CN104477901A - Graphene and preparation method thereof - Google Patents
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Abstract
The invention provides a preparation method of graphene. The preparation method of graphene comprises the following steps: (A) mixing a metal catalyst with water to obtain a metal catalyst aqueous solution; (B) mixing a gel material with the metal catalyst aqueous solution obtained in the step (A), so as to obtain a hydrogel material adsorbed with the metal catalyst, wherein the gel material comprises one of or more than one of starch-type compound, cellulose type compound and synthesis resin; and (C) carrying out heat treatment on the hydrogel material which is adsorbed with the metal catalyst and obtained in the step (B) in presence of protective gas or in a vacuum environment, so as to obtain graphene. The preparation method of graphene has the advantages that the metal catalyst, instead of strong acid or strong base, is adopted for catalyzing, and pollution to the environment is extremely slight; meanwhile, the gel material is taken as a carbon source, a catalyst material can be uniformly dispersed in the gel material bulk phase, reaction efficiency is greatly improved, and cost is reduced.
Description
Technical field
The invention belongs to carbon material technical field, particularly relate to a kind of preparation method and Graphene of Graphene.
Background technology
Graphene (Graphene) is a kind of individual layer sheet structure be made up of carbon atom, and only has the two-dimensional material of a carbon atom thickness.Graphene has all shown excellent performance in a lot, and such as Graphene is almost completely transparent, and only absorb the light of 2.3%, its light transmission is very good; The thermal conductivity of Graphene up to 5300W/mK, higher than carbon nanotube and diamond; Electronic mobility under Graphene normal temperature is more than 15000cm
2/ Vs, higher than CNT (carbon nano-tube) and silicon crystal; The resistivity of Graphene only has 10
-6Ω cm, than copper or silver lower, be the minimum material of current resistivity; In addition Graphene is also current the hardest the thinnest material.Graphene is prepared into the application that powder is more conducive to Graphene, as grapheme material powder can be used as the additive of swelling agent material, improve electric property and the mechanical strength of swelling agent material, grapheme material powder has broad application prospects.
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 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.Oxidation-reduction method is prepared the with low cost of grapheme material powder and is easily realized, but can produce a large amount of waste water, causes severe contamination to environment.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and Graphene of Graphene, preparation method provided by the invention does not adopt strong acid or highly basic to be oxidized, but adopts metal catalyst to carbon source catalysis, and obtain Graphene, environmental pollution is less.
The invention provides a kind of preparation method of Graphene, comprise the following steps:
A) metal catalyst is mixed with water, obtain the aqueous solution of metal catalyst;
B) by gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins;
C) by described step B) hydrogel material being adsorbed with metal catalyst that obtains heat-treats under shielding gas atmosphere or vacuum environment, obtains Graphene.
Preferably, described starchy compounds comprises one or more in carboxymethylated starch, starch acrylonitrile graft multipolymer, starch-polyacrylic acid graft copolymer, starch grafted acrylate polymkeric substance, starch graft acrylamide polymkeric substance, starch-grafted styrene sulfonic acid polymers, starch-grafted vinyl sulfonate copolymers, starch sulphur ortho acid salt grafted propylene hydrochlorate and Starch-Acrylic acid-Acrylamide-MALEIC ANHYDRIDE graft copolymer;
Described cellulose compound comprises one or more in carboxymethylated cellulosic, cellulose graft acrylonitrile hydrolysis product, cellulose graft acrylate polymer, cellulose graft acrylamide polymer, Mierocrystalline cellulose sulphur ortho acid salt grafted propylene hydrochlorate and Mierocrystalline cellulose sulphur ortho acid acrylate.
Preferably, described synthetic resins comprises vinylformic acid and acrylamide copolymer, polyacrylate, polyacrylamide, polyvinyl lactam, polyvinyl alcohol, polyvinyl alcohol-acid anhydrides cross-linking copolymer, vinyl acetate-acrylic copolymer, polyoxyethylene system, acrylamide-acrylicacid salt crosslinking copolymerization thing, polyvinyl alcohol graft copolymerized vinylformic acid, polyacrylic acid-vinyl acetate between to for plastic, polyacrylic acid-vinyl cyanide, acrylate and vinyl acetate copolymerized, vinyl acetate between to for plastic-maleic anhydride copolymer, one or more in polyvinyl alcohol-acid anhydrides cross-linking copolymer and polyvinyl alcohol-acrylate copolymer.
Preferably, described metal catalyst comprises iron(ic) chloride, one or more in iron acetate, ferric sulfate, nickelous chloride, nickel acetate, single nickel salt.
Preferably, the mass ratio of described metal catalyst and described gel like material is 1:(5 ~ 50).
Preferably, described gel like material and described steps A) in mix water used with described metal catalyst mass ratio be 1:(5 ~ 200).
Preferably, described step C) in heat treated temperature be 600 ~ 1000 DEG C;
Described step C) in the heat treated time be 0.5 ~ 10 hour.
Preferably, described step B) specifically comprise:
By barrier agent, gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst;
Described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins;
Described barrier agent comprises inert metal salt.
Preferably, described step C) comprise following concrete steps:
By pore-forming material and described step B) hydrogel material being adsorbed with metal catalyst that obtains mixes, heat-treats, obtain Graphene under shielding gas atmosphere or vacuum environment.
The invention provides a kind of Graphene, make according to the preparation method described in technique scheme.
The invention provides a kind of preparation method of Graphene, comprise the following steps: A) metal catalyst is mixed with water, obtain the aqueous solution of metal catalyst; B) by gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins; C) by described step B) hydrogel material being adsorbed with metal catalyst that obtains heat-treats under shielding gas atmosphere or vacuum environment, obtains Graphene.Preparation method provided by the invention does not use strong acid or highly basic, but adopts metal catalyst to carry out catalysis, and environmental pollution is minimum; Further, preparation method provided by the invention is carbon source with gel like material, and gel like material occurs gel pore when swollen state between polymer chain, and small molecules can at gel pore internal diffusion.And then absorb the catalyzer be dissolved in the water in a large number, metal ion in solvent because the physisorption of gelatinous material focus on gelatinous material body mutually in, after oven dry, the adsorption of catalystic material physically based deformation is adsorbed on the three-dimensional framework of gelatinous material, and the gel like material that the present invention uses has the function of physical adsorption enrichment.Can make catalystic material be dispersed in gelatinous material body mutually in, improve reaction efficiency greatly, thus reduce costs.
In addition, preparation method provided by the invention is simple to operate, is easy to the suitability for industrialized production realizing Graphene.
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 SEM figure of the Graphene 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 2 obtains.
Embodiment
The invention provides a kind of preparation method of Graphene, comprise the following steps: A) metal catalyst is mixed with water, obtain the aqueous solution of metal catalyst; B) by gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins; C) by described step B) hydrogel material being adsorbed with metal catalyst that obtains heat-treats under shielding gas atmosphere or vacuum environment, obtains Graphene.
Preparation method provided by the invention pollutes very little, and reaction efficiency is high, and cost is low.
Metal catalyst mixes with water by the present invention, obtain the aqueous solution of metal catalyst, in the present invention, described metal catalyst preferably includes iron(ic) chloride, one or more in iron acetate, ferric sulfate, nickelous chloride, nickel acetate, single nickel salt, more preferably comprise one or more in nickel acetate, ferric sulfate, single nickel salt and iron(ic) chloride; The mass concentration of described metal catalyst solution is preferably 0.001 ~ 0.1g/mL, is more preferably 0.002 ~ 0.05g/mL; The described water mixed with metal catalyst and gelatinous material is preferably deionized water.
After obtaining the aqueous solution of metal catalyst, the present invention, by the aqueous solution of gel like material and described metal catalyst, obtains the hydrogel material being adsorbed with metal catalyst.In the present invention, described gel like material comprises starchy compounds, one or more in cellulose compound and synthetic resins, described starchy compounds preferably includes carboxymethylated starch, starch acrylonitrile graft multipolymer, starch-polyacrylic acid graft copolymer, starch grafted acrylate polymkeric substance, starch graft acrylamide polymkeric substance, starch-grafted styrene sulfonic acid polymers, starch-grafted vinyl sulfonate copolymers, one or more in starch sulphur ortho acid salt grafted propylene hydrochlorate and Starch-Acrylic acid-Acrylamide-MALEIC ANHYDRIDE graft copolymer, more preferably carboxymethylated starch is comprised, starch-grafted styrene sulfonic acid polymers, one or more in starch-polyacrylic acid graft copolymer and starch acrylonitrile graft multipolymer.
In the present invention, described cellulose compound preferably includes one or more in carboxymethylated cellulosic, cellulose graft acrylonitrile hydrolysis product, cellulose graft acrylate polymer, cellulose graft acrylamide polymer, Mierocrystalline cellulose sulphur ortho acid salt grafted propylene hydrochlorate and Mierocrystalline cellulose sulphur ortho acid acrylate, more preferably comprises one or more in carboxymethylated cellulosic, cellulose graft acrylonitrile hydrolysis product and Mierocrystalline cellulose sulphur ortho acid salt grafted propylene hydrochlorate.
In the present invention, described synthetic resins preferably includes vinylformic acid and acrylamide copolymer, polyacrylate, polyacrylamide, polyvinyl lactam, polyvinyl alcohol, polyvinyl alcohol-acid anhydrides cross-linking copolymer, vinyl acetate-acrylic copolymer, polyoxyethylene system, acrylamide-acrylicacid salt crosslinking copolymerization thing, polyvinyl alcohol graft copolymerized vinylformic acid, polyacrylic acid-vinyl acetate between to for plastic, polyacrylic acid-vinyl cyanide, acrylate and vinyl acetate copolymerized, vinyl acetate between to for plastic-maleic anhydride copolymer, one or more in polyvinyl alcohol-acid anhydrides cross-linking copolymer and polyvinyl alcohol-acrylate copolymer, more preferably vinylformic acid and acrylamide copolymer is comprised, polyacrylamide, polyvinyl lactam, one or more in polyvinyl alcohol-acid anhydrides cross-linking copolymer and polyvinyl alcohol-acrylate copolymer.
In the present invention, described metal catalyst and described gel like material mass ratio be preferably 1:(5 ~ 50), be more preferably 1:(10 ~ 45), be more preferably 1:(15 ~ 40); Described gel like material is preferably 1:(5 ~ 100 with the described mass ratio mixing water used with metal catalyst), be more preferably 1:(10 ~ 50).Water content is too high, and the RESEARCH OF PYROCARBON that in the process of heating, water vapour meeting and catalysis produce reacts and generates carbon monoxide and hydrogen, and affect the yield of final product, water content is too low, metal catalyst can be made to adsorb uneven, affect the effect of catalysis.
Reunite to prevent from producing in graphene growth process, the present invention preferably by the aqueous solution of barrier agent, gel like material and described metal catalyst, obtains the hydrogel material being adsorbed with metal catalyst.In the present invention, described barrier agent preferably includes inert metal salt, more preferably comprises calcium chloride, Repone K, sodium-chlor, magnesium chloride, one or more in potassium sulfate, sodium sulfate and magnesium sulfate, most preferably comprise one or more in calcium chloride, sodium-chlor, sulphate of potash and magesium; The mass ratio of described barrier agent and gel like material is preferably 1:(0.5 ~ 100), be more preferably 1:(5 ~ 50), most preferably be 1:(10 ~ 30).
To described metal catalyst and gel like material, the mixing time in water does not have special restriction in the present invention, and solution all absorbs by described gel like material.
After obtaining being adsorbed with the hydrogel material of metal catalyst, the described hydrogel material being adsorbed with metal catalyst is heat-treated by the present invention under shielding gas atmosphere or vacuum environment, obtains Graphene.In order to make the Graphene obtained have better pore structure, pore-forming material preferably mixes with the described hydrogel material being adsorbed with metal catalyst by the present invention, heat-treats, obtain Graphene under under shielding gas atmosphere or vacuum environment.In the present invention, described shielding gas is preferably rare gas element and/or nitrogen; Described pore-forming material preferably includes one or more in potassium hydroxide, calcium hydroxide, zinc chloride, phosphoric acid and sodium hydroxide, more preferably comprises potassium hydroxide and/or calcium hydroxide; The mass ratio of described pore-forming material and described gel like material is preferably (5 ~ 50): 1, is more preferably (10 ~ 45): 1, most preferably is (15 ~ 40): 1.
In the present invention, described heat treated temperature is preferably 600 ~ 1000 DEG C, is more preferably 700 ~ 900 DEG C, most preferably is 800 ~ 850 DEG C; The described heat treated time is preferably 0.5 ~ 10 hour, is more preferably 1 ~ 9 hour, most preferably is 2 ~ 8 hours.
After completing described thermal treatment, the product that thermal treatment preferably obtains by the present invention carries out pickling and washing successively, to remove metal-salt residual in Graphene.Described pickling acid solution used preferably includes one or more in hydrochloric acid, sulfuric acid and nitric acid; Described washing water used is preferably deionized water; In the present invention, described pickling and washing are method well known to those skilled in the art.
After completing described pickling, the product after pickling is preferably dried by the present invention, obtains Graphene.In the present invention, the temperature of described oven dry is preferably 40 ~ 100 DEG C, is more preferably 50 ~ 90 DEG C, most preferably is 60 ~ 80 DEG C; The present invention does not have special restriction the time to described oven dry, is all removed by moisture.
Present invention also offers a kind of Graphene, prepare according to the preparation method described in technique scheme.
The invention provides a kind of preparation method of Graphene, comprise the following steps: A) metal catalyst is mixed with water, obtain the aqueous solution of metal catalyst; B) by gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins; C) by described step B) hydrogel material being adsorbed with metal catalyst that obtains heat-treats under shielding gas atmosphere or vacuum environment, obtains Graphene.Preparation method provided by the invention does not use strong acid or highly basic, but adopts metal catalyst to carry out catalysis, and environmental pollution is minimum; Further, preparation method provided by the invention is carbon source with gel like material, and gel like material occurs gel pore when swollen state between polymer chain, and small molecules can at gel pore internal diffusion.And then absorb the catalyzer be dissolved in the water in a large number, metal ion in solvent because the physisorption of gelatinous material focus on gelatinous material body mutually in, after oven dry, the adsorption of catalystic material physically based deformation is adsorbed on the three-dimensional framework of gelatinous material, and the gel like material that the present invention uses has the function of physical adsorption enrichment.Can make catalystic material be dispersed in gelatinous material body mutually in, improve reaction efficiency greatly, thus reduce costs.
In addition, preparation method provided by the invention is simple to operate, be easy to the suitability for industrialized production realizing Graphene, and specific productivity is higher, is 20 ~ 50%.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of a kind of Graphene provided by the invention and Graphene being described in detail, but can not limiting the scope of the present invention being understood as.
Embodiment 1
1g nickelous chloride is dissolved in 500ml deionized water, after starch-grafted for 20g styrene sulfonic acid polymers is mixed with above-mentioned solution, in a nitrogen atmosphere, 600 DEG C of process 1h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene, specific productivity is 50%.
The Graphene that the present embodiment obtains by the present invention has carried out scanning electron microscope (SEM) and has detected, and as shown in Figure 1, Fig. 1 is the SEM figure of the Graphene that the embodiment of the present invention 1 obtains to result.As seen from Figure 1, the Graphene that the embodiment of the present invention 1 obtains is mainly three-dimensional drape laminated structure.
Embodiment 2
Be dissolved in by 1g iron(ic) chloride in 500ml deionized water, after being mixed with above-mentioned solution by 5g carboxymethylated starch, in a nitrogen atmosphere, 900 DEG C of process 1h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene, specific productivity is 35%.
The Graphene that the present embodiment obtains by the present invention has carried out scanning electron microscope (SEM) and has detected, and as shown in Figure 2, Fig. 2 is the SEM figure of the Graphene that the embodiment of the present invention 2 obtains to result.As seen from Figure 2, the Graphene that the embodiment of the present invention 2 obtains is mainly three-dimensional drape laminated structure.
Embodiment 3
1g single nickel salt is dissolved in 500ml deionized water, after 50g starch-polyacrylic acid graft copolymer is mixed with above-mentioned solution, in a nitrogen atmosphere, 800 DEG C of process 0.5h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene, specific productivity is 20%.
Embodiment 4
By 1g ferric sulfate solution in 500ml deionized water, after 10g starch acrylonitrile graft multipolymer is mixed with above-mentioned solution, in a nitrogen atmosphere, 1000 DEG C of process 2h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene, specific productivity is 45%.
Embodiment 5
1g iron acetate and 20g Repone K are dissolved in 500ml deionized water, after 10g carboxymethylated cellulosic is mixed with above-mentioned solution, in a nitrogen atmosphere, 1000 DEG C of process 2h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene, specific productivity is 25%.
Embodiment 6
1g ferric sulfate and 10g sodium-chlor are dissolved in 500ml deionized water, after 10g cellulose graft acrylonitrile hydrolysis product is mixed with above-mentioned solution, in a nitrogen atmosphere, 900 DEG C of process 10h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene.
Embodiment 7
1g nickelous chloride and 1g magnesium chloride are dissolved in 1000ml deionized water, after 20g cellulose graft acrylamide polymer is mixed with above-mentioned solution, in a nitrogen atmosphere, 600 DEG C of process 1h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene.
Embodiment 8
1g single nickel salt and 0.1g cupric chloride are dissolved in 500ml deionized water, after 10g Mierocrystalline cellulose sulphur ortho acid salt grafted propylene hydrochlorate is mixed with above-mentioned solution, in a nitrogen atmosphere, 1000 DEG C of process 0.5h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene.
Embodiment 9
1g single nickel salt is dissolved in 500ml deionized water, after 10g vinylformic acid is mixed with above-mentioned solution with acrylamide copolymer, mixes with 50g potassium hydroxide, then in a nitrogen atmosphere, 1000 DEG C of process 0.5h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 10
1g nickelous chloride is dissolved in 200ml deionized water, after 1g polyacrylamide is mixed with above-mentioned solution, mixes with 50g potassium hydroxide, then in a nitrogen atmosphere, 800 DEG C of process 1h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 11
By 1g ferric sulfate solution in 200ml deionized water, after 1g polyvinyl lactam is mixed with above-mentioned solution, mix with 25g potassium hydroxide, then in a nitrogen atmosphere, 1000 DEG C of process 0.5h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 12
By 1g ferric sulfate solution in 200ml deionized water, after 1g polyvinyl alcohol-acid anhydrides cross-linking copolymer is mixed with above-mentioned solution, mix with 40g potassium hydroxide, then in a nitrogen atmosphere, 800 DEG C of process 5h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 13
1g ferric sulfate and 10g sodium-chlor are dissolved in 500ml deionized water, after 10g cellulose graft acrylonitrile hydrolysis product is mixed with above-mentioned solution, mix with 50g potassium hydroxide, in a nitrogen atmosphere, 900 DEG C of process 10h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene.
Embodiment 14
1g ferric sulfate and 10g sodium-chlor are dissolved in 100ml deionized water, after 1g carboxymethylated cellulosic is mixed with above-mentioned solution, mix with 25g potassium hydroxide, in a nitrogen atmosphere, 900 DEG C of process 10h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 15
1g single nickel salt and 10g sodium-chlor are dissolved in 100ml deionized water, after 1g starch acrylonitrile graft multipolymer is mixed with above-mentioned solution, mix with 20g zinc chloride, in a nitrogen atmosphere, 900 DEG C of process 10h, then use dilute hydrochloric acid and washed with de-ionized water post-drying successively, obtain Graphene by product.
Embodiment 16
1g single nickel salt and 10g cupric chloride are dissolved in 100ml deionized water, after 1g polyvinyl alcohol-acrylate copolymer is mixed with above-mentioned solution, mix with 15g zinc chloride, in a nitrogen atmosphere, 600 DEG C of process 5h, then product is used successively dilute hydrochloric acid and washed with de-ionized water post-drying, obtain Graphene.
As can be seen from the above embodiments, preparation method provided by the invention can obtain the Graphene of high-quality, and environmentally safe, reaction efficiency is high, cost is low.
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) metal catalyst is mixed with water, obtain the aqueous solution of metal catalyst;
B) by gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst, described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins;
C) by described step B) hydrogel material being adsorbed with metal catalyst that obtains heat-treats under shielding gas atmosphere or vacuum environment, obtains Graphene.
2. preparation method according to claim 1, it is characterized in that, described starchy compounds comprises one or more in carboxymethylated starch, starch acrylonitrile graft multipolymer, starch-polyacrylic acid graft copolymer, starch grafted acrylate polymkeric substance, starch graft acrylamide polymkeric substance, starch-grafted styrene sulfonic acid polymers, starch-grafted vinyl sulfonate copolymers, starch sulphur ortho acid salt grafted propylene hydrochlorate and Starch-Acrylic acid-Acrylamide-MALEIC ANHYDRIDE graft copolymer;
Described cellulose compound comprises one or more in carboxymethylated cellulosic, cellulose graft acrylonitrile hydrolysis product, cellulose graft acrylate polymer, cellulose graft acrylamide polymer, Mierocrystalline cellulose sulphur ortho acid salt grafted propylene hydrochlorate and Mierocrystalline cellulose sulphur ortho acid acrylate.
3. preparation method according to claim 1, it is characterized in that, described synthetic resins comprises vinylformic acid and acrylamide copolymer, polyacrylate, polyacrylamide, polyvinyl lactam, polyvinyl alcohol, polyvinyl alcohol-acid anhydrides cross-linking copolymer, vinyl acetate-acrylic copolymer, polyoxyethylene system, acrylamide-acrylicacid salt crosslinking copolymerization thing, polyvinyl alcohol graft copolymerized vinylformic acid, polyacrylic acid-vinyl acetate between to for plastic, polyacrylic acid-vinyl cyanide, acrylate and vinyl acetate copolymerized, vinyl acetate between to for plastic-maleic anhydride copolymer, one or more in polyvinyl alcohol-acid anhydrides cross-linking copolymer and polyvinyl alcohol-acrylate copolymer.
4. preparation method according to claim 1, is characterized in that, described metal catalyst comprises iron(ic) chloride, one or more in iron acetate, ferric sulfate, nickelous chloride, nickel acetate, single nickel salt.
5. preparation method according to claim 1, is characterized in that, the mass ratio of described metal catalyst and described gel like material is 1:(5 ~ 50).
6. preparation method according to claim 1, is characterized in that, described gel like material and described steps A) in mix water used with described metal catalyst mass ratio be 1:(5 ~ 200).
7. preparation method according to claim 1, is characterized in that, described step C) in heat treated temperature be 600 ~ 1000 DEG C;
Described step C) in the heat treated time be 0.5 ~ 10 hour.
8. the preparation method according to claim 1 ~ 7 any one, is characterized in that, described step B) specifically comprise:
By barrier agent, gel like material and described steps A) aqueous solution of metal catalyst that obtains, obtain the hydrogel material being adsorbed with metal catalyst;
Described gel like material comprises one or more in starchy compounds, cellulose compound and synthetic resins;
Described barrier agent comprises inert metal salt.
9. the preparation method according to claim 1 ~ 7 any one, is characterized in that, described step C) comprise following concrete steps:
By pore-forming material and described step B) hydrogel material being adsorbed with metal catalyst that obtains mixes, heat-treats, obtain Graphene.
10. a Graphene, makes according to the preparation method described in claim 1 ~ 9 any one.
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| CN105967173B (en) * | 2016-05-06 | 2018-03-30 | 清华大学深圳研究生院 | A kind of Graphene electrodes material of ampuliform hole shape and preparation method thereof |
| CN107500270A (en) * | 2016-06-13 | 2017-12-22 | 郑贵林 | A kind of graphene and preparation method thereof |
| CN111180681A (en) * | 2018-11-12 | 2020-05-19 | 天津师范大学 | High-load lithium-sulfur positive electrode material and preparation method and application thereof |
| CN111180681B (en) * | 2018-11-12 | 2021-06-29 | 天津师范大学 | High-capacity lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN109433154A (en) * | 2018-11-26 | 2019-03-08 | 中国科学院生态环境研究中心 | Three-dimensional netted graphene aerogel, preparation method and its application |
| CN109529888A (en) * | 2018-11-26 | 2019-03-29 | 中国科学院生态环境研究中心 | The heterogeneous fenton catalyst of three-dimensional graphite alkenyl, preparation method and its application |
| CN109529888B (en) * | 2018-11-26 | 2020-10-20 | 中国科学院生态环境研究中心 | Three-dimensional graphene-based heterogeneous Fenton catalyst, and preparation method and application thereof |
| CN116062742A (en) * | 2023-04-06 | 2023-05-05 | 北京航空航天大学 | Preparation method of metal ion crosslinked nano film |
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