CN109942020A - A kind of preparation method of the three-dimensional network composite material of tubular metal oxide/carbon - Google Patents
A kind of preparation method of the three-dimensional network composite material of tubular metal oxide/carbon Download PDFInfo
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- CN109942020A CN109942020A CN201910109107.2A CN201910109107A CN109942020A CN 109942020 A CN109942020 A CN 109942020A CN 201910109107 A CN201910109107 A CN 201910109107A CN 109942020 A CN109942020 A CN 109942020A
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Abstract
The invention belongs to technical field of nano material, specially a kind of preparation method of tubular porous metal oxide/carbon three-dimensional network.Using bi-block copolymer, self assembly is formed by the flexible polymer nano wire with core-shell structure as template to the present invention in a solvent first, then metal ion and organic ligand is added, crystallization obtains Three-D linear metal-organic framework material at room temperature, and further calcining obtains the three-dimensional network material with tubular structure that metal oxide and carbon are combined.The tubular metal oxide/carbon composite material has very big structural advantage, and hollow nanostructures can provide low-density and big specific surface area, effective to reduce quality and charge conveying length；Addition of functional shell due to carbon, the effective accumulation for preventing metal oxide in charge and discharge process, the stability of structure is improved, advanced energy storage and switch technology, such as lithium ion battery, hybrid super capacitor, lithium-sulfur cell, water-splitting and fuel cell are suitable for.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to porous metal oxide/carbon with tubular structure
The preparation method of three dimensional network composite material.
Background technique
Important series of the nanotube-shaped material as functional material, and combining has in functional shell and internal voids
Empty tubular nanostructures assign some peculiar properties, as specific surface area is high, density is low, osmosis is good, charge transmission range
Short and preferable stability etc..Due to its adjustable physics and chemical property, nanotube-shaped material has been demonstrated to have very big
Structural advantage, be suitable for advanced energy storage and switch technology: as be suitable for advanced energy storage and switch technology, such as lithium-ion electric
Pond, hybrid super capacitor, lithium-sulfur cell, water-splitting and fuel cell etc..Therefore by rationally designing, synthesis has tubulose knot
The nano material of structure has highly important theoretical significance to the efficient storage and conversion that further realize the current energy
With production practical value.
The synthetic method of current nanotube-shaped material is mainly template, wherein orientation template mainly has carbon nanometer at present
Pipe, inorganic, metal oxide nano wire, polymer nano rice noodles and metal nano-rod etc..For can further functionalization polymerization
The extensive usage of object nanometer line template is electrostatic spinning, and advantage is produced on a large scale it is clear that simple, easy to operate.But it is quiet
Fibre diameter used in Electrospun is big, and obtained tubular material diameter generally in 100nm or more, cannot obtain smaller pipe
Shape structure.Theoretically the smaller tubular material of diameter can further increase the specific surface area of material, reduce quality and charge biography
Defeated length is more superior in the upper performance of storage and conversion of the energy.Therefore, obtaining smaller size of nanotube-shaped material is to have research
Meaning and application value.
Summary of the invention
It is an object of that present invention to provide a kind of porous metal oxide/carbon three-dimensional network composite wood with tubular structure
The preparation method of material.
The preparation side of porous metal oxide/carbon three-dimensional network composite material provided by the invention with tubular structure
Method, specific steps are as follows:
(1) di-block copolymer is dissolved in good solvent first, the water of a certain proportion of protonation is added dropwise into good solvent, and
It is slowly added to the aqueous solution of DNA, mixing a period of time, the water that enough protonations are added dropwise is then proceeded to, so that block polymer
Pass through electrostatic interaction in a solvent with DNA and hydrophobic effect assembles the flexible polymer nano wire to form core-shell structure, passes through friendship
The polymer nano rice noodles that can be stabilized in a solvent are further obtained after connection core；It will be received finally by the method being repeatedly centrifuged
Rice noodles solution replacement synthesizes solvent required for MOFs at next step；
(2) it is molten that the resulting polymer nano rice noodles solution of step (1), metal salt solution and organic ligand are sequentially added in flask
Liquid quickly rocks uniformly, which is stood still for crystals 24-72 h at room temperature, passes through centrifuge washing, vacuum drying
Afterwards, it obtains being denoted as using polymer nano rice noodles as the three-dimensional netted composite material of the metal organic frame of template/polymer nano rice noodles
MOFs；The metal salt is zinc nitrate hexahydrate and cobalt nitrate hexahydrate；The organic ligand is 2-methylimidazole；
(3) the three-dimensional netted composite material of the resulting metal organic frame of step (2)/polymer nano rice noodles is placed in tube furnace
In, in inert gas, it is warming up to certain temperature, high-temperature calcination for a period of time, then naturally cools to certain at this temperature
Temperature opens boiler tube, continues low temperature calcination for a period of time at this temperature in air, to get to pipe after natural cooling
Porous metal oxide/carbon 3D net composites of shape structure；Wherein, metal oxide ZnCo2O4。
In step (1) of the present invention, the block polymer is polyethylene glycol tetravinyl pyridine (PEG-b-P4VP),
Wherein, PEG chain segment molecular weight is between 2000-20000, and P4VP molecular weight is between 3000-20000；Polymer nano rice noodles
The crosslinking agent of core P4VP is Isosorbide-5-Nitrae-dibromobutane, and the crosslinking degree of P4VP pyridine ring is 5%-100%.
In step (2) of the present invention, solvent needed for MOFs crystallization is anhydrous methanol；Metal ion and organic match when feeding intake
The molar ratio of body is 1:1.8-2.5, (preferred molar ratio 1:2), Zn in metal ion2+And Co2+Molar ratio be 1:0-1:2.
In step (2) of the present invention, the MOFs of synthesis is ZIF-8 and ZIF-67, and wherein metal ion is Zn2+And Co2+, gold
Belong to ion to be provided by zinc nitrate hexahydrate and cobalt nitrate hexahydrate.
In step (3) of the present invention, heating rate is that the preferred heating rate of 0.5-5 DEG C/min(is 1-3 DEG C/min), high temperature is forged
Burning temperature is 750-900 DEG C, calcination time 1h-4h；Calcination atmosphere is argon atmosphere；Low temperature calcination temperature is 250-350 DEG C,
Calcination time is 30min-2h, and calcination atmosphere is air atmosphere.
In the present invention, the tubular diameter of porous metal oxide/carbon 3D net composites of the tubular structure is
30-60 nm, it is adjustable；Metal oxide ZnCo2O4In Zn and Co content it is adjustable.
Tubular metal oxide/carbon composite material prepared by the present invention has very big structural advantage, hollow nanostructures
Low-density and big specific surface area can be provided, it is effective to reduce quality and charge conveying length；And functional shell is due to carbon
Addition, the effective accumulation for preventing metal oxide in charge and discharge process improves the stability of structure, is suitable for advanced
Energy storage and switch technology, such as lithium ion battery, hybrid super capacitor, lithium-sulfur cell, water-splitting and fuel cell.
The beneficial technical effect of the present invention:
(1) the polymer nano rice noodles that the present invention is obtained using self assembly, the nanowire size is adjustable, in high volume can efficiently prepare,
Using this polymer nano rice noodles as template, porous metal oxide/carbon three-dimensional network composite material with tubular structure is prepared,
Method is convenient, without removing template, only need to simply calcine, resulting porous metal oxide/carbon with tubular structure
The tubular diameter of three-dimensional network composite material is small, adjustable (30-60 nm), metal oxide ZnCo2O4In Zn and Co content can
It adjusts；
(2) porous metal oxide/carbon three-dimensional network composite material prepared by the present invention with tubular structure, porous pipe
Wall can provide enough active interface sites, reduce charge transfer path, and the presence of hollow structure and carbon is effectively delayed
The volume change during electrochemical reaction is solved, aggregation of metal oxide nanoparticles during charge and discharge cycles is prevented.
Detailed description of the invention
Fig. 1 is the XRD diagram for the three-dimensional network that the one-dimensional metal organic frame in case study on implementation 1 is compounded to form with nano wire.
Fig. 2 is the XRD diagram for the three-dimensional network that the one-dimensional metal organic frame in case study on implementation 2 is compounded to form with nano wire.
Fig. 3 is the XRD diagram for the three-dimensional network that the one-dimensional metal organic frame in case study on implementation 3 is compounded to form with nano wire.
Fig. 4 is that the TEM for the three-dimensional network that the one-dimensional metal organic frame in case study on implementation 3 is compounded to form with nano wire schemes.
Fig. 5 is porous metal oxide/carbon three-dimensional network composite material with tubular structure in case study on implementation 3
TEM figure.
Fig. 6 is porous metal oxide/carbon three-dimensional network composite material with tubular structure in case study on implementation 3
XRD diagram.
Specific embodiment
Embodiment 1, porous metal oxide/carbon three-dimensional network composite material with tubular structure
Solution is configured first, and the polymer nano rice noodles solution of concentration is diluted to 2 mg/mL with anhydrous methanol, stirs evenly standby
With.Equally using anhydrous methanol as solvent, zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole are each configured to 250 mM's
Solution.
Then above-mentioned 6-10 mL polymer nano rice noodles solution is taken to be added to the 500 mL tapers for filling 160 mL anhydrous methanols
In bottle, after mixing, 10mL zinc nitrate hexahydrate solution is added, after being thoroughly mixed, is rapidly added the 2- methyl miaow of 20 mL
Azoles solution, after rocking 1 min of mixing, room temperature sealing stands 24-72 h.By multiple centrifuge washing, obtained after vacuum drying white
The three-dimensional network that color powder, as one-dimensional metal organic frame ZIF-8 and nano wire are compounded to form, is tubular metal oxide
Persursor material.Its XRD diagram is as shown in Figure 1.
The resulting metallic threadlike organic frame network material of previous step is placed in tube furnace, in inert gas, 5 DEG C/
Min rises to 800 DEG C, 2 h of high-temperature calcination, then naturally cools to 350 DEG C, opens boiler tube, continues low temperature calcination 1 in air
H, cooled to room temperature obtain black powder, and the as three-dimensional network of the porous zinc bloom with tubular structure and carbon is compound
Material.
Embodiment 2, porous metal oxide/carbon three-dimensional network composite material with tubular structure
Solution is configured first, and the polymer nano rice noodles solution of concentration is diluted to 2 mg/mL with anhydrous methanol, stirs evenly standby
With.Equally using anhydrous methanol as solvent, zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole are each configured to 250 mM's
Solution.
Then above-mentioned 6-10 mL polymer nano rice noodles solution is taken to be added to the 500 mL tapers for filling 160 mL anhydrous methanols
In bottle, after mixing, the cobalt nitrate hexahydrate solution of 6.5mL zinc nitrate hexahydrate solution and 3.5 mL is added, is thoroughly mixed
Afterwards, it is rapidly added the 2-methylimidazole solution of 20 mL, after rocking 1 min of mixing, room temperature sealing stands 24-72 h.By multiple
Centrifuge washing, obtains purple powder after vacuum drying, as one-dimensional metal organic frame ZIF-8 and ZIF-67 and nano wire are compound
The three-dimensional network of formation is the persursor material of tubular metal oxide.Its XRD diagram is as shown in Figure 2.
The resulting metallic threadlike organic frame network material of previous step is placed in tube furnace, in inert gas, 5 DEG C/
Min rises to 800 DEG C, 2 h of high-temperature calcination, then naturally cools to 350 DEG C, opens boiler tube, continues low temperature calcination 1 in air
H, cooled to room temperature obtain black powder, the as three-dimensional network of porous zinc cobalt/cobalt oxide and carbon with tubular structure
Composite material, wherein zinc cobalt atom ratio is 2:1.
Embodiment 3, porous metal oxide/carbon three-dimensional network composite material with tubular structure
Solution is configured first, and the polymer nano rice noodles solution of concentration is diluted to 2 mg/mL with anhydrous methanol, stirs evenly standby
With.Equally using anhydrous methanol as solvent, zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole are each configured to 250 mM's
Solution.
Then above-mentioned 6-10 mL polymer nano rice noodles solution is taken to be added to the 500 mL tapers for filling 160 mL anhydrous methanols
In bottle, after mixing, the cobalt nitrate hexahydrate solution of 3.5mL zinc nitrate hexahydrate solution and 6.5 mL is added, is thoroughly mixed
Afterwards, it is rapidly added the 2-methylimidazole solution of 20 mL, after rocking 1 min of mixing, room temperature sealing stands 24-72 h.By multiple
Centrifuge washing, obtains lilac powder after vacuum drying, as one-dimensional metal organic frame ZIF-8 and ZIF-67 and nano wire are multiple
The three-dimensional network formed is closed, is the persursor material of tubular metal oxide.Its XRD diagram is as shown in figure 3, TEM schemes such as Fig. 4 institute
Show.
The resulting metallic threadlike organic frame network material of previous step is placed in tube furnace, in inert gas, 5 DEG C/
Min rises to 800 DEG C, 2 h of high-temperature calcination, then naturally cools to 350 DEG C, opens boiler tube, continues low temperature calcination 1 in air
H, cooled to room temperature obtain black powder, the as three-dimensional network of porous zinc cobalt/cobalt oxide and carbon with tubular structure
Composite material, wherein zinc cobalt atom ratio is 1:2.Its TEM schemes as shown in figure 5, XRD diagram is as shown in Figure 6.
Claims (7)
1. a kind of preparation method of the three-dimensional network composite material of tubular metal oxide/carbon, which is characterized in that specific steps are such as
Under:
(1) di-block copolymer is dissolved in good solvent first, the water of a certain amount of protonation is added dropwise into good solvent, and slowly
The aqueous solution of DNA is added, mixing a period of time, the water that enough protonations are added dropwise is then proceeded to, so that block polymer and DNA
The flexible polymer nano wire to form core-shell structure is assembled by electrostatic interaction and hydrophobic effect in a solvent, after being crosslinked core
Further obtain the polymer nano rice noodles that can be stabilized in a solvent；It is finally by the method being repeatedly centrifuged that nano wire is molten
Liquid is replaced as synthesizing solvent required for MOFs in next step；
(2) it is molten that the resulting polymer nano rice noodles solution of step (1), metal salt solution and organic ligand are sequentially added in flask
Liquid quickly rocks uniformly, which is stood still for crystals 24-72 h at room temperature, passes through centrifuge washing, vacuum drying
Afterwards, it obtains being denoted as using polymer nano rice noodles as the three-dimensional netted composite material of the metal organic frame of template/polymer nano rice noodles
MOFs；The metal salt is zinc nitrate hexahydrate and cobalt nitrate hexahydrate；The organic ligand is 2-methylimidazole；
(3) the three-dimensional netted composite material of the resulting metal organic frame of step (2)/polymer nano rice noodles is placed in tube furnace
In, in inert gas, it is warming up to certain temperature, high-temperature calcination for a period of time, then naturally cools to certain at this temperature
Temperature opens boiler tube, continues low temperature calcination for a period of time at this temperature in air, to get to pipe after natural cooling
Porous metal oxide/carbon 3D net composites of shape structure；Wherein, metal oxide ZnCo2O4 。
2. preparation method according to claim 1, which is characterized in that block polymer described in step (1) is poly- second two
The poly- tetravinyl pyridine (PEG-b-P4VP) of alcohol-, wherein between 2000-20000, P4VP molecular weight exists PEG chain segment molecular weight
Between 3000-20000.
3. preparation method according to claim 1 or 2, which is characterized in that the core P4VP of polymer nano rice noodles in step (1)
Crosslinking agent be Isosorbide-5-Nitrae-dibromobutane, the crosslinking degree of P4VP pyridine ring is 5%-100%.
4. preparation method according to claim 3, which is characterized in that solvent needed for MOFs crystallization is nothing in step (2)
Water methanol；The molar ratio of metal ion and organic ligand is 1:1.8-2.5, Zn in metal ion when feeding intake2+And Co2+Mole
Than for 1:0-1:2.
5. preparation method according to claim 1,2 or 4, which is characterized in that the MOFs synthesized in step (2) is ZIF-8
And ZIF-67, wherein metal ion is Zn2+And Co2+, metal ion provided by zinc nitrate hexahydrate and cobalt nitrate hexahydrate.
6. preparation method according to claim 5, which is characterized in that in step (3), heating rate is 0.5-5 DEG C/min,
High-temperature calcination temperature is 750-900 DEG C, calcination time 1h-4h；Calcination atmosphere is argon atmosphere；Low temperature calcination temperature is 250-
350 DEG C, calcination time 30min-2h, calcination atmosphere is air atmosphere.
7. preparation method according to claim 6, which is characterized in that porous metal oxide/carbon of the tubular structure
3D net composites tubular diameter be 30-60 nm, it is adjustable；Metal oxide ZnCo2O4In Zn and Co content
It is adjustable.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111129468A (en) * | 2019-12-31 | 2020-05-08 | 苏州阿德旺斯新材料有限公司 | One-dimensional metal oxide/carbide composite material and preparation method thereof |
| CN112357906A (en) * | 2020-11-12 | 2021-02-12 | 同济大学 | Nitrogen-doped monomodal ultramicropore carbon nanosheet synthesized by in-situ amorphous cobalt template method, and method and application thereof |
| CN113077992A (en) * | 2021-03-18 | 2021-07-06 | 中国矿业大学 | Co3O4Nanoparticle/porous carbon crosslinked nanosheet array composite electrode and preparation method and application thereof |
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| CN104151336A (en) * | 2014-08-08 | 2014-11-19 | 复旦大学 | Preparation method of metal-organic framework compound with hierarchical pore structure |
Non-Patent Citations (2)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129468A (en) * | 2019-12-31 | 2020-05-08 | 苏州阿德旺斯新材料有限公司 | One-dimensional metal oxide/carbide composite material and preparation method thereof |
| CN111129468B (en) * | 2019-12-31 | 2021-11-16 | 苏州阿德旺斯新材料有限公司 | One-dimensional metal oxide/carbide composite material and preparation method thereof |
| CN112357906A (en) * | 2020-11-12 | 2021-02-12 | 同济大学 | Nitrogen-doped monomodal ultramicropore carbon nanosheet synthesized by in-situ amorphous cobalt template method, and method and application thereof |
| CN113077992A (en) * | 2021-03-18 | 2021-07-06 | 中国矿业大学 | Co3O4Nanoparticle/porous carbon crosslinked nanosheet array composite electrode and preparation method and application thereof |
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Application publication date: 20190628 |