A kind of solid phase cracking process is prepared the method for azepine Graphene and nano metal Graphene
Technical field
The present invention adopts a kind of solid phase cracking technique to prepare azepine Graphene and nano metal grapheme material, belongs to new high-tech material preparation field.
Background technology
Since Geim in 2004 etc. utilize adhesive tape repeatedly to peel off on natural graphite to make Graphene [1], Graphene causes unprecedented sensation in scientific circles because of its unique individual layer sheet hexagonal honeycomb crystalline network, and its unique excellent properties and huge potential using value have caused whole world extensive concern especially.Chemical bonding mode, form the carbon atom of Graphene two-dirnentional structure with sp
2mode hydridization, this hybrid form makes carbon atom and adjacent three carbon atoms form stable C-C key by σ key, has given Graphene high mechanical property [2].The π-electron delocalization that simultaneously a large amount of carbon atoms provide on perpendicular to Graphene plane forms large π key, and electronics can move freely therein, so Graphene all has excellent electroconductibility conventionally.Such as Graphene is a kind of zero gap semiconductor, electronics therein movement velocity can reach 1/300 of the light velocity, and Graphene carrier mobility speed is up to 2 * 10
5cm
2v
-1s
-1deng [3-8].In addition, Graphene also has good thermal property and magnetic performance [9,10].The specific surface area that Graphene is higher makes it at ultracapacitor, Chu Qing, and the fields such as unit molecule chemical sensor have huge potential application [11].
At present, graphite oxide reduction method is to prepare the main method of Graphene, and the method is that graphite is carried out to strong oxide treatment, obtains again it being peeled off and preparing graphene oxide after graphene oxide, finally by crossing reduction processing, obtains Graphene.Structure due to meeting havoc graphene sheet layer in strong oxidising process, although process through reduction, the electron conjugated structure of graphene sheet layer obtains part and recovers, and the property indices of gained grapheme material still exists larger gap with high-quality Graphene.In addition, the oxidising process of graphite needs a large amount of strongly-acid oxygenants as the vitriol oil, concentrated nitric acid and potassium permanganate etc. conventionally, and in reduction process, also need the toxic chemical substances such as hydrazine hydrate or sodium borohydride, not only energy consumption is large, inefficiency, cost is high but also seriously polluted.As patent of invention CN102897756, CN102897757 etc.
Epitaxial growth method is prepared Graphene needs at high temperature, be filled with carbon-source gas (methane, ethane, acetylene etc.), decomposing gas also forms Graphene in substrate, the method needs the above high temperature of 1000 degree, and need hydrogen as reducing gas, working condition is required strictly to long reaction time, productive rate is low, and the use of a large amount of hazardous gases has increased the further application that production cost has also limited Graphene.As patent of invention CN102903616, CN102891074 etc.
The characteristic electron of nitrating capable of regulating device in Graphene, conductivity and the electrochemical stability thereof of raising Graphene.Graphene nitrogen-doping method mainly contains (as patent of invention CN102887498, CN102745678, CN101708837 etc.) such as hydrothermal synthesis method, chemical synthesis, CVD method, plasma sputterings at present, and these method combined coefficienies and quality are generally lower.And in Graphene, mix the common way that metal nanoparticle is electrochemical device modification and electrode modification etc., at present main complex method has (as CN102174702A, CN102136306A etc.) such as oxidation reduction process, electrochemical reducings, the subject matter of these methods is to have a large amount of chemical waste fluids, and nanoparticle is easily assembled.
Therefore, in the urgent need to develop a kind of adopt novel material, method is simple, to equipment without particular requirement, cost is low, efficiency is high, zero pollution, zero release, easily promote the use of, can solve the problems such as the cost existing in existing Graphene technology of preparing is high, efficiency is low, of poor quality, and the azepine Graphene that can once produce from starting material without generation intermediates Graphene and the method for nano metal Graphene.
Phthalocyanine is a class macrocylc compound, and Phthalocyanine center is a 18-π system being comprised of carbon nitrogen conjugated double bond, has a cavity, diameter 2.7 * 10 in ring
-10m.Two hydrogen atoms in center cavity can be replaced by 70 multiple elements, comprise nearly all metallic element and a part of non-metallic element (as shown in Figure 1), and metal oxide etc.And phthalocyanine polymer is made a general reference those polymers that contains phthalocyanine ring structure (as Fig. 2).The present invention will be usingd this compounds as starting raw material, adopt Low Temperature Solid-Phase cracking technique to obtain Graphene class material.
Reference:
[1]Geim?A.K.;Novoselov?K.S.The?Rise?of?Graphene.Nature?Materials2007,6(3):183-191.
[2]Novoselov?K.S.;Jiang?Z.;Zhang?Y.;Room?temperature?quantum?hall?effect?in?graphene.Science,2007,315(5817):1379-1379.
[3]Rao,C.N.R.;Sood,A.K.;Voggu,R.;Subrahmanyam,K.S.Some?Novel?attributes?of?graphene.J.Phys.Chem.Lett.2010,1,572–580.
[4]Kamat,P.V.Graphene-Based?Nanoarchitectures.Anchoring?semiconductor?and?metal?nanoparticles?on?a?two-dimensional?carbon?support.J.Phys.Chem.Lett.2010,1,520–527.
[5]Green,A.A.;Hersam,M.C.Emerging?methods?for?producing?monodisperse?graphene?dispersions.J.Phys.Chem.Lett.2010,1,544–549.
[6]Li,L.S.;Yan,X.Colloidal?graphene?quantum?dots.J.Phys.Chem.Lett.2010,1,2572–2576.
[7]Du,A.;Smith,S.C.Electronic?Functionality?in?graphene-based?nanoarchitectures:discovery?and?design?via?first-Principles?modeling.J.Phys.Chem.Lett.2010,2,73–80.
[8]Kamat,P.V.Graphene-based?nanoassemblies?for?energy?conversion.J.Phys.Chem.Lett.2011,2,242–251.
[9]Balandin?A.A.;Ghosh?S.;Bao?W.;Calizo?I.;Teweldebrhan?D.;Miao?F.Superior?thermal?conductivity?of?single-layer?graphene.Nano.Lett.2008,8(3):902-907.
[10]Ghosh?S.;Calizo?I.;Teweldebrhan?D.;Pokatilov?E.P.;Nika?D.L.;Balandin?A.A.;Extremely?high?thermal?conductivity?of?graphene:prospects?for?thermal?management?applications?in?nanoelectronic?circuits.Applied?Physics?Letters,2008,92(15).
[11]Stoller?M.D.;Park?S.;Zhu?Y.;Graphene-based?ultracapacitors.Nano?Lett.;2008,8(10):3498-3502.
Summary of the invention
The invention provides a kind of method that adopts solid phase cracking technique to prepare azepine Graphene and metallic graphite carbon alkene.It relates to take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, under the conventional atmosphere such as nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia mixing, with reference to the thermochemistry characteristic of raw material, more than 700 degree, disposable cracking prepares nitrogenous Graphene and metallic graphite carbon alkene class material.Its method feature is as follows: with phthalocyanine compound, phthalocyanine polymer and derivative thereof, as unique starting raw material one step solid phase cracking, obtain azepine Graphene and nano metal Graphene class material 1.; 2. cracking temperature is low, energy efficient; 3. adopt protection of inert gas, can in non-nitrogen atmosphere environment, cracking obtain Graphene class material, safe; 4. regulate the experiment parameters such as cracking temperature and gas flow can effectively control the size of Graphene class material, thickness and quality; 5. as catalyzer, can also obtain having the grapheme material of curling behavior usining Copper Foil or nickel foil, its conductivity of raising that can material etc.The Graphene class material that the present invention makes will be applied to the aspects such as single-molecule detection technology, field effect transistor and unicircuit thereof, transparency conductive electrode, electrically conductive ink, field emission source and vacuum electron device thereof, absorbing material, super capacitor and biological device.
Technical solution of the present invention one is as follows:
Step 1: take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, do not do other raw materials and process directly use.
Step 2: in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, once property cracking obtains azepine Graphene class and metallic graphite carbon alkene class material in catalyst-free condition.
Technical solution of the present invention two is as follows:
Step 1: take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, do not do other raw materials and process directly use.
Step 2: in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, having in metal catalyst condition once property cracking obtain having azepine Graphene class and the metallic graphite carbon alkene class material of coiled structure.
Described starting raw material can be commercially available or self-control metallo phthalocyanine and derivative thereof.Preferably one of magnesium-yttrium-transition metal phthalocyanine-like compound and derivative thereof (as Nickel Phthalocyanine, CuPc, FePC, phthalocyanine molybdenum, Cobalt Phthalocyanine, phthalocyanine gold, phthalocyanine is silver-colored and derivative etc.).
Described starting raw material can also be one of nonmetal phthalocyanine class materials such as pure phthalocyanine compound.
Described starting raw material can also be one of containing metal oxide phthalocyanines material.
Described starting raw material can also be one of the polymer that contains phthalocyanine ring structure or the porphyrin polymkeric substance that contains class phthalocyanine ring structure.
Described gas shield refers at conventional shielding gas such as nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixtures; The concrete ratio of gas mixture is between volume ratio 0.1:9.9~1:9; Flow rate control is at 10~50cm
3min
-1between;
Described metal catalyst refers to the metal or alloy such as Copper Foil, copper mesh, nickel foil, nickel foam.
The cracking temperature of described cracking is different according to the thermochemistry characteristic of raw material, more than being generally 700 degree, is preferably 800~1000 degree.
Under preferred cracking temperature, the time that cracking autocatalysis generates graphene sheet layer is 4~24 hours, shortens or extend pyrolysis time to final grapheme material size, and thickness and quality have impact.
In azepine Graphene class material, the acquisition of nitrogen element, from self nitrogen-atoms in phthalocyanine frame, as needs obtain the more nitrogen-atoms of high-content, can pass into the gas mixture of ammonia and rare gas element in cracking process.
In the Graphene class material of containing metal nanoparticle, the acquisition of metal nanoparticle, from the contained metal classification of starting raw material self, be take CuPc as example, obtains the most at last the grapheme material that contains metallic copper nano particle.
The technology of the present invention feature: 1. any compound that contains phthalocyanine ring and derivative thereof all can be used as the starting raw material that obtains azepine Graphene and metallic graphite carbon alkene; 2. for improving material electroconductibility or other character, can increase the final nitrogen content of material by passing into ammonia; 3. regulate the experiment parameters such as cracking temperature, gas flow, gas flow rate can effectively control the size of Graphene class material, thickness and quality; 4. using Copper Foil or nickel foil etc. during as catalyzer, also can obtain having the grapheme material of curling behavior, can improve its conductivity etc.; 5. different raw materials is formulated different temperature programming schemes according to its thermochemistry characteristic; The present invention also provide a kind of in grapheme material disposable new technology of mixing nitrogen and stable metal nano particle.
Accompanying drawing explanation
Fig. 1 Copper Phthalocyanine Molecule structural representation
Fig. 2 individual layer gathers phthalocyanine polymer schematic diagram
The XRD figure spectrum of the grapheme material that contains metallic copper nano particle of Fig. 3 nitrogen atom doping
The grapheme material transmission electron microscope photo that contains metallic copper nano particle of Fig. 4 nitrogen atom doping
The grapheme material XRD figure spectrum of Fig. 5 nitrogen atom doping
The grapheme material transmission electron microscope photo of Fig. 6 nitrogen atom doping
Fig. 7 has the grapheme material transmission electron microscope photo of the nitrogen atom doping of coiled structure
Fig. 8 has the grapheme material stereoscan photograph of petal-like nitrogen atom doping
The grapheme material transmission electron microscope photo that contains metal nickel nano particle of Fig. 9 nitrogen atom doping
The XRD figure spectrum of the grapheme material that contains metal nickel nano particle of Figure 10 nitrogen atom doping
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Without departing from the idea case in the present invention described above, various replacements or the change according to ordinary skill knowledge and customary means, made, all within the scope of the present invention.
Embodiment 1:
The 30.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In quartz tube furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.With slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 800 degree, 800 degree are stablized 8 hours, are finally naturally down to room temperature, obtain the Graphene that contains metallic copper nano particle, and its XRD and transmission electron microscope collection of illustrative plates are shown in Fig. 3 and Fig. 4.
Embodiment 2:
Take homemade CuPc as starting raw material, first as embodiment 1 prepares the Graphene that contains metallic copper nano particle, then use pure HCl, pure H
2sO
4deng strong acid, dissolve, stirring at room obtains the not grapheme material of containing metal particle after several hours, and its XRD, transmission electron microscope are shown in respectively Fig. 5 and Fig. 6.
Embodiment 3:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, take Copper Foil or nickel foil as base material, under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 700 degree, 700 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 8 hours, are finally naturally down to room temperature, obtain having the grapheme material of the nitrogen atom doping of coiled structure with acid treatment, and its shape appearance figure is shown in Fig. 7.
Embodiment 4:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, splitting gas is argon gas/hydrogen gas mixture, and the concrete ratio of gas mixture is volume ratio 0.8:9.2, and flow rate control is at 40cm
3min
-1, simultaneously as embodiment 1 cracking temperature, obtaining thering is the grapheme material that petal-like nitrogen-atoms mixes, its shape appearance figure is shown in Fig. 8.
Embodiment 5:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, as shown in embodiment mono-, splitting gas is argon gas/ammonia gas mixture body, and the concrete ratio of gas mixture is volume ratio 0.5:9.5, and flow rate control is at 30cm
3min
-1, simultaneously as embodiment 1 cracking temperature, obtaining the grapheme material of high nitrogen doped cupric, ultimate analysis shows that nitrogen content mass ratio is 14.05%.
Embodiment 6:
Take Nickel Phthalocyanine as starting raw material, do not do any purification process, in quartz tube furnace, under high-purity argon gas protection, argon gas stream speed control is built in 10cm
3min
-1, its heating schedule is as follows: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 2 hours; With 2 degree per minutes, be warming up to 900 degree, 900 degree are stablized 12 hours, are finally naturally down to room temperature, obtain the Graphene that contains metal nickel nano particle of nitrogen atom doping, and its pattern is shown in Fig. 9, and Figure 10 is the XRD figure of the Graphene that contains metal nickel nano particle.
Embodiment 7:
The 10.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In box atmosphere furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, with slow heat-up rate 5 degree per minutes, being warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 700 degree, at 700 degree, stablize 12 hours, be finally naturally down to room temperature, under above-mentioned intensification scheme, cracking obtains 7.1 grams of metallic graphite carbon alkene class materials.
Embodiment 8:
Take and gather phthalocyanine as starting raw material, do not do any purification process, in quartz tube furnace, take Copper Foil as catalyzer, under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 700 degree, 700 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 8 hours, are finally naturally down to room temperature, obtain having the grapheme material of the nitrogen atom doping of coiled structure.
Embodiment 9:
The 20.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In box atmosphere furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, with slow heat-up rate 5 degree per minutes, being warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 4 hours, are finally naturally down to room temperature, obtain 14.6 grams of Graphene class materials that contain metallic copper nano particle.
Reference examples:
The step of the synthetic method of the nitrating Graphene of Chinese invention patent CN201110204957 is: first clean, drying substrates; At substrate surface, apply the solution that contains catalyzer, this catalyzer is water-soluble metal salt; Under oxygen free condition, the substrate temperature that is coated with catalyzer is risen to 500~1300 ℃, then pass into reducing gas, reducing catalyst, then pass into the organic carbon source compound of gaseous state and the nitrogen source compound of gaseous state and react, obtain described nitrating Graphene, its itrogen content of getter with nitrogen doped is 3.7%.