CN105253874A - Method for preparing three-dimensional microporous graphene totally without participation of solution - Google Patents
Method for preparing three-dimensional microporous graphene totally without participation of solution Download PDFInfo
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Abstract
The invention specifically provides a method for preparing three-dimensional microporous graphene totally without participation of a solution, which belongs to the technical field of inorganic synthesis. The method employs chemical vapor deposition and uses elemental transition metal powder or a compound containing a transition metal element as a catalyst so as to prepare a porous metal catalyst skeleton through high temperature reduction; then chemical vapor deposition is used for growing of graphene so as to obtain three-dimensional graphene with the catalyst skeleton; and a template is removed through direct evaporation at a high temperature under vacuum so as to obtain three-dimensional graphene. The method is simple and convenient to operate, and the obtained graphene can completely copy the shape of the template, which enables the designing space of the shape of a material to be great; no solution participates in the whole process of preparation, elimination of waste liquid is not needed, and the method is friendly to environment and can realize rapid and large-scale preparation of high-quality three-dimensional graphene; and the prepared three-dimensional graphene has the advantages of a small gap, great density and the like and has extensive application prospects in fields like spatial heat conduction, electric conduction, medicine, energy and catalyst carriers.
Description
Technical field
The invention belongs to Inorganic synthese technical field, be specifically related to a kind of method preparing three-dimensional micropore Graphene that whole process participates in without solution.
Background technology
Graphene is a kind of Two-dimensional Carbon material only having monoatomic layer thickness, has the features such as excellent mechanical property, high connductivity, heat conductivility and specific surface area are large.Since Graphene is found, mainly contains four kinds of methods and prepared Graphene; Mechanically peel, solvent (redox) method, epitaxy and chemical Vapor deposition process.Conventional method is solvent method, and this legal system can introduce a large amount of defect and functional group for Graphene, greatly reduces the electroconductibility of Graphene; Chemical vapor infiltration belongs to growing graphene from bottom to top, and the Graphene that this technique is prepared has the advantages that defect is few, quality is high.
Three-dimensional grapheme is the three-dimensional full UNICOM network structure that two-dimensional graphene connects with physics or chemistry with nano belt, nanotube or nanometer sheet, except having two-dimensional graphene performance concurrently, also utilize its porous network feature application in fields such as medicine, the energy, adsorption cleanings.At present, the preparation of most of three-dimensional grapheme adopts the preparation of solvent self-assembly method, and this technique is loaded down with trivial details, complicated and Graphene quality is low.2011, Shenyang Cheng Huiming seminar of metal institute does catalysts template by chemical Vapor deposition process employing nickel foam and prepares three-dimensional grapheme, etch nickel foam with the mixing solutions of iron(ic) chloride and hydrochloric acid, from then on raise the upsurge making Template preparation three-dimensional grapheme of metal.2013, Suzhou nanometer Suo Liuliwei seminar uses chemical Vapor deposition process, adopt transistion metal compound or transition metal simple substance to prepare micropore metal template by high temperature reduction and make catalyzer, prepare the three-dimensional porous Graphene that aperture is less, solvent etched template need be used when aftertreatment equally.
To sum up, no matter be adopt solvent self-assembly method or adopt chemical Vapor deposition process metal to do Template preparation three-dimensional grapheme, in process, have the participation of solvent.Three-dimensional grapheme is prepared in solvent self-assembly can introduce a large amount of defect and functional group, has a strong impact on electrical and thermal conductivity performance; Chemical Vapor deposition process prepares three-dimensional grapheme need remove template with solution etches, has certain destruction and waste liquid has greater environmental impacts to the structure of Graphene.The present invention adopts chemical vapour deposition technique single stage method to prepare three-dimensional grapheme, evaporation removing metal form under elevated temperature in vacuo, thus directly obtain three-dimensional grapheme, be graphene growth process or except catalyst process is all without solution participation, simple and efficiently prepare high quality three-dimensional grapheme.
Summary of the invention
The object of this invention is to provide a kind of easy, efficient and environment amenable three-dimensional micropore graphene preparation method, the method whole process participates in without solution.
The method preparing three-dimensional micropore Graphene that whole process provided by the invention participates in without solution, first, with transition metal elemental powders or containing the compound of transition metal for catalyzer, through high temperature reduction reaction, prepare porous metal catalyst skeleton; Then, utilize chemical Vapor deposition process growing graphene, obtain the three-dimensional grapheme with catalyst backbone; Finally, reactor is vacuumized and raised temperature (exceeding the fusing point of metal form) heating evaporation template, obtain the Graphene with the three-dimensional full UNICOM network structure of high porosity.
The three-dimensional grapheme that the inventive method prepares, by graphene nanobelt or the interconnective network of nanotube, aperture is 1-50um, and density is 0.2-100 milligram every cubic centimetre.
The concrete steps of the inventive method are as follows;
The first step, catalyst pre-treatment: described catalyzer is transition metal elemental powders or the compound containing transition metal, catalyzer is placed in reactor and carries out reduction reaction: heat up with given pace (5-100 degree per minute), rare gas element excluding air is passed into reactor in temperature-rise period, after being warming up to 100-1200 degree Celsius, close rare gas element, change the reducing atmosphere passing into 1-2000 milliliter per minute, reduced anneal 1 minute-10 hours, obtains micropore metal catalyst backbone;
Second step, growing graphene: introduce carbon source to catalyzer place, start growing graphene; Wherein growth temperature is 400-1200 degree Celsius, and growth time is 30 seconds-10 hours, and growth pressure is 1 millitorr-1 normal atmosphere, obtains the three-dimensional grapheme with catalyst backbone after having reacted;
3rd step, solvent-freely go template: after having grown Graphene, the temperature of reactor is continued to be increased to metal evaporation temperature, vacuumize the discharge accelerating metallic vapor simultaneously, after question response completes, be cooled to room temperature, without the need to directly obtaining three-dimensional grapheme through other solvent etched.
In the present invention, described transition metal can be selected from but be not limited to nickel, copper, cobalt, platinum, iron or rubidium.Described transition metal elemental powders particle diameter is 0.1 micron-100 microns.The described compound containing transition metal can be selected from but be not limited to transition metal oxide, transition metal salt or its hydrate.Wherein, for transition metal salt hydrate, it can be dried or the microwave heating water that decrystallizes obtains Anhydrous transition metal-salt or directly carry out high temperature reduction at 50-300 degree Celsius.
In the present invention, described micropore metal template has three-dimensional cross-linked structure, and its aperture is 1 micron-50 microns.
In the present invention, the temperature of reactor in described removing template stage must should to carry out vacuumizing under environment higher than metal catalyst fusing point.
In abovementioned steps (), described reducing atmosphere is (10-1000) than the hydrogen of (0-500) (preferably (10-1000) is than (1-500)) and rare gas element composition primarily of throughput ratio, carrier gas overall flow rate is 1-2000 milliliter per minute, rare gas element one or more mixed gass mainly in the rare gas element such as argon gas, nitrogen.
As one of comparatively preferred scheme; Abovementioned steps (one) reduction reaction temperature is 1000 degrees Celsius, and reducing atmosphere is the hydrogen of 200 milliliters of per minutes.
In abovementioned steps (two), in described chemical vapor deposition processes, the carbon source introduced comprises liquid phase, gas phase, and solid-phase carbon source, and wherein, phase carbon source can be selected from but be not limited to ethanol, propyl alcohol, methyl alcohol, aromatic hydrocarbon and composition thereof; Solid-phase carbon source can be selected from but be not limited to polymethylmethacrylate, polyoxyethylene glycol, polyvinyl alcohol, polydimethylsiloxane, the polymkeric substance such as polyethylene, glucose, the carbohydrates and decolorizing carbon and composition thereof such as Mierocrystalline cellulose; Gas phase carbon source optional from but be not limited to methane, propane, carbonic acid gas and composition thereof.
As one of comparatively preferred scheme, in step (two), carbon source introduces alcohol steam to reaction zone growing graphene with bubbling argon alcohol.
Previous reaction device be heated evenly, the high temperature resistant and a whole set of closed unit that can vacuumize.As one of comparatively preferred scheme, the present invention's reactor used is tube furnace.
Compared with prior art, the present invention at least has following advantages: (single stage method obtains, without the need to aftertreatment) easy and simple to handle, productive rate is high, and equipment requirements is low, and whole process participates in without solution, without the need to getting rid of waste liquid, environmentally friendly, can realize high quality three-dimensional grapheme quick, prepare in a large number; And the three-dimensional grapheme that obtains has space little (100 nanometer-100 microns), the advantages such as density large (can reach 100 milligrams every cubic centimetre), this three-dimensional grapheme is in space conduction, heat conduction, and the aspects such as support of the catalyst, medicine and the energy have wide practical use.
Accompanying drawing explanation
Copper powder scanning electron microscope after Fig. 1 reduced anneal.
The long scanning electron microscope having Graphene on Fig. 2 copper skeleton.
The three-dimensional grapheme of the complete copper of Fig. 3 heating evaporation.
The Raman spectrogram of Fig. 4 Graphene.
Fig. 5 present invention process schematic diagram.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail:
(namely the present invention adopts transition metal elemental powders, salt or its hydrate, oxide compound, presoma) obtain the 3-dimensional metal skeleton with catalytic property through high temperature reduction, utilize chemical vapour deposition technique, under suitable atmosphere, catalytic growth Graphene, directly obtains the three-dimensional grapheme of removing template after process of growth completes by raising temperature of reactor heating volatilization catalyzer.Wherein, transition metal salt hydrate, before high temperature reduction, first obtains Anhydrous transition metal-salt after heating, drying or microwave heating decrystallize water treatment.
One, transition metal simple substance makees catalyzer
Embodiment 1, copper powder make catalyst growth three-dimensional grapheme
First, the preparation work before reaction: get a certain amount of copper powder and be layered in ceramic boat, is placed in tube furnace furnace temperature district by ceramic boat, open vacuum pump and silica tube air pressure inside is evacuated to 5 × 10
-3below holder, close air outlet valve, by under meter pass into flow velocity be the argon gas of 400 milliliters of per minutes by air pressure refunds to normal pressure, continue to pass into argon gas to drain air (this terminates up to reaction, air outlet valve is opened to maintain atmospheric pressure environment), with the speed of 50 centigrade per minutes, tube furnace is warming up to 1000 degrees Celsius.
Secondly, step of reaction: 1. Template preparation; Close argon gas, change the hydrogen reducing annealing copper powder 20 minutes passing into 200 milliliters of per minutes.Prepare three-dimensional micropore network copper mold plate (as Fig. 1) and make catalyzer.2. growth material; Changing the hydrogen of previous step 200 milliliters of per minutes into hydrogen than methane is 10/50 milliliter of per minute, makes carbon source with this mixed gas, and temperature is still 1000 degrees Celsius, and synthesis under normal pressure can obtain Graphene (as Fig. 2) for 20 minutes.3. template is removed; Continue temperature to be risen to 1090 degrees Celsius of maintenances and within 100 minutes, rise to 1100 degrees Celsius of maintenances 60 minutes again, vacuum is evacuated to 5 and is multiplied by 10 by removal template procedure
-3below holder, obtain the three-dimensional grapheme (as Fig. 3) of removing template, and relevant Raman characterizes the Graphene signal (as Fig. 4) demonstrating high quality (almost zero defect).
Embodiment 2, copper powder make catalyst growth three-dimensional grapheme
Preparation method is substantially with embodiment 1, and difference is: in the 2. growth material process in step of reaction, and introduce alcohol steam with the form of bubbling argon alcohol, pass into hydrogen, hydrogen is 10/50 milliliter of per minute than argon gas, makes carbon source with this mixed gas simultaneously.
Embodiment 3, copper powder make catalyst growth three-dimensional grapheme
Preparation method is substantially with embodiment 1, and difference is: the 2. growth material process of step of reaction.After preparing three-dimensional micropore network copper mold plate (as Fig. 1), being taken out to immerse is dissolved with in the methyl-phenoxide solution of polymethylmethacrylate, put into silica tube again, under argon atmosphere, direct (tube furnace can move flexibly) enters 1000 degrees Celsius of furnace temperature district synthesis under normal pressure, 20 minutes obtained Graphenes.
Two, transistion metal compound makes catalyst precursor
Catalyst precursor growing three-dimensional Graphene made by embodiment 4, cupric oxide
Preparation method is substantially with embodiment 1, and difference is: in the 1. Template preparation process in step of reaction, will extend to 60 minutes the recovery time, and make cupric oxide fully be reduced into copper simple substance thus possess catalytic activity.
Three, transition metal salt makes catalyst precursor
Embodiment 5, ventilation breather make catalyst precursor growing three-dimensional Graphene
Preparation method is substantially with embodiment 1, and difference is: the 1. Template preparation technique in the preparation work before reaction and step of reaction.The temperature rise period (tube furnace being warming up to 1000 degrees Celsius with the speed of 50 centigrade per minutes) of preparation work changes into and rose to 250 degrees Celsius with 60 minutes, preheat object and be that decomposing ventilation breather produces cupric oxide, other resolvents (carbonic acid gas and water vapour) are extracted out by vacuum pump, air outlet valve is closed after extracting resolvent out, pass into argon gas by tube furnace refunds normal pressure, continue to pass into argon gas to drain air (this terminates up to reaction, air outlet valve is opened to maintain atmospheric pressure environment), with the speed of 50 centigrade per minutes, tube furnace is warming up to 1000 degrees Celsius.Recovery time in embodiment 1 is extended to 60 minutes by Template preparation technique, makes cupric oxide fully be reduced into copper simple substance thus possess catalytic activity.
Graphene prepared by the present invention is without the need to removing template by traditional solution method etching, the present invention is to provide a kind of directly by the thinking of metal form volatilization, because transition metal is numerous, can not do the related experiment of all elements by horizontal spreading, but its essence is all create certain high temperature and high vacuum removes metal form.
More than illustrate and shown embodiment, unintelligible for limiting design philosophy of the present invention.Hold in technical field of the present invention identical know the knowledgeable can by technical thought of the present invention with various form improvement change, such improvement and change be interpreted as equally belonging in protection scope of the present invention.
Claims (8)
1. the method preparing three-dimensional micropore Graphene that participates in without solution of whole process, is characterized in that concrete steps are as follows:
The first step, catalyst pre-treatment: described catalyzer is transition metal elemental powders or the compound containing transition metal, catalyzer is placed in reactor and carries out reduction reaction: with the ramp of 5-100 centigrade per minute, rare gas element excluding air is passed into reactor in temperature-rise period, after being warming up to 100-1200 degree Celsius, close rare gas element, change the reducing atmosphere passing into 1-2000 milliliter per minute, reduced anneal 1 minute-10 hours, obtains micropore metal catalyst backbone;
Second step, growing graphene: introduce carbon source to catalyzer place, start growing graphene, wherein growth temperature is 400-1200 degree Celsius, and growth time is 30 seconds-10 hours, growth pressure is 1 millitorr-1 normal atmosphere, obtains the three-dimensional grapheme with catalyst backbone after having reacted;
3rd step, solvent-freely go template: after having grown Graphene, the temperature of reactor continued to be increased to metal evaporation temperature, vacuumize the discharge accelerating metallic vapor simultaneously, after question response completes, be cooled to room temperature, namely obtain required three-dimensional micropore Graphene.
2. method according to claim 1, is characterized in that, described transition metal is selected from nickel, copper, cobalt, platinum, iron or rubidium; Described transition metal elemental powders particle diameter is 0.1 micron-100 microns; The described compound containing transition metal is selected from transition metal oxide, transition metal salt or its hydrate; Wherein, for transition metal salt hydrate, it to be dried or the microwave heating water that decrystallizes obtains Anhydrous transition metal-salt or directly carry out high temperature reduction at 50-300 degree Celsius.
3. method according to claim 1, is characterized in that, described micropore metal template has three-dimensional cross-linked structure, and its aperture is 1 micron-50 microns.
4. method according to claim 1, is characterized in that, the temperature of reactor in described removing template stage is higher than metal catalyst fusing point and must carry out vacuumizing under environment.
5. method according to claim 1, it is characterized in that, to be 10-1000 by throughput ratio form than the hydrogen of 1-500 and rare gas element described reducing atmosphere, and carrier gas overall flow rate is 1-2000 milliliter per minute, and rare gas element is one or more mixed gass in argon gas, nitrogen.
6. method according to claim 1, is characterized in that, in described chemical vapor deposition processes, the carbon source introduced comprises liquid phase, gas phase and solid-phase carbon source, and wherein, phase carbon source is selected from ethanol, propyl alcohol, methyl alcohol, and aromatic hydrocarbon and composition thereof; Solid-phase carbon source is selected from polymethylmethacrylate, polyoxyethylene glycol, polyvinyl alcohol, polydimethylsiloxane, polyethylene, glucose, Mierocrystalline cellulose and decolorizing carbon and composition thereof; Gas phase carbon source is selected from methane, propane, carbonic acid gas and composition thereof.
7. method according to claim 1, is characterized in that, described reactor be heated evenly, the high temperature resistant and a whole set of closed unit that can vacuumize.
8. method according to claim 1, is characterized in that, described three-dimensional micropore Graphene, and by graphene nanobelt or the interconnective network of nanotube, aperture is 1-50um, and density is 0.2-100 milligram every cubic centimetre.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108117410A (en) * | 2017-12-19 | 2018-06-05 | 华中科技大学 | A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof |
| CN108636426A (en) * | 2018-03-22 | 2018-10-12 | 西北工业大学 | Three-dimensional order is orientated molybdenum disulfide/graphene high-efficiency photocatalysis hydrogen production composite nano materials and preparation method |
| CN110125385A (en) * | 2019-04-15 | 2019-08-16 | 中国航发北京航空材料研究院 | A kind of preparation method of the graphene Cu-base composites based on fabricated in situ |
| CN110170655A (en) * | 2019-06-04 | 2019-08-27 | 浙江正泰电器股份有限公司 | A kind of preparation method of metal matrix three-dimensional graphene composite material |
| CN110436446A (en) * | 2019-09-20 | 2019-11-12 | 张小云 | A kind of graphene and preparation method thereof |
| CN111484002A (en) * | 2020-04-17 | 2020-08-04 | 南京动量材料科技有限公司 | Preparation method and application of porous graphene membrane |
| CN111825078A (en) * | 2019-04-22 | 2020-10-27 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN112457826A (en) * | 2020-12-24 | 2021-03-09 | 杭州英希捷科技有限责任公司 | Preparation method of thermal interface material based on high-density graphene interconnection network structure |
| CN114804023A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method and application of metal-molten salt for hydrogen production from natural gas and carbon black |
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| CN108117410A (en) * | 2017-12-19 | 2018-06-05 | 华中科技大学 | A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof |
| CN108636426B (en) * | 2018-03-22 | 2020-12-08 | 西北工业大学 | Three-dimensional ordered oriented molybdenum disulfide/graphene high-efficiency photocatalytic hydrogen production composite nano material and preparation method thereof |
| CN108636426A (en) * | 2018-03-22 | 2018-10-12 | 西北工业大学 | Three-dimensional order is orientated molybdenum disulfide/graphene high-efficiency photocatalysis hydrogen production composite nano materials and preparation method |
| CN110125385A (en) * | 2019-04-15 | 2019-08-16 | 中国航发北京航空材料研究院 | A kind of preparation method of the graphene Cu-base composites based on fabricated in situ |
| CN111825078B (en) * | 2019-04-22 | 2021-12-10 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN111825078A (en) * | 2019-04-22 | 2020-10-27 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN110170655A (en) * | 2019-06-04 | 2019-08-27 | 浙江正泰电器股份有限公司 | A kind of preparation method of metal matrix three-dimensional graphene composite material |
| CN110170655B (en) * | 2019-06-04 | 2024-06-04 | 上海新池能源科技有限公司 | Preparation method of metal-based three-dimensional graphene composite material |
| CN110436446A (en) * | 2019-09-20 | 2019-11-12 | 张小云 | A kind of graphene and preparation method thereof |
| CN111484002A (en) * | 2020-04-17 | 2020-08-04 | 南京动量材料科技有限公司 | Preparation method and application of porous graphene membrane |
| CN111484002B (en) * | 2020-04-17 | 2023-06-09 | 南京动量材料科技有限公司 | Preparation method and application of porous graphene film |
| CN112457826A (en) * | 2020-12-24 | 2021-03-09 | 杭州英希捷科技有限责任公司 | Preparation method of thermal interface material based on high-density graphene interconnection network structure |
| CN114804023A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method and application of metal-molten salt for hydrogen production from natural gas and carbon black |
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