CN104163424B - A kind of efficient method preparing the controlled three-dimensional grapheme in aperture - Google Patents
A kind of efficient method preparing the controlled three-dimensional grapheme in aperture Download PDFInfo
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- CN104163424B CN104163424B CN201410405237.8A CN201410405237A CN104163424B CN 104163424 B CN104163424 B CN 104163424B CN 201410405237 A CN201410405237 A CN 201410405237A CN 104163424 B CN104163424 B CN 104163424B
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- 238000000034 method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 27
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 27
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 238000003892 spreading Methods 0.000 abstract description 2
- 230000007480 spreading Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 230000000877 morphologic effect Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
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- 150000001721 carbon Chemical group 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides and a kind ofly by suction filtration, Graphene is depended on foamed metal copper skeleton to control the method for three-dimensional grapheme aperture structure.Mainly comprise following processing step: 1. foamed metal copper is put into the Büchner funnel spreading filter paper, pour graphene oxide dispersion suction filtration into.2. the intermediate obtained is applied one deck polymethylmethacrylate (PMMA), to be immersed in ammonium persulfate solution the copper skeleton that defoams after hydroiodic acid HI reduction, then to be placed in tube furnace and to pass into argon gas and hydrogen mixed gas reduces further and removes polymethylmethacrylate (PMMA).This technical process is simple to operation, process stabilization is with low cost, and pore size and the morphological structure of three-dimensional grapheme can be controlled, provide a kind of efficient stable and prepare porous three-dimensional Graphene and the method controlling its aperture, the three-dimensional network of this product structure is continuous and even, there is absorption and conductivity preferably, have broad application prospects in water treatment and electrochemistry.
Description
Technical field
The present invention relates to the control method of graphene oxide and three-dimensional grapheme preparation and pore texture thereof, belong to materials chemistry preparing technical field.
Background technology
Graphene is a kind of novel carbon nanomaterial, have by the tightly packed bi-dimensional cellular shape crystalline structure of monolayer carbon atom, perfect crystalline network makes it have excellence and the mechanics of uniqueness, electricity, optics and thermal characteristic, comprise high heat conductance, the electronic mobility of superelevation under room temperature, high theoretical specific surface area etc., make the aspects such as quantum device, unicircuit, functional composite material, energy storage material, support of the catalyst such as its scene effect transistor have a wide range of applications potentiality.Graphene can regard two-dimentional macromole as, and marginal existence is outstanding key a lot, and the interaction of covalent linkage and non covalent bond can make graphene sheet layer mutually superpose, assemble, thus formation one is stablized and has the Graphene of certain regular shape.And though two-dimensional graphene is applicable to the application of electron device and transparent conductive film, be difficult to the requirement meeting matrix material, energy storage material.The Graphene of little lamella is difficult to manipulation in practice, therefore want to fully utilize the numerous excellent properties of Graphene and special construction also further its application space of expansion, Graphene being assembled into into stable high quality three-dimensional macro material is a kind of effective approach.
Three-dimensional grapheme refers to that graphene sheet layer forms the material with three-D space structure by tissue construction, the at present self-assembling method preparation adopted based on electrostatic interaction principle, mainly comprises vacuum vapor deposition method, crosslinking, hydrothermal method, collosol and gel sends out and CVD etc. more.Take graphene oxide as the three-dimensional grapheme that presoma self-assembly is prepared, often be difficult to be formed the evenly three-dimensional network coordinated, macrostructure randomness is large, and its pore size and the more difficult control of form, hinder the raising of its electric property and the optimization of three-dimensional structure to a certain extent; And CVD method take carbonaceous gas as carbon source, foamed metal is growing graphene under substrate high temperature, and three-dimensional grapheme quality prepared by this method is high, but energy consumption is comparatively large, and cost is higher.At present, prepare Graphene can realize preparation in macroscopic quantity, low production cost based on redox method, therefore expanding with graphite oxide is that the method for precursor power three-dimensional grapheme has obvious practical significance and application potential.
Summary of the invention
Technical problem: the invention provides a kind of efficient method preparing the controlled three-dimensional grapheme in aperture.The method utilizes the Hummers method improved to prepare graphene oxide, and make its its three-dimensional structure of copying surface being attached to foamed metal by the method for suction filtration, the metal that defoams again after reduction obtains three-dimensional grapheme.
Technical scheme: a kind of efficient method preparing the controlled three-dimensional grapheme in aperture of the present invention comprises the following steps:
A. the preparation of graphene oxide: the Graphite Powder 99 of particle diameter≤30 μm is added in the there-necked flask of ice bath, add the vitriol oil, stir and add SODIUMNITRATE after 5-15 minute, add potassium permanganate after question response and stir, add deionized water after being warming up to the reaction of 40-60 degree subsequently, after solution cooling, eccentric cleaning is carried out to product and obtain graphite oxide;
B. three-dimensional graphene oxide preparation: make it dissolve by ultrasonic for above-mentioned graphite oxide, obtain the amber graphene oxide dispersion that concentration is 0.1-5mg/ml, put into after the foamed metal copper mold plate in required aperture is cut into the caliber size of Büchner funnel in Suction filtration device, pour the graphene oxide dispersion prepared into Büchner funnel again, suction filtration, obtains three-dimensional graphene oxide-foam copper;
C. the removal of foamed metal copper and the reduction of three-dimensional graphene oxide:
1) by suction filtration well and the three-dimensional graphene oxide-foam copper of complete drying immerse in polymethylmethacrylate (950PMMA), make it fully infiltrate the hole post-drying of three-dimensional graphene oxide-foam copper, fix its three-dimensional net structure;
2) the above-mentioned three-dimensional graphene oxide-foam copper being coated with polymethylmethacrylate (950PMMA) is put into hydroiodic acid HI (HI) solution in backlight place, reaction 0.5-3 hour;
3) the three-dimensional graphene oxide after above-mentioned process-foam copper material is taken out, after thoroughly cleaning with deionized water, be immersed in the ammonium persulphate ((NH of 0.1mol/L
4)
2s
2o
8) in solution, until foam copper dissolves completely;
4) will be partially reduced and three-dimensional graphene oxide after the copper that defoams take out after cleaning, put into quartz boat after thorough oven dry and be placed in tube furnace, the gas mixture passing into argon gas and hydrogen is warming up to 300-500 DEG C, be incubated 0.5-3 hour further reduction as three-dimensional intermediate three-dimensional grapheme and remove polymethylmethacrylate (950PMMA), be down to room temperature after reaction terminates, obtain uniform pore diameter and be distributed in the porous three-dimensional Graphene less than foamed metal copper mean pore size used.
Beneficial effect: the present invention is with foamed metal copper for three-dimensional framework, and make graphene oxide copy its vesicular structure by suction filtration, and adopt hydroiodic acid HI and hydrogen reducing, the copper that finally defoams prepares three-dimensional grapheme.Provide and prepare porous three-dimensional Graphene and the new way controlling its pore size and form.Present method cost is low, simple to operate, efficiency is high, can prepare in a large number.Use foamed metal for skeleton to control the pore size of three-dimensional grapheme and form.Adopt the inventive method, can be efficient, stable prepare the controlled three-dimensional grapheme of shape, size, pore size, mass-producing, mass production preparation can be realized.
Embodiment
A. the preparation of graphene oxide:
Graphite Powder 99 is added in the there-necked flask of ice bath, add the vitriol oil 80-120ml of 98%wt, stir and add 0.2-1g SODIUMNITRATE after 5-15 minute.Add potassium permanganate after question response 10-30 minute and stir 30-70 minute.About intensification 40-60 DEG C reaction subsequently added 40-100ml deionized water after 4-8 hour.After solution cooling, eccentric cleaning is carried out to product and obtain graphite oxide.The graphite oxide colloidal sol ultrasonic 0.5-2 hour of acquisition is peeled off, obtains light brown graphene oxide dispersion, make desired concn.
B. three-dimensional graphene oxide preparation:
The foamed metal copper in required aperture is cut into the circular shuttering matched with the Büchner funnel bore of Suction filtration device, soak 20-50s with the dilute hydrochloric acid of 30-50%wt (HCl) and remove oxide on surface, again to put into the Büchner funnel spreading filter paper after washed with de-ionized water, vacuum pump suction filtration is opened, until graphene oxide is drained completely on foam copper surface after pouring graphene oxide dispersion into.
C. the removal of foamed metal copper and the reduction of three-dimensional graphene oxide:
1) by suction filtration well and the three-dimensional graphene oxide-foam copper of complete drying immerses molecular-weight average is in the polymethylmethacrylate (950PMMA) of 950000, after making it fully infiltrate the hole of graphene oxide-foam copper, dry, fix its three-dimensional net structure.
2) the three-dimensional graphene oxide-foam copper being coated with polymethylmethacrylate (950PMMA) is put into hydroiodic acid HI (HI) solution of enough 20-50%wt in backlight place, reaction 0.5-2 hour.
3) material of step (2) is taken out, after thoroughly cleaning with deionized water, be immersed in 100ml the ammonium persulphate ((NH of 0.1-0.5mol/L
4)
2s
2o
8) in solution, until foam copper dissolves completely.
4) cleaning after being taken out by the material of step (3), puts into quartz boat after thoroughly drying and is placed in tube furnace, pass into the gas mixture (Ar:H of argon gas and hydrogen
2=50:50 (sccm)) be warming up to 300-600 DEG C, be incubated 0.5-2 hour further this intermediate product of reduction and remove polymethylmethacrylate (950PMMA), be down to room temperature after reaction terminates, obtain uniform pore diameter and be distributed in porous three-dimensional Graphene in the certain limit slightly less than foamed metal copper aperture used.
Embodiment 1:
(1). 0.5-2g Graphite Powder 99 is added in the there-necked flask of ice bath, adds the vitriol oil 80-120ml of 98%wt, stir and add 0.1-1g SODIUMNITRATE after 5-15 minute.Add potassium permanganate 2-5g after question response 10-30 minute and stir 30-80 minute.About intensification 40-60 DEG C reaction subsequently added 70-100ml deionized water after 3-8 hour.After solution cooling, eccentric cleaning is carried out to product and obtain graphite oxide.The graphite oxide colloidal sol ultrasonic 0.5-1.5 hour of acquisition is peeled off, obtains light brown graphene oxide dispersion, be mixed with the colloid of 3-10mg/ml.
(2). get the foam copper that aperture is 1200 μm, be cut into the circle (d=5-15cm) of Büchner funnel caliber size in Suction filtration device, thoroughly clean with deionized water after soaking 20-60 second with the dilute hydrochloric acid of 30-50%wt (HCl), put into the funnel having completed filter paper after drying, pour suction filtration after 50-150ml graphene oxide dispersion into.
(3). the intermediate product drained completely is immersed 0.5-3 minute in polymethylmethacrylate (950PMMA), dries at 80-150 DEG C after taking out.
(4). the intermediate product being coated with polymethylmethacrylate (950PMMA) is put into 100ml in backlight place, in hydroiodic acid HI (HI) solution of 25-40%wt, reaction 0.5-1.5 hour.
(5). the material of step (4) is taken out, is immersed in 100ml after thoroughly cleaning with deionized water, the ammonium persulphate ((NH of 0.1mol/L
4)
2s
2o
8) in solution, until foam copper dissolves completely.
(6). cleaning after the material of step (5) is taken out, put into quartz boat after thoroughly drying and be placed in tube furnace, pass into the gas mixture (Ar:H of argon gas and hydrogen
2=50:50 (sccm)) be warming up to 300-500 DEG C, insulation 0.5-1.5 hour; Be down to room temperature after reaction terminates, sample is taken out.Obtain the porous three-dimensional Graphene that uniform pore diameter is distributed in 950-1050 μm.
Embodiment 2:
(1). be same as scheme 1, process (1).
(2). get the foam copper that aperture is 800 μm, be cut into the circle of Büchner funnel caliber size in Suction filtration device
(d=5-15cm), thoroughly clean with deionized water after soaking 20-60 second with the dilute hydrochloric acid of 30-50%wt (HCl), after drying, put into the funnel completing filter paper, pour suction filtration after 50-150ml graphene oxide dispersion into.
(3). the intermediate product drained completely is immersed 0.5-3 minute in polymethylmethacrylate (950PMMA), dries at 80-150 DEG C after taking out.
(4). the intermediate product being coated with polymethylmethacrylate (950PMMA) is put into 100ml in backlight place, in hydroiodic acid HI (HI) solution of 25-40%wt, reaction 0.5-1.5 hour.
(5). the material of step (4) is taken out, is immersed in 100ml after thoroughly cleaning with deionized water, the ammonium persulphate ((NH4) of 0.1mol/L
2s
2o
8) in solution, until foam copper dissolves completely.
(6). cleaning after the material of step (5) is taken out, put into quartz boat after thoroughly drying and be placed in tube furnace, pass into the gas mixture (Ar:H of argon gas and hydrogen
2=50:50 (sccm)) be warming up to 300-500 DEG C, insulation 0.5-1.5 hour; Be down to room temperature after reaction terminates, sample is taken out.Obtain the porous three-dimensional Graphene that uniform pore diameter is distributed in 250-400 μm.
Claims (1)
1. efficiently prepare a method for the controlled three-dimensional grapheme in aperture, it is characterized in that the method comprises the following steps:
A. the preparation of graphite oxide: the Graphite Powder 99 of particle diameter≤30 μm is added in the there-necked flask of ice bath, add the vitriol oil, stir and add SODIUMNITRATE after 5-15 minute, add potassium permanganate after question response and stir, add deionized water after being warming up to the reaction of 40-60 degree subsequently, after solution cooling, eccentric cleaning is carried out to product and obtain graphite oxide;
B. three-dimensional graphene oxide preparation: make it dissolve by ultrasonic for above-mentioned graphite oxide, obtain the amber graphene oxide dispersion that concentration is 0.1-5mg/ml, put into after the foamed metal copper mold plate in required aperture is cut into the caliber size of Büchner funnel in Suction filtration device, pour the graphene oxide dispersion prepared into Büchner funnel again, suction filtration, obtains three-dimensional graphene oxide-foam copper;
C. the removal of foamed metal copper and the reduction of three-dimensional graphene oxide:
1) by suction filtration well and the three-dimensional graphene oxide-foam copper of complete drying immerse in polymethylmethacrylate 950PMMA, make it fully infiltrate the hole post-drying of three-dimensional graphene oxide-foam copper, fix its three-dimensional net structure;
2) the above-mentioned three-dimensional graphene oxide-foam copper being coated with polymethylmethacrylate 950PMMA is put into hydroiodic acid HI HI solution in backlight place, reaction 0.5-3 hour;
3) the three-dimensional graphene oxide after above-mentioned process-foam copper material is taken out, after thoroughly cleaning with deionized water, be immersed in the ammonium persulphate (NH of 0.1mol/L
4)
2s
2o
8in solution, until foam copper dissolves completely;
4) will be partially reduced and three-dimensional graphene oxide after the copper that defoams take out after cleaning, put into quartz boat after thorough oven dry and be placed in tube furnace, the gas mixture passing into argon gas and hydrogen is warming up to 300-500 DEG C, be incubated 0.5-3 hour further reduction as three-dimensional intermediate three-dimensional grapheme and remove polymethylmethacrylate 950PMMA, be down to room temperature after reaction terminates, obtain uniform pore diameter and be distributed in the porous three-dimensional Graphene less than foamed metal copper mean pore size used.
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| CN105776186B (en) * | 2014-12-25 | 2018-10-16 | 华中科技大学 | A kind of three-dimensional grapheme porous material preparation method of structure-controllable |
| CN104743547B (en) * | 2015-03-06 | 2016-08-24 | 同济大学 | A kind of preparation method of three-dimensional grapheme macroscopic body |
| CN104843685B (en) * | 2015-04-10 | 2016-08-24 | 四川大学 | Utilize the method that excrement of animals prepares three-dimensional porous class graphene carbon electrode material |
| CN105523546B (en) * | 2016-01-22 | 2018-12-11 | 复旦大学 | A kind of preparation method of three-dimensional grapheme |
| KR101998586B1 (en) * | 2018-02-26 | 2019-07-10 | (주) 디엔디이 | Graphene-based schottky junction solar cells and method manufacturing thereof |
| CN109295333B (en) * | 2018-08-22 | 2024-01-30 | 上海新池能源科技有限公司 | Preparation method of three-dimensional graphene-copper composite material and composite wire and cable |
| CN111628156B (en) * | 2020-06-29 | 2021-08-27 | 蜂巢能源科技有限公司 | Molybdenum-doped porous silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN115893385B (en) * | 2022-12-13 | 2023-07-25 | 之江实验室 | Self-supporting three-dimensional graphene framework, composite material, preparation method and application thereof |
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|---|---|---|---|---|
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN102675880A (en) * | 2012-05-10 | 2012-09-19 | 东南大学 | Preparation method for composite material of multifunctional graphene and polydimethylsiloxane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN102675880A (en) * | 2012-05-10 | 2012-09-19 | 东南大学 | Preparation method for composite material of multifunctional graphene and polydimethylsiloxane |
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Granted publication date: 20160106 |