CN112875692A - Method for preparing large-flake-diameter graphene oxide based on flaky graphene - Google Patents
Method for preparing large-flake-diameter graphene oxide based on flaky graphene Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 28
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 58
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 239000008394 flocculating agent Substances 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000002041 carbon nanotube Substances 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000009830 intercalation Methods 0.000 claims description 14
- 230000002687 intercalation Effects 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000138 intercalating agent Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The invention discloses a method for preparing large-sheet-diameter graphene oxide based on flaky graphene, which is prepared by processing the flaky graphene, and an intercalator is prepared in the preparation process, wherein the intercalator is prepared by taking phosphorus pentoxide, aluminum chloride and glacial acetic acid as raw materials, can well separate a graphite block into graphene, and simultaneously prevents graphene sheets from reuniting and stacking, so that the large-sheet-diameter graphene oxide is more stable, the yield is higher, and a flocculating agent is prepared.
Description
Technical Field
The invention relates to the technical field of graphene preparation, and particularly relates to a method for preparing large-flake-diameter graphene oxide based on flaky graphene.
Background
Graphene (Graphene) is a single-layer sheet-like structure composed of carbon atoms and is a two-dimensional material having a thickness of only one carbon atom. Graphene exhibits excellent properties in many aspects, for example, graphene is almost completely transparent, absorbs only 2.3% of light, and has very good light transmittance; the thermal conductivity coefficient of the graphene is as high as 5300W/m.K, which is higher than that of the carbon nano tube and the diamond; the electron mobility of the graphene at normal temperature exceeds 15000 cm/V.s, and is higher than that of a carbon nanotube and a silicon crystal; the resistivity of the graphene is only 10 omega cm, is lower than that of copper or silver, and is the material with the minimum resistivity at present; graphene is also currently the thinnest but most rigid material. The graphene is prepared into powder, so that the application of the graphene is more facilitated, for example, the graphene material powder can be used as an additive of an expanding agent material, the electrical property and the mechanical strength of the expanding agent material are improved, and the graphene material powder has a wide application prospect.
The large-sheet-diameter graphene oxide prepared by the conventional large-sheet-diameter graphene oxide preparation method contains a large amount of impurities, the yield is low, and the prepared large-sheet-diameter graphene oxide has poor quality, so that the use effect of the product is poor.
Disclosure of Invention
The invention aims to provide a method for preparing large-flake-diameter graphene oxide based on flaky graphene.
The technical problems to be solved by the invention are as follows:
the large-sheet-diameter graphene oxide prepared by the conventional large-sheet-diameter graphene oxide preparation method contains a large amount of impurities, the yield is low, and the prepared large-sheet-diameter graphene oxide has poor quality, so that the use effect of the product is poor.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing large-flake-diameter graphene oxide based on flaky graphene specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid under the condition of temperature of 0-2 ℃, stirring for 0.5-1h under the condition of rotation speed of 150-200r/min, adding an intercalation agent, continuously stirring for 1-1.5h, adding potassium permanganate, stirring for 3-5min under the conditions of rotation speed of 300-350r/min and temperature of 10-15 ℃, and continuously stirring for 3-5h under the condition of temperature of 35-40 ℃ to prepare pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5-1h at the rotation speed of 200-300r/min and the temperature of 90-95 ℃, adding hydrogen peroxide, continuously stirring for 1-1.5h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1-1.5h under the condition of 5-8MHz, adding a flocculating agent, continuing ultrasonic treatment for 10-15min, centrifuging at the rotation speed of 8000r/min, removing precipitates, and distilling the supernatant to obtain the large-sheet-diameter graphene oxide.
Further, the dosage ratio of the crystalline flake graphite, the sodium nitrate, the concentrated sulfuric acid, the intercalation agent and the potassium permanganate in the step S1 is 1g:0.5g:25mL:4g:3g, and the mass fraction of the concentrated sulfuric acid is 98%.
Further, the volume ratio of the pre-oxidized graphene suspension, the deionized water and the hydrogen peroxide in the step S2 is 3:12:2, the mass fraction of the hydrogen peroxide is 30%, and the mass fraction of the dilute hydrochloric acid is 15%.
Further, the using amount to mass ratio of the large-sheet-diameter graphene oxide crude product, the deionized water and the flocculant in the step S3 is 1:20: 0.01.
Further, the intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at the rotation speed of 150-;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and the glacial acetic acid into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 500-800r/min to prepare the intercalation agent.
Further, the dosage ratio of the phosphorus pentoxide and the toluene in the step A1 is 1g:10mL, the dosage ratio of the aluminum chloride and the dimethyl sulfoxide is 1g:10mL, and the dosage volume ratio of the phosphorus pentoxide solution, the aluminum chloride solution and the glacial acetic acid in the step A2 is 1:1: 2.
Further, the flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 2-4h at the rotation speed of 200-300r/min and the temperature of 120-130 ℃, filtering by using a 0.45-0.5 mu m microporous filter membrane, removing filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 70-80 ℃ to obtain the carbon oxide nano tube;
step B2: dispersing the oxidized carbon nano tube in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 2-3h under the condition that the rotating speed is 150-200r/min, adding 1, 3-propylene diamine and toluene, stirring for 5-10min at the temperature of 60-70 ℃, adding acetaldehyde for 1.5-2h under the condition that the temperature is 85-90 ℃, filtering to remove filtrate after the addition is finished, and drying a filter cake to prepare the modified carbon nano tube;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 3-5min at the rotation speed of 300r/min and the temperature of 60-70 ℃, dropwise adding a sodium hydroxide solution, heating to the temperature of 85-90 ℃, continuously stirring for 2-3h, cooling to room temperature, carrying out curing reaction for 20-25h, adding a modified carbon nanotube, carrying out ultrasonic treatment for 2-3h under the frequency of 8-10MHz, drying and grinding to powder under the temperature of 100 ℃ and 110 ℃ to obtain the flocculant.
Further, the using amount ratio of the carbon nanotube and the mixed acid in the step B1 is 1g:5mL, the mixed acid is composed of 98% by mass of concentrated sulfuric acid and 68% by mass of concentrated nitric acid in a volume ratio of 1:3, the using amount ratio of the oxidized carbon nanotube, the p-aminophenol, the 1-hydroxybenzotriazole, the 1, 3-propylenediamine, the toluene and the acetaldehyde in the step B2 is 5g:0.1mol:0.3g:0.1mol:30mL:0.65mol, the using amount ratio of the aluminum chloride, the ferric chloride, the deionized water, the sodium hydroxide solution and the modified carbon nanotube is 1g:0.9g:30mL:3mL:5g, and the concentration of the sodium hydroxide solution is 2 mol/L.
The invention has the beneficial effects that: the invention prepares an intercalator in the process of preparing large-sheet-diameter graphene oxide based on flaky graphene, the intercalator is prepared by taking phosphorus pentoxide, aluminum chloride and glacial acetic acid as raw materials, can well separate graphite blocks into graphene, simultaneously prevents graphene sheets from reuniting and stacking, further enables the large-sheet-diameter graphene oxide to be more stable and higher in yield, and also prepares a flocculating agent, the flocculating agent takes a carbon nano tube as a raw material to react with mixed acid, so that active hydroxyl on the surface of the carbon nano tube is converted into carboxyl to prepare a carbon nano tube oxide, then the carbon nano tube oxide and p-aminophenol are subjected to dehydration condensation under the action of 1-hydroxybenzotriazole, the carboxyl on the carbon nano tube oxide and amino on the p-aminophenol are subjected to polycondensation reaction with 1, 3-propylene diamine and acetaldehyde to prepare a modified carbon nano tube, the modified carbon nanotube surface molecules contain a large amount of nitrogen arc electrons, multiple adsorption sites can be formed, aluminum chloride and ferric chloride are treated simultaneously to prepare polyaluminum ferric chloride, and then the polyaluminum ferric chloride is subjected to ultrasonic treatment with the modified carbon nanotubes, so that the polyaluminum ferric chloride is polymerized and embedded in the surface of the modified carbon nanotubes to prepare the flocculant, the flocculant can rapidly form flocs from impurities in graphene, the sedimentation speed is high, the flocculant is easy to separate from water, the flocculant is less corrosive to equipment, and the prepared graphene oxide with large sheet diameter has better quality.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing large-flake-diameter graphene oxide based on flaky graphene specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 0 ℃, stirring for 0.5h at the rotation speed of 150r/min, adding an intercalating agent, continuously stirring for 1h, adding potassium permanganate, stirring for 3min at the rotation speed of 300r/min and the temperature of 10 ℃, and continuously stirring for 3h at the temperature of 35 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5h at the rotation speed of 200r/min and the temperature of 90 ℃, adding hydrogen peroxide, continuously stirring for 1h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1h under the condition of 5MHz, adding a flocculating agent, continuing ultrasonic treatment for 10min, centrifuging at the rotation speed of 8000r/min, removing precipitates, and distilling the supernatant to obtain the large-sheet-diameter graphene oxide.
The intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at a rotation speed of 150r/min to obtain a phosphorus pentoxide solution, adding aluminum chloride into dimethyl sulfoxide, and stirring at a rotation speed of 200r/min to obtain an aluminum chloride solution;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and glacial acetic acid into a stirring kettle, and stirring for 1h at the rotating speed of 500r/min to obtain the intercalator.
The flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 2 hours at the rotation speed of 200r/min and the temperature of 120 ℃, filtering by using a 0.45-micrometer microporous filter membrane to remove filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 70 ℃ to obtain an oxidized carbon nano tube;
step B2: dispersing oxidized carbon nano tubes in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 2 hours at the rotation speed of 150r/min, adding 1, 3-propylene diamine and toluene, stirring at the temperature of 60 ℃ for 5 minutes, adding acetaldehyde at the temperature of 85 ℃, adding for 1.5 hours, performing reflux reaction at the temperature of 130 ℃ for 3 hours after adding, filtering to remove filtrate, and drying filter cakes to obtain modified carbon nano tubes;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 3min at the rotation speed of 200r/min and the temperature of 60 ℃, dropwise adding a sodium hydroxide solution, heating to 85 ℃, continuously stirring for 2h, cooling to room temperature, carrying out curing reaction for 20h, adding modified carbon nanotubes, carrying out ultrasonic treatment for 2h at the frequency of 8MHz, drying and grinding to powder at the temperature of 100 ℃, and thus obtaining the flocculant.
Example 2
A method for preparing large-flake-diameter graphene oxide based on flaky graphene specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 0 ℃, stirring for 0.5h at the rotation speed of 200r/min, adding an intercalating agent, continuously stirring for 1.5h, adding potassium permanganate, stirring for 3min at the rotation speed of 300r/min and the temperature of 15 ℃, and continuously stirring for 3h at the temperature of 40 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 1h at the rotation speed of 300r/min and the temperature of 90 ℃, adding hydrogen peroxide, continuously stirring for 1h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1h under the condition of 8MHz, adding a flocculating agent, continuing the ultrasonic treatment for 15min, carrying out centrifugation under the condition of 8000r/min, removing precipitates, and distilling supernatant to obtain the large-sheet-diameter graphene oxide.
The intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at a rotation speed of 150r/min to obtain a phosphorus pentoxide solution, adding aluminum chloride into dimethyl sulfoxide, and stirring at a rotation speed of 300r/min to obtain an aluminum chloride solution;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and glacial acetic acid into a stirring kettle, and stirring for 1.5h under the condition that the rotating speed is 500r/min to prepare the intercalation agent.
The flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 2 hours at the rotation speed of 200r/min and the temperature of 130 ℃, filtering by using a 0.5-micron microporous filter membrane to remove filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 70 ℃ to obtain an oxidized carbon nano tube;
step B2: dispersing oxidized carbon nano tubes in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 2 hours at the rotation speed of 200r/min, adding 1, 3-propylene diamine and toluene, stirring at the temperature of 70 ℃ for 5 minutes, adding acetaldehyde at the temperature of 90 ℃, adding for 1.5 hours, performing reflux reaction at the temperature of 140 ℃ for 3 hours after adding, filtering to remove filtrate, and drying filter cakes to obtain modified carbon nano tubes;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 5min at the rotation speed of 300r/min and the temperature of 60 ℃, dropwise adding a sodium hydroxide solution, heating to 85 ℃, continuously stirring for 3h, cooling to room temperature, carrying out curing reaction for 20h, adding modified carbon nanotubes, carrying out ultrasonic treatment for 2h at the frequency of 10MHz, drying and grinding to powder at the temperature of 110 ℃, and thus obtaining the flocculant.
Example 3
A method for preparing large-flake-diameter graphene oxide based on flaky graphene specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 2 ℃, stirring for 1h at the rotation speed of 150r/min, adding an intercalator, continuously stirring for 1h, adding potassium permanganate, stirring for 5min at the rotation speed of 350r/min and the temperature of 10 ℃, and continuously stirring for 5h at the temperature of 35 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5h at the rotation speed of 200r/min and the temperature of 95 ℃, adding hydrogen peroxide, continuously stirring for 1.5h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1.5h under the condition of 5MHz, adding a flocculating agent, continuing ultrasonic treatment for 10min, centrifuging at the rotation speed of 8000r/min, removing precipitates, and distilling supernatant to obtain the large-sheet-diameter graphene oxide.
The intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at a rotation speed of 200r/min to obtain a phosphorus pentoxide solution, adding aluminum chloride into dimethyl sulfoxide, and stirring at a rotation speed of 200r/min to obtain an aluminum chloride solution;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and glacial acetic acid into a stirring kettle, and stirring for 1h at the rotating speed of 800r/min to obtain the intercalator.
The flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 4 hours at the rotation speed of 300r/min and the temperature of 120 ℃, filtering by using a 0.45-micron microporous filter membrane to remove filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 80 ℃ to obtain an oxidized carbon nano tube;
step B2: dispersing oxidized carbon nano tubes in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 3 hours at the rotation speed of 150r/min, adding 1, 3-propylene diamine and toluene, stirring at the temperature of 60 ℃ for 10 minutes, adding acetaldehyde at the temperature of 85 ℃, adding for 2 hours, after adding, carrying out reflux reaction at the temperature of 130 ℃ for 5 hours, filtering to remove filtrate, and drying filter cakes to obtain modified carbon nano tubes;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 3min at the rotation speed of 200r/min and the temperature of 70 ℃, dropwise adding a sodium hydroxide solution, heating to 90 ℃, continuously stirring for 2h, cooling to room temperature, carrying out curing reaction for 25h, adding modified carbon nanotubes, carrying out ultrasonic treatment for 3h at the frequency of 8MHz, drying and grinding to powder at the temperature of 100 ℃, and thus obtaining the flocculant.
Example 4
A method for preparing large-flake-diameter graphene oxide based on flaky graphene specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 2 ℃, stirring for 1h at the rotation speed of 200r/min, adding an intercalator, continuously stirring for 1.5h, adding potassium permanganate, stirring for 5min at the rotation speed of 350r/min and the temperature of 15 ℃, and continuously stirring for 5h at the temperature of 40 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 1h at the rotation speed of 300r/min and the temperature of 95 ℃, adding hydrogen peroxide, continuously stirring for 1.5h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1.5h under the condition of 8MHz, adding a flocculating agent, continuing ultrasonic treatment for 15min, centrifuging at the rotating speed of 8000r/min, removing precipitates, and distilling supernatant to obtain the large-sheet-diameter graphene oxide.
The intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at a rotation speed of 200r/min to obtain a phosphorus pentoxide solution, adding aluminum chloride into dimethyl sulfoxide, and stirring at a rotation speed of 300r/min to obtain an aluminum chloride solution;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and glacial acetic acid into a stirring kettle, and stirring for 1.5h at the rotating speed of 800r/min to obtain the intercalator.
The flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 4 hours at the rotation speed of 300r/min and the temperature of 130 ℃, filtering by using a 0.5-micron microporous filter membrane to remove filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 80 ℃ to obtain an oxidized carbon nano tube;
step B2: dispersing oxidized carbon nano tubes in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 3 hours at the rotation speed of 200r/min, adding 1, 3-propylene diamine and toluene, stirring at the temperature of 70 ℃ for 10 minutes, adding acetaldehyde at the temperature of 90 ℃, adding for 2 hours, performing reflux reaction at the temperature of 140 ℃ for 5 hours after adding, filtering to remove filtrate, and drying a filter cake to obtain modified carbon nano tubes;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 5min at the rotation speed of 300r/min and the temperature of 70 ℃, dropwise adding a sodium hydroxide solution, heating to 90 ℃, continuously stirring for 3h, cooling to room temperature, carrying out curing reaction for 25h, adding modified carbon nanotubes, carrying out ultrasonic treatment for 3h at the frequency of 10MHz, drying and grinding to powder at the temperature of 110 ℃, and thus obtaining the flocculant.
Comparative example 1
Compared with the embodiment 1, the comparative example uses no intercalation agent, and the specific steps are as follows:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 0 ℃, stirring for 0.5h at the rotation speed of 150r/min, adding potassium permanganate, stirring for 3min at the rotation speed of 300r/min and the temperature of 10 ℃, and continuously stirring for 3h at the temperature of 35 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5h at the rotation speed of 200r/min and the temperature of 90 ℃, adding hydrogen peroxide, continuously stirring for 1h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1h under the condition of 5MHz, adding a flocculating agent, continuing ultrasonic treatment for 10min, centrifuging at the rotation speed of 8000r/min, removing precipitates, and distilling the supernatant to obtain the large-sheet-diameter graphene oxide.
Comparative example 2
Compared with the example 1, the comparative example uses no flocculant and comprises the following specific steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid at the temperature of 0 ℃, stirring for 0.5h at the rotation speed of 150r/min, adding an intercalating agent, continuously stirring for 1h, adding potassium permanganate, stirring for 3min at the rotation speed of 300r/min and the temperature of 10 ℃, and continuously stirring for 3h at the temperature of 35 ℃ to prepare a pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5h at the rotation speed of 200r/min and the temperature of 90 ℃, adding hydrogen peroxide, continuously stirring for 1h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1h under the condition of 5MHz frequency, centrifuging at the rotating speed of 8000r/min, removing precipitates, and distilling supernatant to obtain the large-sheet-diameter graphene oxide.
Comparative example 3
The comparative example is common large-sheet-diameter graphene oxide in the market.
The performance test of the large-sheet-diameter graphene oxide prepared in examples 1 to 4 and comparative examples 1 to 3 was performed, and the test results are shown in table 1 below;
TABLE 1
From the above Table 1, the size of the large-diameter graphene oxide prepared in the embodiments 1-4 is 4452-4516cm3The graphene yield is 62.3-62.7%, while the large-sheet-diameter graphene oxide prepared in comparative example 1 has a size of 835 large-sheet-diameter graphene oxide of 40.2%, the large-sheet-diameter graphene oxide prepared in comparative example 2 has a size of 2385 large-sheet-diameter graphene oxide of 45.3%, and the large-sheet-diameter graphene oxide prepared in comparative example 3 has a size of 1083 large-sheet-diameter graphene oxide of 48.6%, which indicates that the large-sheet-diameter graphene oxide prepared by the method has higher yield and better quality.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. A method for preparing large-flake-diameter graphene oxide based on flaky graphene is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: adding crystalline flake graphite and sodium nitrate into a reaction kettle, adding concentrated sulfuric acid under the condition of temperature of 0-2 ℃, stirring for 0.5-1h under the condition of rotation speed of 150-200r/min, adding an intercalation agent, continuously stirring for 1-1.5h, adding potassium permanganate, stirring for 3-5min under the conditions of rotation speed of 300-350r/min and temperature of 10-15 ℃, and continuously stirring for 3-5h under the condition of temperature of 35-40 ℃ to prepare pre-oxidized graphene suspension;
step S2: adding deionized water into the pre-oxidized graphene suspension prepared in the step S1, stirring for 0.5-1h at the rotation speed of 200-300r/min and the temperature of 90-95 ℃, adding hydrogen peroxide, continuously stirring for 1-1.5h, filtering to remove filtrate, washing a filter cake with dilute hydrochloric acid, washing with deionized water until the pH value is 7, and drying to obtain a large-sheet-diameter oxidized graphene crude product;
step S3: adding the large-sheet-diameter graphene oxide crude product and deionized water into a reaction kettle, carrying out ultrasonic treatment for 1-1.5h under the condition of 5-8MHz, adding a flocculating agent, continuing ultrasonic treatment for 10-15min, centrifuging at the rotation speed of 8000r/min, removing precipitates, and distilling the supernatant to obtain the large-sheet-diameter graphene oxide.
2. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 1, wherein the method comprises the following steps: the dosage ratio of the crystalline flake graphite, the sodium nitrate, the concentrated sulfuric acid, the intercalation agent and the potassium permanganate in the step S1 is 1g to 0.5g to 25mL to 4g to 3g, and the mass fraction of the concentrated sulfuric acid is 98%.
3. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 1, wherein the method comprises the following steps: the volume ratio of the pre-oxidized graphene suspension, the deionized water and the hydrogen peroxide in the step S2 is 3:12:2, the mass fraction of the hydrogen peroxide is 30%, and the mass fraction of the dilute hydrochloric acid is 15%.
4. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 1, wherein the method comprises the following steps: the mass ratio of the large-sheet-diameter graphene oxide crude product, the deionized water and the flocculating agent in the step S3 is 1:20: 0.01.
5. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 1, wherein the method comprises the following steps: the intercalation agent is prepared by the following steps:
step A1: adding phosphorus pentoxide into toluene, stirring at the rotation speed of 150-;
step A2: adding the phosphorus pentoxide solution, the aluminum chloride solution and the glacial acetic acid into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 500-800r/min to prepare the intercalation agent.
6. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 5, wherein the method comprises the following steps: the dosage ratio of the phosphorus pentoxide and the toluene in the step A1 is 1g:10mL, the dosage ratio of the aluminum chloride and the dimethyl sulfoxide is 1g:10mL, and the dosage volume ratio of the phosphorus pentoxide solution, the aluminum chloride solution and the glacial acetic acid in the step A2 is 1:1: 2.
7. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 1, wherein the method comprises the following steps: the flocculant is prepared by the following steps:
step B1: adding a carbon nano tube and mixed acid into a reaction kettle, refluxing for 2-4h at the rotation speed of 200-300r/min and the temperature of 120-130 ℃, filtering by using a 0.45-0.5 mu m microporous filter membrane, removing filtrate, washing a filter cake by using deionized water until the pH value is 7, and drying at the temperature of 70-80 ℃ to obtain the carbon oxide nano tube;
step B2: dispersing the oxidized carbon nano tube in deionized water, adding p-aminophenol and 1-hydroxybenzotriazole, reacting for 2-3h under the condition that the rotating speed is 150-200r/min, adding 1, 3-propylene diamine and toluene, stirring for 5-10min at the temperature of 60-70 ℃, adding acetaldehyde for 1.5-2h under the condition that the temperature is 85-90 ℃, filtering to remove filtrate after the addition is finished, and drying a filter cake to prepare the modified carbon nano tube;
step B3: adding aluminum chloride, ferric chloride and deionized water into a reaction kettle, stirring for 3-5min at the rotation speed of 300r/min and the temperature of 60-70 ℃, dropwise adding a sodium hydroxide solution, heating to the temperature of 85-90 ℃, continuously stirring for 2-3h, cooling to room temperature, carrying out curing reaction for 20-25h, adding a modified carbon nanotube, carrying out ultrasonic treatment for 2-3h under the frequency of 8-10MHz, drying and grinding to powder under the temperature of 100 ℃ and 110 ℃ to obtain the flocculant.
8. The method for preparing graphene oxide with large flake diameter based on flaky graphene according to claim 7, wherein the method comprises the following steps: the using amount ratio of the carbon nano tube and the mixed acid in the step B1 is 1g:5mL, the mixed acid is composed of 98% by mass of concentrated sulfuric acid and 68% by mass of concentrated nitric acid in a volume ratio of 1:3, the using amount ratio of the oxidized carbon nano tube, the p-aminophenol, the 1-hydroxybenzotriazole, the 1, 3-propylene diamine, the toluene and the acetaldehyde in the step B2 is 5g:0.1mol:0.3g:0.1mol:30mL:0.65mol, the using amount ratio of the aluminum chloride, the ferric chloride, the deionized water, the sodium hydroxide solution and the modified carbon nano tube is 1g:0.9g:30mL:3mL:5g, and the concentration of the sodium hydroxide solution is 2 mol/L.
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