CN109867780A - It is a kind of to keep the organic polymer of MOFs pattern, preparation method and application - Google Patents
It is a kind of to keep the organic polymer of MOFs pattern, preparation method and application Download PDFInfo
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- CN109867780A CN109867780A CN201910165435.4A CN201910165435A CN109867780A CN 109867780 A CN109867780 A CN 109867780A CN 201910165435 A CN201910165435 A CN 201910165435A CN 109867780 A CN109867780 A CN 109867780A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
It is a kind of to keep the organic polymer of MOFs pattern, preparation method and application, belong to organic polymer technical field.The organic polymer for keeping MOFs pattern is prepared by the organic ligand auto polymerization in metal organic frame (MOFs), the Carbon Materials that resulting polymers have maintained after original MOFs pattern and carbonization also maintain original pattern, and gained Carbon Materials all show excellent performance in the electrode material as lithium ion battery, sodium-ion battery and supercapacitor.
Description
Technical field
It is prepared the present invention relates to one kind by the organic ligand auto polymerization in metal organic frame (MOFs) and keeps MOFs
The organic polymer of pattern, the Carbon Materials that resulting polymers have maintained after original MOFs pattern and carbonization also maintain original
Pattern, gained Carbon Materials can lithium ion battery, sodium-ion battery, in terms of application, belong to organic polymer
Object technical field.
Background technique
Metal organic frame (MOFs) due to its selectable ingredient, programmable structure and adjustable nano-space by
Extensive concern [Furukawa H., Cordova K.E., O ' Keeffe M., Yaghi O.M.The chemistry and
applications of metal-organic frameworks[J].Science,2013,341,1230444].Pass through tune
The MOFs with many special appearances, such as spherical shape, cube, octahedron, length can be prepared in section ligand and metal ion
Cube etc., resulting pattern and structure are of great significance to its subsequent performance and application, and existing MOFs has certain
Macroscopic view or surface structure are made of carrying out accumulation or weak coordination as MOFs unit, to be coordinated in the follow-up heat treatment process
Key, which is easily broken off, causes pattern to destroy, therefore researchers explore various methods to keep the pattern of MOFs, for example are added and hand over
Join [Kitao T., Zhang Y., Kitagawa S., the et al.Hybridization of MOFs such as polymerization in agent and hole
And polymers [J] .Chem.Soc.Rev., 2017,46,3108], but both modes are all complex, process is numerous
It is trivial, it by the ligand direct polymerization of MOFs is to select well without any additive.The present invention passes through further
So that the organic ligand between resulting MOFs structural unit carries out auto polymerization, the MOFs pattern that is further maintained has for processing
Machine polymer.
Summary of the invention
In view of the above problems in the prior art, the present invention is prepared for keeping the organic polymer of MOFs pattern by one-step method
Object solves prior art entirety MOFs appearance or macrostructure instability problem.
Technical scheme is as follows to achieve the above object.
A kind of organic polymer keeping MOFs pattern.
A kind of preparation method for the organic polymer keeping MOFs pattern, which is characterized in that by by metal organic frame
Organic ligand carries out cross-linked polymeric and is maintained the organic polymer of MOFs pattern in structural unit.
A kind of further preparation method of the organic polymer of holding MOFs pattern described above, which is characterized in that the
A kind of method: directly choosing organic ligand and metal salt make raw material, is generated using solvent thermal reaction and keeps the organic of MOFs pattern
Polymer, i.e., the self-crosslinking of organic ligand, which polymerize, in the condition realization MOFs structural unit by controlling solvent thermal reaction is protected
Hold the organic polymer of MOFs pattern；Or second method: MOFs material is directly heat-treated in a solvent, so that MOFs
The self-crosslinking polymerization of organic ligand in structural unit.
The further preferred embodiment of the present invention is: MOFs material in the organic ligand and second method in first method
The organic ligand of material is selected from p-phenylenediamine, o-phenylenediamine, m-phenylene diamine (MPD), toluenediamine, naphthylenediamine and their derivative
One kind.
The further preferred embodiment of the present invention is: the metal salt in first method is mantoquita, cobalt salt, molysite, zinc salt, silver
One of salt and nickel salt, anion can be NO3 -、Cl-、SO4 -One of.The metal choosing of MOFs material in second method
From one of copper, cobalt, iron, zinc, silver and nickel.
The further preferred embodiment of the present invention is: the temperature of solvent thermal reaction described in first method is 80-180 DEG C, molten
The agent thermal response time is at least 24 hours.The solvent of solvent heat is preferably methanol.The condition of second method is solvent thermal reaction
Or heat under normal pressure: the temperature of solvent thermal reaction is 80-180 DEG C, and the solvent thermal reaction time is at least 12 hours；Often
The temperature of pressure heat treatment is 100-200 DEG C, and heating time is at least 16 hours.
Obtained polymer material is carbonized, so that the structure of carbonization front and back keeps identical, the temperature of carbonization is
500-1000 DEG C, soaking time 0-5h.
The present invention realizes the ligand in MOFs as monomer, polymerize under the metal ion facilitation of MOFs itself,
Resulting polymers have maintained the pattern of MOFs.
One kind of the invention is prepared by the organic ligand auto polymerization in metal organic frame (MOFs) keeps MOFs pattern
Organic polymer, resulting polymers maintained original MOFs pattern and carbonization after Carbon Materials also maintain original shape
Looks.The pattern for having maintained MOFs is realized first, and strengthens the chemical bonding between charcoal skeleton, so that the pattern knot of MOFs
Structure is more stable, at the same be carbonized after gained carbon also maintain original structure i.e. directly by the high temperature carbonization under inert gas at
Reason just obtains the Carbon Materials with original MOFs consistent appearance.
In addition the present invention also provides resulting Carbon Materials as lithium ion battery, sodium-ion battery, supercapacitor
The application of electrode material.
The invention proposes one kind without any additive, and the side of its pattern is kept in MOFs treatment process
Method.It chooses organic ligand and metal salt makees raw material, the MOFs structure with different-shape is obtained using solvent thermal reaction, passes through control
The condition of solvent thermal reaction processed, due to the weak coordination between ligand and metal ion, in MOFs with know from experience itself
Self-crosslinking polymerize under metal ion facilitation, and resulting polymers have maintained original pattern of MOFs.To resulting polymers
Carry out the available Carbon Materials for keeping pattern of pyrolysis processing.And the Carbon Materials being prepared as lithium ion battery, sodium from
Excellent performance is all shown when sub- battery and the electrode material of supercapacitor.
Detailed description of the invention
Attached drawing 1 is the scanning nuclear microprobe figure of the product of different solvents hot time: the scanning electron microscope (SEM) photograph of 1min product
(a1), the transmission electron microscope picture (a2-a3) of 1min product；The scanning electron microscope (SEM) photograph (b1) of 30min product, the transmission electricity of 30min product
Mirror figure (b2-b3)；The scanning electron microscope (SEM) photograph (c1) of 1h product, the transmission electron microscope picture (c2-c3) of 1h product；The scanning electricity of product for 24 hours
Mirror figure (d1), for 24 hours transmission electron microscope picture (d2-d3) of product.
Attached drawing 2 is the X ray diffracting spectrum (a) and infrared spectrogram (b) of the product of different solvents hot time.
Attached drawing 3 is the scanning electron microscope (SEM) photograph (a) and transmission electron microscope picture (b) of the Carbon Materials after the pyrolysis of poly- p-phenylenediamine.
Attached drawing 4 is when hollow box assembles charcoal ball as lithium ion battery negative material in 50mA g-1Under preceding charge and discharge three times
Electric curve.
Attached drawing 5 be charcoal nanometer sheet as anode material of lithium-ion battery when high rate performance figure.
Attached drawing 6 be fiber interweaving carbon plate as electrode material for super capacitor when in 1A g-1Under cycle performance figure.
Attached drawing 7 is that the spherical metal organic framework materials of box assembling are directly heat-treated the scanning electron microscope of the poly- p-phenylenediamine of gained
Scheme (a) and transmission electron microscope picture (b).
Attached drawing 8 is that the X-ray of poly- p-phenylenediamine obtained by the spherical metal organic framework materials of box assembling are directly heat-treated is spread out
Penetrate map (a) and infrared spectrogram (b).
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples, but the present invention is not limited to following embodiments.
Embodiment 1
0.76g p-phenylenediamine and 1.69g copper nitrate are dissolved in ethyl alcohol, mixed solution are transferred in reaction kettle, solvent
80 DEG C of reactions of heat for 24 hours, are maintained the poly- p-phenylenediamine product of MOFs pattern by centrifugal drying.It will be heavy in initial mixed liquor
Starch is taken out and (thinks that the reaction time is 1min), is denoted as the product of 1min, then the solvent heat time is that the product of 30min and 1h is same
Sample, which collects, studies its forming process.Obtained poly- p-phenylenediamine is heat-treated under 600 DEG C of atmosphere of inert gases simultaneously
Carbon Materials are obtained, and are used as lithium ion battery negative material.
As shown in 1 scanning electron microscope of attached drawing, when p-phenylenediamine and copper nitrate admixed together, spherical production can be quickly formed
Object, by transmission electron microscope it can be seen that the surface of sphere is uniform-distribution with little particle.When being 30min when solvent heat, sphere table
The particle growth in face is at box like structure.In conjunction with shown in attached drawing 2, there are some in the X ray diffracting spectrum of 1min and 30min product
Sharp diffraction maximum illustrates that p-phenylenediamine is successfully coordinated with copper nitrate, that is, obtains the spherical metal organic frame of box assembling.
As shown in Fig. 1, when reacted between when extending to 1h again, there is hollow structure, and the reaction time is longer, it is hollow
Degree is higher, and the spherical structure of box assembling at this time is still maintained.And in fig 2 it can be seen that in 1h and infrared spectroscopy for 24 hours
All there is 1594cm-1And 1500cm-1The absorption peak at place respectively represents C=in C=N stretching vibration and the benzene shape ring in quinone shape ring
C stretching vibration illustrates the formation of poly- p-phenylenediamine.These results illustrate that p-phenylenediamine is real under the facilitation of bivalent cupric ion
Self-crosslinking polymerization is showed, and the poly- p-phenylenediamine obtained has maintained the box-like assembling spherical morphology of metal organic frame.And
This special appearance remains to be maintained after pyrolysis processing as shown in Fig. 3.
Attached drawing 4 is when pyrolysis gained hollow box assembles charcoal ball as lithium ion battery negative material in 50mA g-1Under before
Charging and discharging curve three times.It can be found that its reversible capacity is up to 1316mAh g for the first time-1, illustrate its excellent storage lithium performance.
Embodiment 2
0.76g o-phenylenediamine and 2.04g cobalt nitrate are dissolved in ethyl alcohol, mixed solution are transferred in reaction kettle, solvent
120 DEG C of reactions of heat for 24 hours, are maintained the poly-o-phenylenediamine product of MOFs pattern by centrifugal drying.To obtained poly- adjacent benzene
Diamines is heat-treated at 700 DEG C and obtains Carbon Materials, and is used as anode material of lithium-ion battery.
Complexation reaction initially first occurs reacting for o-phenylenediamine and cobalt nitrate, sheet metal organic backbone is generated, with molten
The progress of agent thermal response, o-phenylenediamine self-crosslinking form nano-sheet poly-o-phenylenediamine.After carrying out high temperature pyrolysis processing to it, obtain
To porous charcoal nanometer sheet, using it as the negative electrode material of sodium-ion battery, its high rate performance is tested, as shown in Fig. 5,
When current density is up to 10A g-1When, storage sodium capacity remains to reach 86.1mAh g-1, illustrate its excellent high rate performance.
Embodiment 3
0.76g m-phenylene diamine (MPD) and 1.74g ferric nitrate are dissolved in ethyl alcohol, mixed solution are transferred in reaction kettle, solvent
150 DEG C of reactions of heat for 24 hours, are maintained the poly m-phenylene diamine product of MOFs pattern by centrifugal drying.To obtained poly- isophthalic
Diamines is heat-treated at 800 DEG C and obtains Carbon Materials, and is used as the electrode material of supercapacitor.
Initially complexation reaction first occurs for m-phenylene diamine (MPD) and ferric nitrate reacting, and generates the organic bone of sheet metal of fiber interweaving
Frame, with the progress of solvent thermal reaction, m-phenylene diamine (MPD) self-crosslinking forms poly m-phenylene diamine, and the pattern of metal organic framework is able to
It keeps, resulting polymers is pyrolyzed to obtain the carbon plate of fiber interweaving, using it as the electrode material of supercapacitor, it is recycled
Performance is tested, as a result as shown in Fig. 6, in 1A g-1Current density under recycle 5000 times after, specific capacity is substantially without declining
Subtract, illustrates it with excellent cycle performance.
Embodiment 4
0.76g p-phenylenediamine and 2.0g zinc nitrate are dissolved in ethyl alcohol, mixed solution are transferred in reaction kettle, solvent heat
180 DEG C of reactions for 24 hours, are maintained the poly- p-phenylenediamine product of MOFs pattern by centrifugal drying.To obtained poly- to benzene two
Amine is heat-treated at 1000 DEG C and obtains Carbon Materials, and using it as the negative electrode material of sodium-ion battery.
Complexation reaction initially first occurs reacting for p-phenylenediamine and zinc nitrate, reguline metal organic backbone is generated, with molten
The progress of agent thermal response, p-phenylenediamine self-crosslinking form blocky poly- p-phenylenediamine, blocky Carbon Materials are obtained after being pyrolyzed to it,
As anode material of lithium-ion battery, in 1A g-1Current density under recycle 1000 times, capacity remains to be maintained at 150mAh g-1。
Embodiment 5
0.76g p-phenylenediamine and 1.69g copper nitrate are dissolved in ethyl alcohol, mixed solution are transferred in reaction kettle, solvent
150 DEG C of reaction 30min of heat obtain the spherical metal organic framework materials of box assembling by centrifugal drying.It is dispersed in ethyl alcohol
In at 120 DEG C solvent heat treatment 12h, centrifugal drying obtain poly- p-phenylenediamine.Simultaneously to obtained poly- p-phenylenediamine 900
Heat treatment obtains Carbon Materials under DEG C atmosphere of inert gases, and using it as electrode material for super capacitor.
As shown in Fig. 7, the poly- p-phenylenediamine of gained has maintained the box-like assembling spherical structure of metal organic frame.Such as
Shown in attached drawing 8a, the characteristic diffraction peak of the spherical metal organic framework materials of heat treatment back box assembling disappears, and in attached drawing 8b
It can be seen that there are 1594cm in infrared spectroscopy-1And 1500cm-1The absorption peak at place illustrates the formation of poly- p-phenylenediamine.Pyrolysis institute
Electrode material of the Carbon Materials as supercapacitor when, in 5A g-1Current density under recycle 5000 times after capacity can also
95% is kept, illustrates it with excellent cycle performance.
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make various equivalent variation or replacement on the premise of without prejudice to spirit of the invention,
These equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (10)
1. a kind of organic polymer for keeping MOFs pattern.
2. a kind of preparation method for the organic polymer for keeping MOFs pattern, which is characterized in that by by metal organic frame knot
Organic ligand carries out cross-linked polymeric and is maintained the organic polymer of MOFs pattern in structure unit.
3. preparation method according to claim 2, which is characterized in that specifically include two methods；First method: directly
It chooses organic ligand and metal salt makees raw material, the organic polymer of MOFs structure type is generated using solvent thermal reaction, that is, is passed through
The condition of control solvent thermal reaction realizes that the self-crosslinking of organic ligand in MOFs structural unit polymerize the MOFs pattern that is maintained
Organic polymer；Second method: MOFs material is directly heat-treated in a solvent, so that organic in MOFs structural unit
The self-crosslinking of ligand polymerize.
4. preparation method described in accordance with the claim 3, which is characterized in that the organic ligand in first method and second
In method the organic ligand of MOFs material be selected from p-phenylenediamine, o-phenylenediamine, m-phenylene diamine (MPD), toluenediamine, naphthylenediamine and it
One of derivative；
Metal salt in first method is one of mantoquita, cobalt salt, molysite, zinc salt, silver salt and nickel salt, and anion can be
NO3 -、Cl-、SO4 -One of；The metal of MOFs material is selected from one of copper, cobalt, iron, zinc, silver and nickel in second method.
5. preparation method described in accordance with the claim 3, which is characterized in that the temperature of solvent thermal reaction described in first method is
80-180 DEG C, the solvent thermal reaction time is at least 24 hours；The condition of second method is for solvent thermal reaction or under normal pressure
Heat treatment: the temperature of solvent thermal reaction is 80-180 DEG C, and the solvent thermal reaction time is at least 12 hours；Heat under normal pressure
Temperature be 100-200 DEG C, heating time is at least 16 hours.
6. preparation method described in accordance with the claim 3, which is characterized in that the solvent of two methods solvent heat is methanol.
7. according to the described in any item preparation methods of claim 2-6, which is characterized in that resulting polymers have maintained original
MOFs pattern.
8. according to the organic polymer for the holding MOFs pattern that the described in any item preparation methods of claim 2-6 obtain.
9. the organic polymer of the holding MOFs pattern obtained according to the described in any item preparation methods of claim 2-6 is answered
With obtained polymer material being carbonized, so that the structure of carbonization front and back keeps identical, the temperature of carbonization is 500-1000
DEG C, soaking time 0-5h.
10. the organic polymer of the holding MOFs pattern obtained according to the described in any item preparation methods of claim 2-6 is answered
With, which is characterized in that Carbon Materials as lithium ion battery, sodium-ion battery, supercapacitor electrode material application.
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Cited By (6)
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| CN110491686A (en) * | 2019-08-28 | 2019-11-22 | 齐鲁工业大学 | A kind of preparation method and application of bimetallic organic coordination compounds electrode material |
| CN111454579A (en) * | 2020-04-26 | 2020-07-28 | 张荣虎 | Nano nickel ferrite loaded graphene-based wave-absorbing material and preparation method thereof |
| CN112657555A (en) * | 2020-12-01 | 2021-04-16 | 南昌航空大学 | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof |
| CN113712045A (en) * | 2021-08-31 | 2021-11-30 | 厦门大学 | Preparation method of silver nanoparticle composite antibacterial material based on metal organic framework |
| CN114744148A (en) * | 2022-04-01 | 2022-07-12 | 三峡大学 | Preparation method of hard carbon cathode of high-rate-performance sodium ion battery |
| CN116333327A (en) * | 2023-02-20 | 2023-06-27 | 华中科技大学 | Water-based sodium ion battery anode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110491686A (en) * | 2019-08-28 | 2019-11-22 | 齐鲁工业大学 | A kind of preparation method and application of bimetallic organic coordination compounds electrode material |
| CN111454579A (en) * | 2020-04-26 | 2020-07-28 | 张荣虎 | Nano nickel ferrite loaded graphene-based wave-absorbing material and preparation method thereof |
| CN112657555A (en) * | 2020-12-01 | 2021-04-16 | 南昌航空大学 | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof |
| CN112657555B (en) * | 2020-12-01 | 2022-06-17 | 南昌航空大学 | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof |
| CN113712045A (en) * | 2021-08-31 | 2021-11-30 | 厦门大学 | Preparation method of silver nanoparticle composite antibacterial material based on metal organic framework |
| CN113712045B (en) * | 2021-08-31 | 2022-04-08 | 厦门大学 | Preparation method of silver nanoparticle composite antibacterial material based on metal organic framework |
| CN114744148A (en) * | 2022-04-01 | 2022-07-12 | 三峡大学 | Preparation method of hard carbon cathode of high-rate-performance sodium ion battery |
| CN116333327A (en) * | 2023-02-20 | 2023-06-27 | 华中科技大学 | Water-based sodium ion battery anode material and preparation method and application thereof |
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