CN106867018B - A method for synthesizing microporous conductive polymer materials with nanoreactor - Google Patents
A method for synthesizing microporous conductive polymer materials with nanoreactor Download PDFInfo
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Abstract
The present invention relates to a kind of method with the synthetic microporous conductive polymer material of nano-reactor, this method with the synthetic microporous conductive polymer material of nano-reactor first synthesizes the nano-reactor of organic inorganic hybridization first；And its microscopic appearance is characterized using scanning electron microscope, while also its structure is characterized with x-ray diffractometer；Secondly the present invention uses the nano-reactor as template again, there is by electrochemical method synthesis the polythiophene of the three-dimensional structure of regular pore structure inside it, with reversible redox cycle volt-ampere property, conductivity 0.1S/cm is micropore conductive polymer material.The present invention synthesizes the conductive polymer material with microcellular structure as template using nano-reactor for the first time, to obtain the novel polythiophene with microcellular structure.
Description
Technical field
The present invention relates to the synthesis technical fields of the conductive polymer material with microcellular structure, and in particular to a kind of with receiving
The method of the rice synthetic microporous conductive polymer material of reactor.
Background technique
At past several years, research group all over the world went into overdrive to design and develop new material, preparation consciously
Porous organic frame (POFs) with specific function of the size range from several nanometers to several hundred nanometers, including covalently have machine frame
Frame (COFs), metal organic frame (MOFs material) and micropore conjugated polymer (CMPs).Recently, there is unique electronics and light
The porous organic frame of electrical property has caused the great interest of scientist.Since organic conductive porous material is answered in photovoltaic
Great potential in, people have put into more and more energy to the research of this kind of material.This kind of material is in super electricity
Container, battery, microelectronics, sensor etc. are all widely used.Conventional conducting polymer such as polyaniline, polyhenylene,
Polythiophene has obtained good development, but they are the polymer for the linear backbone that one-dimensional (1D) has extremely low surface region.
Two-dimentional (2D) has also been synthesized in succession based on the porous polymer of conjugation organic ligand, such as electroactive organic frame
(EOFs), CMPs and COFs etc., although these materials all show the electrical property of redox, doping or photoinduction,
Its conductivity is very low, this may be from the inefficient stacking in p- system.If the conducting polymer of linear backbone is synthesized three
The structure for tieing up (3D), can thus obtain the conductive material for having both high porosity and high conductivity.
(MOFs, this is led to as made of multiple tooth organic ligand and the coordination of metal ion or metal cluster to metal organic framework
Coordinate bond (also referred to as secondary structure unit (SBU) is built up) is crossed, represents a kind of novel porous materials with adjustable aperture, knot
The diversity of structure and programmable function.MOFs membrane material has been extensively studied, and is stored as in gas, gas separation, carbon
Capture, catalysis, a new class of functional material that sensing etc. is widely used, however summarize the use of all about MOFs material
The document on way is it was found that these documents are all largely in report MOFs material in gas liquid separation, gas absorption and storage
Deposit the application with optics etc., about in electrochemistry application or it is very few.
Summary of the invention
The object of the present invention is to provide a kind of method with the synthetic microporous conductive polymer material of nano-reactor, this use
The method of the synthetic microporous conductive polymer material of nano-reactor uses the membrane material of organic inorganic hybridization as nano-reactor
Polythiophene is synthesized, which makes a big difference with previous polythiophene material, has well-regulated microcellular structure, together
When have both electric conductivity.
The technical solution adopted by the present invention to solve the technical problems is: this synthetic microporous conductive high with nano-reactor
The method of molecular material includes the following steps:
Step 1: the synthesis of the nano-reactor of organic inorganic hybridization:
(1), the pretreatment of carrier platinized platinum: with volumetric concentration being 20%- after the sand paper polishing of 500 mesh of carrier platinized platinum is clean
50% hydrochloric acid solution corrodes 20-30 seconds, cleans 3 times with EtOH Sonicate after taking out in hydrochloric acid solution, and 30 minutes every time, finally
It is cleaned by ultrasonic 3 times with deionized water, 30 minutes every time, room temperature was dried spare；Length 3-5cm, the wide 1-1.5cm of carrier platinized platinum,
With a thickness of 0.5-2mm；
(2), carrier platinized platinum is modified with MIL-68 crystal seed: crystal seed being dissolved in water and is made into emulsion, by the emulsion brush of formation
On the two sides of carrier platinized platinum, painting crystal seed number is at least primary, until carrier platinized platinum desired zone is smeared uniform, carrier platinized platinum
Reserving 0.5-1cm and being not coated with region is to do electrode use later；The carrier platinized platinum that crystal seed has been modified is placed in 45-80 degree baking oven
Drying overnight, obtains the carrier platinized platinum substrate modified by crystal seed；Solution for dissolving MIL-68 crystal seed be DMF or chloroform or
Acetone；
(3), the preparation of the MIL-68 film of organic inorganic hybridization: not by the carrier platinized platinum obtained in the previous step modified with crystal seed
The one end for applying crystal seed is tiltedly stood upward to be placed in the ptfe autoclave lining with stainless steel casing, and the mother of MIL-68 is added
Liquid, the height of mother liquor are more than the upper edge of polyaniline；It is put into 120 degree of baking ovens crystallization 3 days, is taken out after reaction from reaction kettle, it is cooling
It is taken out to room temperature, after opening after film rinses for several times with methanol, the characteristics of natural air drying obtains Pt/MIL-68 film, the film is exactly to use
MIL-68 film is overgrowed on the region of crystal seed modification, and unmodified region is still smooth clean carrier platinized platinum, the film is just
It is the template for synthesizing porous polythiophene, is called nano-reactor；
Step 2: using the nano-reactor synthesizing new polythiophene of synthesis, specific synthesis process is as follows:
(1), nano-reactor is first immersed in 1-5h in 0.1-0.5M thiophene solution, in the duct of porous MIL-68 film
MIL-68 film nano-reactor is made in interior absorption thiophene；
(2), the MIL-68 film nano-reactor prepared using upper step, prepares polythiophene using three with cyclic voltammetry
Electrode method, reference electrode are Ag/AgCl electricity grades, are platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene,
Electrolyte is 1-3M KCl solution, includes the thiophene of 0.1-0.2 M in electrolyte, first with nitrogen drum before electrolyte electrolysis
Bubble 20 minutes to remove oxygen therein；Potential scan range is -1.0-1.0V, and sweeping speed is 5-30 mV/s, and temperature is 25-50 °
Porous MIL-68 film-polythiophene composite film can be obtained in C, whole process scanning 10-50 circle；
(3), template is gone:
Obtained porous MIL-68 film-polythiophene composite film is immersed in the hydrochloric acid solution of PH=3-6, at this time MIL-68
Film dissolution, has in solution a large amount of gray precipitates to occur, this is organic acid ligand in MIL-68 structure and obtained polythiophene powder
The mixture at end, is filtered with membrane filter after carrier vector platinized platinum is taken out with tweezers, obtains grey matter, by the grey matter
With a small amount of repeated multiple times cleaning filtering of ethyl alcohol, the powder of dark brown is obtained, then the powder is washed with water to neutrality, 60 degree of bakings
Case drying, obtains the polythiophene of the three-dimensional structure with regular pore structure, has reversible redox cycle volt-ampere property, leads
Electric rate is 0.1S/cm, is micropore conductive polymer material.
The pretreatment of carrier platinized platinum in above scheme step 1: body is used after the sand paper polishing of 500 mesh of carrier platinized platinum is clean
The hydrochloric acid solution that product concentration is 50% corrodes 20-30 seconds, is cleaned 3 times, every time 30 points after taking out in hydrochloric acid solution with EtOH Sonicate
Clock is finally cleaned by ultrasonic 3 times with deionized water, and 30 minutes every time, room temperature was dried spare；Length 1cm, the wide 5cm of platinum Pt piece are carried,
With a thickness of 0.5mm.
The carrier platinized platinum that crystal seed has been modified is placed in 60 degree of baking ovens in above scheme step 1 and is dried overnight.
In above scheme step 2 (1), nano-reactor is immersed in 2h in 0.2M thiophene solution, in porous MIL-68 film
Duct in adsorb thiophene, be made MIL-68 film nano-reactor.
In above scheme step 2 (2), polythiophene is prepared using three-electrode method with cyclic voltammetry, reference electrode is
Ag/AgCl electricity grade is platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene, and electrolyte is that 3M KCl is molten
Liquid includes the thiophene of 0.1 M in electrolyte, is first bubbled 20 minutes with nitrogen before electrolyte electrolysis to remove oxygen therein
Gas；Potential scan range is -0.2-1.0V, and sweeping speed is 10mV/s, and temperature is 25 °C, and 20 circle of whole process scanning can be obtained more
Hole MIL-68 film-polythiophene composite film.
Hydrochloric acid solution PH=3 in above scheme step 2 (3).
The present invention has first synthesized nano-reactor first.And its microscopic appearance is carried out using scanning electron microscope
Characterization, while also its structure is characterized with x-ray diffractometer.Secondly the present invention uses the nano-reactor as mould again
Plate passes through electrochemical method synthesizing new high molecular material inside it.The features of the present invention is that anti-using nanometer for the first time
Device is answered as template to synthesize the conductive polymer material with microcellular structure, to obtain novel with microcellular structure
Polythiophene.
The invention has the following advantages:
The present invention uses the porous MOF film with tridimensional network for nano-reactor, in electrochemical synthesis
Cyclic voltammetry synthesizes polythiophene, due to the swiftness and non-intellectual that polythiophene synthesizes in the duct of nano-reactor, then
It is poly- by being synthesized under the polythiophene and conventional situation of this kind of method synthesis in conjunction with the special tridimensional network of MOF film template
The structure of thiophene and property difference.The polythiophene obtained by characterizing the present invention, test result are shown with regular pore structure
The polythiophene of three-dimensional structure has passed through porous MOF film and has prepared for nano-reactor, has reversible redox cycle
Volt-ampere property, conductivity 0.1S/cm show good characteristic of semiconductor, that is to say, that the porous poly- thiophene that the present invention synthesizes
Pheno has apparent difference compared with traditional polythiophene, not only in structure, pore structure occurs, and property also no longer phase
Seemingly, the porous polythiophene that the present invention synthesizes is a kind of electroactive porous material of tool, is the conduction with three-dimensional open-framework
Porous material.
Detailed description of the invention
Fig. 1 prepares schematic diagram for template Pt electrode；
Fig. 2 is nano-reactor schematic diagram；
Fig. 3 is the electron scanning figure of nano-reactor MIL-68 crystal seed on Pt electrode.
Fig. 4 is the electron scanning figure of nano-reactor MIL-68 film on Pt electrode.
Fig. 5 is the X-ray diffraction spectrogram of nano-reactor MIL-68 film on Pt electrode.
Fig. 6 is the cyclic voltammetry curve for synthesizing polythiophene.
Fig. 7 is the N for synthesizing polythiophene2Adsorption curve.
Fig. 8 is the infrared figure for the polythiophene that embodiment 1 obtains.
Fig. 9 is the infrared figure for the polythiophene that embodiment 2 obtains.
Figure 10 is the infrared figure for the polythiophene that embodiment 3 obtains.
Specific embodiment
The present invention will be further described below with reference to the drawings:
Embodiment 1:
This method with the synthetic microporous conductive polymer material of nano-reactor includes the following steps:
(1), it is molten with 20% hydrochloric acid after the sand paper polishing of 500 mesh of platinized platinum (cm × 0.5 of 1 cm × 5 mm) is clean
It corrosion 20-30 seconds, is cleaned 3 times after being taken out in hydrochloric acid with EtOH Sonicate, it is 30 minutes every time, finally clear with deionized water ultrasound
It washes 3 times, every time 30 minutes.Room temperature is dried.By the two sides of the platinized platinum of the emulsion brush of MIL-68 crystal seed after the pre-treatment, (1cm is not
The ground of painting is convenient to do electrode use later).It is placed in 60 degree of baking ovens and is dried overnight, for dissolving with the platinized platinum that crystal seed has been modified
The solution of MIL-68 crystal seed can be chloroform.
(2), tiltedly standing to be placed on upward by one end that the platinized platinum obtained in the previous step modified with crystal seed is not coated with crystal seed has not
It becomes rusty in the ptfe autoclave lining of outer steel shell, the mother liquor of MIL-68 is added, the height of mother liquor is more than the upper edge of polyaniline.It puts
Enter in 120 degree of baking ovens crystallization 3 days, reaction kettle is taken out after reaction, is cooled to room temperature, film is taken out after opening and is rinsed for several times with methanol
Afterwards, natural air drying obtains Pt/MIL-68 film nano-reactor.
Step 2: using the nano-reactor synthesizing new polythiophene of synthesis, specific synthesis process is as follows:
Nano-reactor is first immersed in 2h in 0.2M thiophene solution, adsorbs thiophene in the duct of porous MIL-68 film,
MIL-68 film nano-reactor is made；
The MIL-68 film nano-reactor prepared using upper step, prepares polythiophene with cyclic voltammetry, reference electrode is Ag/
AgCl electricity grade is platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene, electrolyte be 3M KCl solution its
In include 0.1M thiophene, this electrolyte electrolysis before first with nitrogen be bubbled 20 minutes to remove oxygen therein.Potential is swept
Retouching range is -0.2 to 1.0V, and sweeping speed is 10 mV/s, and temperature is 25 °C, and porous MIL- can be obtained in 20 circle of whole process scanning
68 films-polythiophene composite film.
It goes template: obtained porous MIL-68 film-polythiophene composite film being immersed in the hydrochloric acid solution of PH=3, is dissolved away
MIL-68 template, we are existing to take out carrier platinized platinum with tweezers.Acquired solution is filtered with membrane filter, obtains grey matter, will
The grey matter can be obtained by the powder of dark brown with a small amount of repeated multiple times cleaning filtering of ethyl alcohol, then the powder water is clear
It is washed till neutrality, 60 degree of baking oven drying obtain the polythiophene of the three-dimensional structure with regular pore structure, have reversible redox
Cyclic voltammetric property, conductivity 0.1S/cm are micropore conductive polymer material.
Embodiment 2:
This 1 difference of embodiment of the method with the synthetic microporous conductive polymer material of nano-reactor, only with following
When ring voltammetry prepares polythiophene, the concentration of thiophene is 0.2 M in electrolyte.
Embodiment 3:
This 1 difference of embodiment of the method with the synthetic microporous conductive polymer material of nano-reactor, only with following
When ring voltammetry prepares polythiophene, scanning speed (sweeping speed) is 20 mV/s.
Embodiment 4:
This method with the synthetic microporous conductive polymer material of nano-reactor includes the following steps:
(1), it is molten with 50% hydrochloric acid after the sand paper polishing of 500 mesh of platinized platinum (cm × 0.5 of 1 cm × 5 mm) is clean
It corrosion 20-30 seconds, is cleaned 3 times after being taken out in hydrochloric acid with EtOH Sonicate, it is 30 minutes every time, finally clear with deionized water ultrasound
It washes 3 times, every time 30 minutes.Room temperature is dried.By the two sides of the platinized platinum of the emulsion brush of MIL-68 crystal seed after the pre-treatment, (1cm is not
The ground of painting is convenient to do electrode use later).It is placed in 60 degree of baking ovens and is dried overnight, for dissolving with the platinized platinum that crystal seed has been modified
The solution of MIL-68 crystal seed can be DMF.
(2), tiltedly standing to be placed on upward by one end that the platinized platinum obtained in the previous step modified with crystal seed is not coated with crystal seed has not
It becomes rusty in the ptfe autoclave lining of outer steel shell, the mother liquor of MIL-68 is added, the height of mother liquor is more than the upper edge of polyaniline.It puts
Enter in 120 degree of baking ovens crystallization 3 days, reaction kettle is taken out after reaction, is cooled to room temperature, film is taken out after opening and is rinsed for several times with methanol
Afterwards, natural air drying obtains Pt/MIL-68 film nano-reactor.
Step 2: using the nano-reactor synthesizing new polythiophene of synthesis, specific synthesis process is as follows:
Nano-reactor is first immersed in 2h in 0.2M thiophene solution, adsorbs thiophene in the duct of porous MIL-68 film,
MIL-68 film nano-reactor is made；
The MIL-68 film nano-reactor prepared using upper step, prepares polythiophene with cyclic voltammetry, reference electrode is Ag/
AgCl electricity grade is platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene, electrolyte be 3M KCl solution its
In include 0.1M thiophene, this electrolyte electrolysis before first with nitrogen be bubbled 20 minutes to remove oxygen therein.Potential is swept
Retouching range is -0.2 to 1.0V, and sweeping speed is 10 mV/s, and temperature is 25 °C, and porous MIL- can be obtained in 20 circle of whole process scanning
68 films-polythiophene composite film.
It goes template: obtained porous MIL-68 film-polythiophene composite film being immersed in the hydrochloric acid solution of PH=3, is dissolved away
MIL-68 template, we are existing to take out carrier platinized platinum with tweezers.Acquired solution is filtered with membrane filter, obtains grey matter, will
The grey matter can be obtained by the powder of dark brown with a small amount of repeated multiple times cleaning filtering of ethyl alcohol, then the powder water is clear
It is washed till neutrality, 60 degree of baking oven drying obtain the polythiophene of the three-dimensional structure with regular pore structure, utilize N2Adsorption curve characterization
Its microcellular structure, while by its electric conductivity of conductivity test, micropore polythiophene material prepared by the present invention has reversible
Redox cycle volt-ampere property, conductivity 0.1S/cm are micropore conductive polymer material.
The present invention uses the porous MOF film with tridimensional network for nano-reactor, in electrochemical synthesis
Cyclic voltammetry synthesizes polythiophene, due to the swiftness and non-intellectual that polythiophene synthesizes in the duct of nano-reactor, then
In conjunction with the special tridimensional network of MOF film template, the polythiophene that is synthesized by this kind of method may with closed under conventional situation
At polythiophene structure and property have some differences, by characterizing the polythiophene that finally obtains, this kind of method synthesis of discovery
Polythiophene, test result show with regular pore structure three-dimensional structure polythiophene by porous MOF film be nanometer
Reactor prepares, and has reversible redox cycle volt-ampere property, and conductivity 0.1S/cm shows good half
Conductor characteristics, that is to say, that the porous polythiophene that the present invention synthesizes not only has in structure obvious compared with traditional polythiophene
Difference, there is pore structure, and property is also no longer similar, porous polythiophene prepared by the present invention be it is a kind of have it is electroactive
Porous material.One kind has the conductive porous material of three-dimensional open-framework.
Claims (5)
1. a kind of method with the synthetic microporous conductive polymer material of nano-reactor, it is characterised in that:
Step 1: the synthesis of the nano-reactor of organic inorganic hybridization:
(1), the pretreatment of carrier platinized platinum: with volumetric concentration being 20%-50%'s after the sand paper polishing of 500 mesh of carrier platinized platinum is clean
Hydrochloric acid solution corrodes 20-30 seconds, cleans 3 times with EtOH Sonicate after taking out in hydrochloric acid solution, 30 minutes every time, finally spend from
Sub- water is cleaned by ultrasonic 3 times, and 30 minutes every time, room temperature was dried spare；Length 3-5cm, the wide 1-1.5cm of carrier platinized platinum, with a thickness of
0.5-2mm；
(2), carrier platinized platinum is modified with MIL-68 crystal seed: crystal seed being dissolved in water and is made into emulsion, the emulsion brush of formation is being carried
The two sides of body platinized platinum, painting crystal seed number is at least primary, and until carrier platinized platinum desired zone is smeared uniformly, carrier platinized platinum will be stayed
It is to do electrode use later that 0.5-1cm, which is not coated with region, out；The carrier platinized platinum that crystal seed has been modified is placed in 45-80 degree baking oven and is dried
Overnight, the carrier platinized platinum substrate modified by crystal seed is obtained；Solution for dissolving MIL-68 crystal seed is DMF or chloroform or third
Ketone；
(3), the carrier platinized platinum obtained in the previous step modified with crystal seed the preparation of the MIL-68 film of organic inorganic hybridization: is not coated with crystalline substance
One end of kind is tiltedly stood upward to be placed in the ptfe autoclave lining with stainless steel casing, and the mother liquor of MIL-68 is added,
The height of mother liquor is more than the upper edge of crystal seed or carrier platinized platinum；It is put into 120 degree of baking ovens crystallization 3 days, is taken out after reaction from reaction kettle,
It is cooled to room temperature, is taken out after opening after film rinses for several times with methanol, the characteristics of natural air drying obtains Pt/MIL-68 film, the film is just
It is to overgrow with MIL-68 film on the region modified with crystal seed, and unmodified region is still smooth clean carrier platinized platinum, it should
Film is exactly the template for synthesizing porous polythiophene, is called nano-reactor；
Step 2: polythiophene is synthesized using the nano-reactor of synthesis, specific synthesis process is as follows:
(1), nano-reactor is first immersed in 1-5h in 0.1-0.5M thiophene solution, in the duct interior suction of porous MIL-68 film
MIL-68 film nano-reactor is made in attached thiophene；
(2), the MIL-68 film nano-reactor prepared using upper step, prepares polythiophene using three electrodes with cyclic voltammetry
Method, reference electrode are Ag/AgCl electricity grades, are platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene, electrolysis
Liquid is 1-3M KCl solution, includes the thiophene of 0.1-0.2 M in electrolyte, is first bubbled 20 with nitrogen before electrolyte electrolysis
Minute is to remove oxygen therein；Potential scan range is -1.0-1.0V, and sweeping speed is 5-30 mV/s, and temperature is 25-50 °C, whole
Porous MIL-68 film-polythiophene composite film can be obtained in a process scanning 10-50 circle；
(3), template is gone:
Obtained porous MIL-68 film-polythiophene composite film is immersed in the hydrochloric acid solution of pH=3-6, MIL-68 film is molten at this time
Solution has in solution a large amount of gray precipitates to occur, this is organic acid ligand in MIL-68 structure and obtained polythiophene powder
Mixture is filtered with membrane filter after taking out carrier vector platinized platinum with tweezers, obtains grey matter, by the grey matter with less
The repeated multiple times cleaning filtering of the ethyl alcohol of amount, obtains the powder of dark brown, then the powder is washed with water to neutrality, 60 degree of baking ovens dry
It is dry, the polythiophene of the three-dimensional structure with regular pore structure is obtained, there is reversible redox cycle volt-ampere property, conductivity
It is micropore conductive polymer material for 0.1S/cm.
2. the method according to claim 1 with the synthetic microporous conductive polymer material of nano-reactor, it is characterised in that:
The pretreatment of carrier platinized platinum in the step one: it is 50% that volumetric concentration is used after the sand paper polishing of 500 mesh of carrier platinized platinum is clean
Hydrochloric acid solution corrode 20-30 seconds, cleaned 3 times, 30 minutes every time, finally spent with EtOH Sonicate after being taken out in hydrochloric acid solution
Ionized water is cleaned by ultrasonic 3 times, and 30 minutes every time, room temperature was dried spare；Length 5cm, the wide 1cm of platinum Pt piece are carried, with a thickness of
0.5mm。
3. the method according to claim 2 with the synthetic microporous conductive polymer material of nano-reactor, it is characterised in that:
The carrier platinized platinum that crystal seed has been modified is placed in 60 degree of baking ovens in the step one and is dried overnight.
4. the method according to claim 3 with the synthetic microporous conductive polymer material of nano-reactor, it is characterised in that:
In the step two (2), polythiophene is prepared using three-electrode method with cyclic voltammetry, reference electrode is Ag/AgCl electricity
Grade is platinum filament to electrode, and working electrode is the Pt/MIL-68 film for having adsorbed thiophene, and electrolyte is 3M KCl solution, electrolyte
In include 0.1 M thiophene, the electrolyte electrolysis before first with nitrogen be bubbled 20 minutes to remove oxygen therein；Potential scan
Range is -0.2-1.0V, and sweeping speed is 10mV/s, and temperature is 25 °C, and porous MIL-68 film-can be obtained in 20 circle of whole process scanning
Polythiophene composite film.
5. the method according to claim 4 with the synthetic microporous conductive polymer material of nano-reactor, it is characterised in that:
Hydrochloric acid solution pH=3 in the step two (3).
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| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
| CN102993646A (en) * | 2012-12-05 | 2013-03-27 | 常州大学 | Polythiophene nanometer conductive composite material and preparation method thereof |
| US20130313193A1 (en) * | 2012-05-25 | 2013-11-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| CN106459590A (en) * | 2014-03-27 | 2017-02-22 | 巴斯夫欧洲公司 | Porous membranes comprising metal-organic frameworks |
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| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
| US20130313193A1 (en) * | 2012-05-25 | 2013-11-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| CN102993646A (en) * | 2012-12-05 | 2013-03-27 | 常州大学 | Polythiophene nanometer conductive composite material and preparation method thereof |
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