CN102926272A - Process for preparing biomedical graphene oxide paper - Google Patents
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- CN102926272A CN102926272A CN2012104347765A CN201210434776A CN102926272A CN 102926272 A CN102926272 A CN 102926272A CN 2012104347765 A CN2012104347765 A CN 2012104347765A CN 201210434776 A CN201210434776 A CN 201210434776A CN 102926272 A CN102926272 A CN 102926272A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000003814 drug Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 229940079593 drug Drugs 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 8
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical group II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000153 Povidone-iodine Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229960001621 povidone-iodine Drugs 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229960000479 ceftriaxone sodium Drugs 0.000 claims description 4
- FDRNWTJTHBSPMW-GNXCPKRQSA-L disodium;(6r,7r)-7-[[(2e)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-3-[(2-methyl-6-oxido-5-oxo-1,2,4-triazin-3-yl)sulfanylmethyl]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound [Na+].[Na+].S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)/C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C([O-])=NN1C FDRNWTJTHBSPMW-GNXCPKRQSA-L 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229940098465 tincture Drugs 0.000 claims description 4
- 239000009306 yunnan baiyao Substances 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 206010072170 Skin wound Diseases 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000029663 wound healing Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000007794 irritation Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 206010052428 Wound Diseases 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a process for preparing biomedical graphene oxide paper and belongs to the field of biomedical materials. According to the process, a graphene oxide bought from market serves as a raw material, and a product is obtained through ultrasonic oscillating dispersion, solid-liquid separation and drug loading. The biomedical graphene oxide paper prepared by the process has the advantages of being controllable in thickness, large in specific surface area, abundant in pore structure, good in adsorptivity, strength and flexibility, free from toxicity and bacteria, free from irritation on human bodies and cohesiveness on skin wounds, environment-friendly and the like. The process is simple in technology, convenient to operate, low in production cost, beneficial to popularization and application and the like. The product prepared by the process can be widely applied to medical external application materials which are used for treating skin wounds (such as burns), promoting wound healing and the like, and the product can also be used for electrode materials of super-capacitors and environmental protection materials for adsorption, purification and the like.
Description
Technical field
The invention belongs to the bio-medical material technical field, be specifically related to the preparation method of outer compress material bio-medical graphene oxide paper.
Background technology
Graphene (Graphene) refers to the graphite of a carbon (C) atomic layer level thickness, between the carbon-to-carbon by sp
2The covalent bond link is the netted aspect of hexagon, is considered to the basic structural unit of fullerene, CNT and graphite.Graphene paper is the material that is the paper shape on the macroscopic view that is formed by the Graphene self assembly.Have the characteristics such as high strength, quality is light, absorption property is excellent.The outer compress material of tradition comprises gauze, bandage etc., although characteristics, the so far still extensive use in various types of wounds such as they have water imbibition and heat insulating ability is good, heat resistance and alkali resistance are better.But owing to after their absorb wound exudate, often can cause wound infection because secretion oozes out to pollute, and easy adhesion wound etc. when removing outer compress material.For solve the outer compress material adhesion wound of tradition, not every bacterium, the shortcoming such as insulating power is poor and hemostasis, blood coagulation be bad, people adopt the whole bag of tricks to improve the performance of the outer compress material of this class, such as dipping, coating and chemistry or physical modification method, but effect is all undesirable.Carbon-based material is because the characteristics such as good absorption property, nontoxic aseptic, heat resistance are subject to people's extensive concern, Graphene as a kind of of carbon-based material since its excellent characteristic be considered to have wide practical use in this respect.
Existing medical graphite alkene material preparation method, it is the patent of 201110063663.4 " bacterial cellulose/graphene composite material and preparation method thereof " such as application number, disclosed method is: at first prepare moistening bacteria cellulose product, again Graphene pulverized, stirred and make graphene dispersing solution, then graphene dispersing solution and bacteria cellulose are mixed, prepare bacterial cellulose/graphene composite material by Separation of Solid and Liquid again.The major defect of the method is: process conditions are complicated, and are consuming time long, and single with the compound types of drugs of Graphene, are not suitable with the requirement of large-scale production.And for example application number is the patent of 95115437.0 " method of using expansion graphite as wound auxiliary material ", disclosed method is: at first prepare the expanded graphite pulvis, hybrid medicine in the graphite pulvis applies this mixing powder at hospital gauze or carbon fiber surface at last and is pressed into band-type product again.The major defect of the method is: only be to apply to cause drug powder easily to come off on the surface to cause medical value to reduce with expanded graphite only take normal gauze as main body, easily with the skin wound bonding and cause patient's misery, that fails to take full advantage of Graphene enriches pore structure and the advantages such as high strength, pliability.
Summary of the invention
The object of the invention is to the deficiency for existing bio-medical grapheme material, a kind of preparation method of bio-medical graphene oxide paper is provided, has thickness controlled, specific area is large, pore structure is abundant, strong to the body fluid adsorptivity, intensity is high, pliability good, with the skin wound no adhesion, the characteristic such as can be recycled; It is simple, easy to operate that the method has technique, and production cost is low, be suitable for the advantages such as large-scale production.
The technical scheme that realizes the object of the invention is: a kind of preparation method of bio-medical graphene oxide paper as raw material, obtains product through sonic oscillation dispersion, Separation of Solid and Liquid, drug loading with commercial graphene oxide.The concrete steps of described method are as follows:
(1) sonic oscillation disperses
Take commercial graphene oxide as raw material, quality (g) according to graphene oxide: the quality of auxiliary material (g): the ratio of the volume of solvent (ml) is 1: 0～1: 20～100 ratio, graphene oxide and auxiliary material are joined in the solvent, after stirring, be under 150～500W in hyperacoustic power output, carry out sonic oscillation and disperseed 30～120 minutes, just obtain the dispersion mixed liquor of graphene oxide and auxiliary material.
Wherein: described solvent is absolute ethyl alcohol or deionized water etc.;
Described auxiliary material is CNT or activated carbon fiber or carbon fiber or carbon nano-fiber etc.
(2) Separation of Solid and Liquid
(1) step with (1) graphene oxide that makes of step and the dispersion mixed liquor of auxiliary material, adopted 100～300ml to carry out Separation of Solid and Liquid with the vacuum filtration instrument of filter membrane after finishing, and collected respectively parting liquid (being solvent) and solid residue.The parting liquid (being solvent) of collecting is carried out recycling.
Wherein: the nylon leaching film of described filter membrane or teflon membrane filter etc.
(3) drug loading
(2) step finish after, the solid residue of collecting in (2) step uniformly sprays medicament (being Povidone-Iodine Solution or PVP-I or the tincture of iodine) or spraying medicine (being Yunnan Baiyao or ceftriaxone sodium) and obtains the solid residue that load has medicine, then the solid residue that load is had medicine, drying is 0.5～2 hour under temperature is 40～80 ℃, just obtains bio-medical graphene oxide paper.
Wherein: described medicament is povidone-iodine or Povidone-Iodine Solution or the tincture of iodine, and medicine is Yunnan Baiyao or or ceftriaxone sodium.
After the present invention adopts technique scheme, have following effect:
(1) the inventive method prepare bio-medical graphene oxide paper nontoxic aseptic, strong to human body nonirritant, absorption property, can not cause adhesion to be conducive to skin wound healing with skin wound.
(2) the inventive method prepare bio-medical graphene oxide paper thickness between 0.5～3mm, the aperture mainly is distributed between 6～50nm, specific area arrives greatly 100m
2More than/the g, have good pore structure and distribute and absorption property.The fibrous auxiliary material that is evenly distributed simultaneously is mechanical property well, can its mechanical strength of Effective Raise and pliability.
(3) the inventive method adopts sonic oscillation dispersion and Separation of Solid and Liquid and drying etc., need not high-temperature process, and energy consumption is low.
(4) the inventive method need not catalyst, can also recycling to the solvent in the production process, without " three wastes " discharging, belong to recycling economy, and this can reduce production costs, and is conducive to again environmental protection.
(5) technique of the present invention is simple, and is easy to operate, and production equipment is few, thereby further reduce cost, easy to utilize, is suitable for large-scale production.
The bio-medical graphene oxide paper that adopts the inventive method to prepare, the medical external dressing material that can be widely used in treatment skin trauma (such as burn) and promotion wound healing etc. also can be used for environmental protection material and the electrode material for super capacitor such as absorption, purification.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the present embodiment 1 bio-medical graphene oxide paper,
Among the figure: 1 is carrying medicament, and 2 is the graphene oxide lamella, and 3 is activated carbon fiber.
The specific embodiment
Below in conjunction with the specific embodiment, further specify the present invention.
The concrete steps of a kind of bio-medical graphene oxide Preparation Method made of paper are as follows:
(1) sonic oscillation disperses
Quality (g) according to graphene oxide: the quality of auxiliary material (g): the volume of solvent (ml) is than the ratio that is 1: 0.5: 50, graphene oxide and auxiliary material are put into solvent, after stirring, be under the 500W at the ultrasonic wave output frequency, carry out sonic oscillation and disperseed 60 minutes, obtain the dispersion mixed liquor of graphene oxide and auxiliary material.
Wherein: described auxiliary material is activated carbon fiber;
Described solvent is absolute ethyl alcohol.
(2) Separation of Solid and Liquid
(1) step finish after, adopt 200ml with the vacuum filtration instrument of teflon membrane filter, (1) graphene oxide prepared of step and the dispersion mixed liquor of auxiliary material activated carbon fiber are carried out Separation of Solid and Liquid, collect respectively parting liquid (being anhydrous ethanol solvent) and solid residue, the parting liquid (being anhydrous ethanol solvent) of collecting is carried out recycling.
(3) drug loading
(2) step finish after, spray uniformly medicine Yunnan Baiyao on the surface of the solid residue of collecting in (2) step, just obtaining load has the solid residue of medicine, then the solid residue that load is had medicine, drying is 60 minutes under temperature 60 C, just prepares bio-medical graphene oxide paper.
A kind of bio-medical graphene oxide Preparation Method made of paper is with embodiment 1, wherein:
In (1) step, the quality of graphene oxide (g): the quality of auxiliary material (g): the volume of solvent (ml) is than being 1: 1: 100, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 120 minutes.
Wherein: described auxiliary material is CNT;
Described solvent is deionized water.
In (2) step, the mixed liquor that adopts 300ml with the vacuum filtration instrument of nylon leaching film (1) step to be prepared carries out Separation of Solid and Liquid.
In (3) step, uniformly spray the medicament tincture of iodine on (2) surface that goes on foot the solid residue of collecting, just obtain the solid residue that load has medicine, wherein: drying is 120 minutes under temperature is 80 ℃.
A kind of bio-medical graphene oxide Preparation Method made of paper is with embodiment 1, wherein:
In (1) step, the quality of graphene oxide (g): the quality of auxiliary material (g): the volume of solvent (ml) is than being 1: 0: 20, and ultrasonic frequency is 150W, and the ultrasonic Separation time is 80 minutes.
Wherein: described auxiliary material is CNT;
Described solvent is deionized water.
In (2) step, the mixed liquor that adopts graphene oxide that 100ml prepared for (1) step with the vacuum filtration instrument of teflon membrane filter and auxiliary material to disperse carries out Separation of Solid and Liquid.
In (3) step, uniformly spray the medicament Povidone-Iodine Solution on (2) surface that goes on foot the solid residue of collecting, wherein: drying is 30 minutes under temperature is 100 ℃.
Embodiment 4
A kind of bio-medical graphene oxide Preparation Method made of paper is with embodiment 1, wherein:
In (1) step, the quality of graphene oxide (g): the quality of auxiliary material (g): the volume of solvent (ml) is than being 1: 0.2: 20, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 30 minutes.
Wherein: described auxiliary material is carbon nano-fiber;
Described solvent is deionized water.
In (2) step, the mixed liquor that adopts 150ml with the vacuum filtration instrument of nylon leaching film (1) step to be prepared carries out Separation of Solid and Liquid.
In (3) step, the surface of the solid residue of collecting in (2) step uniformly sprays the poly-iodine dimension of medicament ketone, wherein: temperature be 40 ℃ lower dry 60 minutes.
Embodiment 5
A kind of bio-medical graphene oxide Preparation Method made of paper is with embodiment 1, wherein:
In (1) step, the quality of graphene oxide (g): the quality of auxiliary material (g): the volume of solvent (ml) is than being 1: 0.5: 100, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 120 minutes.
Wherein: described auxiliary material is carbon fiber;
Described solvent is absolute ethyl alcohol.
In (2) step, the mixed liquor that adopts 200ml with the vacuum filtration instrument of teflon membrane filter (1) step to be prepared carries out Separation of Solid and Liquid.
In (3) step, spray uniformly the medicine ceftriaxone sodium on the surface of the solid residue of collecting in (2) step, wherein: temperature be 60 ℃ lower dry 60 minutes.
Result of the test
The bio-medical graphene oxide paper that embodiment 1 is prepared carries out scanning electron microscopic observation, specific area and pore Structure Analysis, absorption property test, and its stereoscan photograph as shown in Figure 1.
From test result analysis as can be known, by the graphene-based paper of bio-medical of embodiment 1 gained, thickness is about 3mm, and the B.E.T. specific area is 158.88m
2/ g; Average pore size is 25.83nm, and the aperture mainly is distributed between the 10-50nm, good adsorption performance.
Claims (2)
1. the preparation method of a bio-medical graphene oxide paper is characterized in that the concrete steps of described method are as follows:
(1) sonic oscillation disperses
Take commercial graphene oxide as raw material, quality according to graphene oxide: the quality of auxiliary material: the ratio of the volume of solvent is the ratio of 1g: 0～1g: 20～10ml, graphene oxide and auxiliary material are joined in the solvent, after stirring, be under 150～500W in hyperacoustic power output, carry out that sonic oscillation disperseed 30～120 minutes and the dispersion mixed liquor that just obtains graphene oxide and auxiliary material; (2) Separation of Solid and Liquid
(1) step with (1) graphene oxide that makes of step and the dispersion mixed liquor of auxiliary material, adopted 100～300ml to carry out Separation of Solid and Liquid with the vacuum filtration instrument of filter membrane after finishing, and collected respectively parting liquid and solid residue;
(3) drug loading
(2) step finish after, on the solid residue of (2) step collection, evenly spray medicament or spraying medicine and obtain the solid residue that load has medicine, then the solid residue that load is had medicine, drying is 0.5～2 hour under temperature is 40～80 ℃, just obtains bio-medical graphene oxide paper.
2. according to the preparation method of a kind of bio-medical graphene oxide paper claimed in claim 1, it is characterized in that:
Described solvent is absolute ethyl alcohol or deionized water;
Described auxiliary material is CNT or activated carbon fiber or carbon fiber or carbon nano-fiber;
Described filter membrane is nylon leaching film or teflon membrane filter;
Described medicament is povidone-iodine or Povidone-Iodine Solution or the tincture of iodine, and medicine is Yunnan Baiyao or or ceftriaxone sodium.
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Cited By (9)
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| CN103449421A (en) * | 2013-08-23 | 2013-12-18 | 上海第二工业大学 | Preparation method of heat conduction and insulation graphene oxide paper |
| CN103482620A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Graphene oxide or reduced graphene base mesh material and preparation method thereof |
| CN103482621A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Oxidized or deoxidated graphene-based macro material and preparing method thereof |
| CN104129779A (en) * | 2014-06-27 | 2014-11-05 | 桂林浩新科技服务有限公司 | Preparation method of graphene-containing nano paper |
| CN104977194A (en) * | 2014-04-10 | 2015-10-14 | 北京雷根生物技术有限公司 | Method of accelerating sample treatment with addition of graphene |
| CN105544306A (en) * | 2015-11-26 | 2016-05-04 | 张建刚 | Making method of graphene oxide-containing antibiosis and mildew prevention wallpaper |
| CN108421082A (en) * | 2018-04-23 | 2018-08-21 | 闫金银 | The preparation method of graphene oxide wound dressing with antibacterial anti-scar double action |
| CN109331780A (en) * | 2018-11-29 | 2019-02-15 | 长沙学院 | A kind of preparation method of activated carbon fibre/grapheme tube composite material |
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| CN103449421B (en) * | 2013-08-23 | 2015-10-28 | 上海二工大资产经营有限公司 | A kind of preparation method of heat conductive insulating graphene oxide paper |
| CN103482620B (en) * | 2013-09-11 | 2016-01-20 | 黄镇东 | Oxidation or reduced graphene base net grid material and preparation method thereof |
| CN103482620A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Graphene oxide or reduced graphene base mesh material and preparation method thereof |
| CN103482621A (en) * | 2013-09-11 | 2014-01-01 | 黄镇东 | Oxidized or deoxidated graphene-based macro material and preparing method thereof |
| CN103482621B (en) * | 2013-09-11 | 2016-01-20 | 黄镇东 | Oxidation or reduced graphene base macroscopic material and preparation method thereof |
| CN104977194B (en) * | 2014-04-10 | 2018-08-14 | 北京雷根生物技术有限公司 | A method of addition graphene accelerates sample process |
| CN104977194A (en) * | 2014-04-10 | 2015-10-14 | 北京雷根生物技术有限公司 | Method of accelerating sample treatment with addition of graphene |
| CN104129779A (en) * | 2014-06-27 | 2014-11-05 | 桂林浩新科技服务有限公司 | Preparation method of graphene-containing nano paper |
| CN105544306A (en) * | 2015-11-26 | 2016-05-04 | 张建刚 | Making method of graphene oxide-containing antibiosis and mildew prevention wallpaper |
| CN108421082A (en) * | 2018-04-23 | 2018-08-21 | 闫金银 | The preparation method of graphene oxide wound dressing with antibacterial anti-scar double action |
| CN109331780A (en) * | 2018-11-29 | 2019-02-15 | 长沙学院 | A kind of preparation method of activated carbon fibre/grapheme tube composite material |
| CN109331780B (en) * | 2018-11-29 | 2021-03-30 | 长沙学院 | Preparation method of activated carbon fiber/graphene tube composite material |
| CN113652885A (en) * | 2021-07-19 | 2021-11-16 | 南京信息工程大学 | Preparation method and application of bacterial cellulose-reinforced graphene oxide paper |
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