CN103204499A - Method for preparing spongy graphene - Google Patents
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Abstract
The invention relates to a method for preparing spongy graphene. The method comprises the steps: with graphite oxide as a raw material, preparing spongy oxidized graphene by lyophilization, wherein the prepared spongy oxidized graphene is used as a precursor; putting the prepared precursor into a crucible; then putting the crucible into a micro-wave vacuum sintering furnace, and irradiating by microwaves after vacuumizing, so as to obtain the spongy graphene. The prepared spongy graphene has a loose and porous unique structure, so that the spongy graphene has wide application prospect in the fields such as a super capacitor, a hydrogen storage material, a sensor and an adsorbing material. According to the method, microwave energy is instantaneously converted into internal energy of a sample based on a high-energy microwave irradiation mode; and by drastic thermal motion of molecules, oxygen-containing groups on the oxidized graphene are reduced into gas which rapidly volatiles and escape. Thus, the graphene can be obtained in a reducing manner and the loose and porous spongy aggregation structure can be remained.
Description
Technical field
The invention belongs to Graphene technology of preparing category, belong to the graphene preparation method of spongy specific morphology.
Background technology
Graphene refers to closely arrange the two-dimentional atomic crystal material that constitutes by carbon atom below 10 layers.Because its particular structure and excellent performances such as electricity, calorifics and mechanics, Graphene is with a wide range of applications at aspects such as nano electron device, matrix material, solar cell, ultracapacitor, hydrogen storage materials.Than film like, pulverous Graphene, spongy Graphene has bigger specific surface area and surface property, more loose pore structure and surface tissue, has bigger using value in fields such as ultracapacitor, absorption, support of the catalyst.But also there is not very effective method quick synthetic obtaining at present aspect the spongy Graphene.And the work that utilizes microwave technology to prepare spongy Graphene is not seen in report especially as yet.
For microwave technology, on radar science and technology, ADS directed energy weapon, microwave oven, plasma generator, Radio Network System (as cell phone network, bluetooth, satellite television and WLAN technology etc.), sensing system, had extensively and important use.In order to prevent microwave to the interference of radio communication, broadcasting, radar, clearly the regulation frequency range that can be applicable to microwave heating and microwave drying has only four sections in the world, and namely be respectively: L section, frequency are 890～940MHz, and centre wavelength is 0.330m; S section, frequency are 2.40～2.50GHz, and centre wavelength is 0.122m; C section, frequency are 5.725～5.875GMHz, and centre wavelength is 0.052m; K section, frequency are 22.0～22.25GHz, and centre wavelength is 0.008m.In order to prevent that civilian microwave power from causing interference to radio communication, broadcasting, TV and radar etc., provision wavelengths is specifically designed to radar at the wave band of 1-25cm in the world, rest part is used for the telecommunication transmission, only use L section and S section in the household microwave oven, and the frequency that can be used for application such as industry, scientific research and medical science is mainly 915MHz, 2.45GHz, 28GHz.Therefore, very limited in the frequency range of the available microwave preparation material of reality.But utilize the rapid heating characteristic of microwave and to carry out the preparation of functional materials synthetic, still obtained very big development, comprised also that wherein microwave technology prepares paper and the patent of Graphene.
Analyzing the research paper published can find, it is generally not ideal enough that existing microwave method prepares efficient, the effect of Graphene.Analyze The above results and can find that these processing are by lower powered microwave substantially, with the regulation frequency range of 2.45GHz, irradiation graphite oxide and obtain Graphene can't realize that owing to lower energy density original position is peeled off/reduced rapidly and thoroughly.Therefore, the product that these researchs and application obtain nearly all is the more graphene nanometer sheet of lamella stacking or Graphene microplate (be Graphene nano-sheets, or Graphene sheets), but not real Graphene (Graphene).Wherein, the Xue Lu equality of the Wang Can of East China University of Science etc., Nanjing Aero-Space University, utilize household microwave oven (power≤900W) peel off and reduction-oxidation graphite, though auxiliary at organic solvent respectively, or solid state process has obtained Graphene in peeling off, or the Graphene microplate, but exist the residual of oxygen groups in the product, functional performance such as the electricity of the Graphene that is unfavorable for fully volatilizing, calorifics.
About utilizing microwave technology to prepare the patent of Graphene, the representational application number that mainly contains University Of Tianjin's application is 201010281619.6, patent name is: the method for microwave radiation preparation and purifying Graphene under the vacuum, in this invention, " graphite oxide is placed reactor, form under 0.01Pa～10KPa pressure, employings frequency is 300MHz～300GHz; power is that the microwave of 50W～2000W carries out radiation 2s～600s to graphite oxide, graphite oxide be heated cleavage acquisition Graphene ".For preventing the interference to communication, remote sensing, military use etc., the microwave frequency band that can be applied to heat and handle material according to the rules is very limited but as previously mentioned.In addition, the microwave exposure under high vacuum very easily causes phenomenons such as " sparkings ", thereby causes the dissipation of micro-wave energy, and microwave sources such as magnetron are caused damage.Therefore, in this patent, in all wave band microwave of 300MHz～300GHz, carry out being limited under the vacuum microwave exposure of 0.1Pa, not only unrealistic, also exist certain danger.In addition, verity and the feasibility of this patent that let us not go into the question now, as carry out the microwave radiation of power lower limit 50W according to this patent, restriction based on the required quantization of energy absorption of reaction, its energy density is the required potential barrier that can't go beyond chemical reaction from principle, can not realize that consequently the microwave of Graphene peels off reduction.And if improve microwave power, as using the microwave power upper limit only up to 2000W, what obtain according to the many pieces of researchs of reporting previously as can be known, will be the more Graphene microplate of the number of plies (Graphene sheets), the also Graphene of non-real meaning (Graphene).
Summary of the invention
Technical problem to be solved by this invention is: a kind of simple and efficient method for preparing spongy Graphene efficiently is provided.
For addressing the above problem, the technical solution used in the present invention is: a kind of method for preparing spongy Graphene, comprise the steps: to adopt lyophilization, and be raw material with the graphite oxide, prepare spongiform graphene oxide as presoma; The presoma that makes is put into crucible, then crucible is put into the microwave vacuum sintering oven, vacuumize the back and carry out irradiation with microwave, obtain spongy Graphene.
The porosity of described presoma is not less than 20%.
During described vacuumizing, microwave vacuum sintering oven internal gas pressure scope is 15～50KPa.
The power range of described microwave is 4～10kW.
The time range of described irradiation is: 10～200 seconds.
Described crucible is made by the material that does not absorb microwave.Described crucible is made by aluminum oxide or silica material.
The invention has the beneficial effects as follows: (1) process is simply quick, easy to operate.Graphene oxide is the excellent microwave absorbing medium, when suffering microwave exposure, can rapidly micro-wave energy be converted into heat energy.Whole microwave radiation process is very fast, only needs time of extremely lacking, and can finish microwave cleavage and the reduction of graphene oxide.
(2) non-environmental-pollution in the preparation process, the technology environmental protection.
(3) controllability is strong: by adjusting power and the time of vacuum tightness, microwave exposure, can control the porosity of the spongy Graphene of product.
(4) product property homogeneous.Microwave radiation belongs to body phase penetration heating, and is irrelevant with the accumulation form of sample, modes of emplacement etc., can not cause the performance of product difference to occur because the residing position of presoma is different.
Embodiment
Below by specific embodiment a kind of method for preparing spongy Graphene of the present invention is described in further detail.
A kind of method for preparing spongy Graphene comprises the steps: to adopt lyophilization, is raw material with the graphite oxide, prepares spongiform graphene oxide as presoma, and the porosity of presoma is not less than 20%; The presoma that makes is put into crucible, and described crucible is made by the material that does not absorb microwave.Described crucible is made by aluminum oxide or silica material, then crucible is put into the microwave vacuum sintering oven, in order to improve the microwave treatment effect, should as much as possible crucible be placed the central position of the multimode cavity of microwave vacuum sintering oven, being evacuated to microwave vacuum sintering oven internal gas pressure scope is 15～50KPa, vacuumize the back and open microwave, the power range of microwave is 4～10kW, the microwave irradiation time scope is: 10～200 seconds, after microwave treatment finishes, open vacuum valve, wait the multimode cavity air pressure balance after, in crucible, can obtain spongy loose porous Graphene.
Embodiment 1:
Earlier prepare spongy graphene oxide as presoma with lyophilization.Utilizing the Hummers method to prepare on the basis of graphite oxide, getting the 1.5g graphite oxide and be dissolved in the 150ml deionized water, 40 ℃ of water-baths and magnetic agitation 20 minutes obtain the finely dispersed graphite oxide aqueous solution.Use freeze drier, earlier the freezing chamber temperature is down to-50 ℃, put into the graphite oxide aqueous solution again, about 1 hour of quick-frozen, open vacuum pump after solidifying fully, vacuum tightness is maintained below the 100Pa, the freezing chamber temperature is about-10～0 ℃, kept this state about 24 hours, and allowed water distil fully and namely obtain spongy graphene oxide presoma.Utilize nitrogen absorption continuous flow method, the porosity of determining spongy graphene oxide presoma is 40%.
The spongy graphene oxide of 1g is put into aluminum oxide (Al
2O
3) in the crucible, crucible is placed on the central position of microwave vacuum sintering oven resonator cavity.Be evacuated to 25KPa after closing fire door, microwave power and irradiation time are set at 4.5kW and 60 seconds respectively, then sample are carried out microwave exposure.Processing obtains the spongy product of black after finishing in crucible.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 48%, uses X-ray diffraction (XRD) to prove that product is Graphene, utilizes high-resolution-ration transmission electric-lens, can confirm that carbocyclic ring lamella accumulation horizon number is distributed between 2～5 layers basically.
Utilize the comprehensive thermal analyzer of STA449F3 type thermogravimetric/differential thermal, find with the thermal properties analysis that 10 ℃/min heat-up rate carries out in ℃ scope of room temperature～1000, except 50 ℃ of slight fluctuations that initial air-flow causes, the sample quality free of losses, in view of the temperature of oxydants such as dehydration general more than 100 ℃, therefore can determine that after High-Power Microwave was handled, anaerobic was residual in the product.
Embodiment 2:
Spongy graphene oxide presoma preparation process by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 30%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 0.5kW and 200 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 50KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 33%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 3～8 layers.
Embodiment 3:
Spongy graphene oxide presoma preparation process by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 60%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 8kW and 30 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 30KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 65%, use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, carbocyclic ring lamella accumulation horizon number and exists more individual layer or double-layer graphite alkene structure basically between 4～7 layers.
Embodiment 4:
Spongy graphene oxide presoma preparation process by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 45%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is set at 10kW and 15 seconds respectively, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then at 15KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 49%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies and mainly is distributed between 2～4 layers.
Embodiment 5:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 50%.
The vacuum microwave irradiation process keeps microwave power 4.5kW constant with embodiment 1, and adjusting irradiation time is 100 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 40KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 60%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 4～6 layers.
Embodiment 6:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 70%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 5kW and 40 seconds, and vacuum tightness is 20KPa in the microwave resonator, then sample is carried out microwave exposure.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 79%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 3～8 layers.
Embodiment 7:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 40%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 3kW and 180 seconds, and vacuum tightness is below the 50KPa in the microwave resonator, then sample is carried out microwave exposure.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 47%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 4～6 layers.
Embodiment 8:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 25%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 4kW and 50 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 30KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 30%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 5～7 layers.
Embodiment 9:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 20%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 10kW and 30 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 40KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 22%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 2～7 layers.
Embodiment 10:
Spongy graphene oxide presoma preparation method by adjusting the concentration of the graphite oxide aqueous solution, obtains spongy presoma with embodiment 1, and its porosity is 80%.
The vacuum microwave irradiation process is with embodiment 1, adjusts microwave power and irradiation time and is respectively 6kW and 90 seconds, and the vacuum degree control of resonator cavity is carried out microwave exposure to sample then below 30KPa.After processing finishes, in crucible, obtain the spongy product of black.Utilize nitrogen absorption continuous flow method, measuring the product porosity is 86%, uses X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens proof product to be Graphene, and the carbocyclic ring lamella is piled up the number of plies mainly between 4～8 layers.
Comparative Examples 1: with the contrast of using the liquid-phase reduction method to prepare Graphene.
The liquid-phase reduction method is the most common graphene oxide method of reducing.Spongy graphene oxide presoma preparation method and operation are with embodiment 1, and the product porosity is 40%.Get the 1g graphene oxide, add the 200ml deionized water, behind the wiring solution-forming, the spongy of graphene oxide namely destroyed.
At 80 ℃ of following heating in water bath, add 10g sodium borohydride or hydrazine hydrate as reductive agent, react after 2 hours, remove washing and suction filtration with deionized water, 40 ℃ of dryings 24 hours down obtain powdery graphite alkene.
Similar to the liquid phase chemical reduction method, the solvent thermal reduction method is also carried out reduction reaction in solution, since all that graphene oxide is water-soluble before the reaction, after finishing, reaction also all to carry out drying treatment again, therefore pulverous Graphene product can only be obtained, spongy Graphene can't be prepared.There is certain harm in a large amount of uses of poisonous chemical reagent such as hydrazine hydrate, sodium borohydride to environment simultaneously.
Comparative Examples 2: hot reducing method is handled the effect comparison of spongy graphene oxide
Spongy graphene oxide presoma preparation method and operation are with embodiment 1, and the product porosity is 40%.
Retort furnace is heated to 1000 ℃ and constant temperature, takes by weighing the spongy graphene oxide of 1g again, put into aluminum oxide (Al
2O
3) crucible, put into the retort furnace of 1000 ℃ of constant temperature rapidly after building crucible cover.Take out sample after 1 minute and observe, find the expanded one-tenth graphite worm of graphite oxide.Utilize scanning electron microscopic observation, the graphite synusia is curled, and is still keeping crosslinked between the synusia, and the thickness of synusia reduces, but thickness only reaches micron order, can't obtain Graphene.In addition, the thermal reduction under the normal pressure atmospheric environment has also caused sample that serious oxidation has taken place, and loss of material is bigger.
Comparative Examples 3: vacuum low energy microwave spoke is handled the effect comparison of graphite oxide
The preparation of the Graphene that carries out according to patent " method of microwave radiation preparation and purifying Graphene under the vacuum, CN 201010281619.6) " contrasts.
Because obtaining the microwave generator of other frequency ranges, can only utilize frequency for the magnetron of 915MHz and 2.45GHz as microwave source, at the microwave power of 50W～2000W, carry out the processing of graphite oxide under 0.01Pa～10KPa vacuum pressure condition respectively.When attempting microwave power with 50W and carry out irradiation, in any case conversion vacuum pressure and irradiation time all do not realize peeling off/reducing of graphite oxide.When the microwave power with 2kW carried out irradiation, cleavage took place in graphite oxide in the time of about 40 seconds, and had removed oxy radical.But utilize high-resolution-ration transmission electric-lens to detect as seen, the products distribution inequality is being mingled with more 10 multilayers even the more multi-layered carbocyclic ring packed structures of being stacked in, and effect, the efficient peeling off/reduce are not ideal.
Comparative Examples 4:900W microwave exposure liquid phase method is handled result's contrast of graphite oxide
East China University of Science utilizes " microwave exposure liquid phase method " (Wang Can, Wang Yanli, Zhan Liang, Deng the .. Journal of Inorganic Materials, 2012,27:769-774.) ", at the 120mg graphite oxide that is dispersed in the high boiling N-Methyl pyrrolidone of 40ml (NMP) organic solvent; utilize the Glanz microwave oven irradiation 3 minutes of 900W, obtained greatly the Graphene about the 2-5 layer.Although the use of organic solvent makes the lamella stacking of Graphene thinner, compare with vapor phase process, because treatment temp is difficult to rise to thousands of degree, removing of oxygen is not thorough, and residual oxygen is greatly about 13.2～13.6wt%.And there is the harm of chronic intoxicating in N-Methyl pyrrolidone (NMP) organic solvent, can cause the central nervous system dysfunction, cause the pathology of respiratory organs, kidney, vascular system etc., the working space maximum permissible concentration must not surpass 100mg/m3, so environmental issue is very important link.
Comparative Examples 5:800W microwave solid phase is peeled off the effect comparison of graphene oxide
Nanjing Aero-Space University utilizes " the microwave solid phase is peeled off method " (Xue Luping, Zheng Mingbo, Shen Chenfei, Deng the .. Chinese Journal of Inorganic Chemistry, 2010,26:1375-1381), graphite oxide has been carried out the microwave treatment 30～240 seconds that power is 800W, what obtain is the Graphene microplate (Graphene sheets) that exists oxygen residual, functional performance such as the electricity of the Graphene that is unfavorable for fully volatilizing, calorifics.
Comparative Examples 6:300W microwave solid phase is peeled off the effect comparison of graphene oxide
(SHANMUGHARAJ A M such as Janowska, CHOI W S, LEE C W.Electrochemical performances of graphene nanosheets prepared through microwave radiation.Journal of Power Sources, 2011,196:10249-10253.) expanded graphite is dispersed in supersound process 30min behind the ammonia soln, the heats 1h of recycling 300W～2h, what obtain is tens layers Graphene microplate basically.
Comparative example's summary:
Hot reducing method principle and microwave exposure method are similar, and graphene oxide is carried out quick high-temp thermal treatment, make the oxygen-containing functional group of graphene oxide resolve into CO
2, gas such as water vapour and overflowing.Use hot reducing method to handle spongy graphene oxide, on principle, should can obtain spongiform Graphene equally.But in the Comparative Examples and fail to prepare Graphene, its reason is that temperature rise rate is lower.When temperature rise rate is at least 2000 ℃/min, the temperature that reaction is carried out just can obtain spongiform graphene oxide more than 1000 ℃ the time.This just needs harsh treatment condition such as higher temperature and great temperature rise rate, so this method is very high to the requirement of experiment equipments such as heating installation, vacuum pump, and cost is also high.In addition, in order to prevent that graphene oxide is direct oxidation into CO
2, need ultravacuum (＜10-5Torr, about 1.3 * 10-3Pa) or protect the reaction environment of gas in a large number.And this is for the requirement that improves heat conduction efficiency, runs counter to again.And the vacuum microwave radiotreatment based on high-energy-density that the present invention uses, simple and fast, science is feasible, can realize operating with effect on re-set target.
The above embodiments are principle and the effect thereof of illustrative the invention only, and the embodiment of part utilization, but not is used for restriction the present invention; Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (7)
1. method for preparing spongy Graphene, it is characterized in that: comprising the steps: to adopt lyophilization, is raw material with the graphite oxide, prepares spongiform graphene oxide as presoma; The presoma that makes is put into crucible, then crucible is put into the microwave vacuum sintering oven, vacuumize the back and carry out irradiation with microwave, obtain spongy Graphene.
2. a kind of method for preparing spongy Graphene according to claim 1, it is characterized in that: the porosity of described presoma is not less than 20%.
3. a kind of method for preparing spongy Graphene according to claim 1, it is characterized in that: during described vacuumizing, microwave vacuum sintering oven internal gas pressure scope is 15～50KPa.
4. a kind of method for preparing spongy Graphene according to claim 1, it is characterized in that: the power range of described microwave is 4～10kW.
5. a kind of method for preparing spongy Graphene according to claim 1, it is characterized in that: the time range of described irradiation is: 10～200 seconds.
6. a kind of method for preparing spongy Graphene according to claim 1, it is characterized in that: described crucible is made by the material that does not absorb microwave.
7. a kind of method for preparing spongy Graphene according to claim 6, it is characterized in that: described crucible is made by aluminum oxide or silica material.
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| CN110234601A (en) * | 2016-08-31 | 2019-09-13 | 新泽西州立拉特格斯大学 | High-quality graphene and the method that it is produced by the microwave reduction of graphene oxide |
| CN106629681A (en) * | 2016-12-27 | 2017-05-10 | 东南大学 | Preparation method of graphene foam |
| CN106985238A (en) * | 2017-03-27 | 2017-07-28 | 南通海鹰木业股份有限公司 | A kind of preparation method of the timber of composite graphite alkene layer |
| CN107328826A (en) * | 2017-08-08 | 2017-11-07 | 肇庆高新区长光智能技术开发有限公司 | A kind of portable ethanol detection means |
| US10562098B2 (en) * | 2017-10-12 | 2020-02-18 | Central Iron And Steel Research Institute | High throughput micro-synthesis method of multi-component materials |
| CN108246268A (en) * | 2018-01-08 | 2018-07-06 | 兰州理工大学 | A kind of graphene oxide adsorbing material of Aminosilylation and preparation method thereof |
| CN108358191A (en) * | 2018-05-10 | 2018-08-03 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of low defect graphene and preparation method thereof |
| CN114031071A (en) * | 2021-09-28 | 2022-02-11 | 云南华谱量子材料有限公司 | Method and equipment for preparing graphene by microwave excitation catalysis self-propagating |
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