CN102674325A - Method for preparing graphene by using laminated dihydroxy metal hydroxide - Google Patents
Method for preparing graphene by using laminated dihydroxy metal hydroxide Download PDFInfo
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Abstract
The invention relates to a method for preparing graphene by using a laminated dihydroxy metal hydroxide, belonging to the fields of nano material and the preparation technology of the nano material. According to the method, the laminated dihydroxy metal hydroxide is taken as a catalyst precursor, the catalyst precursor is pretreated to obtain a laminated dihydroxy metal oxide which can be taken as a graphene deposition template; and then, chemical vapor deposition and purification are carried out to obtain graphene. The method is simple and easy and is beneficial to macro quantity preparation of graphene to promote the industrial application of graphene.
Description
Technical field
The present invention relates to the method for a kind of Graphene preparation, particularly a kind ofly prepare the method for Graphene, belong to nano material and preparing technical field thereof based on the layer dihydroxy metal hydroxides.
Background technology
Graphene is since the reports such as professor An Deliehaimu of Univ Manchester UK in 2004; Its perfect structure has caused various countries scientists and engineers' great attention with excellent performance, and then has developed its application at numerous areas such as field-effect transistor, unicircuit, single-molecule detection device, nesa coating, matrix material, energy storage material, support of the catalyst.The magnanimity preparation of material is its performance of research and prerequisite and the basis of exploring its application.The at present existing multiple method for preparing Graphene is peeled off method, chemical stripping method, silicon carbide epitaxial growth method and chemical Vapor deposition process like micromechanics.Wherein, Compare with other several kinds of preparing methods; Chemical Vapor deposition process has that operation is simple, prepared graphene is of high quality, can realize large area deposition and be easy to transfer to advantage such as using on the various matrixes, become the main method of preparation high quality Graphene at present gradually.
The process of process for preparing graphenes by chemical vapour deposition generally is to utilize carbon compounds such as methane as carbon source, through it in the grow process of Graphene of matrix surface pyrolytic decomposition.The growth mechanism of process for preparing graphenes by chemical vapour deposition mainly is divided into two kinds: a kind of is that carbon mechanism is analysed in carburizing; The matrix that promptly has higher molten carbon amount for nickel etc.; The carbon atom that the carbon source cracking produces infiltrates when high temperature in the matrix, when low temperature, separates out from inside again and crystallizes into Graphene; Another kind is a surface growth mechanism, promptly has the low matrix that dissolves the carbon amount for copper etc., and the carbon atom that the carbon source cracking generates under the high temperature is adsorbed on matrix surface, and then nucleating growth becomes Graphene.1999, Kim etc. were utilized in SiO
2Sedimentary metal nickel film is a matrix on the/Si substrate; With methane is carbon source, prepares large-area few layer graphene (Kim KS, et al.Nature; 2009; 457:706-710), and successfully Graphene is intactly shifted from matrix, thereby started the upsurge of process for preparing graphenes by chemical vapour deposition.Grain-size is little, the number of plies is difficult to problems such as control because the Graphene that adopts the Ni film to grow exists; The Ruoff study group in texas,U.S university Austin branch school utilizes the Cu paper tinsel to be carbon source as matrix, methane; Grow size and can reach single-layer graphene (the Li XS of centimetre-sized; Et al.Science, 2009,324:1312-1314).In addition, high great an ancient unit of weight study group of Inst. of Physics, CAS adopts monocrystalline Ru as matrix, under the growth conditions of ultrahigh vacuum(HHV) and 1000oC, prepare millimetre-sized single crystal graphite alkene (Pan Y, et al.Adv.Mater., 2009,21:2777-2780).Although the method that above-mentioned employing metal is a matrix through process for preparing graphenes by chemical vapour deposition can obtain large-area, high-quality Graphene; But the lower and transfer process more complicated of matrix price productive rate more expensive, Graphene in this method, and be unfavorable for that the magnanimity of grapheme material prepares.
Research shows, the MOX of a part, like Natural manganese dioxide etc., also can be used as Graphene deposit matrix.Rummeli etc. are matrix with Natural manganese dioxide, be carbon source with multiple hydrocarbon polymer, successfully deposit few layer graphite linings at low temperatures, and through simple acid cleaning process at mgo surface; Obtain nano-graphene material (RummeliMH; Et al.ACS Nano, 2010,4:4206-4210).It is that growing substrate, methane are carbon source that the Ningguo of China University Of Petroleum Beijing celebrating etc. is further adopted Natural manganese dioxide, in fluidized-bed reactor, prepare in large quantities grapheme material (Ning GQ, et al.Chem.Commun., 2011,47:5976-5978).The advantage that with the MOX to be that the method for matrix growth grapheme material has with low cost, process simple and be easy to amplify is the comparison effective means of batch preparations Graphene.Yet Natural manganese dioxide matrix at present commonly used is because the Graphene that its shape often and irregularity, causes preparing is second-rate.
Layer dihydroxy metal hydroxides (Layered Double Hydroxide is abbreviated as LDH) is a kind of hydrotalcite-like material.The intercalation compound of LDH is called intercalation material (LDHs), and the vertical ordered arrangement of two-dimentional laminate that its most classical structure is a nanometer scale forms three-dimensional crystalline structure, and its laminate metallic element is mainly magnesium and aluminium, is covalent bonding between atom; There is negatively charged ion in interlayer, with weak chemical bond, is connected with the main body laminate like ionic linkage, hydrogen bond etc.The laminate skeleton has positive charge, and interlayer anion is balance with it, and integral body presents electroneutral.Its chemical constitution is generally: M
2+ 1-xM
3+ x(OH)
2A
N- X/nMH
2O.Wherein, M
3+Be the ionic radius trivalent metal ion close, A with magnesium
N-Be n valency negatively charged ion.LDH often is hexagonal sheet structure, and it is of a size of tens nanometer and does not wait to several microns, and its sheet structure has thermostability preferably.The LDH particle can have fluidisation behavior preferably through agglomeration in fluidized-bed in addition, and it is with low cost, if with the matrix of LDHs as the growth grapheme material, then is expected to obtain controllable size, better quality, Graphene cheaply.
Summary of the invention
The object of the present invention is to provide a kind ofly to prepare the method for Graphene, enriched the template kind of preparation Graphene, can obtain controllable size, better quality, Graphene cheaply, advance the applied research of Graphene based on the layer dihydroxy metal hydroxides.
The present invention provides a kind of and prepares the method for Graphene based on the layer dihydroxy metal hydroxides, it is characterized in that this method carries out as follows:
1) the layer dihydroxy metal hydroxides is put into reactor drum as catalyst precursor; The chemical constitution general formula of wherein said layer dihydroxy MOX sheet is M
2+ 1-xM
3+ x(OH)
2A
N- X/nMH
2O;
Wherein: M
2+With M
3+Molar ratio be 1～4, x is M
3+With (M
2++ M
3+) molar ratio; M is the number of middle water molecule; M
2+Be Mg
2+, Ca
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+And Cu
2+In one or more, M
3+Be Al
3+, Co
3+, Fe
3+And Ru
3+In one or more, A
N-Be n valency negatively charged ion, corresponding negatively charged ion is Cl
-, OH
-, NO
3 -, SO
4 2-And CO
3 2-In one or more, corresponding negatively charged ion also comprises organic anion and contains Mo or the isopoly-acid of W or heteropolyacid anions;
2) the layer dihydroxy metal hydroxides is warming up to pretreatment temperature and carries out calcining pretreatment, described pretreatment temperature is 300～1200 ° of C;
3) in reactor drum, feed the mixed gas of carbon source, hydrogen and carrier gas; Hydrogen wherein: carbon-source gas: the volume ratio of carrier gas is 0～2: 1: 0.1～6; Under the temperature of reaction of 600～1200 ° of C, react; Through chemical vapor deposition processes, on layer dihydroxy MOX sheet, deposit Graphene;
4) product that obtains after the chemical vapour deposition is purified, obtain highly purified Graphene.
The air speed of described chemical vapor deposition processes is 1～5000hr
-1, gas speed is 0.01～5m/s; Described reactor drum adopts fixed bed, moving-bed, fluidized-bed or their combination; Calcining pretreatment atmosphere is one or several the mixture in nitrogen, argon gas and the helium; Said carbon source adopts one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon; Described carrier gas is one or several the mixture in nitrogen, argon gas, the helium.
Compare prior art, the present invention has following advantage and beneficial effect: the present invention can pass through the component and the effective number of plies, shape and the size of controlling Graphene of size of control reaction conditions and layer dihydroxy metal hydroxides, and productive rate is higher.The layer dihydroxy metal hydroxides, the carbon source that adopt in this method are cheap and easy to get, are convenient to engineering amplification and batch process, for the practical applications of Graphene is laid a good foundation.
Description of drawings:
Fig. 1 is the stereoscan photograph of the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform.
Fig. 2 is the XRD spectra of the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform.
Fig. 3 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the typical low power stereoscan photograph of the Graphene of method preparation of the present invention.
Fig. 4 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the typical high power stereoscan photograph of the Graphene of method preparation of the present invention.
Fig. 5 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the typical transmission electron microscope photo of the Graphene of method preparation of the present invention.
Fig. 6 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the typical high-resolution-ration transmission electric-lens photo of the Graphene of method preparation of the present invention.
Fig. 7 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the Raman collection of illustrative plates of the Graphene of method preparation of the present invention.
Fig. 8 is with the two dihydroxy metal hydroxides of Mg/Al LDHs binary stratiform, with CH
4Be carbon source, utilize the thermogravimetric analysis result of the Graphene of method preparation of the present invention.
Fig. 9 uses Co/Al LDHs, with CH
4Be carbon source, utilize the stereoscan photograph of the Graphene of method preparation of the present invention.
Figure 10 uses Fe/Mg/Al LDHs, with CH
4Be carbon source, utilize the stereoscan photograph of the Graphene of method preparation of the present invention.
Embodiment
A kind of step for preparing the method for Graphene based on the layer dihydroxy metal hydroxides provided by the invention is:
1) the layer dihydroxy metal hydroxides is put into reactor drum as catalyst precursor; The chemical constitution general formula of wherein said layer dihydroxy MOX sheet is M
2+ 1-xM
3+ x(OH)
2A
N- X/nMH
2O;
Wherein: M
2+With M
3+Molar ratio be 1～4, x is M
3+With (M
2++ M
3+) molar ratio; M is the number of middle water molecule; M
2+Be Mg
2+, Ca
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+And Cu
2+In one or more, M
3+Be Al
3+, Co
3+, Fe
3+And Ru
3+In one or more, A
N-Be n valency negatively charged ion, corresponding negatively charged ion is Cl
-, OH
-, NO
3 -, SO
4 2-And CO
3 2-In one or more, corresponding negatively charged ion also comprises organic anion and contains Mo or the isopoly-acid of W or heteropolyacid anions;
2) the layer dihydroxy metal hydroxides is warming up to pretreatment temperature and carries out calcining pretreatment, described pretreatment temperature is 300～1200 ° of C;
3) in reactor drum, feed the mixed gas of carbon source, hydrogen and carrier gas; Hydrogen wherein: carbon-source gas: the volume ratio of carrier gas is 0～2: 1: 0.1～6; Under the temperature of reaction of 600～1200 ° of C, react; Through chemical vapor deposition processes, on layer dihydroxy MOX sheet, deposit Graphene;
4) product that obtains after the chemical vapour deposition is purified, obtain highly purified Graphene.
The air speed of described chemical vapor deposition processes is 1～5000hr
-1, gas speed is 0.01～5m/s; Described reactor drum adopts fixed bed, moving-bed, fluidized-bed or their combination; Calcining pretreatment atmosphere is one or several the mixture in nitrogen, argon gas and the helium; Said carbon source adopts one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon; Described carrier gas is one or several the mixture in nitrogen, argon gas, the helium.
Through several concrete embodiment the present invention is further described below.
Embodiment 1: based on preparing Graphene in the Mg/Al LDHs fixed bed
With Mg, Al atomic ratio be the Mg/Al LDHs of 2:1 as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.This catalyzer pattern can know that referring to Fig. 1 its primary structure is uniform sheet hexagon.The XRD spectra of Fig. 2 shows that this catalyzer is typical layer dihydroxy metal hydroxides structure, and its percent crystallinity is high.Use argon gas to be carrier gas, its flow is 600sccm.Temperature rise rate with 10 ° of C/min under this atmosphere is raised to 950 ° of C of pretreatment temperature with temperature of reactor by room temperature, keeps 10min then; Afterwards with maintain at 950 ° of C, feed the gas mixture of carbon source methane, hydrogen and argon gas, wherein hydrogen: methane: the volume ratio of argon gas is 0.1: 1: 0.2, the air speed in the control reaction process is 400hr
-1Gas speed is 0.4m/s, carries out chemical vapor deposition processes.Close carbon source methane and H2 behind the 10min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6hr with the NaOH aqueous solution of 3mol/L earlier remove the aluminum oxide in the product in the purification of products device under 180 ° of C; Again its HCl aqueous solution with 1mol/L is handled 6hr under 80 ° of C and remove the Natural manganese dioxide in the product; Can obtain grapheme material; Its macro morphology can see that referring to Fig. 3 resulting grapheme material is hexagonal sheet structure; The further high resolution scanning electromicroscopic photograph of Fig. 4 can see that the size of this grapheme material is about 2 microns.It is the hexagon sheet structure that is of a size of about 2 microns that the transmission electron microscope photo that Fig. 5 shows further specifies resulting grapheme material.The high-resolution-ration transmission electric-lens photo of Fig. 6, its number of plies can be seen graphite linings structure clearly at 1 ~ 3 layer.In the Raman collection of illustrative plates of Fig. 7, the grapheme material defective that lower D peak and the explanation of the ratio at G peak make is less, and the thermogravimetric result of Fig. 8 shows that resulting grapheme material purity is high, and quality is good.
Embodiment 2: based on preparing Graphene in the Mg/Al LDHs fluidized-bed.
With Mg, Al atomic ratio be the Mg/Al LDHs of 4:1 as catalyzer, get 1g and place in the quartzy fluidized-bed reactor.Use nitrogen to be carrier gas, its flow is 2000sccm.Under this atmosphere, temperature of reactor is raised to 1200 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 1200 ° of C, feed carbon source methane, the gas mixture of hydrogen and nitrogen, wherein hydrogen: methane: the volume ratio of nitrogen is 2: 1: 2, the air speed of controlling in the reaction process is 200hr
-1Gas speed is 0.1m/s, carries out chemical vapor deposition processes.Close carbon source methane and hydrogen behind the 30min, take out solid product after under nitrogen atmosphere, being cooled to room temperature.Solid product is handled 6hr with the HCl aqueous solution of 1mol/L earlier remove the Natural manganese dioxide in the product in the purification of products device under 80 ° of C; Again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C and remove the aluminum oxide in the product, can obtain grapheme material.
Embodiment 3: based on preparing Graphene in the Co/Al LDHs fixed bed.
With Co, Al atomic ratio be the Co/Al LDHs of 1:1 as catalyzer, get 50mg and place in the fixed-bed reactor.Use helium to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 300 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 1 ° of C/min; Afterwards temperature of reaction is risen to 800 ° of C, feed the gas mixture of carbon source ethene and helium, therein ethylene: the volume ratio of helium is 1: 6, and the air speed in the control reaction process is 50hr
-1Gas speed is 0.05m/s, carries out chemical vapor deposition processes.Close ethene behind the 10min, take out solid product after under helium atmosphere, being cooled to room temperature.Solid product is handled 6hr with the HCl aqueous solution of 1mol/L earlier remove the Natural manganese dioxide in the product in the purification of products device under 80 ° of C; Again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C and remove the aluminum oxide in the product; Can obtain grapheme material, its stereoscan photograph is referring to Fig. 8.
Embodiment 4: based on preparing Graphene in the Fe/Mg LDHs fixed bed.
With Fe, Mg atomic ratio be the Fe/Mg LDHs of 2:1 as catalyzer, get 100mg and place in the fixed-bed reactor.Use the gas mixture of argon gas and nitrogen to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1200 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 5 ° of C/min; Afterwards with maintain at 1200 ° of C, feed carbon source CO, the gas mixture of argon gas and helium, wherein CO: argon gas: the volume ratio of helium is 1: 0.1: 0.1, the air speed of controlling in the reaction process is 5000hr
-1Gas speed is 5m/s, carries out chemical vapor deposition processes.Close CO behind the 30min, after being cooled to room temperature under the gas mixture atmosphere of argon gas and helium, take out solid product.Solid product as in the purification of products device, is handled 6hr with the HCl aqueous solution of 1mol/L and carried out purifying under 80 ° of C, can obtain grapheme material.
Embodiment 5: based on preparing Graphene in the Ni/Al LDHs fixed bed.
With Ni, Al atomic ratio be the Ni/Al LDHs of 2:1 as catalyzer, get 50mg and place in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 100sccm.Under this atmosphere, temperature of reactor is raised to 600 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 15 ° of C/min; Afterwards with maintain at 600 ° of C, feed the gas mixture of carbon source YLENE and argon gas, wherein YLENE: the volume ratio of argon gas is 1: 6, the air speed of controlling in the reaction process is 1hr
-1Gas speed is 0.01m/s, carries out chemical vapor deposition processes.Close YLENE behind the 30min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product as in the purification of products device, is handled 6hr with the HCl aqueous solution of 1mol/L and carried out purifying under 80 ° of C, can obtain grapheme material.
Embodiment 6: based on preparing Graphene in the Fe/Mg/Al LDHs fixed bed.
With Fe, Mg, Al atomic ratio be 0.2: 2: 1 Fe/Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use nitrogen to be carrier gas, its flow is 500sccm.Under this atmosphere, temperature of reactor is raised to 500 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 10 ° of C/min; Afterwards temperature of reactor is transferred to 800 ° of C of temperature of reaction, feed the gas mixture of carbon source propylene and nitrogen, wherein propylene: the volume ratio of nitrogen is 1: 5, and the air speed in the control reaction process is 300hr
-1Gas speed is 0.2m/s, carries out chemical vapor deposition processes.Close propylene behind the 10min, take out solid product after under nitrogen atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material, its stereoscan photograph is referring to Fig. 9.
Embodiment 7: based on preparing Graphene in the Cu/Mg/Al LDHs fixed bed.
With Cu, Mg, Al atomic ratio be 0.3: 2: 1 Cu/Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 300sccm.Under this atmosphere, temperature of reactor is raised to 1000 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 15 ° of C/min; Afterwards with maintain at 1000 ° of C, feed the gas mixture of carbon source ethane and argon gas, wherein ethane: the volume ratio of argon gas is 1: 2, the air speed of controlling in the reaction process is 200hr
-1Gas speed is 0.1m/s, carries out chemical vapor deposition processes.Close ethane behind the 10min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 8: based on preparing Graphene in the Co/Ni/Mg/Al LDHs fixed bed.
With Co, Ni, Mg, Al atomic ratio is 0.2: 0.2: 2: 1 Co/Ni/Mg/Al LDHs gets 50mg and places in the fixed-bed reactor as catalyzer.Use argon gas to be carrier gas, its flow is 500sccm.Under this atmosphere, temperature of reactor is raised to 700 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 10 ° of C/min; Afterwards temperature of reactor is maintained 700 ° of C, feed the gas mixture of carbon source acetylene and argon gas, wherein acetylene: the volume ratio of argon gas is 1: 1, and the air speed in the control reaction process is 10hr
-1Gas speed is 0.01m/s, carries out chemical vapor deposition processes.Close acetylene and H behind the 20min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 9: with Fe/Mg/Al-Mo LDHs is that catalyst precursor prepares Graphene through fixed bed.
With Fe, Mg, Al atomic ratio is that 0.2: 2: 1 Fe/Mg/Al LDHs is as catalyzer, with this catalyzer calcination 30min under the temperature of 450 ° of C, in air atmosphere; Again the product after the calcination being impregnated in pH value is 2h in 8.0 ammonium molybdate and the aqueous sodium hydroxide solution, the Fe/Mg/Al-Mo LDHs catalyzer that filter, freeze-drying obtains the molybdenum acid ion intercalation.Getting 50mg places in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 100sccm.Under this atmosphere, temperature of reactor is raised to 800 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 5min with the temperature rise rate of 10 ° of C/min; Afterwards with maintain at 800 ° of C, feed the gas mixture of carbon source propane and argon gas, wherein propane: the volume ratio of argon gas is 1: 0.3, the air speed of controlling in the reaction process is 400hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close propane behind the 10min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 10: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 3: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 500sccm.Under this atmosphere, temperature of reactor is raised to 900 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 900 ° of C, feed the gas mixture of carbon source hexanaphthene, hydrogen and argon gas, wherein hydrogen: hexanaphthene: the volume ratio of argon gas is 0.5: 1: 5, the air speed in the control reaction process is 100hr
-1Gas speed is 0.1m/s, carries out chemical vapor deposition processes.Close carbon source hexanaphthene and H behind the 10min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 11: based on preparing Graphene in the Mg/Al LDHs moving-bed.
With Mg, Al atomic ratio be 2.5: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the moving-burden bed reactor.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 800 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 800 ° of C, feed the gas mixture of carbon source normal hexane, hydrogen and argon gas, wherein hydrogen: normal hexane: the volume ratio of argon gas is 2: 1: 6, the air speed in the control reaction process is 100hr
-1Gas speed is 0.1m/s, carries out chemical vapor deposition processes.Close carbon source normal hexane and H behind the 10min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 12: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 2: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 100sccm.Under this atmosphere, temperature of reactor is raised to 800 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 800 ° of C, feed the gas mixture of carbon source ethanol, hydrogen and argon gas, wherein hydrogen: ethanol: the volume ratio of argon gas is 0.2: 1: 1, the air speed in the control reaction process is 300hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close carbon source ethanol and H2 behind the 20min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 13: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 1: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use argon gas to be carrier gas, its flow is 100sccm.Under this atmosphere, temperature of reactor is raised to 900 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 900 ° of C, feed the gas mixture of carbon source methyl alcohol, hydrogen and argon gas, wherein hydrogen: methyl alcohol: the volume ratio of argon gas is 0.2: 1: 0.5, the air speed in the control reaction process is 250hr
-1Gas speed is 0.2m/s, carries out chemical vapor deposition processes.Close carbon source methyl alcohol and H2 behind the 30min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 14: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 2: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use nitrogen to be carrier gas, its flow is 300sccm.Under this atmosphere, temperature of reactor is raised to 1000 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 1000 ° of C, feed the gas mixture of carbon source Sweet natural gas, hydrogen and argon gas, wherein hydrogen: Sweet natural gas: the volume ratio of argon gas is 0.2: 1: 1, the air speed in the control reaction process is 300hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close carbon source Sweet natural gas and H behind the 30min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 15: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 2: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use the gas mixture of nitrogen and argon gas to be carrier gas, its flow is 200sccm.Under this atmosphere, temperature of reactor is raised to 850 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 850 ° of C, feed the gas mixture of carbon source benzene, hydrogen and argon gas, wherein hydrogen: benzene: the volume ratio of argon gas is 0.2: 1: 1, the air speed in the control reaction process is 300hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close carbon source benzene and H behind the 30min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 16: based on preparing Graphene in the Mg/Al LDHs fixed bed.
With Mg, Al atomic ratio be 2: 1 Mg/Al LDHs as catalyzer, get 50mg and place in the fixed-bed reactor.Use the gas mixture of nitrogen and argon gas to be carrier gas, its flow is 200sccm.Under this atmosphere, temperature of reactor is raised to 750 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards with maintain at 750 ° of C, feed the gas mixture of carbon source toluene, hydrogen and argon gas, wherein hydrogen: toluene: the volume ratio of argon gas is 0.2: 1: 1, the air speed in the control reaction process is 300hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close carbon source toluene and H behind the 30min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Embodiment 17: prepare Graphene in the combined reactor based on Mg/Al LDHs fixed bed and fluidized-bed.
With Mg, Al atomic ratio be 2: 1 Mg/Al LDHs as catalyzer, get 500mg and place in the fluidized-bed reactor.Use nitrogen to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 850 ° of C of pretreatment temperature by room temperature and carries out pre-treatment 10min with the temperature rise rate of 20 ° of C/min; Afterwards carrier gas flux is heightened to 3000sccm; Pretreated catalyzer in the fluidized-bed is blown in the fixed-bed reactor that temperature is 950 ° of C; Feed the gas mixture of carbon source methane, hydrogen and argon gas in this reactor drum; Hydrogen wherein: methane: the volume ratio of argon gas is 0.2: 1: 1, and the air speed in the control reaction process is 300hr
-1Gas speed is 0.3m/s, carries out chemical vapor deposition processes.Close carbon source methane and H2 behind the 30min, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6h with the HCl aqueous solution of 1mol/L earlier in the purification of products device, again its NaOH aqueous solution with 3mol/L is handled 6hr under 180 ° of C under 80 ° of C, can obtain grapheme material.
Claims (6)
1. one kind prepares the method for Graphene based on the layer dihydroxy metal hydroxides, it is characterized in that this method carries out as follows:
1) the layer dihydroxy metal hydroxides is put into reactor drum as catalyst precursor; The chemical constitution general formula of wherein said layer dihydroxy MOX sheet is M
2+ 1-xM
3+ x(OH)
2A
N- X/nMH
2O;
Wherein: M
2+With M
3+Molar ratio be 1～4, x is M
3+With (M
2++ M
3+) molar ratio; M is the number of middle water molecule; M
2+Be Mg
2+, Ca
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+And Cu
2+In one or more, M
3+Be Al
3+, Co
3+, Fe
3+And Ru
3+In one or more, A
N-Be n valency negatively charged ion, corresponding negatively charged ion is Cl
-, OH
-, NO
3 -, SO
4 2-And CO
3 2-In one or more, corresponding negatively charged ion also comprises organic anion and contains Mo or the isopoly-acid of W or heteropolyacid anions;
2) the layer dihydroxy metal hydroxides is warming up to pretreatment temperature and carries out calcining pretreatment, described pretreatment temperature is 300～1200 ° of C;
3) in reactor drum, feed the mixed gas of carbon source, hydrogen and carrier gas; Hydrogen wherein: carbon-source gas: the volume ratio of carrier gas is 0～2: 1: 0.1～6; Under the temperature of reaction of 600～1200 ° of C, react; Through chemical vapor deposition processes, on layer dihydroxy MOX sheet, deposit Graphene;
4) product that obtains after the chemical vapour deposition is purified, obtain highly purified Graphene.
2. prepare the method for Graphene according to claim 1 is said based on the layer dihydroxy metal hydroxides, it is characterized in that: the air speed of the reaction process described in the step 3) is 1～5000hr
-1, gas speed is 0.01～5m/s.
3. saidly prepare the method for Graphene based on the layer dihydroxy metal hydroxides according to claim 1 or 2, it is characterized in that: described reactor drum adopts fixed bed, moving-bed, fluidized-bed or their combination.
4. saidly preparing the method for Graphene according to claim 1 or 2, it is characterized in that: step 2 based on the layer dihydroxy metal hydroxides) calcining pretreatment atmosphere is one or several the mixture in nitrogen, argon gas and the helium.
5. saidly prepare the method for Graphene based on the layer dihydroxy metal hydroxides according to claim 1 or 2, it is characterized in that: carbon source described in the step 3) adopts one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon.
6. saidly prepare the method for Graphene based on the layer dihydroxy metal hydroxides according to claim 1 or 2, it is characterized in that: the carrier gas described in the step 3) is one or several the mixture in nitrogen, argon gas, the helium.
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