CN104591176A - Method for preparing graphene - Google Patents
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- CN104591176A CN104591176A CN201510057842.5A CN201510057842A CN104591176A CN 104591176 A CN104591176 A CN 104591176A CN 201510057842 A CN201510057842 A CN 201510057842A CN 104591176 A CN104591176 A CN 104591176A
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Abstract
The invention provides a method for preparing graphene. The method comprises the following steps: (A) mixing a biomass material, an anionic surfactant and water to carry out a hydrothermal reaction at a temperature of 150-250 DEG C for 1-24 hours to obtain a precursor; (B) mixing a metal catalyst with the precursor obtained in the step (A) to obtain a precursor containing the metal catalyst; and (C) heating the precursor containing the metal catalyst obtained in the step (B) to obtain graphene. According to the preparation method, the biomass material is used as a carbon source, the biomass material reacts under a hydrothermal condition to generate a gaseous-phase product, the anionic surfactant can be used for enriching bubbles and the biomass material in a bulk phase solution, and the bubbles are used as a template to form hollow carbon spheres so as to obtain the precursor which has a relatively thin spherical shell layer and relatively high surface activity and can be easily catalyzed by a metal catalyst, and graphene having relatively high graphitizing degree can be obtained.
Description
Technical field
The invention belongs to carbon material technical field, particularly relate to a kind of preparation method of Graphene.
Background technology
Graphene is two-dimensional material the thinnest in the world, thickness be only hairline 200,000/, its intensity is but the highest in known materials, more taller than best iron and steel 100 times, and the power needed for single-layer graphene breaking same cross-sectional is 200 times of steel.Research finds, the peak pressure that the Graphene of 100nm can bear reaches about 2.9 micro-oxen, the Graphene fracture that the pressure being equivalent to applying 55 newton just can make 1m long.If make the graphene film that 100nm is thick, then can bear the pressure of about 20,000 newton, so can carry the article of about two tons of weights with the packing bag that Graphene is made, fully indicating Graphene is the material that intensity is maximum in the world.
In recent years, people constantly explore novel method to improve the output of Graphene, at present, multiple method can be adopted to prepare grapheme material powder, as mechanically peel method, oxidation-reduction method, crystal epitaxy method, chemical Vapor deposition process, organic synthesis method and stripping carbon nanotube method etc.In these methods, mechanically peel method and epitaxial growth method preparation efficiency very low, be difficult to satisfied large-scale needs.Although chemical Vapor deposition process can obtain large size continuous print graphene film, be only applicable to micro-nano electron device or transparent conductive film, but can not meet the extensive demand in energy storage material and functional composite material field.More stable in oxidation reduction process, use comparatively extensive, but owing to needing to use a large amount of strong acid and strong oxidizer in redox processes, as concentrated nitric acid, the vitriol oil, potassium permanganate or Potcrate etc., not only very large pollution is brought to environment, also can bring certain danger to operating process.
Catalytic activation method is a kind of method preparing Graphene newly, catalytic activation method is carbon source with biological material, and the functional group's physical adsorption utilizing biological surface abundant or ion exchange metal ion, mix with pore-forming material, carbonization under high temperature inert atmosphere, prepares porous graphene.Because catalytic activation method does not use strong acid and strong oxidizer, therefore, environmental pollution is less, but the Graphene adopting existing catalytic activation technology to prepare can only make material surface greying, the overall degree of graphitization of biological material is not high, affects quality product.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene, the degree of graphitization of the Graphene adopting preparation method provided by the invention to obtain is higher, and the quality product obtained is better.
The invention provides a kind of preparation method of Graphene, comprise the following steps:
A) biological material, anion surfactant and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour;
B) by metal catalyst and described steps A) presoma that obtains mixes, and obtains the presoma containing metal catalyst;
C) by described step B) heating containing the presoma of metal catalyst of obtaining, obtain Graphene.
Preferably, described biological material comprises one or more in glucose, sucrose, fructose, sorbose, semi-lactosi and seminose.
Preferably, described anion surfactant comprises one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and sodium stearate.
Preferably, the mass ratio of described biological material and described anion surfactant is (10 ~ 50): 1.
Preferably, described step B) in metal catalyst comprise in molysite, ferrous salt, nickel salt and cobalt salt one or more.
Preferably, described metal catalyst and described steps A) mass ratio of presoma that obtains is (0.01 ~ 1): 1.
Preferably, described step C) in heating temperature be 800 ~ 1200 DEG C;
The time of described heating is 1 ~ 5 hour.
Preferably, described steps A) presoma that obtains is hollow ball structure, the thickness of described hollow ball spherical shell is 2 ~ 30nm.
Preferably, described steps A) specifically comprise:
Biological material, anion surfactant, hydrofluoric acid and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour;
The volumetric molar concentration of described hydrofluoric acid is 0.01 ~ 2mol/L.
Preferably, described step B) specifically comprise: by pore-forming material and described steps A) presoma containing metal catalyst that obtains mixes, heats, obtain Graphene;
Described pore-forming material comprises one or more in water vapor, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, sodium oxide and sodium hydroxide;
Described pore-forming material and described steps A) in the mass ratio of biological material be (1 ~ 5): 1.
The invention provides a kind of preparation method of Graphene, comprise the following steps: A) biological material, anion surfactant and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour; B) by metal catalyst and described steps A) presoma that obtains mixes, and obtains the presoma containing metal catalyst; C) by described step B) heating containing the presoma of metal catalyst of obtaining, obtain Graphene.Preparation method provided by the invention take biological material as carbon source, and biological material reaction under hydrothermal conditions can produce gaseous products, as CO
2, CO and H
2deng, described anion surfactant can these bubbles of enrichment and the biological material in body phase solution, and be that template forms carbon hollow ball with bubble, the carbon hollow ball shell obtained is thinner and be rich in a large amount of anion surfactant, anion surfactant is dissociated into electronegative group in aqueous, more easily adsorb the metal ion with positive charge such as iron, nickel, in follow-up heat-processed, carbon hollow ball is more easily by metal catalyst catalysis, obtains the Graphene that degree of graphitization is higher.
Further, the present invention can also carry out fluoridation in water-heat process, carries out fluorinated modified to the carbon hollow ball obtained, and makes carbon hollow ball have stronger electronegativity, is more conducive to the metallics of adsorption zone positive electricity.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the TEM figure of the presoma that the embodiment of the present invention 1 obtains;
Fig. 2 is the SEM figure of the Graphene that the embodiment of the present invention 1 obtains;
Fig. 3 is the TEM figure of the Graphene that the embodiment of the present invention 1 obtains;
Fig. 4 is the specific surface area figure of the Graphene that the embodiment of the present invention 1 obtains;
Fig. 5 is the porosity figure of the Graphene that the embodiment of the present invention 1 obtains;
Fig. 6 is the Raman spectrum of the Graphene that the embodiment of the present invention 1 obtains;
Fig. 7 is the SEM figure of the presoma that the embodiment of the present invention 2 obtains;
Fig. 8 is the TEM figure of the presoma that comparative example 1 of the present invention obtains;
Fig. 9 is the SEM figure of the Graphene that comparative example 1 of the present invention obtains;
Figure 10 is the TEM figure of the Graphene that comparative example 1 of the present invention obtains.
Embodiment
The invention provides a kind of preparation method of Graphene, comprise the following steps:
A) biological material, anion surfactant and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour;
B) by metal catalyst and described steps A) presoma that obtains mixes, and obtains the presoma containing metal catalyst;
C) by described step B) heating containing the presoma of metal catalyst of obtaining, obtain Graphene.
The degree of graphitization of the Graphene adopting preparation method provided by the invention to obtain is higher, and the quality product obtained is better.
Biological material, anion surfactant and water mix by the present invention, carry out hydro-thermal reaction, obtain presoma, described biological material, anion surfactant and water preferably mix by the present invention, carry out ultrasonic, then the mixture of ultrasonic mistake is carried out hydro-thermal reaction, obtain presoma.In the present invention, described biological material preferably includes one or more in glucose, sucrose, fructose, sorbose, semi-lactosi and seminose, more preferably comprises one or more in glucose, sucrose and seminose; Described anion surfactant preferably includes one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and sodium stearate, more preferably comprises sodium lauryl sulphate and/or Sodium dodecylbenzene sulfonate; Mix water used with described biological material and anion surfactant and be preferably deionized water.In the present invention, the mass ratio of described biological material and described anion surfactant is (10 ~ 50): 1, is more preferably (12 ~ 30): 1, most preferably is 15:1; The mass ratio of described biological material and water is preferably 1:(8 ~ 15), be more preferably 1:(9 ~ 13), most preferably be 1:(10 ~ 12).
In order to make the presoma obtained have stronger electronegativity, described biological material, anion surfactant preferably mix with hydrofluoric acid solution by the present invention, carry out ultrasonic, obtain presoma.In the present invention, the volumetric molar concentration of described hydrofluoric acid solution is preferably 0.01 ~ 2mol/L, is more preferably 0.05 ~ 1.5mol/L, most preferably is 0.1 ~ 0.5mol/L, and the consumption of the present invention to described hydrofluoric acid does not have special restriction.
In the present invention, described ultrasonic temperature is preferably 20 ~ 30 DEG C, is more preferably 25 DEG C; The described ultrasonic time is preferably 3 ~ 10min, is more preferably 5 ~ 8min.
Complete described ultrasonic after, the ultrasonic mixture obtained is carried out hydro-thermal reaction by the present invention, obtains presoma.In the present invention, described hydro-thermal reaction refers in the pressurized vessel of sealing, take water as solvent, the chemical reaction carried out under the condition of High Temperature High Pressure.In the present invention, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, is preferably 170 ~ 210 DEG C, is more preferably 180 DEG C; The time of described hydro-thermal reaction is preferably 1 ~ 24 hour, is more preferably 8 ~ 20 hours, most preferably is 10 ~ 18 hours, is the most preferably 12 ~ 16 hours; The pressure of the present invention to described hydro-thermal reaction does not have special restriction, makes the temperature in described airtight pressurized vessel reach above-mentioned requirements.The present invention preferably carries out described hydro-thermal reaction in a kettle..In the present invention, the presoma that described hydro-thermal reaction obtains has hollow ball structure, and the thickness of described hollow ball spherical shell is preferably 2 ~ 30nm, is more preferably 5 ~ 20nm, most preferably is 10 ~ 15nm.
After completing described hydro-thermal reaction, the presoma obtained preferably is carried out drying by the present invention, obtains dry presoma.In the present invention, the temperature of described drying is preferably 60 ~ 100 DEG C, is more preferably 70 ~ 90 DEG C, most preferably is 80 DEG C; The time of described drying is preferably 8 ~ 12 hours, is more preferably 10 ~ 11 hours.
After obtaining presoma, metal catalyst mixes with the presoma obtained by the present invention, obtains the presoma containing metal catalyst.In the present invention, described metal catalyst preferably includes one or more in molysite, ferrous salt, nickel salt and cobalt salt, be more preferably one or more in iron(ic) chloride, nickelous chloride, nickel acetate, iron acetate, ferric sulfate, single nickel salt, the Tripotassium iron hexacyanide and yellow prussiate of potash, most preferably comprise one or more in nickelous chloride, iron(ic) chloride, the Tripotassium iron hexacyanide and nickel acetate; The mass ratio of described metal catalyst and described presoma is preferably (0.01 ~ 1): 1.The present invention preferably adopts metal catalyst solution to mix with described presoma, obtains the presoma containing metal catalyst.In the present invention, the volumetric molar concentration of described metal catalyst solution is preferably 0.01 ~ 0.1mol/L, is more preferably 0.05 ~ 0.08mol/L.
Described presoma preferably floods by the present invention in described metal catalyst solution, described metal catalyst is made to be attached on described presoma, in the present invention, described metal catalyst mainly through deposition mode be combined with described presoma, while also have part metals catalyzer be by functional group between adsorption be combined with described presoma.In the present invention, the time of described dipping is preferably 1 ~ 10 hour, is more preferably 2 ~ 8 hours.After completing above-mentioned dipping, the solution after dipping preferably filters by the present invention, removes liquid, obtains solid.In the present invention, method well known to those skilled in the art is filtered into described in.
After completing filtration, the solid that described filtration obtains preferably is carried out drying by the present invention, obtains the dry presoma containing metal catalyst.In the present invention, 60 ~ 100 DEG C are preferably to the temperature of the drying of the solid that described filtration obtains, are more preferably 70 ~ 90 DEG C, most preferably be 80 DEG C; 8 ~ 12 hours are preferably to the time of the drying of the solid that described filtration obtains, are more preferably 10 ~ 11 hours.
After obtaining the presoma containing metal catalyst, the described presoma containing metal catalyst heats by the present invention, obtains Graphene.The described presoma containing metal catalyst preferably mixes with pore-forming material by the present invention, heats, obtains Graphene.In the present invention, described pore-forming material preferably includes one or more in water vapor, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, sodium oxide and sodium hydroxide, more preferably comprise one or more in sodium hydroxide, potassium hydroxide and water vapour, most preferably be potassium hydroxide; The mass ratio of described pore-forming material and the described presoma containing metal catalyst is preferably (1 ~ 5): 1, is more preferably 2:1.
The present invention is by after described pore-forming material and the described presoma mixing containing metal catalyst, preferably first dry, and then heats, and obtains Graphene.In the present invention, the drying of described pore-forming material and the precursor mixture containing metal catalyst is method well known to those skilled in the art.
The present invention preferably heats the mixture of described pore-forming material with the presoma containing metal catalyst under shielding gas atmosphere, obtains Graphene.In the present invention, described shielding gas is preferably rare gas element and/or nitrogen.In the present invention, the temperature of described heating is preferably 800 ~ 1200 DEG C, is more preferably 900 ~ 1100 DEG C, most preferably is 1000 DEG C; The time of described heating is preferably 1 ~ 5 hour, is more preferably 2 ~ 4 hours.The present invention preferably adopts the method for intensification to reach above-mentioned Heating temperature, and the speed of described intensification is preferably 3 ~ 8 DEG C/min, is more preferably 4 ~ 6 DEG C/min, most preferably is 5 DEG C/min.
After completing described heating, the present invention preferably carries out pickling and filtration successively by heating the product obtained, to remove wherein residual metal catalyst.In the present invention, described pickling acid solution used be preferably in hydrochloric acid, sulfuric acid and nitric acid one or both, the dipping time of described pickling is preferably 0.5 ~ 8 hour, is more preferably 1 ~ 7 hour, most preferably is 2 ~ 6 hours.
After completing described pickling, the product after pickling is preferably carried out solid-liquid separation by the present invention, removes liquid, obtains Graphene.In the present invention, described solid-liquid separation is preferably filters, described in be filtered into the technique means that those skilled in the art commonly use.
After completing described solid-liquid separation, the product that described solid-liquid separation obtains preferably is carried out drying by the present invention, obtains Graphene.In the present invention, described drying is preferably dries, and the temperature of described oven dry is preferably 100 ~ 150 DEG C, is more preferably 90 ~ 140 DEG C, most preferably is 100 ~ 120 DEG C; The time of described oven dry is preferably 8 ~ 12 hours, is more preferably 10 hours.
The specific surface area of the Graphene obtained according to above-mentioned preparation method is preferably 1000 ~ 2000cm
3/ g, is more preferably 1200 ~ 1800cm
3/ g; The aperture of described Graphene is preferably 1 ~ 10nm, is more preferably 2 ~ 9nm, most preferably is 3 ~ 8nm.
After obtaining Graphene, Graphene has been carried out scanning electron microscope detection (SEM) by the present invention, and result shows, Graphene provided by the invention is lamella pattern, and degree of graphitization is higher, and graphenic surface is distributed with a large amount of micropores.
The present invention adopts full-automatic specific surface area and micropore Physisorption Analyzer to have detected the specific surface area and porosity of the Graphene that the present invention obtains, and result shows, the porous graphene specific surface obtained is comparatively large, at 1000 ~ 2000cm
3/ g; Void distribution is mainly 1 ~ 10nm.
The present invention has carried out Raman spectrum detection to the Graphene obtained, and result shows, the porous graphene obtained has certain degree of graphitization.
The invention provides a kind of preparation method of Graphene, comprise the following steps: A) biological material, anion surfactant and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour; B) by metal catalyst and described steps A) presoma that obtains mixes, and obtains the presoma containing metal catalyst; C) by described step B) heating containing the presoma of metal catalyst of obtaining, obtain Graphene.Preparation method provided by the invention take biological material as carbon source, and biological material reaction under hydrothermal conditions can produce gaseous products, as CO
2, CO and H
2deng, described anion surfactant can these bubbles of enrichment and the biological material in body phase solution, and be that template forms carbon hollow ball with bubble, the carbon hollow ball shell obtained is thinner and be rich in a large amount of anion surfactant, anion surfactant is dissociated into electronegative group in aqueous, more easily adsorb the metal ion with positive charge such as iron, nickel, in follow-up heat-processed, carbon hollow ball is more easily by metal catalyst catalysis, obtains the Graphene that degree of graphitization is higher.
Further, the present invention can also carry out fluoridation in water-heat process, carries out fluorinated modified to the carbon hollow ball obtained, and makes carbon hollow ball have stronger electronegativity, is more conducive to the metallics of adsorption zone positive electricity.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method to a kind of Graphene provided by the invention is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
Get 10g glucose, 1g sodium lauryl sulphate, adding 150ml concentration is in the hydrofluoric acid aqueous solution of 0.01mol/l, then by ultrasonic 5 minutes of the glucose solution that obtains, pour in reactor, at 180 DEG C, carry out hydro-thermal reaction, after reaction 10h, 80 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml and contain in 1g potassium ferricyanide solution, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.Mix with KOH with the ratio of the mass ratio 1:1 of KOH according to containing the presoma of iron ion, dry, 1000 DEG C, calcine 2h under inert atmosphere, temperature rise rate is 5 DEG C/min, the product that calcining obtains is through the salt acid elution of 1mol/L, filter, by filtering, the solid obtained is dry at 120 DEG C, obtains porous graphene.
The present invention has carried out transmission electron microscope detection (TEM) to the presoma that the present embodiment obtains, and as shown in Figure 1, Fig. 1 is the TEM figure of the presoma that the embodiment of the present invention 1 obtains to result; As seen from Figure 1, the presoma that the present embodiment obtains is hollow ball structure, and thickness is 2 ~ 30nm.
The present invention has carried out scanning electron microscope detection (SEM) to the Graphene that the present embodiment obtains, and as shown in Figure 2, Fig. 2 is the SEM figure of the porous graphene that the embodiment of the present invention 1 obtains to result;
The present invention has carried out transmission electron microscope detection (TEM) to the Graphene that the present embodiment obtains, and as shown in Figure 3, Fig. 3 is the TEM figure of the Graphene that the embodiment of the present invention 1 obtains to result.As can be seen from Fig. 2 and Fig. 3, the grapheme material that the embodiment of the present invention 1 obtains is three-dimensional lamella pattern, and porous graphene surface arrangement has a large amount of micropores, and size is mainly 1 ~ 10nm.
The present invention tests the specific surface area of the Graphene that the present embodiment obtains according to technique scheme, and as shown in Figure 4, Fig. 4 is the specific surface area figure of the Graphene that the embodiment of the present invention 1 obtains to result.As seen from Figure 4, the Graphene specific surface obtained is comparatively large, between 1000 ~ 2000cm3/g.
The present invention tests the porosity of the Graphene that the present embodiment obtains according to technique scheme, and as shown in Figure 5, Fig. 5 is the porosity figure of the Graphene that the embodiment of the present invention 1 obtains to result.As seen from Figure 5, void distribution is mainly 1 ~ 10nm.
The present invention has carried out Raman spectrum (Raman) to the Graphene that the present embodiment obtains and has detected, and as shown in Figure 6, Fig. 6 is the Raman spectrum of the Graphene that the embodiment of the present invention 1 obtains to result.As seen from Figure 6, the Graphene obtained has certain degree of graphitization.
Embodiment 2
Get 20g glucose, 1g Sodium dodecylbenzene sulfonate, add 150ml deionized water, then by ultrasonic 5 minutes of the glucose solution that obtains, pour in reactor, at 150 DEG C, carry out hydro-thermal reaction, after reaction 6h, 80 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml containing in 0.5g ferric chloride Solution, ultrasonic 15 minutes, leave standstill 10h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.800 DEG C, calcine 2h under inert atmosphere, temperature rise rate is 5 DEG C/min, calcines the product that obtains through the salt acid elution of 1mol/L, filters, will filter the solid obtained dry at 120 DEG C, and obtain Graphene.
The present invention has carried out scanning electron microscope detection (SEM) to the presoma that the present embodiment obtains, and as shown in Figure 7, Fig. 7 is the SEM figure of the presoma that the embodiment of the present invention 2 obtains to result; As seen from Figure 7, the presoma that the present embodiment obtains is laminated structure.
Embodiment 3
Get 50g sucrose, 1g sodium lauryl sulphate, add 300ml deionized water, then by ultrasonic 5 minutes of the sucrose solution that obtains, pour in reactor, at 250 DEG C, carry out hydro-thermal reaction, after reaction 24h, 80 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml containing in the nickel chloride solution of 0.8g, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing nickel ion presoma.Mix with KOH with the ratio of the mass ratio 1:3 of KOH according to containing the presoma of nickel ion, dry, 1200 DEG C, calcine 2h under inert atmosphere, temperature rise rate is 5 DEG C/min, the product that calcining obtains is through the salt acid elution of 1mol/L, filter, by filtering, the solid obtained is dry at 120 DEG C, obtains porous graphene.
Embodiment 4
Get 30g glucose, 1g sodium laurylsulfonate, adding 300ml concentration is in the hydrofluoric acid aqueous solution of 0.01mol/l, then by ultrasonic 5 minutes of the glucose solution that obtains, pour in reactor, at 250 DEG C, carry out hydro-thermal reaction, after reaction 1h, 80 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml containing in the potassium ferricyanide solution of 0.4g, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.Mix with KOH with the ratio of the mass ratio 1:2 of KOH according to containing the presoma of iron ion, dry, 1000 DEG C, calcine 2h under inert atmosphere, temperature rise rate is 5 DEG C/min, the product that calcining obtains is through the salt acid elution of 1mol/L, filter, by filtering, the solid obtained is dry at 120 DEG C, obtains Graphene.
Embodiment 5
Get 40g seminose, 1g Sodium dodecylbenzene sulfonate, adding 300ml concentration is in the hydrofluoric acid aqueous solution of 2mol/l, then by ultrasonic 5 minutes of the mannose solution that obtains, pour in reactor, at 200 DEG C, carry out hydro-thermal reaction, after reaction 5h, 60 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml containing in the potassium ferricyanide solution of 1g, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.Mix with KOH with the ratio of the mass ratio 1:5 of KOH according to containing the presoma of iron ion, dry, 1000 DEG C, calcine 2h under inert atmosphere, temperature rise rate is 5 DEG C/min, the product that calcining obtains is through the salt acid elution of 1mol/L, filter, by filtering, the solid obtained is dry at 120 DEG C, obtains porous graphene.
Embodiment 6
Get 10g glucose, 1g sodium lauryl sulphate, adding 300ml concentration is in the hydrofluoric acid aqueous solution of 1mol/l, then by ultrasonic 5 minutes of the glucose solution that obtains, pour in reactor, at 170 DEG C, carry out hydro-thermal reaction, after reaction 16h, 80 DEG C of dryings, obtain presoma.
Get 1g presoma, join 100ml containing in the potassium ferricyanide solution of 0.01g, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.Mix with KOH with the ratio of the mass ratio 1:1 of KOH according to containing the presoma of iron ion, dry, 900 DEG C, calcine 1h under inert atmosphere, temperature rise rate is 5 DEG C/min, the product that calcining obtains is through the salt acid elution of 1mol/L, filter, by filtering, the solid obtained is dry at 120 DEG C, obtains porous graphene.
Comparative example 1
Get 10g glucose, add 150ml deionized water, poured in reactor after ultrasonic for the glucose solution obtained 5 minutes, at 180 DEG C, carry out hydro-thermal reaction, after reaction 12h, reaction solution is dry at 80 DEG C, obtain presoma.
Get 1g presoma, join 100mL containing in the potassium ferricyanide solution of 1g, ultrasonic 15 minutes, leave standstill 4h, filter, by filtering, the solid obtained is dry at 80 DEG C, obtains containing iron ion presoma.1:1 and KOH mixing in mass ratio, after drying 1000 DEG C, calcine 2h under nitrogen atmosphere, temperature rise rate is 5 DEG C/min, and calcine the product that the obtains salt acid elution through 1mol/L, filter, 120 DEG C of dryings, obtain Graphene.
The present invention has carried out transmission electron microscope detection (TEM) to the presoma that this comparative example obtains, and as shown in Figure 8, Fig. 8 is the TEM figure of the presoma that comparative example 1 of the present invention obtains to result; As seen from Figure 8, the presoma that this comparative example obtains is solid sphere structure.
The present invention has carried out scanning electron microscope detection (SEM) to the Graphene that this comparative example obtains, and as shown in Figure 9, Fig. 9 is the SEM figure of the Graphene that comparative example 1 of the present invention obtains to result;
The present invention has carried out transmission electron microscope detection (TEM) to the Graphene that this comparative example obtains, and as shown in Figure 10, Figure 10 is the TEM figure of the Graphene that comparative example 1 of the present invention obtains to result.As can be seen from Fig. 9 and Figure 10, the grapheme material that comparative example 1 of the present invention obtains is the lamella pattern of fold, but lamella is thicker, and degree of graphitization is lower.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for Graphene, comprises the following steps:
A) biological material, anion surfactant and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour;
B) by metal catalyst and described steps A) presoma that obtains mixes, and obtains the presoma containing metal catalyst;
C) by described step B) heating containing the presoma of metal catalyst of obtaining, obtain Graphene.
2. preparation method according to claim 1, is characterized in that, described biological material comprises one or more in glucose, sucrose, fructose, sorbose, semi-lactosi and seminose.
3. preparation method according to claim 1, is characterized in that, described anion surfactant comprises one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and sodium stearate.
4. preparation method according to claim 1, is characterized in that, the mass ratio of described biological material and described anion surfactant is (10 ~ 50): 1.
5. preparation method according to claim 1, is characterized in that, described step B) in metal catalyst comprise in molysite, ferrous salt, nickel salt and cobalt salt one or more.
6. preparation method according to claim 1, is characterized in that, described metal catalyst and described steps A) mass ratio of presoma that obtains is (0.01 ~ 1): 1.
7. preparation method according to claim 1, is characterized in that, described step C) in heating temperature be 800 ~ 1200 DEG C;
The time of described heating is 1 ~ 5 hour.
8. preparation method according to claim 1, is characterized in that, described steps A) presoma that obtains is hollow ball structure, the thickness of described hollow ball spherical shell is 2 ~ 30nm.
9. the preparation method according to claim 1 ~ 8 any one, is characterized in that, described steps A) specifically comprise:
Biological material, anion surfactant, hydrofluoric acid and water are mixed, carry out hydro-thermal reaction, obtain presoma, the temperature of described hydro-thermal reaction is 150 ~ 250 DEG C, and the time of described hydro-thermal reaction is 1 ~ 24 hour;
The volumetric molar concentration of described hydrofluoric acid is 0.01 ~ 2mol/L.
10. the preparation method according to claim 1 ~ 8 any one, is characterized in that, described step B) specifically comprise: by pore-forming material and described steps A) mixing containing the presoma of metal catalyst of obtaining, heat, obtain Graphene;
Described pore-forming material comprises one or more in water vapor, potassium hydroxide, potassium oxide, zinc chloride, phosphoric acid, sodium oxide and sodium hydroxide;
Described pore-forming material and described steps A) in the mass ratio of biological material be (1 ~ 5): 1.
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| CN104925796A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Preparation method of porous graphene |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
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| CN106335898A (en) * | 2016-08-23 | 2017-01-18 | 黄云鸿 | Preparation method of graphene and graphene |
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| CN115893384A (en) * | 2022-11-28 | 2023-04-04 | 南开大学 | Synthesis method of porous graphene nanosheet with biomass as raw material |
| CN115893384B (en) * | 2022-11-28 | 2024-03-08 | 南开大学 | Synthesis method of porous graphene-like nanosheets with biomass as raw material |
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