CN109368620A - A kind of preparation method of extra small sub-nanometer hole porous graphene - Google Patents
A kind of preparation method of extra small sub-nanometer hole porous graphene Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of extra small sub-nanometer hole porous graphene, and graphene oxide powder and metal carbonyl are distinguished dispersion component dispersion liquid, and mixing carries out first time solvent thermal reaction, and metal oxide nano point is made and loads grapheme material；Metal oxide nano point load graphene is placed in the environment for being passed through high-purity argon gas protection gas, anneals, is washed off after cooling, dry, extra small sub-nanometer hole porous graphene is made.The preparation method can realize etching of the graphene surface less than 1 nano-pore, and regulate and control aperture size in nanoscale, guarantee the homogeneity in aperture.The uniform load of extra small metal oxide ensure that the homogeneity for carving hole, the aperture of nano particle can direct regulation and control carve the size in hole.Compared with common graphene carves hole method, aperture of the present invention is smaller, and size controlling is more accurate, uniform, and preparation method is simple, substantially increases the control precision in aperture, is easy to industrial applications.
Description
Technical field
The invention belongs to porous graphene technical field of material, it is related to a kind of extra small sub-nanometer hole porous graphene
Preparation method.
Background technique
Graphene be one kind by carbon atom with SP2Hybridized orbit forms the flat film that hexangle type is in honeycomb lattice, only
The two-dimensional material of one carbon atom thickness.2004, Univ Manchester UK physicist An Deliehaimu and Constant
Ding Nuowoxiao love, successfully isolates graphene from graphite in an experiment.Graphene is can to accomplish single layer of carbon atom
Two-dimensional arrangements, the normal rigid of graphene honeycomb lattice, at room temperature, the speed for transmitting electronics are all faster than known conductor.Graphene
Atomic-scale structure it is very special, since graphene is substantially a kind of transparent, good conductor, it is saturating to be also adapted to manufacture
Bright Touch Screen, tabula rasa, solar battery, Semiconductor Physics, in terms of have significant application value.Grapheme material is also
It is a kind of excellent modifying agent, in terms of new energy field such as supercapacitor, lithium ion battery, due to its high conductance, height
Specific surface area is applicable to as electrode material.Since graphene has extra-high surface area to mass ratio, graphene can
With the conductive electrode for supercapacitor.It is existing that scientist thinks that the storage energy density of this supercapacitor can be greater than
Capacitor.But graphene is a kind of two-dimensional material of sheet, during using graphene, often relates to the biography of substance
It passs and spreads, such as the diffusion of electrolyte, the transmitting of carrier, the diffusion of gas.Because of the stacking of two-dimensional sheet material, use
It is unfavorable for substance transmitting in the process, seriously affects the performance of graphene performance.Furthermore the electronics in graphene transmits speed in interlayer
Degree is fast, but when electronics is injected on electrolyte or other substances adsorbed from graphene is relatively difficult.
Original graphite alkene or the graphene film of chemical modification are easy to interact by pi-pi accumulation and Van der Waals force weighs each other
It is folded to form irreversible aggregate, lead to the reduction of its property, including the specific surface area and much lower mass diffusion seriously reduced
Rate.In addition, needing additional processing or additive, this may further decrease stone when graphene film manufactures final products
The overall performance of black alkene.The expansible system of processable graphene and its massive material with high-specific surface area and design porosity
It is standby most important for many practical applications.Porous graphene is the structural derivative of graphene, refers in graphene
With the material of nanoscale hole hole in two-dimensional surface.Unique nano-pore structure in porous graphene lamella, makes it have higher
Specific surface area；It is transmitted in porous graphene all directions in addition, the presence of nano-pore has conducive to substance, promotes carbon-coating in liquid
It is come into full contact in phase system with other substances.The excellent characteristic of porous graphene make its energy storage and transition material (lithium from
Sub- battery, supercapacitor etc.), bio-sensing, water pollution processing and water pollution detection etc. fields have huge application potential.
Development is simple, economic, controllable porous graphene magnanimity preparation method be applied to it is very crucial.The system of porous graphene at present
Preparation Method mainly has template, ion beam bombardment method and chemical solution etching, but when preparing porous graphene in aforementioned manners,
It is generally difficult to control aperture, it is also difficult to realize batch production.It is by a kind of convenient mild scarce so that chemical solution etches as an example
Sunken-etching reaction has the porous graphene for enriching plane nano hole to prepare surface.Oxygen is usually heated under agitation
Graphite alkene and etching oxidation agent preparation.But etachable material and graphite oxide alkene reaction, etching process is not easy to control, is easy
Many fragments are generated, size, the number of the surface holes of the porous graphene of preparation not can control.Therefore, there is an urgent need to one kind more
Added with effect, pure, volume production and the method for preparing porous graphene for capableing of high-precision control aperture.
Summary of the invention
The purpose of the present invention is to provide a kind of more efficient, pure, volume production extra small sub-nanometer hole porous graphenes
Preparation method, and using this method prepare porous graphene when, being capable of high-precision control aperture.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of extra small sub-nanometer hole porous graphene
Preparation method, specifically:
1) 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and solid carbonyl metal respectively, and graphene oxide powder is added
In nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5 ~ 5 hour, it is made into the graphene oxide that mass-volume concentration is 0.5~5g/L
Suspension；The ratio that 1.25 microlitres of octylames need to be matched in 1 milligram of graphene oxide powder again, takes octylame；By solid carbonyl metal and
Octylame is added in nitrogen-nitrogen dimethylformamide, and ultrasonic disperse 0.5~5 hour, being made into total volume was graphene oxide suspension body
First dispersion solution of product 20%~50%, the first dispersion solution is uniformly mixed with graphene oxide suspension, 100 DEG C~
Solvent thermal reaction 0.5~5 hour at a temperature of 200 DEG C is made metal oxide nano point and loads grapheme material；
Alternatively, 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and liquid carbonyl metal, by graphene oxide powder respectively
It is added in nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5~5 hour, is made into the oxidation that mass-volume concentration is 0.5~5g/L
Graphene suspension；Liquid carbonyl metal is added in nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5~5 hour, is made into matter
The second dispersion solution that volumetric concentration is 0.5~5g/L is measured, the second dispersion solution and graphene oxide suspension are uniformly mixed,
Solvent thermal reaction 0.5 ~ 5 hour at a temperature of 100~200 DEG C is made metal oxide nano point and loads graphene；
2) metal oxide nano point load graphene is placed in the environment for being passed through high-purity argon gas protection gas, with 5 DEG C/min of liter
Warm rate is warming up to 300~1000 DEG C and keeps the temperature 1~5h, cooled to room temperature, salt acid elution, then is washed with distilled water, and dries
It is dry, extra small sub-nanometer hole porous graphene is made.
Preparation method of the present invention using metal carbonyl as presoma, on the surface of graphene Load Balanced distribution metal oxide
Nano particle, and as template, the preparation of sub-nanometer hole graphene is realized by carbon-thermal reduction, and by metal carbonyl
Selection, addition ratio, annealing temperature and time of metal carbonyl controlled, obtain controlling in the different holes of Nano grade
The porous graphene nano material of diameter is suitble to industrialized production so that control accurate pore size, improves utilization efficiency.Hole
Introducing effectively graphene film can be prevented to stack again, make obtained and there is good electric conductivity, energy storage with turn
The fields such as conversion materials (lithium ion battery, supercapacitor etc.), bio-sensing, water pollution processing and water pollution detection have huge
Application potential.
Detailed description of the invention
Fig. 1 is the process flow diagram using preparation method of the present invention synthesis porous graphene.
Fig. 2 is the phenogram of the stannic oxide/graphene nano material used in preparation method of the present invention, wherein a, and b is surface sweeping electricity
Sub- microscope figure；C, d are transmission electron microscope figure.
Fig. 3 is the phenogram of porous graphene nano material made from embodiment 1, in which: a is XRD characterization；B is Raman
Spectral characterization.
Fig. 4 is the chemical property figure of porous graphene nano material made from embodiment 1, in which: a is cyclic voltammetry
The result of measurement；B is the result of constant current charge-discharge hair measurement；C is non-porous graphene and porous graphene in same scan speed
The comparing result of cyclic voltammetry under rate；D is the comparing result of non-porous graphene and porous graphene electrochemical impedance.
Fig. 5 is the transmission electron microscope figure and particle of carbonyl cobalt and product after graphene oxide solvent heat in embodiment 1
Particle diameter distribution statistical results chart, in which: a, b are the transmission electron microscope figure of supported by cobalt oxide graphene, and c is grain diameter point
Cloth statistical results chart.
Fig. 6 be 1 carbonyl cobalt of embodiment with 650 DEG C of graphene oxide composite material carve hole after transmission electron microscope figure and aperture
Diameter distribution statistics result, wherein a, b are the transmission electron microscope phenogram of sub-nanometer hole porous graphene, and c is pore-size distribution
Statistical result.
Fig. 7 be in embodiment 2 after carbonyl nickel and graphene oxide solvent heat the transmission electron microscope phenogram of product with
Particle size distribution statistical results chart, wherein a, b are the transmission electron microscope figure of nickel oxide loaded graphene, and c is particle
Diameter distribution statistics result figure.
Fig. 8 is that carbonyl iron presoma loads graphene oxide composite material and 700 DEG C to carve the transmitted electron behind hole aobvious in embodiment 2
Micro mirror figure and pore-size distribution statistical results chart, wherein a, b are the transmission electron microscope figure of porous graphene, and c is pore-size distribution
Statistical results chart.
Fig. 9 is the transmission electron microscope of carbonyl iron and product after graphene oxide solvent heat in embodiment 2 and embodiment 3
Figure and particle size distribution statistical results chart.
Figure 10 is that carbonyl iron presoma loads transmitted electron of the graphene oxide after 800 DEG C of high temperature carve hole in embodiment 4
Microscope figure and pore-size distribution statistical results chart, wherein a, b are the transmission electron microscope figure of porous graphene, and c is aperture point
Cloth statistical results chart.
Figure 11 is that carbonyl iron presoma loads transmitted electron of the graphene oxide after 900 DEG C of high temperature carve hole in embodiment 4
Microscope figure.
Specific embodiment
The technical scheme in the embodiment of the invention is clearly and completely described below.
The present invention provides a kind of extra small sub-nanometer hole and the preparation method of the porous graphene of aperture controllable, techniques
Process is as shown in Figure 1, the preparation method specifically:
1) 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and solid carbonyl metal respectively, by graphene oxide powder plus
Enter in nitrogen-nitrogen dimethylformamide (DMF), ultrasonic disperse 0.5 ~ 5 hour, is made into the oxygen that mass-volume concentration is 0.5~5g/L
Graphite alkene suspension；The ratio for needing 1.25 microlitres of octylames in 1 milligram of graphene oxide powder again, takes octylame；By solid carbonyl
Base Metal and octylame are added in nitrogen-nitrogen dimethylformamide, and ultrasonic disperse 0.5 ~ 5 hour, being made into total volume was graphene oxide
First dispersion solution is uniformly mixed with graphene oxide suspension, is packed by the first dispersion solution of suspension vol 20% ~ 50%
In 50 milliliters of reaction kettles, which is placed in baking oven, 100~200 DEG C at a temperature of solvent thermal reaction 0.5 ~ 5 hour,
Metal oxide nano point is made and loads grapheme material；
Alternatively, 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and liquid carbonyl metal, by graphene oxide powder respectively
It is added in nitrogen-nitrogen dimethylformamide (DMF), ultrasonic disperse 0.5 ~ 5 hour, being made into mass-volume concentration is 0.5~5g/L's
Graphene oxide suspension；Liquid carbonyl metal is added in nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5 ~ 5 hour, is made into
The second dispersion solution that mass-volume concentration is 0.5~5g/L, the second dispersion solution and graphene oxide suspension are uniformly mixed,
100~200 DEG C at a temperature of solvent thermal reaction 0.5 ~ 5 hour, be made metal oxide nano point load graphene；
Solid carbonyl metal uses one of carbonyl cobalt, manganese carbonyl, tungsten carbonyl, molybdenum carbonyl, two kinds, three kinds or four kinds, when
When using more than one, each component is mixed with any mass ratio.
Liquid carbonyl metal uses one of carbonyl iron, carbonyl nickel or two kinds；When using two kinds, carbonyl iron and carbonyl
Base nickel is mixed with any mass ratio.
2) metal oxide nano point load graphene is put into porcelain boat, which is placed in tube furnace, by high-purity
Argon gas protects gas, is warming up to 300~1000 DEG C with 5 DEG C/min of heating rate and keeps the temperature 1~5h, cooled to room temperature is used
Powder obtained by salt acid elution, to remove the metal oxide on surface, then is washed with distilled water, and to remove demineralizing acid, drying is made super
Small sub-nanometer hole (< 1nm) porous graphene.
The mechanism of preparation method of the present invention: the nitrogen of graphene-nitrogen dimethylformamide dispersion liquid and metal-carbonyl precursor
Mixing, and choose whether that octylame is added depending on the type of presoma, then carry out solvent thermal reaction, in reaction process, metal carbonyl
Decarbonylated reaction, and carry out in atomic level level and graphene it is compound, according to control presoma and surfactant plus
Enter the parameters such as amount and reaction temperature, time, can accurately control the nucleation uniformity coefficient of metal oxide nano point and big
It is small；When annealing, metal oxide is combined due to directly passing through metal-oxygen-carbon key with graphene surface, with the liter of temperature
It is high, it may occur that carbon-thermal reduction, the carbon atom on graphene will form carbon monoxide or carbon dioxide and be purged off, the hole of formation
Hole is occupied by metal oxide nano point；After metal oxide being removed using hydrochloric acid after the completion of annealing, successfully obtain porous stone
Black alkene.
Due to control porous graphene surface apertures obtained less than 1 nanometer, if the metallic oxide precursor of selection
Body is improper, is difficult to form less than 1 nanometer metal oxide nano point below during solvent heat, it is therefore desirable to selection
Metal oxide supported graphene presoma is by one of carbonyl cobalt, carbonyl iron or carbonyl nickel or a variety of to obtain.
Using in porous graphene made from preparation method of the present invention contain nitrogen base and oxy functional groups.
Lack layer graphite oxide using by sheet prepared by improved Hummers method in preparation method step 1) of the present invention
Alkene, the sheet lack the Scanning Electron microscope figure (SEM) of layer graphene oxide, and as shown in a figure and b figure of Fig. 2, which lacks layer
The transmission electron microscope figure (TEM) of graphene oxide, as shown in the c figure and d figure of Fig. 2.Figure it is seen that the oxidation stone
Black alkene is large stretch of graphene, and the piece number of plies of graphene oxide is 1~2 layer, after the controllable graphene oxide of this sheet thickness is
Continuous graphene surface carves hole and provides the foundation.And from high resolution transmission electron microscopy on piece, graphene oxide table
Face does not have any impurity.
Embodiment 1
20 milligrams of graphene oxide powders, 10 milligrams of carbonyl cobalts and 25 microlitres of octylames are taken, nitrogen-nitrogen is added in graphene oxide powder
In dimethylformamide, ultrasonic disperse 5 hours, it is made into the graphene oxide suspension that mass-volume concentration is 1g/L；By carbonyl
Cobalt and octylame are added in nitrogen-nitrogen dimethylformamide, and ultrasonic disperse 3 hours, being made into total volume was graphene oxide suspension body
First dispersion solution of product 20% ~ 50%, the first dispersion solution are uniformly mixed with graphene oxide suspension, are packed into 50 milliliters of reactions
In kettle, which is placed in baking oven, 170 DEG C at a temperature of solvent thermal reaction 0.5 ~ 5 hour, be made oxidation cobalt nano dots
Load graphene；Oxidation cobalt nano dots load graphene is put into porcelain boat, which is placed in tube furnace, high-purity argon is passed through
Gas shielded gas is warming up to 650 DEG C with 5 DEG C/min of heating rate and keeps the temperature 2h, cooled to room temperature, obtained by salt acid elution
Powder, then be washed with distilled water, it dries, the porous graphene of extra small sub-nanometer hole and aperture controllable is made.
During solvent thermal reaction, along with the raising of temperature decarbonylated reaction occurs for carbonyl cobalt, to form original
The cobalt atom of sub- rank is nucleated on the surface of graphene with the help of surfactant and surface of graphene oxide functional group
And be uniformly distributed, oxidation cobalt nano dots are formed, while DMF is decomposed to form dimethylamine, N doping reaction is carried out to graphene, nitrogen is former
The introducing of son can promote the electric conductivity of material, so that the porous graphene has good chemical property.
Porous graphene made from embodiment 1 is characterized, XRD diagram, if a in Fig. 3 schemes, is shown in figure, this is more
Hole graphene is diffraction maximum occur at 24.5 ° in 2 θ, with document (K. H. Liao, A. Mittal, S. Bose, C.
Leighton, K. A. Mkhoyan and C. W. Macosko, ACS Nano, 2011,5,1253.) graphite in
Diffraction maximum position consistency illustrates to use final product made from preparation method of the present invention for graphene；But diffraction maximum is wide
Change, this is because the randomness of graphite flake layer increases and caused by the decline of the integrality of crystal structure degree.The drawing of the porous graphene
Graceful spectrogram, such as the b figure in Fig. 3, it can be seen that the porous graphene has 2 apparent Raman peaks (peak G and the peak D), respectively
Sp2 carbon atom and sp3 carbon atom are represented, the peak D and the intensity rate at the peak G are larger, show that porous graphene surface has significantly
Defect.
The chemical property figure of porous graphene made from embodiment 1, as shown in Figure 4.A figure in Fig. 4 is cyclic voltammetric
Method measurement result curve graph；B figure in Fig. 4 is constant current charge-discharge measurement result curve graph；C figure in Fig. 4 is non-porous graphite
The cyclic voltammetry comparative result figure of alkene and porous graphene；D figure in Fig. 4 is the electricity of non-porous graphene and porous graphene
Chemical impedance comparing result figure.When carrying out electrochemical property test, electrolyte used is that molal volume concentration is 1 mol/L
Metabisulfite solution, voltage window is selected as -1~0 V, and the highest specific capacitance for measuring porous graphene material is 170 F/g, table
Bright this kind of material has excellent capacitance characteristic.Cyclic voltammetry curve sweeps speed to the shape swept greatly under speed close to rectangle from small,
Show that this kind of material has excellent capacitance characteristic and high rate performance.By the way that non-porous graphene is swept with porous graphene identical
The cyclic voltammetry curve comparison under rate is retouched it is found that porous graphene has higher electrochemical specific capacity, this is because graphite
After alkene surface has pore structure abundant, is conducive to contact of the electrode surface with electrolyte, electric double layer capacitance behavior can be utilized
Store more charges, thus have higher specific capacitance, in addition, by both electrochemical impedance spectrum analysis it is recognized that while
The equivalent series resistance of non-porous graphene and porous graphene is not much different, but in low frequency range, porous graphene is than non-porous stone
Black alkene shows smaller Charge-transfer resistance, this is also indicated that using porous graphene made from preparation method of the present invention with excellent
Different chemical property.It can be used for electrode material for super capacitor, battery electrode conductive additive, sewage treatment and biology
Sensing material etc..
The transmission electron microscope figure of the oxidation cobalt nano dots load graphene obtained of embodiment 1, such as a figure and b in Fig. 5
Shown in figure, as can be seen from the figure graphene surface does not have the reunion of bulky grain, and oxidation cobalt nano dots distribute very evenly, the oxygen
Change the average diameter of particles of cobalt nano dots load graphene surface in 0.86 ran, such as the c figure in Fig. 5.
The transmission electron microscope figure of sub-nanometer hole porous graphene is made in embodiment 1, as shown in fig. 6, a in Fig. 6 schemes
The nano dot removal of graphene surface is shown with b figure, and there are highly uniform hole, the porous graphene surfaces on surface
The size in aperture about in 0.9 ran, is shown in Fig. 7 c.
Embodiment 2
20 milligrams of graphene oxide powders are taken, is added in nitrogen-nitrogen dimethylformamide (DMF), ultrasonic disperse 0.5 ~ 5 hour, matches
The graphene oxide suspension for being 1g/L at mass-volume concentration；50 milligrams of carbonyl nickels are taken, is scattered in DMF, is made into mass body
The second dispersion solution that product concentration is 0.5 ~ 5g/L, the second dispersion solution and graphene oxide suspension are uniformly mixed, at 170 DEG C
At a temperature of solvent thermal reaction 0.5 ~ 5 hour, be made nickel oxide nano point load graphene；Metal oxide nano point loads stone
Black alkene is put into porcelain boat, which is placed in tube furnace, gas is protected by high-purity argon gas, with 5 DEG C/min of heating rate liter
Temperature is to 650 DEG C and keeps the temperature 2h, cooled to room temperature, the powder obtained by salt acid elution, to remove the metal oxide on surface, then
It is washed with distilled water, to remove demineralizing acid, extra small sub-nanometer hole porous graphene is made in drying.
Nickel oxide nano point obtained load graphene penetrates electron microscope picture in embodiment 2, as shown in fig. 7, in Fig. 7
A figure and b figure, graphene surface there is no apparent bulky grain to reunite, nickel oxide nano point is distributed very uniform, surface apertures
Size about in 0.9 ran, see in Fig. 7 c figure.
It can be seen that the difference due to metal oxide nano point size, the porous stone obtained after annealing from Fig. 5 and Fig. 7
The pore size of black alkene can also be regulated and controled.
Use carbonyl nickel similar as the process of precursor preparation porous graphene material.It is worth noting that, carbonyl nickel
For greenish liquid, low boiling point itself is readily volatilized, at high temperature easily nucleating growth on the surface of graphene, therefore does not need
Surfactant is added, since the adsorption energy of nickle atom on the surface of graphene is different from cobalt atom, needed for metal oxide nucleation
The formation wanted can also difference, therefore the size of metal oxide nano point difference is formed by after solvent heat.
Embodiment 3
20 milligrams of graphene oxide powders are taken, is added in nitrogen-nitrogen dimethylformamide (DMF), ultrasonic disperse 0.5 ~ 5 hour, matches
The graphene oxide suspension for being 1g/L at mass-volume concentration；50 milligrams of carbonyl irons are taken, is scattered in DMF, is made into mass body
The carbonyl iron that product concentration is 0.5 ~ 5g/L disperses solution, and carbonyl iron is dispersed solution and graphene oxide suspension is uniformly mixed,
170 DEG C at a temperature of solvent thermal reaction 0.5 ~ 5 hour, be made ferric oxide nano point load graphene；Ferric oxide nano point is negative
It carries graphene to be put into porcelain boat, which is placed in tube furnace, gas is protected by high-purity argon gas, with 5 DEG C/min of heating speed
Rate is warming up to 650 DEG C and keeps the temperature 2h, cooled to room temperature, the powder obtained by salt acid elution, to remove the metal oxidation on surface
Object, then be washed with distilled water, to remove demineralizing acid, extra small sub-nanometer hole porous graphene is made in drying.
The point of ferric oxide nano made from embodiment 3 loads the transmission electron microscope figure of graphene, as shown in Figure 8.In Fig. 8
Figure a and figure b, the nano dot removal of graphene surface, and there are highly uniform biggish hole, surface apertures on surface
Size about in 7.11 rans, see the figure c in Fig. 8.
It can be seen that the hole of oxidate nano point load graphene surface obtained from the figure c in the figure c and Fig. 8 in Fig. 6
Diameter is of different sizes, this difference shows the metal oxygen that different metal-carbonyl precursors are formed when solvent thermal reaction loads graphene
Compound nano particle is different, and in annealing process, the nano-pore of formation can difference.It, can by selecting different metal carbonyls
To indirectly control the size of porous graphene even aperture, facilitate industrialization large scale preparation.Equally, before being using manganese carbonyl, molybdenum, tungsten
Body also available similarly sized metal oxide nano point is driven, porous graphene can be obtained in annealing.
Embodiment 4
Graphene oxide is taken, is added in DMF, ultrasonic disperse 2 hours, it is outstanding to be made into the graphene oxide that mass-volume concentration is 1g/L
20 milliliters of supernatant liquid.It takes 50 milligrams of carbonyl irons to be scattered in DMF and is made into 5g/L carbonyl iron dispersion liquid, take 2 milliliters of carbonyl iron dispersion liquids
Be uniformly mixed, be transferred in reaction kettle with graphene oxide suspension, 170 DEG C solvent heat 2 hours, after the reaction was completed by product benefit
With dehydrated alcohol and distilled water centrifuge washing, then it is freeze-dried；Ferric oxide nano point is made and loads graphene, which receives
The transmission electron microscope figure of rice point load graphene, such as Fig. 9 a, b, the average diameter of particles on surface is in 3.16 rans (figure
9c).
Ferric oxide nano point load graphene obtained above is taken to be divided into three parts, every portion is respectively put into a porcelain boat,
One porcelain boat is transferred in a tube furnace, high-purity argon gas protection gas is passed through in three tube furnaces,
First tube furnace is warming up to 500 DEG C with 5 DEG C of heating rates per minute, and keeps the temperature 2h, then cooled to room temperature,
The transmission electron microscope figure of material after annealing is shown in d figure and e figure in Fig. 9, the average diameter of particles of material surface after the annealing
In 5.52 rans, Fig. 9 f is seen.
Second tube furnace is warming up to 600 DEG C with 5 DEG C of heating rates per minute, and keeps the temperature 2h, then naturally cools to
Room temperature, the transmission electron microscope figure of material after annealing are shown in the g figure and h figure in Fig. 9, and the particle of material surface is flat after the annealing
Equal diameter is shown in Fig. 9 i in 7.4 rans.
Third tube furnace is warming up to 700 DEG C with 5 DEG C of heating rates per minute, and keeps the temperature 2h, then naturally cools to
Room temperature, the transmission electron microscope figure of material after annealing are shown in the j figure and k figure in Fig. 9, and the particle of material surface is flat after the annealing
Equal diameter is shown in Fig. 9 l in 16.56 rans.
Gained black powder has just obtained having extra small sub-nanometer by the iron oxide that salt acid elution removes surface after annealing
The grapheme material in hole.
If ferric oxide nano point load graphene annealed at 800 DEG C, the transmitted electron of porous graphene obtained is aobvious
Micro mirror figure, such as Figure 10 a and 10b, the size of surface apertures is about in 14.76 rans, such as Figure 10 c.
Ferric oxide nano point loads graphene and anneals at 900 DEG C, the transmission electron microscope figure of porous graphene obtained,
Such as Figure 11, surface apertures size is about in 88 rans.
The above results show in annealing process, metal oxide nanoparticles on the surface of graphene due to longitudinal slip effect,
Mutually reunite, more under high-temperature, the agglomeration of metal oxide is more obvious, and finally formed nano-pore can be poor
Not.By the selection of different annealing, the size of porous graphene even aperture has been directly controlled.Equally, this method is equally applicable to
It the use of manganese carbonyl, molybdenum, tungsten is the porous graphene nano material that presoma obtains similar aperture size.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Implementation of the invention
The detailed description of example is not intended to limit scope of the claimed invention, but is merely representative of selected embodiment of the invention.
Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts all
Other embodiments shall fall within the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of extra small sub-nanometer hole porous graphene, it is characterised in that: the preparation method specifically:
1) 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and solid carbonyl metal respectively, and graphene oxide powder is added
In nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5 ~ 5 hour, it is made into the graphene oxide that mass-volume concentration is 0.5~5g/L
Suspension；The ratio that 1.25 microlitres of octylames need to be matched in 1 milligram of graphene oxide powder again, takes octylame；By solid carbonyl metal and
Octylame is added in nitrogen-nitrogen dimethylformamide, and ultrasonic disperse 0.5~5 hour, being made into total volume was graphene oxide suspension body
First dispersion solution of product 20%~50%, the first dispersion solution is uniformly mixed with graphene oxide suspension, 100 DEG C~
Solvent thermal reaction 0.5~5 hour at a temperature of 200 DEG C is made metal oxide nano point and loads grapheme material；
Alternatively, 1 ︰ 0.5~5 in mass ratio, takes graphene oxide powder and liquid carbonyl metal, by graphene oxide powder respectively
It is added in nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5~5 hour, is made into the oxidation that mass-volume concentration is 0.5~5g/L
Graphene suspension；Liquid carbonyl metal is added in nitrogen-nitrogen dimethylformamide, ultrasonic disperse 0.5~5 hour, is made into matter
The second dispersion solution that volumetric concentration is 0.5~5g/L is measured, the second dispersion solution and graphene oxide suspension are uniformly mixed,
Solvent thermal reaction 0.5 ~ 5 hour at a temperature of 100~200 DEG C is made metal oxide nano point and loads graphene；
2) metal oxide nano point load graphene is placed in the environment for being passed through high-purity argon gas protection gas, with 5 DEG C/min of liter
Warm rate is warming up to 300~1000 DEG C and keeps the temperature 1~5h, cooled to room temperature, salt acid elution, then is washed with distilled water, and dries
It is dry, extra small sub-nanometer hole porous graphene is made.
2. the preparation method of extra small sub-nanometer hole as described in claim 1 porous graphene, it is characterised in that: in the step 1)
Solid carbonyl metal uses one of carbonyl cobalt, manganese carbonyl, tungsten carbonyl, molybdenum carbonyl, two kinds, three kinds or four kinds, works as use
More than one when, each component is mixed with any mass ratio.
3. the preparation method of extra small sub-nanometer hole as described in claim 1 porous graphene, it is characterised in that: in the step 1)
Liquid carbonyl metal uses one of carbonyl iron, carbonyl nickel or two kinds；When using two kinds, carbonyl iron and carbonyl nickel are to appoint
Mass ratio of anticipating mixes.
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| CN112301731A (en) * | 2020-11-03 | 2021-02-02 | 江苏科技大学 | Heat-conducting nylon 6/graphene composite fiber and preparation method thereof |
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