CN101618870B - Method for synthesizing graphite alkene by coordination assembly - Google Patents
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Abstract
The invention relates to a synthetic method of graphite alkene, in particular to a method for synthesizing the graphite alkene by coordination assembly, solving the problems of hardly controlled size, poor production safety, uneven thickness, high production cost, complicate reaction equipment, strict reaction conditions, low yield, and the like existed in the prior preparation method so that the industrialized production is difficult. The method of the invention comprises the following steps: (1) pretreating a carbon source with coordinating groups; (2) adding into a solvent; pretreating; adding a catalyst and stirring; (3) coordinating and assembling; (4) pre-carbonizing; (5) thermally treating; and (6) returning acid and washing and drying distilled water to obtain the graphite alkene. The graphite alkene of the invention has even appearance, a single or multi-layer two-dimensional layered structure, a size of 500 nanometers -5 micrometers, favorable conductivity and wide range of application. The invention has simple technology, low cost, high yield, simple equipment, strong production safety, controllable product size and easily realized industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of Graphene.
Background technology
Graphene is a kind of carbonaceous novel material by the tightly packed one-tenth two-dimensional layer of carbon atom crystalline network.In view of Graphene excellent crystallinity and electricity and outstanding electronics, thermodynamics, mechanical property with and the potential using value, existing more and more scholars participates in the research of the synthetic and performance of Graphene.
The synthetic method of Graphene mainly contains at present: micromechanics partition method, oriented growth method, pyrolytic silicon carbide (SiC) method and chemical dispersion method.
The micromechanics stripping means is directly to strip down from bigger high orientation graphite crystal (HOPG), its size is wayward, the factory length foot is supplied the graphene platelet of usefulness reliably, expect the graphene platelet of length foot supply usefulness, need expend a large amount of raw materials, thereby increase production cost.
The epitaxy method is to utilize growth matrix atomic structure " kind " to go out Graphene, at first allow carbon atom infiltrate ruthenium down at 1150 ℃, cooling then, after being cooled to-850 ℃, a large amount of carbon atoms of Xi Shouing will float to the ruthenium surface before, the carbon atom of the individual layer of lens shape " isolated island " has been covered with whole stromal surface, and finally they can grow up to a complete layer graphene.After the first layer covered 80%, the second layer began growth.The Graphene of bottom can produce the intensive interaction with ruthenium, and just almost separates fully with ruthenium behind the second layer, only remaining light current coupling, and the single-layer graphene thin slice that obtains performance is satisfactory.But the graphene platelet that adopts this method to produce is often in uneven thickness, and the bonding between Graphene and the matrix can influence the characteristic of carbon-coating.Because the matrix of using is the rare metal ruthenium, cost an arm and a leg, increase the production cost height, output is lower.
Pyrolytic silicon carbide is to remove Si by heating monocrystalline 6H-SiC, decomposites the Graphene lamella on monocrystalline (0001) face.Detailed process is: the sample that will obtain through oxygen or hydrogen etching processing by the electron-bombardment heating, is removed oxide compound under high vacuum.After determining that with Auger electron spectrum the oxide compound on surface is removed fully, constant temperature 1min～20min after heating makes it temperature and is increased to 1250～1450 ℃ then, thus form as thin as a wafer graphite linings.Because of Graphene thickness is determined by Heating temperature, be difficult to the Graphene that the preparation big area has single thickness, described equipment complexity and reaction conditions are harsh, and difficulty realizes industrialization.
Chemical dispersion method be with graphite oxide and water with the mixed of 1mg/mL, to the clear no particulate material of solution, add an amount of hydrazine with ultra-sonic oscillation at 100 ℃ of backflow 24h, produce the black particle shape precipitation, filter, oven dry promptly gets Graphene.Sasha Stankovich etc. utilizes chemical dispersion method to make the Graphene of thickness about for 1nm.Hydrazine toxicity is poison extremely, and eyes are had hormesis, can cause the retardance inflammation, and skin and mucous membrane are also had strong corrosive nature, and production security is poor.
In sum, existing graphene preparation method exists that size is wayward, production security is poor, in uneven thickness, problem such as production cost is high, reaction required equipment complexity, severe reaction conditions, productive rate are low, thereby is difficult to suitability for industrialized production.
Summary of the invention
The objective of the invention is to have in order to solve existing graphene preparation method that size is wayward, production security is poor, in uneven thickness, production cost is high, reaction required equipment complexity, severe reaction conditions, problem such as yield poorly, thereby be difficult to suitability for industrialized production; Thereby provide the method for synthesizing graphite alkene by coordination assembly.
The method of synthesizing graphite alkene by coordination assembly of the present invention is finished by following step: one, adopt ultrasonic method, acidic treatment or alkaline purification method that the carbon source with coordinating group is carried out pre-treatment; Two, the carbon source that will have a coordinating group joins in the solvent, having the carbon source of coordinating group and the mass ratio of solvent is 1: 2～100, thermal treatment 2～8h under 120 ℃ of conditions then, be that 40～90 ℃, stirring velocity are to add catalyzer under 100～350r/min condition in temperature again, stir 4～24h then, wherein having the carbon source of coordinating group and the mass ratio of catalyzer is 1: 0.05～2, and described solvent is a kind of or wherein several mixing in water, ethanol and the ethylene glycol; Three, coordination assembling: adopt ultrasonic method, hydrothermal method or microwave method that the resultant through step 2 is handled; Four, under temperature is 200～400 ℃, protection of inert gas, with the pre-carbonization 1～6h of the resultant of step 3; Five, the heat-up rate with 2～20 ℃/min rises to 550～1200 ℃ by room temperature, the pre-carbonization resultant of thermal treatment 5min～8h under 550～1200 ℃ of conditions again, and wherein the heat-treating atmosphere flow is 20～1500mL/min, heat-treating atmosphere is a rare gas element; Six, with the resultant of sour circumfluence method treatment step five, be washed with distilled water to the pH=7 of washing lotion again, drying under 90～120 ℃ of conditions or vacuum-drying 2～8h under 60～80 ℃ of conditions then; Promptly obtain Graphene.
The carbon source that has coordinating group described in the step 1 is anion-cation exchange resin, the macroporous resin with coordinating group with coordinating group, have the resin of coordinating group or have the high molecular polymer of coordinating group.Described anion-cation exchange resin with coordinating group is acrylic acid series weak base anion-exchange resin, the polystyrene strongly basic anion exchange resin with coordinating group with coordinating group, have the amphoteric ion-exchange resin of coordinating group or have the acrylic acid type cation exchange resin of coordinating group.Described macroporous resin with coordinating group is that the macroporous acrylic with coordinating group is resin and the macropore phenylethylene resin series with coordinating group.Resin with coordinating group is thiourea resin, the thiol resin with coordinating group with coordinating group, have the aminocarboxylic acid resin of coordinating group or have the aminophosphonic acid resin of coordinating group.High molecular polymer with coordinating group is obtained through microemulsion polymerization method, microwave method or hydrothermal method processing by high molecular polymer; Described high molecular polymer is a kind of or wherein several mixing in polymethyl acrylic acid, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyacrylamide, poly furfuryl alcohol, polyaniline, poly-imines, urethane, the poly-glucosamine.
Catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, nickelous acetate, cupric chloride, copper sulfate or cupric nitrate.The described sour circumfluence method step of step 6 is as follows: in mass concentration was 6%～30% acid solution, the 4～16h that refluxes under 70～150 ℃ of conditions had promptly finished sour reflow treatment; Wherein acid solution is hydrochloric acid soln, salpeter solution, phosphoric acid solution or acetum.
The present invention adopts wide material sources, the inexpensive carbon source with coordinating group to prepare Graphene, has improved output on the one hand, greatly reduces synthetic cost on the other hand.The productive rate of Graphene of the present invention is more than 99.985%.Adopt different carbon source and catalyzer to control product size, reliably the Graphene of factory length foot supply usefulness.The inventive method makes the pattern homogeneous of Graphene, has the Graphene of individual layer or multilayered structure, and size is in 500nm～5 mu m ranges, and electroconductibility is good, electric conductivity more than 180S/cm, applied range; Can be applicable to aspects such as fuel cell, super-capacitor, field-effect transistor, organic solar batteries and catalysis.The toxicity of raw material of the present invention is little, has improved the security of producing greatly; Mature technologies such as ultrasonic, the hydro-thermal that adopts, thermal treatment, pre-carbonization, acid backflow, required equipment is simple, reaction conditions is gentle, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the two-dimentional Graphene of embodiment 38 preparations; Fig. 2 is the atomic force microscope photo of the two-dimentional Graphene of embodiment 38 preparations; Fig. 3 is the height sectional view at Fig. 2 line segment place; Fig. 4 is the Raman spectrogram of the two-dimentional Graphene of embodiment 38 preparations.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for present embodiment synthesizing graphite alkene by coordination assembly is finished by following step: one, adopt ultrasonic method, acidic treatment or alkaline purification method that the carbon source with coordinating group is carried out pre-treatment (activation has the carbon source of coordinating group); Two, the carbon source that will have a coordinating group joins in the solvent, having the carbon source of coordinating group and the mass ratio of solvent is 1: 2～100, thermal treatment 2～8h under 120 ℃ of conditions then, be that 40～90 ℃, stirring velocity are to add catalyzer under 100～350r/min condition in temperature again, stir 4～24h then, wherein having the carbon source of coordinating group and the mass ratio of catalyzer is 1: 0.05～2, and described solvent is a kind of or wherein several mixing in water, ethanol and the ethylene glycol; Three, coordination assembling: adopt ultrasonic method, hydrothermal method or microwave method that the resultant through step 2 is handled (purpose is the abundant coordination assembling of coordinating group that makes in catalyst ion and the carbon source); Four, under temperature is 200～400 ℃, protection of inert gas, with the pre-carbonization 1～6h of the resultant of step 3; Five, the heat-up rate with 2～20 ℃/min rises to 550～1200 ℃ by room temperature, the pre-carbonization resultant of thermal treatment 5min～8h under 550～1200 ℃ of conditions again, and wherein the heat-treating atmosphere flow is 20～1500mL/min, heat-treating atmosphere is a rare gas element; Six, with the resultant of sour circumfluence method treatment step five, be washed with distilled water to the pH=7 of washing lotion again, drying under 90～120 ℃ of conditions or vacuum-drying 2～8h under 60～80 ℃ of conditions then; Promptly obtain Graphene.
The present embodiment method makes the pattern homogeneous of Graphene, has the Graphene of individual layer or multilayered structure, and size is in 500nm～5 mu m ranges, and electric conductivity is more than 180S/cm; The productive rate of Graphene is more than 99.985% in the present embodiment.
Embodiment two: what present embodiment and embodiment one were different is: the carbon source that has coordinating group described in the step 1 is anion-cation exchange resin, the macroporous resin with coordinating group with coordinating group, have the resin of coordinating group or have the high molecular polymer of coordinating group.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment two were different is: described anion-cation exchange resin with coordinating group is acrylic acid series weak base anion-exchange resin, the polystyrene strongly basic anion exchange resin with coordinating group with coordinating group, have the amphoteric ion-exchange resin of coordinating group or have the acrylic acid type cation exchange resin of coordinating group.Other step and parameter are identical with embodiment two.
Have the polystyrene strongly basic anion exchange resin of coordinating group such as D201 * 7 polystyrene strongly basic anion exchange resins that resin company limited of Langfang City Nanjing University produces; Have the acrylic acid series weak base anion-exchange resin of coordinating group such as the D311 macroreticular weakly base acrylic acid type anion exchange resin that east, Anhui, Tianzhang City, Anhui Province chemical industry company limited produces; Amphoteric ion-exchange resin with coordinating group is TP-1 highly basic, the slightly acidic polystyrene amphoteric ion-exchange resin that Zhejiang Province Zhengguan Industry Co., Ltd produces; Have the acrylic acid type cation exchange resin of coordinating group such as 110 (111) acrylic acid type cation exchange resins of Anhui Samsung resin Science and Technology Ltd. supply.
Embodiment four: what present embodiment and embodiment three were different is: the carbon source with coordinating group described in the step 1 is the polystyrene strongly basic anion exchange resin that has the acrylic acid series weak base anion-exchange resin of coordinating group or have coordinating group, and carbon source adds thermal treatment 3～6h in the entry in the step 2.Other step and parameter are identical with embodiment three.
Embodiment five: what present embodiment and embodiment two were different is: described macroporous resin with coordinating group is that the macroporous acrylic with coordinating group is resin or the macropore phenylethylene resin series with coordinating group.Other step and parameter are identical with embodiment two.
Macroporous acrylic with coordinating group is the D301 macropore acidulous acrylic acid series anion exchange resin that resin such as resin company limited of Langfang City Nanjing University produce, and has the macropore phenylethylene resin series of coordinating group such as the large hole strong acid styrene system cation exchange resin D001 of Anhui Samsung resin Science and Technology Ltd. supply.
Embodiment six: what present embodiment and embodiment two were different is: the resin with coordinating group is thiourea resin, the thiol resin with coordinating group with coordinating group, have the aminocarboxylic acid resin of coordinating group or have the aminophosphonic acid resin of coordinating group.Other step and parameter are identical with embodiment two.
Have the thiourea resin of coordinating group such as the C610 thiourea resin that Xi-an Electric Power Resin Factory produces, have the thiol resin of coordinating group such as the C620 thiol resin that Xi-an Electric Power Resin Factory produces, have the aminocarboxylic acid resin of coordinating group such as the C800 aminocarboxylic acid resin that Xi-an Electric Power Resin Factory produces, have the aminophosphonic acid resin of coordinating group such as the C900 aminophosphonic acid resin that Xi-an Electric Power Resin Factory produces.
Embodiment seven: what present embodiment and embodiment two were different is: the high molecular polymer with coordinating group is handled through microemulsion polymerization method, microwave method or hydrothermal method by high molecular polymer and is obtained.
Embodiment eight: what present embodiment and embodiment seven were different is: the high molecular polymer that adopts the microemulsion polymerization method preparation to have coordinating group is undertaken by following step: in temperature is under 40～90 ℃ of conditions, high molecular polymer is carried out micro-emulsion polymerization 2～48h, promptly finish the pre-treatment of carbon source.Other step and parameter are identical with embodiment seven.
Embodiment nine: what present embodiment and embodiment seven were different is: the high molecular polymer that adopts the microwave method preparation to have coordinating group is undertaken by following step: be under the condition of 2.0～6.0kW at microwave intensity, to high molecular polymer microwave treatment 2～10min, promptly finish the pre-treatment of carbon source.Other step and parameter are identical with embodiment seven.
Embodiment ten: what present embodiment and embodiment seven were different is: the high molecular polymer that adopts Hydrothermal Preparation to have coordinating group is undertaken by following step: under 140～180 ℃ of conditions, to high molecular polymer hydrothermal treatment consists 4-16h.Other step and parameter are identical with embodiment seven.
Embodiment 11: what present embodiment and embodiment seven to ten were different is: described high molecular polymer is a kind of or wherein several mixing in polymethyl acrylic acid, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyacrylamide, poly furfuryl alcohol, polyaniline, poly-imines, urethane, the poly-glucosamine.Other step and parameter are identical with embodiment seven to ten.
When the present embodiment high molecular polymer is mixture, can be between the various high molecular polymers by any than mixing.
Embodiment 12: present embodiment and embodiment one to 11 are different: adopt ultrasonic method pre-treatment carbon source to be finished by following step in the step 1: the carbon source that adopts the ultrasonic method pre-treatment to have coordinating group is finished by following step: in frequency is under 3～7KHz condition, to having the carbon source supersound process 0.5～2.5h of coordinating group.Other step and parameter are identical with embodiment one to 11.
Embodiment 13: what present embodiment and embodiment one to 11 were different is: the carbon source that adopts the acidic treatment pre-treatment to have coordinating group in the step 1 is finished by following step: it is in 10～15% the hydrochloric acid soln that the carbon source that will have a coordinating group joins mass concentration, supersound process 2～6h.Other step and parameter are identical with embodiment one to 11.
The present embodiment ultrasonic frequency is that 20～30KHz, ultrasonic power are 300～400W.
Embodiment 14: what present embodiment and embodiment one to 11 were different is: the carbon source that adopts the pre-treatment of alkaline purification method to have coordinating group in the step 1 is finished by following step: it is in 8～14% the sodium hydroxide solution that the carbon source that will have a coordinating group joins mass concentration, supersound process 1.5～5h.Other step and parameter are identical with embodiment one to 11.
The present embodiment ultrasonic frequency is that 30～40KHz, ultrasonic power are 500～600W.
Embodiment 15: what present embodiment and concrete mode one to 14 were different is: the catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, nickelous acetate, cupric chloride, copper sulfate or cupric nitrate.Other step and parameter are identical with embodiment one to 14.
After the catalyzer process step 6 acid treatment of present embodiment, catalyst recovery liquid can recycle, once more as the catalyzer for preparing two-dimentional graphene nano carbon material.
Embodiment 16: what present embodiment and embodiment one to 15 were different is: the described ultrasonic method of step 3 is to be under 4～8KHz condition in frequency, ultrasonic 2～20h.Other step and parameter are identical with embodiment one to 15.
Embodiment 17: what present embodiment and embodiment one to 15 were different is: the described hydrothermal method of step 3 is under 140～180 ℃ of conditions, hydrothermal treatment consists 4～16h.Other step and parameter are identical with embodiment one to 15.
Embodiment 18: what present embodiment and embodiment one to 15 were different is: the described microwave method of step 3 is to react 5～10min under microwave intensity is the condition of 2.0～6.0KW.Other step and parameter are identical with embodiment one to 15.
Embodiment 19: what present embodiment and embodiment one to 16 were different is: the described rare gas element of step 4 is a kind of or wherein several mixing in nitrogen, argon gas, the helium.Other step and parameter are identical with embodiment one to 16.
When the present embodiment rare gas element is gas mixture, can be between various rare gas elementes by any than mixing.
Embodiment 20: what present embodiment and embodiment one to 19 were different is: pre-carbonization temperature is 250～350 ℃ in the step 4.Other step and parameter are identical with embodiment one to 19.
Embodiment 21: what present embodiment and embodiment one to 19 were different is: pre-carbonization temperature is 300 ℃ in the step 4.Other step and parameter are identical with embodiment one to 19.
Embodiment 22: what present embodiment and embodiment one to 21 were different is: pre-carbonization time is 2～5h in the step 4.Other step and parameter are identical with embodiment one to 21.
Embodiment 23: what present embodiment and embodiment one to 21 were different is: pre-carbonization time is 4h in the step 4.Other step and parameter are identical with embodiment one to 21.
Embodiment 24: what present embodiment and embodiment one to 23 were different is: the heat-treating atmosphere flow is 80～1200mL/min in the step 5.Other step and parameter are identical with embodiment one to 23.
Embodiment 26: what present embodiment and embodiment one to 23 were different is: the heat-treating atmosphere flow is 300～90mL/min in the step 5.Other step and parameter are identical with embodiment one to 23.
Embodiment 27: what embodiment and embodiment one to 26 were different is: thermal treatment temp is 600～1000 ℃ in the step 5.Other step and parameter are identical with embodiment one to 26.
Embodiment 28: what embodiment and embodiment one to 26 were different is: thermal treatment temp is 800 ℃ in the step 5.Other step and parameter are identical with embodiment one to 26.
Embodiment 29: what embodiment and embodiment one to 28 were different is: heat treatment time is 30min～6h in the step 5.Other step and parameter are identical with embodiment one to 28.
Embodiment 30: what embodiment and embodiment one to 29 were different is: heat treatment time is 3h in the step 5.Other step and parameter are identical with embodiment one to 29.
The embodiment hentriaconta-: what present embodiment and embodiment one to 30 were different is: the described rare gas element of step 5 is a kind of or wherein several mixing in nitrogen, argon gas, the helium.Other step and parameter are identical with embodiment one or 30.
When the present embodiment rare gas element is gas mixture, can be between various rare gas elementes by any than mixing.
Embodiment 32: present embodiment and embodiment one to hentriaconta-different be: the described sour circumfluence method step of step 6 is as follows: in mass concentration is 6%～30% acid solution, 4～the 16h that refluxes under 70～150 ℃ of conditions has promptly finished sour reflow treatment; Wherein acid solution is hydrochloric acid soln, salpeter solution, phosphoric acid solution or acetum.Other step and parameter are identical with embodiment one or hentriaconta-.
Embodiment 33: the preparation method of present embodiment two dimension graphene nano carbon material is finished by following step: one, under 70～80 ℃ of temperature, p-poly-phenyl amine carries out the polyaniline that micro-emulsion polymerization 3～6h obtains having coordinating group, is supersound process 0.5～2.5h under 3～7KHz condition in ultrasonic frequency then; Two, the polyaniline that 3g is had a coordinating group is added to the water, and behind 120 ℃ of hydrothermal treatment consists 3h, adds the 0.02moL iron nitrate under 45 ℃, 150～210r/min stirring velocity, stirs 6h; Three, under microwave intensity is the condition of 2.0～6.0kW, react 5～10min then, make the abundant coordination assembling of catalyst ion and the polar group in the polyaniline with coordinating group; Four, be under 200 ℃ of conditions in nitrogen atmosphere, pre-carbonization temperature, the step 3 product is carried out pre-carbonization 3h; Five, the heat-up rate with 8 ℃/min rises to 1000 ℃ by room temperature, is that argon gas, heat-treating atmosphere flow are that 80mL/min, thermal treatment temp are under 1000 ℃ of conditions at heat-treating atmosphere, and the step 3 product is heat-treated 2h; Six, the product of step 4 being added to the 150mL mass concentration is in 18% the nitric acid, and the 6h that refluxes under 80 ℃ of conditions is washed with distilled water to the pH=7 of washing lotion, is obtaining two-dimentional graphene nano carbon material behind the oven dry 5h under 90 ℃ of conditions then.
Rising to 200 ℃ temperature rise rate by room temperature in the present embodiment is 3 ℃/min.
The transmission electron microscope photo of this Graphene as shown in Figure 1, as can be seen from the figure, the microscopic appearance of product is a two-dimensional layered structure, size is about about 800nm.The atomic force microscope photo of this Graphene as shown in Figure 2, as can be seen from the figure sample topography homogeneous.From the height sectional view of Fig. 3 as can be seen, product is single-layer graphene.The Raman spectrogram of this Graphene sharp-pointed 2D peak occurs as shown in Figure 4 about 2700 wave numbers, further prove the generation of Graphene.
Claims (3)
1. the method for synthesizing graphite alkene by coordination assembly is characterized in that the method for synthesizing graphite alkene by coordination assembly is finished by following step: one, adopt ultrasonic method, acidic treatment or alkaline purification method that the carbon source with coordinating group is carried out pre-treatment; Two, the carbon source that will have a coordinating group joins in the solvent, having the carbon source of coordinating group and the mass ratio of solvent is 1: 2～100, thermal treatment 2～8h under 120 ℃ of conditions then, be that 40～90 ℃, stirring velocity are to add catalyzer under 100～350r/min condition in temperature again, stir 4～24h then, wherein having the carbon source of coordinating group and the mass ratio of catalyzer is 1: 0.05～2, and described solvent is a kind of or wherein several mixing in water, ethanol and the ethylene glycol; Three, coordination assembling: adopt ultrasonic method, hydrothermal method or microwave method that the resultant through step 2 is handled; Four, under temperature is 200～400 ℃, protection of inert gas, with the pre-carbonization 1～6h of the resultant of step 3; Five, the heat-up rate with 2～20 ℃/min rises to 550～1200 ℃ by room temperature, the pre-carbonization resultant of thermal treatment 5min～8h under 550～1200 ℃ of conditions again, and wherein the heat-treating atmosphere flow is 20～1500mL/min, heat-treating atmosphere is a rare gas element; Six, with the resultant of sour circumfluence method treatment step five, be washed with distilled water to the pH=7 of washing lotion again, drying under 90～120 ℃ of conditions or vacuum-drying 2～8h under 60～80 ℃ of conditions then; Promptly obtain Graphene; Wherein, the carbon source that has coordinating group described in the step 1 is the anion-cation exchange resin with coordinating group, macroporous resin with coordinating group, have the resin of coordinating group or have the high molecular polymer of coordinating group, described anion-cation exchange resin with coordinating group is the acrylic acid series weak base anion-exchange resin with coordinating group, have the polystyrene strongly basic anion exchange resin of coordinating group or have the acrylic acid type cation exchange resin of coordinating group, described macroporous resin with coordinating group is that the macroporous acrylic with coordinating group is resin and the macropore phenylethylene resin series with coordinating group, described resin with coordinating group is the thiourea resin with coordinating group, thiol resin with coordinating group, have the aminocarboxylic acid resin of coordinating group or have the aminophosphonic acid resin of coordinating group, described high molecular polymer with coordinating group is through microemulsion polymerization method by high molecular polymer, microwave method or hydrothermal method processing obtain, and described high molecular polymer is a polymethyl acrylic acid, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyacrylamide, poly furfuryl alcohol, polyaniline, poly-imines, urethane, a kind of or wherein several mixing in the poly-glucosamine; Catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, nickelous acetate, cupric chloride, copper sulfate or cupric nitrate.
2. the method for synthesizing graphite alkene by coordination assembly according to claim 1 is characterized in that the described rare gas element of step 4 is a kind of or wherein several mixing in nitrogen, argon gas, the helium; The described rare gas element of step 5 is a kind of or wherein several mixing in nitrogen, argon gas, the helium.
3. the method for synthesizing graphite alkene by coordination assembly according to claim 1 and 2, it is characterized in that the described sour circumfluence method step of step 6 is as follows: in mass concentration is 6%～30% acid solution, 4～the 16h that refluxes under 70～150 ℃ of conditions has promptly finished sour reflow treatment; Wherein acid solution is hydrochloric acid soln, salpeter solution, phosphoric acid solution or acetum.
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| CN105504341B (en) * | 2015-11-20 | 2017-06-16 | 营口圣泉高科材料有限公司 | A kind of compound and preparation method thereof and a kind of macromolecular material and preparation method thereof |
| CN105253875B (en) * | 2015-10-20 | 2017-03-29 | 天津大学 | Graphene-supported carbon nanobelts array three-dimensional composite material and preparation method thereof |
| WO2017084507A1 (en) | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | Graphene-containing modified latex as well as preparation method therefor and application thereof |
| CN105525377B (en) | 2015-11-26 | 2018-08-17 | 济南圣泉集团股份有限公司 | A kind of functional regenerated cellulose fibre and its preparation method and application |
| CN109401635A (en) * | 2018-09-21 | 2019-03-01 | 三峡大学 | Graphene Aqueous Adhesives and preparation method thereof |
| CN111193042B (en) * | 2018-11-14 | 2021-08-13 | 河北大学 | Nitrogen-doped graphene @ copper-iron ball composite material and preparation method and application thereof |
| CN114789192A (en) * | 2022-03-23 | 2022-07-26 | 无锡市政设计研究院有限公司 | Method for remediating petroleum hydrocarbon contaminated soil |
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