CN106495134A - Three-dimensional porous graphene and preparation method thereof - Google Patents
Three-dimensional porous graphene and preparation method thereof Download PDFInfo
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- CN106495134A CN106495134A CN201611002194.4A CN201611002194A CN106495134A CN 106495134 A CN106495134 A CN 106495134A CN 201611002194 A CN201611002194 A CN 201611002194A CN 106495134 A CN106495134 A CN 106495134A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 82
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 230000007704 transition Effects 0.000 claims abstract description 38
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 37
- 238000005342 ion exchange Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- -1 iron ion Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007603 infrared drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of three-dimensional porous Graphene, comprises the following steps：Ion-exchange type resin is carried out ion exchange with the solution of transition-containing metal ion and obtains transition-containing metal ion crossover resin；The transition-containing metal ion crossover resin is dried process；The dried transition-containing metal ion crossover resin and solid base are mixed to get mixture；Heating is carried out to the mixture using intermittent microwave heating and obtains carbide resin；After acid neutralization is added in the carbide resin obtain three-dimensional porous Graphene.Above-mentioned preparation method raw material are easy to get, production equipment is simple, and operation is simple, it is to avoid prepare three-dimensional grapheme material using particular device, and production cost is substantially reduced.
Description
Technical field
The present invention relates to technical field of graphene preparation, more particularly to a kind of three-dimensional porous Graphene and its preparation side
Method.
Background technology
Graphene (Graphene) be by carbon atom tightly packed into individual layer two dimension (2D) carbonaceous material.Graphene due to
Extensively concerned with performances such as fabulous electricity, optics, machineries.At present, mechanical stripping method, epitaxial growth method, chemical gaseous phase
After sedimentation, chemical reduction method etc. can prepare Graphene (Graphene G or electronation graphene oxide rGO) and its functionalization
Derivative.
Three-dimensional (3D) Graphene typically refers to two dimension (2D) the Graphene assembly with 3D structures, is Graphene in recent years
The new type functional material of chemical field.The physicochemical property that 3D grapheme materials not only have Graphene intrinsic, which is three-dimensional porous
Micro/nano structure also to make which have that specific surface area big, high mechanical strength, electronic conduction ability be superior and mass transfer is quick concurrently etc. excellent
Characteristic.These unique properties make 3D Graphenes and its composite receive much concern in material science.Integrate 2D Graphenes
The Graphene assembly with specific three dimensional (3D) structure is built, and then the excellent function element of processability is for expansion graphite
The macroscopic view application of alkene is significant.
At present, preparing the conventional method of 3D Graphenes has the hot method of directed flow construction from part, solvent/water, substrate interface assembling
Method and chemical vapour deposition technique.However, the cost for 3D Graphenes being prepared by said method is general higher, limit which and develop.
Content of the invention
Be based on this, it is necessary to the problem of the method high cost of three-dimensional grapheme is prepared for tradition, there is provided a kind of three-dimensional many
Hole Graphene and preparation method thereof.
A kind of preparation method of three-dimensional porous Graphene, comprises the following steps：
Ion-exchange type resin is carried out ion exchange with the solution of transition-containing metal ion and obtains transition-containing metal ion
Crossover resin；
The transition-containing metal ion crossover resin is dried process；
The dried transition-containing metal ion crossover resin and solid base are mixed to get mixture；
Heating is carried out to the mixture using intermittent microwave heating and obtains carbide resin；And
After acid neutralization is added in the carbide resin obtain three-dimensional porous Graphene.
Wherein in one embodiment, the ion-exchange type resin be cation exchange resin, the transition metal
At least one of the ion in iron ion, nickel ion and cobalt ions.
Wherein in one embodiment, the quality of the ion-exchange type resin and the solution of the transition-containing metal ion
CEC<4.50mmol/g.
Wherein in one embodiment, at least one of the solid base in NaOH and potassium hydroxide.
Wherein in one embodiment, the transition-containing metal ion crossover resin and solid base by after the drying
In the step of being mixed to get mixture, the transition-containing metal ion crossover resin after the drying with the volume ratio of solid base is
1:4～1:10.
Wherein in one embodiment, described the mixture is carried out heating by intermittent microwave heating obtain carbonization
The step of resin, specifically includes：
The mixture is put into the first container, first container has protection cap；
First container is positioned in second container, activated carbon in the second container, is filled；
The second container is heated using intermittent microwave heating.
Wherein in one embodiment, described heating is carried out to the mixture using intermittent microwave heating obtain carbonization
In the step of resin, each heat time is 2min～8min, and alternately the time interval of heating is 10s～50s, the number of times of heating
For 2～30 times.
Wherein in one embodiment, described heating is carried out to the mixture using intermittent microwave heating obtain carbonization
In the step of resin, the power of heating is 800W～1500W.
Wherein in one embodiment, the acid is at least one in hydrochloric acid and sulfuric acid.
A kind of three-dimensional porous Graphene, is obtained according to the preparation method of above-mentioned three-dimensional porous Graphene.
The preparation method of above-mentioned three-dimensional porous Graphene by the way of heating using microwave, first by ion-exchange type resin with
The solution of transition-containing metal ion carries out ion exchange and obtains transition-containing metal ion crossover resin, by transition-containing metal ion
Crossover resin is dried, then is mixed to get mixture with solid base, mixture is carried out by the method for alternate microwave heating plus
Heat obtains carbide resin, and washing and drying after carbide resin acid neutralization is obtained three-dimensional porous grapheme material, preparation side
Method raw material are easy to get, production equipment is simple, and operation is simple, it is to avoid prepare three-dimensional grapheme material using particular device,
Production cost is substantially reduced.
Description of the drawings
Fig. 1 is the process chart of the preparation method of the three-dimensional porous Graphene of an embodiment；
Raman spectrograms of the Fig. 2 for the three-dimensional porous Graphene of embodiment 1；
X-ray diffraction spectrograms of the Fig. 3 for the three-dimensional porous Graphene of embodiment 1；
Stereoscan photographs of the Fig. 4 for the three-dimensional porous Graphene of embodiment 1.
Specific embodiment
Three-dimensional porous Graphene and preparation method thereof is carried out further below in conjunction with specific embodiment and accompanying drawing
Explanation.
Fig. 1 is referred to, the preparation method of the three-dimensional porous Graphene of an embodiment is comprised the following steps：
Step S10, the solution of ion-exchange type resin and transition-containing metal ion is carried out ion exchange obtain containing transition
Metal ion exchanged type resin.
Wherein in an embodiment, ion-exchange type resin specifically cation exchange resin mainly includes benzene
Ethene system and acrylic acid series this two big series, additionally, ion-exchange type resin can be to be made up of other organic monomers polymerizations, such as
Phenolic aldehyde system, epoxy, vinylpyridine system and ureaformaldehyde system etc..Wherein in an embodiment, the particle diameter of ion-exchange type resin
For 1～5cm, ion-exchange type cross-linkage of resin is 80～90%.
In the solution of transition-containing metal ion, transition metal ions is selected from the iron ion, nickel ion and cobalt with catalytic property
At least one in ion.Resin can obtain grapheme material by heating under the catalytic action of transition metal.Contain transition
The anions of metal ion are selected from SO4 2-、SiO3 2-、PO4 3-、CO3 2-、SO3 2-、S2O3 2-、S2-、Cl-、Br-、I-、NO3 -、
NO2 -In at least one, it is believed that as long as the anion in solution can be formed with transition metal ions water-soluble strong
Electrolytic salt.The concentration of the solution of transition-containing metal ion is 0.01mol/L～10mol/L, specifically, Ke Yishi
0.1mol/L～10mol/L.
When the solution of ion-exchange type resin and transition-containing metal ion is carried out ion exchange, ion-exchange type resin with
The quality CEC of the solution of transition-containing metal ion<4.50mmol/g.Under this condition, ion-exchange reactions can be with
Fully carry out.Specifically, ion-exchange type resin is placed in exchange column, then keeps certain flow velocity to lead to in ion exchange column
Enter transition-containing metal ion solution, the reaction condition for carrying out ion-exchange reactions is：The pH of transition-containing metal ion solution be 0～
14；Maximum operation (service) temperature：Hydrogen≤100 DEG C, sodium form≤120 DEG C；Transition expansion rate %：(Na+→H+)≤10；Work is exchanged to be held
Amount：>=1000mmol/l (wet)；The height of ion-exchange reactions exchange column：50cm；Time：About 30 minutes；Operation flow velocity：10
M/h～45 ms/h.
Step S20, transition-containing metal ion crossover resin is dried process.
Wherein in an embodiment, it is which is dried in vacuum to transition-containing metal ion crossover resin dried process
Dry in case.Vacuum is less than 0.1～0.5 atmospheric pressure, and the temperature of drying and processing is 60 DEG C～150 DEG C, drying and processing when
Between be 3～24 hours, time of specific drying and processing is 12～24 hours.In another embodiment, to containing transition
Metal ion exchanged type resin dried process may be used also
So that using drying naturally or infrared drying, during using infrared drying, penetration power is strong, rate of drying
Hurry up.
Step S30, by drying after transition-containing metal ion crossover resin and solid base be mixed to get mixture.
Wherein in an embodiment, at least one of the solid base in NaOH and potassium hydroxide.Contain transition
Metal ion exchanged type resin is 1 with the volume ratio of solid base:4～1:10.By transition-containing metal ion crossover resin with solid
State alkali is mixed the churned mechanically mode that mainly adopt so that both are sufficiently mixed uniformly.
Step S40, mixture is carried out heating by intermittent microwave heating obtain carbide resin.
Wherein in an embodiment, when alternate microwave heating is carried out to mixture, mixture is put into first first
In container, mixture is not more than 80% in the ratio of the first vessel volume；First container has protection cap, can be located at first
On container, play a part of sealing and starvation, protection mixture is not oxidized.First container is positioned over second container
In, specifically, the first volume of a container is placed on the first container in second container less than 1/3rd of second container volume
Afterwards, in second container, filling absorbent charcoal material is filled up to container.Specifically, the first container and second container can be crucible or
Person's aluminium-foil containers.
Wherein in an embodiment, when carrying out alternate microwave heating to mixture, the time of heating is 2min every time
～8min, alternately the time interval of heating is 10s～50s, and the number of times of heating is 2～30 times.Just have when carrying out heating using microwave micro-
Ripple stove is heated, and the power of heating using microwave is 800W～1500W.By the way of heating using microwave, than used by conventional method
Time greatly reduces, and reaction rate is improved.And the characteristic using cationic exchange resin adsorption filtering metal ion, and using friendship
For the 3D loose structures that microwave heating method can retain cationic ion-exchange resin to greatest extent.Meanwhile, in the effect of solid base
Under, be conducive to separating carbon-coating, so as to prepare 3D porous graphene materials.
Step S50, in carbide resin add acid neutralization after obtain three-dimensional porous Graphene.
Wherein in an embodiment, in carbide resin, acid neutralization is added specifically to adopt in hydrochloric acid and sulfuric acid at least
One kind, the concentration of the acid for being used is 0.1mol L-1～4mol L-1.Carry out sour neutralisation treatment to obtain to carbide resin for neutrality
Three-dimensional porous Graphene.Add sour neutralisation treatment to be mainly used for neutralizing the highly basic in material, make three-dimensional porous Graphene
Three-dimensional structure shows.
In another embodiment, after be neutralized carbide resin acid, then washed with water, it is right to generally require
Carbide resin carries out repeatedly washing with the impurity in carbide resin of going out.After the completion of washing, by way of centrifugation or suction filtration
Carbide resin and water are separated, then isolated carbide resin is dried process.Carbide resin is dried
Processing can be carried out in convection oven or vacuum drying oven, carry out drying and processing, it is also possible to by drying in the air naturally below 180 DEG C
The mode of dry or infrared drying.By said method, using solid base and transition-containing metal ion crossover mixed with resin
Three-dimensional porous Graphene is prepared, acid is reused and is neutralized process, also reduce the usage amount of bronsted lowry acids and bases bronsted lowry, environmental pollution is little.
The preparation method of above-mentioned three-dimensional porous Graphene by the way of heating using microwave, first by ion-exchange type resin with
The solution of transition-containing metal ion carries out ion exchange and obtains transition-containing metal ion crossover resin, by transition-containing metal ion
Crossover resin is dried, then is mixed to get mixture with solid base, mixture is carried out by the method for alternate microwave heating plus
Heat obtains carbide resin, and washing and drying after carbide resin acid neutralization is obtained three-dimensional porous grapheme material, preparation side
Method raw material are easy to get, production equipment is simple, and operation is simple, it is to avoid prepare three-dimensional grapheme material using particular device,
Production cost is substantially reduced.
Meanwhile, three-dimensional porous Graphene high income is prepared by said method, more than 60% yield can be reached.
It is specific embodiment part below.
Raw material information used in specific embodiment such as table 1：
Table 1
Embodiment 1
Take 100g cation exchanges resin I fully to exchange with 10L 0.1mol/L nickel chloride solutions, obtain containing nickel from
The exchanger resin of son, cation exchange resin I are 100g with the quality CEC of nickel chloride solution.After fully exchanging
The exchanger resin containing nickel ion be put into vacuum drying oven and be vacuum dried 12 hours, the temperature of vacuum drying oven is 60 degree, will drying
The rear exchanger resin containing nickel ion and NaOH by volume 1:5 ratio is sufficiently mixed by mechanical agitation, mechanical agitation
Time be 1h, speed is 1000rpm.Said mixture is put into the crucible that capacity is 300mL, protection cap is covered, by this earthenware
Crucible is put in the crucible that another capacity is 1000mL, and is filled up inside 1000mL crucibles with activated carbon.Big crucible is put into family expenses
1500W power microwave stoves are heated by intermittent microwave heating, and heating schedule is heating 2 minutes every time, the time interval of heating
For 30 seconds, heating times were 30 times, obtain carbide resin.After cooling 3 hours, carbide resin is put into 1000mL beakers and is passed through
1mol/L sulfuric acid is neutralized to neutrality, is then washed with deionized suction filtration, after 180 DEG C of vacuum drying ovens are dried obtains 3D porous classes
Grapheme material.
Embodiment 2
Take 10g cation exchanges resin II fully to exchange with 10L 1mol/L copperas solutions, obtain containing ferrous iron
The exchanger resin of ion, cation exchange resin II are 10g with the quality CEC of copperas solution.Fully will hand over
The resin containing ferrous ion after changing is put into vacuum drying oven and is vacuum dried 24 hours, and the temperature of vacuum drying oven is 80 degree, will dry
The resin containing ferrous ion after dry and KOH by volume 1:10 ratio is sufficiently mixed by mechanical agitation, mechanical agitation
Time be 2h, speed is 800rpm.Said mixture is put into the crucible that capacity is 30mL, protection cap is covered, by this crucible
It is put in the crucible that another capacity is 100mL, and is filled up inside 100mL crucibles with activated carbon.Big crucible is put into family expenses 800W
Power microwave stove is heated by intermittent microwave method, and heating schedule is heating 5 minutes every time, and the time interval of heating is 10 seconds, plus
Hot number of times is 10 times, obtains carbide resin.After cooling 3 hours, carbide resin is put into 100mL beakers by 0.5mol/L hydrochloric acid
Neutralization acid is neutral, is then washed with deionized suction filtration, after 100 DEG C of vacuum drying ovens are dried obtains 3D porous class Graphene materials
Material.
Embodiment 3
Take 1g cation exchanges resin II fully to exchange with 1L 1mol/L cobalt nitrate solutions, obtain containing cobalt ions
Exchanger resin, cation exchange resin II are 1g with the quality CEC of cobalt nitrate solution.Containing after fully exchanging
The exchanger resin for having cobalt ions is put into vacuum drying oven and is vacuum dried 24 hours, and the temperature of vacuum drying oven is 100 degree, by drying after
Exchanger resin containing cobalt ions and KOH by volume 1:4 ratio is sufficiently mixed by mechanical agitation, the churned mechanically time
For 3h, speed is 500rpm.Said mixture is put into the crucible that capacity is 20mL, protection cap is covered, this crucible is put into separately
During one capacity is for the crucible of 100mL, and filled up inside 100mL crucibles with activated carbon.Big crucible is put into family expenses 800W power micro-
Ripple stove is heated by intermittent microwave method, and heating schedule is heating 8 minutes every time, and the time interval of heating is 50 seconds, heating times
For 2 times, carbide resin is obtained.After cooling 3 hours, carbide resin is put into 100mL beakers by the acid neutralization of 0.5mol/L sulfuric acid
Sour neutral, suction filtration is then washed with deionized, after 90 DEG C of vacuum drying ovens are dried, obtains 3D porous class grapheme materials.
The Raman spectrogram of the three-dimensional porous Graphene of embodiment 1 is illustrated in figure 2, it can be seen that at two
The G bands at the G peaks of～1580cm-1 and in～2700cm-1 are most significantly characterized in that, show to have synthesized three-dimensional porous Graphene material
Material.
The X-ray diffraction spectrogram of the three-dimensional porous Graphene of embodiment 1 is illustrated in figure 3, it can be seen that occurring
The characteristic peak of multi-layer graphene, further demonstrates that and has synthesized three-dimensional porous grapheme material.
The stereoscan photograph of the three-dimensional porous Graphene of embodiment 1 is illustrated in figure 4, can be with from stereoscan photograph
Find out that Graphene has three-dimensional structure.
Each technical characteristic of embodiment described above arbitrarily can be combined, for making description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of preparation method of three-dimensional porous Graphene, it is characterised in that comprise the following steps：
Ion-exchange type resin is carried out ion exchange with the solution of transition-containing metal ion and obtains transition-containing metal ion exchange
Type resin；
The transition-containing metal ion crossover resin is dried process；
The dried transition-containing metal ion crossover resin and solid base are mixed to get mixture；
Heating is carried out to the mixture using intermittent microwave heating and obtains carbide resin；And
After acid neutralization is added in the carbide resin obtain three-dimensional porous Graphene.
2. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the ion-exchange type tree
Fat is cation exchange resin, at least one of the transition metal ions in iron ion, nickel ion and the cobalt ions.
3. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the ion-exchange type tree
The quality CEC of fat and the solution of the transition-containing metal ion<4.50mmol/g.
4. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the solid base is selected from hydrogen
At least one in sodium oxide molybdena and potassium hydroxide.
5. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that described by the drying after
Transition-containing metal ion crossover resin and solid base the step of be mixed to get mixture in, after the drying containing transition gold
Category ion-exchange type resin is 1 with the volume ratio of solid base:4～1:10.
6. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that described by the mixture
The step of heating obtains carbide resin is carried out by intermittent microwave heating to specifically include：
The mixture is put into the first container, first container has protection cap；
First container is positioned in second container, activated carbon in the second container, is filled；
The second container is heated using intermittent microwave heating.
7. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the employing intermittent microwave
During heating is carried out the step of heating obtains carbide resin to the mixture, each heat time is 2min～8min, alternately
The time interval of heating is 10s～50s, and the number of times of heating is 2～30 times.
8. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the employing intermittent microwave
During heating is carried out the step of heating obtains carbide resin to the mixture, the power of heating is 800W～1500W.
9. the preparation method of three-dimensional porous Graphene according to claim 1, it is characterised in that the acid is hydrochloric acid and sulphur
At least one in acid.
10. a kind of three-dimensional porous Graphene, it is characterised in that the three-dimensional porous graphite according to any one of claim 1～9
The preparation method of alkene is obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113752640A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Lightweight electromagnetic shielding tarpaulin and preparation method thereof |
| CN113756090A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Preparation method and application of electromagnetic shielding function layer material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104986758A (en) * | 2015-06-25 | 2015-10-21 | 厦门凯纳石墨烯技术有限公司 | Three-dimensional network graphene for lithium battery and preparing method thereof |
-
2016
- 2016-11-14 CN CN201611002194.4A patent/CN106495134B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104986758A (en) * | 2015-06-25 | 2015-10-21 | 厦门凯纳石墨烯技术有限公司 | Three-dimensional network graphene for lithium battery and preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨颖等: "《石墨烯基复合材料的制备及性能研究》", 31 December 2015, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113752640A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Lightweight electromagnetic shielding tarpaulin and preparation method thereof |
| CN113756090A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Preparation method and application of electromagnetic shielding function layer material |
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