CN108976818A - The porous orderly carbon-point of one kind is based on cellulose composite material and the preparation method and application thereof - Google Patents
The porous orderly carbon-point of one kind is based on cellulose composite material and the preparation method and application thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 98
- 239000001913 cellulose Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 26
- 150000001875 compounds Chemical class 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 238000005411 Van der Waals force Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229910021536 Zeolite Inorganic materials 0.000 description 30
- 239000010457 zeolite Substances 0.000 description 30
- 235000010980 cellulose Nutrition 0.000 description 18
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 150000003851 azoles Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of porous orderly carbon-points to be based on cellulose composite material and the preparation method and application thereof.This method utilizes the effects of Van der Waals force between the presoma metal ion or cluster and nano-cellulose molecule of metal organic frame (MOFs) power, makes presoma uniform adsorption on nano-cellulose surface；It is added after organic ligand through coordinate bond self assembly in nano-cellulose surface homoepitaxial metal organic frame, a kind of porous orderly carbon-point composite material is prepared in the space that removing guest molecule leaves porous material after high temperature carbonization.Preparation method raw material sources of the invention are extensive, and compared with traditional porous carbon preparation method for material, operating procedure is simple, easily controllable, reproducibility is high.Metal organic frame (MOFs) of the invention/compound porous carbon material of nano-cellulose has big specific surface area, good pore-size distribution, electric conductivity and excellent heat stability, and excellent performance is shown in fields such as catalysis, electrochemistry.
Description
Technical field
Preparation method and electrochemical applications field the present invention relates to porous orderly carbon-point based on cellulose composite material, tool
Body is related to the porous orderly carbon-point of one kind and is based on cellulose composite material and the preparation method and application thereof.
Background technique
Metal organic frame (MOFs) has three-dimensional structure, good thermal stability and high specific surface area.But due to gold
Belong to organic frame (MOFs) material electric conductivity itself it is not high, therefore be often used as presoma or sacrifice template pass through pyrocarbon
Change to prepare nanoporous carbon materials, prepared porous carbon materials not only specific surface area with higher, high porosity, and
And electric conductivity is higher, resistance is lower, therefore, is more and more applied to the oxygen of electrode material for super capacitor, fuel cell
The fields such as reduction reaction and electrode material of lithium battery.
Nano-cellulose (NanoCelluloses) is a kind of natural reproducible resource, has excellent mechanical performance, huge
Big specific surface area, high-crystallinity, high-hydrophilic, the high grade of transparency, low-density, load other nano actives frequently as basis material
The composite material of material preparation is for various aspects such as energy storage, catalysis, medicine.Due to nano-cellulose have big specific surface area,
The characteristics such as modification, biocompatibility and good mechanical performance, so being the first choice for preparing carbon materials material precursor.Therefore,
Develop it is a kind of simple, using nano-cellulose be efficiently that there is porous carbon materials of matrix and preparation method thereof important reality to anticipate
Justice.
Hetero atom rich in can prepare element doping porous carbon materials, Ke Yizeng in metal organic frame (MOFs)
Add electric conductivity, the wetability of material.In addition, material can be increased to a certain extent introducing nano-cellulose as second level carbon source
The Kong Rong and specific surface area of material, the two have complementary advantages, and keep it more excellent in application field performance.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, it is an object of the invention to more for metal organic frame (MOFs)
Form, the structure feature of hole carbon material introduce second level carbon source nano-cellulose, provide the porous orderly carbon-point of one kind and are based on cellulose
The preparation method of composite material.
Form another object of the present invention is to provide the porous orderly carbon-point based on cellulose composite material and
Structure.The porous orderly carbon-point of this method preparation has multistage aperture, big specific surface area, good based on cellulose composite material
Electric conductivity and stability the features such as.
The object of the invention is also to provide the porous orderly carbon-points of one kind to be based on cellulose composite material as super
The application of grade capacitor electrode material.
The purpose of the present invention is realized by following technical solution.
A kind of porous preparation method of the orderly carbon-point based on cellulose composite material, includes the following steps:
(1) preparation of nano-cellulose uniform dispersion: in a solvent by nano-cellulose dispersion, ultrasonic disperse obtains Nanowire
Tie up plain uniform dispersion；
(2) porous orderly carbon-point is based on cellulose composite material precursor preparation: by the presoma gold of metal organic frame MOFs
Belong to ion or cluster is added into nano-cellulose dispersion liquid, ultrasound, stirring；Organic ligand is added, stirring is stood, and use is organic
Ion-cleaning is spent after solvent centrifuge washing again, re-dry obtains porous orderly carbon-point and is based on cellulose composite material presoma；
(3) calcining carbonization: porous orderly carbon-point is based on cellulose composite material presoma, and high temperature cabonization is burnt under an inert atmosphere
Knot obtains metal organic frame (MOFs)/porous orderly carbon-point and is based on cellulose composite material.
Further, in step (1), the nano-cellulose is obtained by acidolysis or oxidized fibre material.
Further, in step (1), the nano-cellulose uniform dispersion is obtained by following steps:
Filter paper (or microcrystalline cellulose) is added in the sulfuric acid of 64wt% and hydrolyzes (the sulfuric acid of filter paper (or microcrystalline cellulose) and 64wt%
Solid-liquid ratio be 2:35 g/ml), stir 45min at 45 DEG C, then be added 5 times of reaction solution deionized water terminate reaction；Instead
It answers gained suspension to be centrifuged repeatedly with deionized water and washs the extra acid solution of removal, centrifugal condition 10000rmp, 6min, then thoroughly
Analysis is until the pH of water-dialyzing is constant；Dialyzate is directly dispersing in solvent and obtains nano-cellulose uniform dispersion, Huo Zheleng
Jelly is dried to obtain solid nano-cellulose, and redisperse obtains nano-cellulose uniform dispersion in a solvent.
Further, in step (1), the concentration of the nano-cellulose uniform dispersion is 4~10 mg/ml.
Further, in step (1), the solvent is methanol, ethyl alcohol or deionized water.
Further, in step (2), the metal organic frame (MOFs)/nano-cellulose uniform dispersion matter
Amount is than being 1:1~8:1.
Further, in step (2), the time of the ultrasound is 10~60min.
Further, in step (2), the temperature being stirred to react is 25~60 DEG C, and the time is 2 ~ 6h.
Further, in step (2), in step (2), the organic solvent is methanol；It is described centrifugation be using centrifugation or
The method of vacuum filtration removes the solvent in solution；The washing is 3 ~ 6 times.
Further, in step (2), the drying is 25~60 DEG C of temperature under vacuum conditions, dry 12~for 24 hours.
Further, in step (2), the mass ratio of the nano-cellulose and dispersing agent is 1:200 ~ 1:500.
Further, in step (2), the ligand is organic ligand.
Further, in step (3), the temperature of the calcining carbonization is 900 ~ 1100 DEG C, and the time is 5 ~ 7h.
Further, the nano-cellulose can also be made in the following way: 350ml is added in 20g filter paper
In the sulfuric acid of 64wt%, 45min hydrolysis is stirred at 45 DEG C；5 times of reaction solution of deionized water is then added and terminates reaction, terminates
Gained suspension is centrifuged repeatedly washing with deionized water and removes extra acid solution after reaction, and centrifugal condition is 10000rpm,
6min；It is dialysed again until the pH of water-dialyzing is constant.
The porous orderly carbon-point of one kind as made from preparation method described in any of the above embodiments is based on cellulose composite material.
The present invention also provides a kind of porous orderly carbon-points to be based on cellulose composite material in electrode material for super capacitor
In application.
Compared with prior art, the present invention has the advantage that and technical effect:
(1) porous orderly carbon-point of the invention be based on cellulose composite material have a large amount of mesoporous and micropore coexisting structures and compared with
Big specific surface area.
(2) the method for the present invention raw material sources are extensive, the preparation method raw material sources of invention are abundant, it is renewable, green,
Environmental protection, and operating procedure is simple, easily controllable, favorable reproducibility, easily realization industrial-scale production；
(3) porous orderly carbon-point of the invention is good based on cellulose composite material structure composition, has in catalysis and electrochemical field
Have broad application prospects.
(4)) it in the present invention, by taking one of metal organic frame (MOFs) zeolite imidazole skeleton ZIF-8 as an example, prepares
The compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose, wherein performance optimal proportion be
Nano-cellulose is 1:4 relative to the presoma zinc nitrate hexahydrate quality of zeolite imidazole skeleton (ZIF-8).
Detailed description of the invention
Fig. 1 is zeolite imidazole skeleton (the ZIF-8)/compound porous nitrogen-doped nanometer of nano-cellulose prepared in embodiment 1
The scanning electron microscope (SEM) photograph of Bacilliform carbon material.
Fig. 2 is zeolite imidazole skeleton (ZIF-8)/rodlike carbon of the compound porous nitrogen-doped nanometer of nano-cellulose in embodiment 1
The nitrogen adsorption desorption curve graph of material.
Fig. 3 is zeolite imidazole skeleton (the ZIF-8)/compound porous nitrogen-doped nanometer of nano-cellulose prepared in embodiment 1
The pore size distribution curve figure of Bacilliform carbon material.
Fig. 4 is zeolite imidazole skeleton (the ZIF-8)/compound porous nitrogen-doped nanometer of nano-cellulose prepared in embodiment 1
The supercapacitor chemical property curve graph of Bacilliform carbon material.
Specific embodiment
Embodiment 1
The preparation of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose, specifically includes
Following steps:
(1) preparation of nano-cellulose uniform dispersion: in deionized water by nano-cellulose dispersion, ultrasonic disperse obtains
Nano-cellulose uniform dispersion, concentration 4mg/ml.
(2) zeolite imidazole skeleton (ZIF-8)/nano-cellulose precursor preparation: 480mg zinc nitrate hexahydrate is added to
(zinc nitrate hexahydrate and nano-cellulose are mixed under the deionized water dispersion liquid stirring condition of the nano-cellulose of 30ml 4mg/ml
Mass ratio is 4:1), after stirring 4h under room temperature, 1.056g organic ligand methylimidazole is added in ultrasonic 30min, is stirred after 4h
To uniformly mixed white turbid；It is washed with deionized three times with methanol centrifuge washing four times, then 60 DEG C of vacuum drying 12h,
Obtain zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma.
(3) calcining carbonization: by zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma under nitrogen atmosphere protection
950oC carburizing sintering 5h obtains zeolite imidazole skeleton (ZIF-8)/rodlike carbon materials of the compound porous nitrogen-doped nanometer of nano-cellulose
Material.
Zeolite imidazole skeleton (ZIF-8)/compound porous nitrogen-doped nanometer Bacilliform carbon material of nano-cellulose of preparation is swept
Electron microscope is retouched as shown in Figure 1, can be seen that ZIF-8 even particle size, about 20nm by a in Fig. 1；By that can be seen by b in Fig. 1 and c
Honeycomb structure, and nano-cellulose rough surface are formed to nano-cellulose is overlapping, covers a large amount of graininess ZIF-8 particles；
It can be seen that ZIF-8 is grown on nano-cellulose visibly homogeneously by d in Fig. 1, it was demonstrated that this synthetic method success synthetic zeolite miaow
The compound porous nitrogen-doped nanometer Bacilliform carbon material of azoles skeleton (ZIF-8)/nano-cellulose.
The nitrogen of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose of preparation
Aspiration desorption curve figure and graph of pore diameter distribution as shown in Fig. 2, by a in Fig. 2 it is found that preparation zeolite imidazole skeleton (ZIF-8)/receive
The rice compound porous nitrogen-doped nanometer Bacilliform carbon material of cellulose, apparent hysteresis loop demonstrates mesoporous deposit in adsorption desorption curve
By b in Fig. 2 it is found that the porous carbon materials of preparation have multistage pore-size distribution.
The heat of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose of preparation
Test result is resurveyed as shown in figure 3, being increased to 800 in temperatureoWhen C, material loss about 7% illustrates that material has excellent thermostabilization
Property.
The electricity of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose of preparation
Test chemical figure illustrates the material as super as shown in figure 4, nearly rectangle is presented in cyclic voltammetry curve it can be seen from a in Fig. 4
Grade capacitor material is with double layer characteristic and has preferable high rate performance；Charging and discharging curve is left it can be seen from b in Fig. 4
It is right symmetrical, it can show that specific capacitance is 172F/g from the curve；C, which can be seen that, in Fig. 4 increases in current density from 0.1A/g
When 10A/g, that is, current density expand 100 times, capacity retention 63%, further illustrate the material have good times it is forthright
Energy.D can be seen that after the circle of circulation 5000 in Fig. 4, capacity retention 94.5%, illustrate that the material has good circulation steady
It is qualitative.
Embodiment 2
The preparation of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose, specifically includes
Following steps:
(1) preparation of nano-cellulose uniform dispersion: in ethanol by nano-cellulose dispersion, ultrasonic disperse obtains nanometer
Cellulose uniform dispersion, concentration 4mg/ml.
(2) zeolite imidazole skeleton (ZIF-8)/nano-cellulose precursor preparation: 120mg zinc nitrate hexahydrate is added to
(zinc nitrate hexahydrate and nanofiber quality after being mixed under the alcohol dispersion liquid stirring condition of the nano-cellulose of 30ml 4mg/ml
Amount is than being 1:1), ultrasonic 30min after stirring 4h under room temperature, is added 264mg organic ligand methylimidazole, obtains after stirring 4h
Uniformly mixed white solution；It is washed with deionized three times, then 60 DEG C of vacuum drying 12h, is obtained with methanol centrifuge washing four times
To zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma.
(3) calcining carbonization: by zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma under nitrogen atmosphere protection
1000oC carburizing sintering 5h obtains zeolite imidazole skeleton (ZIF-8)/rodlike carbon materials of the compound porous nitrogen-doped nanometer of nano-cellulose
Material.
The compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose of preparation has
Good chemical property (specific capacitance 107F/g).
Embodiment 3
The preparation of the compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose, specifically includes
Following steps:
(1) preparation of nano-cellulose uniform dispersion: in methyl alcohol by nano-cellulose dispersion, ultrasound (power 800W,
40kHz, similarly hereinafter) dispersion, obtain nano-cellulose uniform dispersion, concentration 4mg/ml.
(2) zeolite imidazole skeleton (ZIF-8)/nano-cellulose precursor preparation: 960mg zinc nitrate hexahydrate is added to
(zinc nitrate hexahydrate and nanofiber quality after being mixed under the methanol dispersion liquid stirring condition of the nano-cellulose of 30ml 4mg/ml
Amount is than being 8:1), ultrasonic 30min(power 800W, 40kHz, similarly hereinafter), after stirring 4h under room temperature, 2.112g dimethyl miaow is added
Azoles obtains uniformly mixed white solution after stirring 4h；It is washed with deionized three times with methanol centrifuge washing four times, then 60 DEG C
It is dried in vacuo 12h, obtains zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma.
(3) calcining carbonization: by zeolite imidazole skeleton (ZIF-8)/nano-cellulose presoma under nitrogen atmosphere protection
1100oC carburizing sintering 5h obtains zeolite imidazole skeleton (ZIF-8)/rodlike carbon materials of the compound porous nitrogen-doped nanometer of nano-cellulose
Material.
The compound porous nitrogen-doped nanometer Bacilliform carbon material of zeolite imidazole skeleton (ZIF-8)/nano-cellulose of preparation has
Good chemical property (specific capacitance 128F/g).
Claims (9)
1. a kind of porous preparation method of the orderly carbon-point based on cellulose composite material, which comprises the steps of:
(1) preparation of nano-cellulose uniform dispersion: in a solvent by nano-cellulose dispersion, ultrasonic disperse obtains Nanowire
Tie up plain uniform dispersion；
(2) porous orderly carbon-point is based on cellulose composite material precursor preparation: by the presoma gold of metal organic frame MOFs
Belong to ion or cluster is added into nano-cellulose dispersion liquid, ultrasound, stirring；Organic ligand is added, stirring is stood, and use is organic
Ion-cleaning is spent after solvent centrifuge washing again, re-dry obtains porous orderly carbon-point and is based on cellulose composite material presoma；
(3) calcining carbonization: porous orderly carbon-point is based on cellulose composite material presoma, and high temperature cabonization is burnt under an inert atmosphere
Knot obtains porous orderly carbon-point and is based on cellulose composite material.
2. preparation method according to claim 1, which is characterized in that in step (1), the nano-cellulose is to pass through acid
Solution or oxidized fibre material obtain；The solvent is methanol, ethyl alcohol or deionized water.
3. preparation method according to claim 1, which is characterized in that in step (1), the nano-cellulose is evenly dispersed
The concentration of liquid is 4~10 mg/ml.
4. preparation method according to claim 1, which is characterized in that in step (2), metal has machine frame in the dispersion liquid
Frame presoma and nano-cellulose mass ratio are 1:1~8:1.
5. preparation method according to claim 1, which is characterized in that in step (2), time of the ultrasound is 10~
60min；The temperature being stirred to react is 25~60 DEG C, and the time is 2 ~ 6h.
6. preparation method according to claim 1, which is characterized in that in step (2), the organic solvent is methanol；Institute
Stating centrifugation is the solvent removed in solution using the method for centrifugation or vacuum filtration；The drying is temperature under vacuum conditions
25~60 DEG C, dry 12~for 24 hours；The mass ratio of nano-cellulose and dispersion liquid is 1:200 ~ 1:500.
7. preparation method according to claim 1, which is characterized in that in step (3), the temperature of the calcining carbonization is
900 ~ 1100 DEG C, the time is 5 ~ 7h.
8. the porous orderly carbon-point of one kind as made from claim 1-7 described in any item preparation methods is based on cellulose composite wood
Material.
9. the porous orderly carbon-point of one kind according to any one of claims 8 is based on cellulose composite material as electrode material for super capacitor
Application.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109728284A (en) * | 2019-01-02 | 2019-05-07 | 齐鲁工业大学 | A kind of metal-modified three-dimensional carbon net carried metal organic backbone is as lithium/positive electrode of sodium-sulfur cell material preparation method |
| CN109759064A (en) * | 2019-01-11 | 2019-05-17 | 江苏理工学院 | A kind of Co@C/ biomass catalyzing agent and its preparation method and application |
| CN109794246A (en) * | 2019-01-11 | 2019-05-24 | 江苏理工学院 | A kind of monolithic devices honeycomb Ni@C/C catalyst and its preparation method and application |
| CN110157085A (en) * | 2019-05-16 | 2019-08-23 | 广州大学 | A kind of antibiotic plastic and preparation method thereof using ZIF-8 |
| CN110227357A (en) * | 2019-06-29 | 2019-09-13 | 华南理工大学 | A kind of flexibility can cut nano-cellulose/covalent organic framework composite membrane and preparation method thereof |
| CN110265669A (en) * | 2019-05-30 | 2019-09-20 | 南京源恒能源科技有限公司 | N doping carbonization bacteria cellulose-base graded porous carbon composite material and preparation method |
| CN112844313A (en) * | 2021-01-12 | 2021-05-28 | 顾晓凡 | Environment-friendly nanofiber material capable of rapidly adsorbing heavy metal ions and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142538A (en) * | 2017-06-27 | 2017-09-08 | 陕西科技大学 | A kind of preparation method of metal organic frame composite antibacterial fibre cellulose fiber filler |
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
| CN107808944A (en) * | 2017-10-25 | 2018-03-16 | 北京理工大学 | Porous MOF/CNFs composites for lithium anode protection |
| CN108049238A (en) * | 2017-11-20 | 2018-05-18 | 陕西科技大学 | One kind is based on cellulose base/ZIF-67 composite materials and preparation method thereof |
| CN108142420A (en) * | 2017-12-06 | 2018-06-12 | 陕西科技大学 | A kind of anti-biotic material and preparation method thereof |
-
2018
- 2018-07-02 CN CN201810709982.XA patent/CN108976818A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
| CN107142538A (en) * | 2017-06-27 | 2017-09-08 | 陕西科技大学 | A kind of preparation method of metal organic frame composite antibacterial fibre cellulose fiber filler |
| CN107808944A (en) * | 2017-10-25 | 2018-03-16 | 北京理工大学 | Porous MOF/CNFs composites for lithium anode protection |
| CN108049238A (en) * | 2017-11-20 | 2018-05-18 | 陕西科技大学 | One kind is based on cellulose base/ZIF-67 composite materials and preparation method thereof |
| CN108142420A (en) * | 2017-12-06 | 2018-06-12 | 陕西科技大学 | A kind of anti-biotic material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| ZEHUI LI，等: "Cabron materials derived from chitosan/cellulose cryogel-supported zeolite imidazole frameworks for potential supercapacitor application", 《CARBOHYDRATE POLYMERS》 * |
| 冯权莉，等: "《微波-活性炭纤维处理有机废气》", 30 June 2017, 冶金工业出版社 * |
| 刘旷野，等: "纳米纤维素在制浆造纸工业中的应用研究", 《中国造纸》 * |
| 刘玉荣，等: "《介孔碳材料的合成及应用》", 30 June 2012, 国防大学出版社 * |
| 谢昆，等: "《纳米技术在水污染控制中的应用》", 30 June 2014, 武汉大学出版社 * |
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| CN109728284B (en) * | 2019-01-02 | 2022-04-19 | 齐鲁工业大学 | Preparation method of metal-modified three-dimensional carbon net loaded metal organic framework as lithium/sodium-sulfur battery positive electrode material |
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| CN109794246B (en) * | 2019-01-11 | 2021-08-24 | 江苏理工学院 | Integrated honeycomb Ni @ C/C catalyst and preparation method and application thereof |
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