CN110407192A - Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame - Google Patents
Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame Download PDFInfo
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- CN110407192A CN110407192A CN201910765058.8A CN201910765058A CN110407192A CN 110407192 A CN110407192 A CN 110407192A CN 201910765058 A CN201910765058 A CN 201910765058A CN 110407192 A CN110407192 A CN 110407192A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 75
- 239000011022 opal Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004005 microsphere Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- -1 is then dispensed Chemical compound 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 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
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- AUEPDNOBDJYBBK-UHFFFAOYSA-N [Si].[C-]#[O+] Chemical compound [Si].[C-]#[O+] AUEPDNOBDJYBBK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
It the present invention relates to the use of metal organic frame and prepare three-dimensional order graded porous carbon photonic crystal method, using silica opal as template, metal organic framework compound is synthesized in die clearance, silica and ordered porous carbon complex are formed by high temperature cabonization, obtains the classifying porous carbon photonic crystal of three-dimensional order after removing silica opal template.Compared with prior art, the technology and feature of present invention combination photonic crystal, metal organic frame and porous carbon materials three, prepare three-dimensional order, classifying porous and uniform pore diameter carbon photonic crystal, it be solved perfectly conventional porous carbon material there are the problem of, provide more choices for porous carbon materials.
Description
Technical field
The present invention relates to photonic crystal fields, and it is more to prepare three-dimensional order point more particularly, to a kind of utilization metal organic frame
The method of the carbon photonic crystal in hole.
Background technique
Photonic crystal, which refers to, to be arranged and shape by the two kinds or more of materials with differing dielectric constant in space periodicity
At a kind of novel artificial material.The semiconductor material of the similar regulation electronics of photonic crystal, can the direction of propagation to photon and
Position is propagated effectively to be regulated and controled.Therefore, photonic crystal is received in fields such as sensing response, display devices and is widely ground
Study carefully.But due to the limitation by conventional photonic crystals material, the application field of photonic crystal also receives many restrictions.
Therefore, photon crystal material is widened, so that photonic crystal is broken through traditional becoming using bottleneck for photoelectric sensing and response field can
Energy.
Carbon is that a kind of element abundant is stored in nature, and carbon material is also the indispensable important substance of daily life.
In all kinds of carbon materials, porous carbon materials have highly developed pore structure, big specific surface area and excellent electric conductivity, and
The prices of raw materials are cheap, and manufacturing process is mature, are easy to the features such as being mass produced, are widely used in catalysis, Molecular Adsorption and energy
Many fields such as source storage and conversion.According to the size in aperture, porous carbon materials are divided into three classes: micro-pore carbon material (<
2nm), meso-porous carbon material (2~50nm) and macropore carbon material (> 50nm).
The pore structure distribution of porous carbon materials and pore size will affect its practical application performance.However it is traditional more
The gap distribution of hole carbon material is disorderly and unsystematic, and pore size is also inhomogenous, not only affects the application performance of material, also limits
The control accurate of material property.Therefore, in conjunction with the periodic feature of photonic crystal space structure, three-dimensional order, aperture are prepared
Uniform porous material.Uniform pore size not only ensure that the homogeneity of material reaction, be also control accurate material property
Provide unlimited possibility.
After searching and discovering the prior art, Chang Haitao seminar uses lotion as soft template poromerics, tool
Body is shown in Shi Ang, and Chang Haitao emulsion template method prepares the Shandong research [J] the chemical industry of phenolic resin base porous carbon materials, 2017,46
(04):7-10].This porous material is similar with conventional porous materials, although having three-dimensional continuous poriferous, the structure in hole is simultaneously
It is not that periodic regular arranges, the characteristic without photonic crystal, meanwhile, the size in hole can not accomplish in the same size.Secondly,
The aperture size of this porous material having has reached micron order, is unable to satisfy the application requirement of many nanoscales.
Chinese patent CN102718204A discloses a kind of preparation method of three-dimensional ordered macroporous porous carbon, its main feature is that packet
Include following steps: firstly, passing through 250 nanometers of spherical shape two of method for hydrolysis anamorphic zone fluorescence using tetraethyl orthosilicate as silicon source
Silicon-carbon oxide particle.Later, preparing spherical SiO 2 carbon particle obtained is made into preparing spherical SiO 2 carbon particle aqueous solution.It connects
, aqueous solution obtained is added in silicone oil, strong stirring.Then, turbid obtained is stood, and is evaporated water.Then, by institute
The washed separation of product n-hexane obtained, obtains silica photonic crystal.Finally, using silica photonic crystal as mould
Plate cooperates carbon source, and three-dimensional ordered macroporous porous carbon is obtained after hot setting.But in the method that is related to of this patent, titanium dioxide
Silicon photonic crystal positive template is using the method stood, and the degree of order of photonic crystal is not high and preparation method is more complicated.Secondly, should
The porous carbon that method is prepared only has single macropore to constitute, and without orderly micropore, causes specific surface area smaller, is unfavorable for carving
Draw the performance of material.
Summary of the invention
It is organic using metal that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
The method that frame prepares three-dimensional order graded porous carbon photonic crystal, prepared carbon photonic crystal have three-dimensional order, classification
The features such as porous, aperture is uniform and high-specific surface area.
The purpose of the present invention can be achieved through the following technical solutions:
Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame, is with silica opal
Template synthesizes metal organic framework compound in die clearance, forms silica and ordered porous carbon by high temperature cabonization
Compound obtains the classifying porous carbon photonic crystal of three-dimensional order after removing silica opal template.
Silica opal template is to be self-assembled into silica opal template by silicon dioxide microsphere.
The diameter of the silicon dioxide microsphere is 100nm-800nm.
Self assembling process is that silicon dioxide microsphere is distributed in deionized water or dehydrated alcohol, is then encapsulated, will be clear
Tungsten foil, lead foil or carbon paper of wash clean etc. are inserted into silicon dioxde solution, controlled at 25 DEG C of -60 DEG C of progress photonic crystals
Self assembly.
Metal organic framework compound is synthesized in die clearance and uses following steps: silica template is immersed into metal
In the precursor liquid of organic frame, precursor liquid is adsorbed in die clearance through capillary action, heating reaction forms silica
And metal organic frame compound.
In the precursor liquid of the metal organic frame, metal salt is zinc nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, manganese nitrate
Deng, organic ligand is 2-methylimidazole, solution be methanol, n,N-Dimethylformamide or n,N-Dimethylformamide it is independent molten
Mixed solution between liquid or three.
The molar ratio of above-mentioned metal salt and organic ligand is 1:1-1:8.
The temperature of heating reaction is 50 DEG C -90 DEG C, time 3h-8h.
Silica and metal organic frame compound are put into tube furnace, are heat-treated in inert atmosphere, metal-carbide
Organic frame uses hydrofluoric acid dips after taking-up, remove silica opal template, obtains three-dimensional order graded porous carbon photon
Crystal.
Heat treatment temperature is 600 DEG C -1200 DEG C, time 3h-8h, hydrofluoric acid concentration 5-30wt%, and soaking time is
6h-24h。
In the existing preparation method of porous carbon, mostly common soft template or the preparation of hard template method, the preparation of soft template method
In the process, carbon is easily shunk in sintering process, and the porous carbon of formation is unordered and aperture is different, and hard template using itself without specific knot
The carbon source of structure, therefore the porous carbon aperture formed is single, specific surface area is insufficient.Metal organic frame itself is a kind of microcosmic orderly
Material, the appearance of metal organic frame be selected as constructing for three-dimensional order graded porous carbon photonic crystal and provide possibility,
Facts proved that and a kind of selection well.
The technology and feature of present invention combination photonic crystal, metal organic frame and porous carbon materials three, prepare three
Tie up orderly, classifying porous and uniform pore diameter carbon photonic crystal, it be solved perfectly conventional porous carbon material there are the problem of, be
Porous carbon materials provide more choices.
The three-dimensional order carbon photonic crystal being prepared using specified raw material of the present invention and method has classification
Porous structure also possesses the orderly micropore formed after metal-carbide organic frame in addition to the macropore that removal silica leaves,
Therefore there is bigger specific surface area, be more advantageous to the performance for portraying material.
Compared with prior art, the three-dimensional order graded porous carbon photonic crystal that the present invention is prepared has and tradition
The different graded porous structure of photonic crystal, in addition to removal silica template leave macropore while, also have with metal
The micropore that machine frame is carbonized.The equal size in the hole of the two is uniform, regular.While increasing material specific surface area, also make
Material is obtained to be provided with more using possible.
Detailed description of the invention
Fig. 1 is silica opal template stereoscan photograph；
Fig. 2 is the stereoscan photograph of silica and metal organic frame compound；
Fig. 3 is the stereoscan photograph of carbon photonic crystal；
Fig. 4 is the stereoscan photograph of carbon photonic crystal；
Fig. 5 is the transmission electron microscope photo of carbon photonic crystal；
Fig. 6 is the scanning transmission electron microscope photo of carbon photonic crystal.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame, is 100nm- by diameter
800nm is that silicon dioxide microsphere is self-assembled into silica opal template, and self assembling process is to disperse silicon dioxide microsphere
It into deionized water or dehydrated alcohol, then encapsulates, tungsten foil, lead foil or carbon paper for cleaning up etc. is inserted into silica
In solution, controlled at the self assembly of 25 DEG C of -60 DEG C of progress photonic crystals.Obtained silica template immersion metal is had
In the precursor liquid of machine frame, precursor liquid is adsorbed in die clearance through capillary action.Before the metal organic frame used
It drives in liquid, metal salt is zinc nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, manganese nitrate etc., and organic ligand is 2-methylimidazole, solution
For the mixed solution between the independent solution of methanol, N,N-dimethylformamide or N,N-dimethylformamide or three.Gold
The molar ratio for belonging to salt and organic ligand is 1:1-1:8.Silica and gold are formed controlled at 50-90 DEG C of heating reaction 3-8h
Belong to organic frame compound, then silica and metal organic frame compound are put into tube furnace, in inert atmosphere, control
Temperature processed is 600-1200 DEG C of heat treatment 3h-8h, metal-carbide organic frame, the hydrofluoric acid for being 5-30wt% with concentration after taking-up
6-24h is impregnated, silica opal template is removed, obtains three-dimensional order graded porous carbon photonic crystal.
More detailed case study on implementation below, by following case study on implementation further illustrate technical solution of the present invention with
And the technical effect that can be obtained.
Embodiment 1
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, leaf deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
0.5%, the silicon dioxide microsphere ethanol solution that diameter is 300nm instills in vial, and drop is full, while slant setting is cleaned
Leaf.Vial is put into air dry oven, temperature remains 35 DEG C, until ethanol solution volatilization completely, obtains in vial
Obtain silica opal template.Preparing metal organic frame precursor liquid, by 0.58g cabaltous nitrate hexahydrate, 0.492g 2- methyl
10min is mixed in imidazoles, 25mL methanol and 25mL n,N-Dimethylformamide.Silica opal template is immersed
In metal organic frame precursor liquid, 3h is stood, moves to 70 DEG C of reaction 8h in baking oven, silica is obtained and metal organic frame is multiple
Close object.Compound is put into tube furnace, 800 DEG C of heat treatment 6h in inert atmosphere.It takes out, for 24 hours with 20wt% hydrofluoric acid dips.
It is cleaned with deionized water, 60 DEG C of dryings, obtains three-dimensional order graded porous carbon photonic crystal.
Embodiment 2
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, leaf deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
1%, the silicon dioxide microsphere ethanol solution that diameter is 500nm instills in vial, and drop is full, while the tungsten that slant setting is cleaned
Piece.Vial is put into air dry oven, temperature remains 45 DEG C, until ethanol solution volatilization completely, obtains in vial
Silica opal template.Preparing metal organic frame precursor liquid, by nine nitric hydrate cobalt of 0.81g, 0.492g 2- methyl miaow
10min is mixed in azoles, 25mL methanol and 25mL n,N-Dimethylformamide.Silica opal template is immersed into gold
Belong in organic frame precursor liquid, stand 3h, move to 90 DEG C of reaction 8h in baking oven, obtains silica and metal organic frame is compound
Object.Compound is put into tube furnace, 900 DEG C of heat treatment 6h in inert atmosphere.It takes out, for 24 hours with 30wt% hydrofluoric acid dips.With
Deionized water cleaning, 60 DEG C of dryings obtain three-dimensional order graded porous carbon photonic crystal.
Embodiment 3
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, lead foil deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
2%, the silicon dioxide microsphere ethanol solution that diameter is 250nm instills in vial, and drop is full, while the lead that slant setting is cleaned
Foil.Vial is put into air dry oven, temperature remains 35 DEG C, until ethanol solution volatilization completely, obtains in vial
Silica opal template.Preparing metal organic frame precursor liquid, by 0.492g cabaltous nitrate hexahydrate, 0.592g 2- methyl
10min is mixed in imidazoles, 25mL methanol and 25mL n,N-Dimethylformamide.Silica opal template is immersed
In metal organic frame precursor liquid, 3h is stood, moves to 90 DEG C of reaction 8h in baking oven, silica is obtained and metal organic frame is multiple
Close object.Compound is put into tube furnace, 1000 DEG C of heat treatment 6h in inert atmosphere.It takes out, with 30wt% hydrofluoric acid dips
24h.It is cleaned with deionized water, 60 DEG C of dryings, obtains three-dimensional order graded porous carbon photonic crystal.
Embodiment 4
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, carbon paper deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
3%, the silicon dioxide microsphere ethanol solution that diameter is 600nm instills in vial, and drop is full, while the carbon that slant setting is cleaned
Paper.Vial is put into air dry oven, temperature remains 35 DEG C, until ethanol solution volatilization completely, obtains in vial
Silica opal template.Preparing metal organic frame precursor liquid, by 0.483g cabaltous nitrate hexahydrate, 0.592g 2- methyl
10min is mixed in imidazoles, 25mL methanol and 25mL n,N-Dimethylformamide.Silica opal template is immersed
In metal organic frame precursor liquid, 3h is stood, moves to 70 DEG C of reaction 8h in baking oven, silica is obtained and metal organic frame is multiple
Close object.Compound is put into tube furnace, 700 DEG C of heat treatment 6h in inert atmosphere.It takes out, for 24 hours with 20wt% hydrofluoric acid dips.
It is cleaned with deionized water, 60 DEG C of dryings, obtains three-dimensional order graded porous carbon photonic crystal.
Embodiment 5
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, leaf deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
3%, the silicon dioxide microsphere aqueous solution that diameter is 100nm instills in vial, and drop is full, while the tungsten that slant setting is cleaned
Piece.Vial is put into air dry oven, temperature remains 25 DEG C, until deionized water volatilization completely, obtains in vial
Silica opal template.Preparing metal organic frame precursor liquid, by zinc nitrate, 2-methylimidazole, methanol is mixed
10min, wherein the molar ratio of zinc nitrate and 2-methylimidazole is 1:1.Silica opal template immersion metal there is into machine frame
In frame precursor liquid, 3h is stood, moves to 50 DEG C of reaction 8h in baking oven, obtains silica and metal organic frame compound.It will answer
It closes object to be put into tube furnace, 600 DEG C of heat treatment 8h in inert atmosphere.It takes out, for 24 hours with 5wt% hydrofluoric acid dips.Use deionized water
Cleaning, 60 DEG C of dryings obtain three-dimensional order graded porous carbon photonic crystal.
Embodiment 6
The vial deionized water for being used for self-assembled silicon dioxide opal template is cleaned by ultrasonic 20min, until
It is 3 times few, leaf deionized water, acetone, isopropanol and alcohol are respectively cleaned by ultrasonic 20min, equal drying for standby.It is by concentration
3%, the silicon dioxide microsphere aqueous solution that diameter is 800nm instills in vial, and drop is full, while the tungsten that slant setting is cleaned
Piece.Vial is put into air dry oven, temperature remains 60 DEG C, until deionized water volatilization completely, obtains in vial
Silica opal template.Preparing metal organic frame precursor liquid, by ferric nitrate, 2-methylimidazole, N, N- dimethyl formyl
10min is mixed in amine, and wherein the molar ratio of ferric nitrate and 2-methylimidazole is 1:8.Silica opal template is immersed
In metal organic frame precursor liquid, 3h is stood, moves to 90 DEG C of reaction 3h in baking oven, silica is obtained and metal organic frame is multiple
Close object.Compound is put into tube furnace, 1200 DEG C of heat treatment 3h in inert atmosphere.It takes out, with 30wt% hydrofluoric acid dips 6h.
It is cleaned with deionized water, 60 DEG C of dryings, obtains three-dimensional order graded porous carbon photonic crystal.
Fig. 1 is the silica opal template stereoscan photograph being prepared, from the figure, it can be seen that therein two
Silica arrangement is fine and close, and height is complete orderly.Fig. 2 be silica and metal organic frame it is compound after obtained silica and
The stereoscan photograph of metal organic frame compound, it can be seen from the figure that metal organic frame uniformly coats silica table
Face.Fig. 3-5 is respectively the stereoscan photograph and transmission electron microscope photo of carbon photonic crystal, and carbon photonic crystal aperture size is uniform,
Three-dimensional order arrangement, structure are very smooth.Fig. 6 is carbon photonic crystal scanning transmission photo, wherein BF is the bright of carbon photonic crystal
Picture, C, O, N be respectively carbon in carbon photonic crystal, oxygen, nitrogen spectral distribution.There it can be seen that the carbon being prepared
Photonic crystal nitrogen rich in provides very big benefit for the electrochemical applications etc. of carbon photonic crystal.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in guarantors of the invention
Within the scope of shield.
Claims (9)
1. preparing three-dimensional order graded porous carbon photonic crystal method using metal organic frame, which is characterized in that this method exists
Metal organic framework compound is synthesized in the gap of silica opal template, form silica by high temperature cabonization and is had
The porous carbon complex of sequence obtains the classifying porous carbon photonic crystal of three-dimensional order after removing silica opal template.
2. according to claim 1 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, silica opal template is to be self-assembled into silica opal template by silicon dioxide microsphere, it will
Silicon dioxide microsphere is distributed in deionized water or dehydrated alcohol, is then dispensed, tungsten foil, lead foil or the carbon that will be cleaned up
Paper is inserted into silicon dioxde solution, controlled at the self assembly of 25 DEG C of -60 DEG C of progress photonic crystals.
3. according to claim 2 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, the diameter of the silicon dioxide microsphere is 100nm-800nm.
4. according to claim 1 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, synthesizing metal organic framework compound in die clearance uses following steps: silica template is immersed
In the precursor liquid of metal organic frame, precursor liquid is adsorbed in die clearance through capillary action, heating reaction forms dioxy
SiClx and metal organic frame compound.
5. according to claim 4 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, the metal salt used is zinc nitrate, nickel nitrate, ferric nitrate, nitric acid in the precursor liquid of the metal organic frame
Cobalt or manganese nitrate, for the organic ligand used for 2-methylimidazole, solution is methanol, n,N-Dimethylformamide or N, N- dimethyl
Acetamide it is one or more.
6. according to claim 5 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, the molar ratio of the metal salt and the organic ligand is 1:1-1:8.
7. according to claim 4 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, the temperature of heating reaction is 50 DEG C -90 DEG C, time 3h-8h.
8. according to claim 1 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, silica and metal organic frame compound are put into tube furnace, it is heat-treated in inert atmosphere, carbonization gold
Belong to organic frame, hydrofluoric acid dips are used after taking-up, remove silica opal template, obtains three-dimensional order graded porous carbon light
Sub- crystal.
9. according to claim 8 prepare three-dimensional order graded porous carbon photonic crystal method using metal organic frame,
It is characterized in that, heat treatment temperature is 600 DEG C -1200 DEG C, time 3h-8h, hydrofluoric acid concentration 5-30wt%, soaking time
For 6h-24h.
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