating speed
It is continuously stirred for 80-100r/min, keeps system temperature to be less than 3 DEG C and react 27-33 minutes；Then it is slowly added to Gao Meng several times
Sour potassium, keeping temperature of reaction system to be no more than 15 DEG C, the reaction was continued 2-3 hours, then raises temperature to 30-40 DEG C, reaction 2.5-3 is small
When；
2. 1. reaction solution that step obtains then is warming up to 78-82 DEG C and deionized water is added to react 25-35 minutes；Later slowly
Hydrogen peroxide and being maintained in 28-38 DEG C of water-bath is added persistently to stir, until solution becomes glassy yellow, solution surface do not have bubble or
Until number of bubbles is seldom；The volume of the deionized water is 2.5~3 with concentrated sulfuric acid volume ratio:1.5~1, the dioxygen
The hydrogen peroxide for being 25%~30% containing mass fraction in water；
3. after removal step 2. gained reaction solution in metal ion, then by residual reaction liquid vacuum filtration and centrifuge washing
To neutrality, vacuum drying later obtains graphene oxide powder；
4. ultrasonic disperse is added in deionized water to get to graphene oxide in the graphene oxide powder for finally 3. obtaining step
Dispersion liquid；
The mass ratio of graphite and potassium permanganate, sodium nitrate is graphite：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；
When step (3) is reacted, using ultraviolet (UV) cure lamp to graphene mixed solution ultraviolet irradiation 30-120 minutes.
2. a kind of environmentally friendly method for preparing graphene according to claim 1, it is characterised in that：The dense sulphur
H containing mass fraction 98% in acid2SO4。
3. a kind of environmentally friendly method for preparing graphene according to claim 2, it is characterised in that：The graphite
For the natural scale structure of 200 mesh.
4. a kind of environmentally friendly method for preparing graphene according to claim 1, it is characterised in that：In step (3)
Vacuum freeze drying temperature is not less than -45 DEG C, pressure 40-50Pa, and drying time is 40-50 hours.
5. a kind of environmentally friendly method for preparing graphene according to claim 1, it is characterised in that：Step (3) is washed
When washing：Alternately washed 15 times using low-speed centrifugal washing and high speed centrifugation washing or more, the low-speed centrifugal speed is 1500-
2000rmp, the high speed centrifugation speed are 10000-12000rmp.
6. a kind of environmentally friendly method for preparing graphene according to claim 1 or 5, it is characterised in that：Step
(3) dilute hydrochloric acid that cleaning solution used is deionized water when washing or mass fraction is 3%.
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| CN111384197B (en) * | 2020-03-20 | 2021-11-05 | 杭州高烯科技有限公司 | Defect-state graphene/semiconductor heterojunction photoelectric detector |
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