CN104037432A - High polymer-modified metal organic framework material composite membrane, and preparation and application thereof - Google Patents
High polymer-modified metal organic framework material composite membrane, and preparation and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a high polymer-modified metal organic framework material composite membrane and a preparation method and application thereof. A preparation method for a metal organic framework material comprises a step of subjecting terephthalic acid, chromium nitrate nonahydrate, hydrofluoric acid and water to a reaction and a step of carrying out modification by using trifluoromethanesulfonic anhydride and concentrated sulfuric acid. The prepared modified metal organic framework material is dispersed in a high polymer solution so as to obtain a membrane casting solution; the membrane casting solution is successively subjected to filtering, standing and defoaming and then is used to prepare a membrane through tape casting; and drying, quenching, acidifying with a sulfur acid solution, washing and drying are successively carried out so as to obtain the high polymer-modified metal organic framework material composite membrane. The composite membrane prepared in the invention has high proton conductivity and is directly applicable to a fuel cell.
Description
Technical field
The present invention relates to composite membrane, be specifically related to a kind of macromolecule-modified metal organic framework materials composite membrane and preparation and application, belong to fuel battery proton exchange film technical field.
Background technology
Proton Exchange Membrane Fuel Cells is the representative of new forms of energy, and proton exchange membrane is one of core component of Proton Exchange Membrane Fuel Cells, and the proton conductivity of reinforced film is the key that improves battery combination property.Sulfonated polyether-ether-ketone because of its cost low, thermal stability, mechanical performance and features good methanol diffusion resistance and become one of proton exchange membrane material of greatest concern.Yet low the remaining of the proton conductivity of this film restricting one of bottleneck of applying.Proton transfer is generally divided into two kinds of mechanism: a kind of is transportation mechanism, and namely proton completes diffusion by the form of proton hydrate, such as H
3o
+, H
5o
2 +and H
9o
4 +; Another kind is Hopping mechanism, and proton completes to contiguous hydrone or functional group the transmission of jumping from a hydrone or functional group by hydrogen bond network.Based on this, in film, build continuous high-efficient hydrogen bond network and increase film inner proton and transmit the effective means that site is its proton conductivity of raising.Metal organic frame material is a kind of novel crystalline material with high-sequential structure, has the continuous pore passage structure of three-dimensional of huge specific area and high-sequential.By to its modification with on can lead the functional group of proton, can improve and lead proton carrier density, build the proton transfer passage of high-efficiency and continuous in membrane, thereby promote the proton conductivity of film.
Summary of the invention
The object of the present invention is to provide a kind of macromolecule-modified metal organic framework materials composite membrane and its preparation method and application.The proton exchange membrane of preparing with the method, for direct methanol fuel cell, has good performance.Composite membrane has following main feature: the metal organic frame material 1) using is the metal organic frame material that is numbered MIL101; 2) by rear modification method, made on metal organic frame material webs a large amount of sulfonate radicals as proton donor and proton transfer site; 3) metal ion in metal organic frame material is as a kind of lewis acid, hydrolysis can occur and form hydroxyl, together promotes to form hydrogen bond network in the passage of metal organic frame material, thereby promote proton conduction with sulfonic acid group.The membrane material that the method makes has good proton conduction characteristic, can be used for direct methanol fuel cell.
It is main membrane material that macromolecule-modified metal organic framework materials composite membrane of the present invention be take macromolecule and modified metal organic framework materials MIL101, wherein, the metal organic frame material MIL101 being modified is that the G. F é rey of French Lavoisier research institute synthesizes first, and report and called after Materials of institute Lavoisier No. 101 in the paper that is 10.1126/science.1116275 in digital object sign (doi), be abbreviated as the metal organic frame material of MIL101, chemical formula Cr
3x(H
2o)
2oH (O
2c)C
6h
4(CO
2)
3nH
2o, wherein X is fluorine ion or hydroxyl, the natural number that n is 0 ~ 25, Cubic structure cell crystal, structure cell length of side a=8.8869nm.
Metal organic frame material is through reprocessing, is doped in polymeric membrane after making to be directly connected to sulfonic acid group on its part phenyl ring again.The phenyl ring being sulfonated accounts for the 10-20% of phenyl ring sum.Metal organic frame material usage is high molecular 2.5-10%.The preparation method of this macromolecule-metal organic frame Material cladding film is as follows:
1) preparation of MIL101 metal organic frame material
According to digital object, be designated the synthetic MIL101 of method in the paper of 10.1126/science.1116275.Under room temperature, the mixed in molar ratio by terephthalic acid (TPA), nine water chromic nitrates, hydrofluoric acid, water with 1:1:1:265,200
ounder C, react after 8 hours the metal organic frame material that centrifuge washing, dry call number are MIL101.
2) the sulfonated modification of MIL101 metal organic frame material
In MIL101 metal organic frame material, add nitromethane, the concentrated sulfuric acid, trifluoromethyl sulfonic acid anhydride, metal organic frame material, nitromethane, the volume ratio of the concentrated sulfuric acid and trifluoromethyl sulfonic acid anhydride is 1:60:0.50:0.89-1:60:0.75:2.17,30
oc reacts 1-3 h, obtains the metal organic frame material of sulfonated modification after centrifuge washing.
3) preparation of composite membrane
Under room temperature, take the ultrasonic dispersing and dissolving of metal organic frame material of a certain amount of modification in nitrogen dimethylformamide, then add macromolecule, stirring obtains casting solution, wherein, the consumption of above-mentioned macromolecule, modification organic framework materials be take following proportioning and is determined: the 2.5-10% that the amount of the metal organic frame material of modification in casting solution is high molecule mass, high molecule mass is the 2.5-12.5% of nitrogen dimethylformamide quality.
Film forming after the deaeration of casting solution filtering and standing.Concrete steps comprise filtering and standing deaeration 1-2h, and by casting solution curtain coating on glass plate, and it is dry to be placed in baking oven, through temperature, is then 110-120
oafter C heat treatment 1-2 h, be placed in 2 M sulfuric acid and process 10-24 h, afterwards with deionized water rinsing until cleaning solution is neutrality, wet film is placed in to 50-60
ounder C, vacuumize obtains macromolecule-metal organic frame Material cladding film.
Described macromolecule is sulfonated polyether-ether-ketone, sulfonated polyether ketone or sulfonated polyether sulfone.
Macromolecule-metal organic frame Material cladding film prepared by said method, as direct methanol fuel cell, its methyl alcohol (2 M) permeability is 7.39-6.15 * 10
-7cm
2/ s, under room temperature, proton conductivity is 0.202-0.292 * 10
-2s/cm(100% relative humidity), especially 40
oc, under 20% relative humidity, through 90 min tests, the proton conductivity of composite membrane reaches as high as 0.080658 S/cm.
The invention has the advantages that: the preparation process of metal organic frame material is simple, and structure is controlled uniform particle diameter, cheapness.Metal is hydrolyzed in the regular 3 D pore canal of metal organic frame material as lewis acid and produces hydroxyl, in conjunction with sulfonate radical, has formed the continuous orderly hydrogen bond network that can promote proton conduction.In addition, metal organic frame material and macromolecule have good compatibility, and the dispersion in film is more even.Prepared composite membrane has good proton conduction characteristic, can be used as direct methanol fuel cell film.
Accompanying drawing explanation
Fig. 1 is high power profile scanning electron microscope (FESEM) photo of sulfonated polyether-ether-ketone film made in comparative example.
Fig. 2 is high power profile scanning electron microscope (FESEM) photo of sulfonated polyether-ether-ketone-metal organic frame Material cladding film made in embodiment 3.
Fig. 3 is the schematic diagram of testing apparatus and the description of some physical quantitys.
Embodiment
The test of all embodiment proton conductivities be all by two-probe method test membrane level to impedance, and calculate and obtain by membrane impedance.Film is placed between two electrodes, and applies 200g pressure and make itself and electrode contact good.Testing concussion voltage used is 20 mV, and frequency is 10Hz-100kHz, and test electrode used therein is platinum (Pt) metal wire that 1mm diameter, purity are 99.95%.Proton conductivity computing formula is: proton conductivity=two electrode spacing/film thickness/film water is put down to impedance/film width.Device schematic diagram and mentioned some physical quantitys are as shown in Figure 3.
Embodiment 1
Mixed in molar ratio by terephthalic acid (TPA), nine water chromic nitrates, hydrofluoric acid, water with 1:1:1:265,220
oc, corresponding saturated steam is depressed reaction 8h, with 15
othe speed of C/min is lowered the temperature until 40
oc, centrifuge washing, 60
ovacuumize 24 h under C, the metal organic frame material that call number is MIL101.Take 1.5 g metal organic frame materials and join in 100 mL round-bottomed flasks, add wherein 90 mL nitromethanes, then add the 0.75mL concentrated sulfuric acid, 2.71mL trifluoromethyl sulfonic acid anhydride, 30
oc reacts 1 h, must modify the metal organic frame material of sulfonic acid after centrifuge washing.
Take the metal organic frame material that 0.015 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 1).
Embodiment 2
According to the method preparation of embodiment 1, modify the metal organic frame material of sulfonic acid.Take the metal organic frame material that 0.030 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 2).
Embodiment 3
According to the method preparation of embodiment 1, modify the metal organic frame material of sulfonic acid.Take the metal organic frame material that 0.0450 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 3).
Embodiment 4
According to the method preparation of embodiment 1, modify the metal organic frame material of sulfonic acid.Take the metal organic frame material that 0.060 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 4).
Embodiment 5
Mixed in molar ratio by terephthalic acid (TPA), nine water chromic nitrates, hydrofluoric acid, water with 1:1:1:265,220
oc, corresponding saturated steam is depressed reaction 8h, with 15
othe speed of C/min is lowered the temperature until 40
oc, centrifuge washing, 60
othe metal organic frame material that under C, vacuumize 24 h call numbers are MIL101.Take 1.5 g metal organic frame materials and join in 100 mL round-bottomed flasks, add wherein 90 mL nitromethanes, then add the 1.12 mL concentrated sulfuric acids, 3.26 mL trifluoromethyl sulfonic acid anhydrides, 30
oc reacts 1 h, must modify the metal organic frame material of sulfonic acid after centrifuge washing.
Take the metal organic frame material that 0.045 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 5).
Embodiment 6
Mixed in molar ratio by terephthalic acid (TPA), nine water chromic nitrates, hydrofluoric acid, water with 1:1:1:265,220
oc, corresponding saturated steam is depressed reaction 8h, with 15
othe speed of C/min is lowered the temperature until 40
oc, centrifuge washing, 60
othe metal organic frame material that under C, vacuumize 24 h call numbers are MIL101.Take 1.5 g metal organic frame materials and join in 100 mL round-bottomed flasks, add wherein 90 mL nitromethanes, then add the 0.75 mL concentrated sulfuric acid, 1.33 mL trifluoromethyl sulfonic acid anhydrides, 30
oc reacts 1 h, must modify the metal organic frame material of sulfonic acid after centrifuge washing.
Take the metal organic frame material that 0.045 g modifies sulfonic acid and join in 6 mL nitrogen dimethylformamides, disperse after 8 h, the sulfonated polyether-ether-ketone to adding 0.6 g in above-mentioned solution, stirs 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone-metal organic frame Material cladding film (film 6).
Comparative example
0.6 g sulfonated polyether-ether-ketone is joined in 6 mL nitrogen dimethylformamides, stir 24 h.After deaeration, casting solution is poured on to curtain coating on clean glass plate, and is placed in baking oven 60
ounder C, dry 12 h, are then warming up to 80
oc is dried 12 h, finally by 120
oafter C annealing in process, film is taken off and is placed in 2 M sulfuric acid and processes 24 h, more repeatedly rinse to neutrality with deionized water.Finally by wet film 60
oc vacuumize 12 h obtain sulfonated polyether-ether-ketone film (film 7).
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, film 4, film 5, methanol permeability and the proton conductivity of the prepared film 7 of film 6 and comparative example.
aroom temperature, the proton conductivity under 100% relative humidity,
b70
oc, the proton conductivity under 100% relative humidity.
Adding of modified metal organic framework materials, why can improve the proton conductivity of sulfonated polyether-ether-ketone, be because the modified metal organic framework materials adding has produced following effect: 1) Cr
3+as a kind of lewis acid, effectively in structural framing, built the path of hydrogen bond network as proton transfer, proton can be transported with Hopping mechanism; 2) in frame structure, modified a large amount of sulfonate radicals, these sulfonate radicals are as efficient proton transfer site, can the transmission so that proton jumps faster; 3) interface of organic polymer and inorganic matter can form the passage that is separated, and these passages can be so that proton efficiently passes through by delivery mechanism.
Comparative example 3,5,6 is known, in the process of sulfonation, amount (the amount sum of the concentrated sulfuric acid and the trifluoromethanesulfanhydride anhydride) positive correlation within the specific limits of acid in proton conductivity and solution, yet too much acid will heavy corrosion metal organic frame material, make its proton conductivity on the contrary not as relatively low No. 3 of acid concentration, therefore can not too pursue proton conductivity, add excess acid.Optimum range is at metal organic frame material, nitromethane, and the concentrated sulfuric acid, between the ratio 1:60:0.50:1.81-1:60:0.75:2.17 of trifluoromethyl sulfonic acid anhydride.This is due to the sulfonation modifying process to metal organic frame material MIL101, it is parent's electricity replacement process of a phenyl ring, two carboxylic acids due to terephthalic acid (TPA), and the effect of the chromium ion of coordination with it, the cloud density of the phenyl ring in metal organic frame material MIL101 is declined, parent's electricity replaces difficulty and rises, therefore need to first have strong sulfonating agent trifluoromethyl sulfonic acid anhydride and the concentrated sulfuric acid to produce the intermediate product SO with strong sulfonation ability
4h-O-SO
2tf(Tf is trifluoromethyl), afterwards again by SO
4h-O-SO
2there is parent's electricity and replace in Tf attack phenyl ring.Sulfuric acid, the amount that trifluoromethyl sulfonic acid anhydride adds has affected SO
4h-O-SO
2the total amount that Tf produces, thus the amount (sulfonation degree) of modifying sulfonate radical on metal organic frame material affected.The principle being promoted by above mentioned proton conductivity, changes in order to have affected proton conductivity the impact of sulfonation degree, therefore amount (the amount sum of the concentrated sulfuric acid and the trifluoromethanesulfanhydride anhydride) positive correlation of acid in proton conductivity and solution.Yet excessive sour adding will dissolution of metals organic framework materials, therefore can not add.
Comparative example 1,2,3,4 can draw, in film-forming process, ratio proton conductivity between 1:200:20-2:200:20 of the metal organic frame material of the modification sulfonic acid adding, nitrogen dimethylformamide, sulfonated polyether-ether-ketone is better, and the ratio of the extreme point that proton conductivity is the highest drops in this scope, this is adding because of very few modified metal organic framework materials, very micro-on the impact of film proterties, and too much adding will cause filling coagulation and the interference of inorganic material, therefore need to add in right amount.
Claims (8)
1. macromolecule-modified metal organic framework materials composite membrane, is characterized in that it is with macromolecule, and sulfonic acid modified metal organic frame material MIL101 is that material is prepared.
2. the preparation method of macromolecule-modified metal organic framework materials composite membrane as claimed in claim 1, it is characterized in that comprising the steps: the preparation of modified metal organic framework materials MIL101, the sulfonated modification of modified metal organic framework materials MIL101 and the preparation of composite membrane.
3. a preparation method for macromolecule-modified metal organic framework materials composite membrane as claimed in claim 2, it is characterized in that described MIL101 modified metal organic framework materials take terephthalic acids, nine water chromic nitrates, hydrofluoric acid and water as raw material synthetic.
4. the preparation method of macromolecule-modified metal organic framework materials composite membrane as claimed in claim 3, it is characterized in that described MIL101 metal organic frame material prepared by the following method: terephthalic acid (TPA), nine water chromic nitrates, hydrofluoric acid, water are with the mixed in molar ratio reaction of 1:1:1:265, centrifuge washing vacuumize.
5. the preparation method of macromolecule-modified metal organic framework materials composite membrane as claimed in claim 2, the sulfonated modification that it is characterized in that described MIL101 metal organic frame material is carried out by the following method: in MIL101 metal organic frame material, add nitromethane, the concentrated sulfuric acid, trifluoromethyl sulfonic acid anhydride hybrid reaction, modified metal organic framework materials, nitromethane, the mass ratio of the concentrated sulfuric acid and trifluoromethyl sulfonic acid anhydride is 1:60:0.50:0.89-1:60:0.75:2.17.
6. the preparation method of macromolecule-modified metal organic framework materials composite membrane as claimed in claim 2, the preparation method who it is characterized in that composite membrane is as follows: by the ultrasonic dispersing and dissolving of MIL101 metal organic frame material in nitrogen dimethylformamide, add macromolecular material, stirring obtains casting solution, the 2.5-10% that in casting solution, the amount of MIL101 is high molecule mass, film forming after filtering and standing deaeration.
7. a preparation method for the macromolecule-modified metal organic framework materials composite membrane as described in claim 2-6, is characterized in that described macromolecule is sulfonated polyether-ether-ketone, sulfonated polyether ketone or sulfonated polyether sulfone.
8. macromolecule-modified metal organic framework materials composite membrane as claimed in claim 1 is as the purposes of direct methanol fuel cell film.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670018A (en) * | 2016-02-25 | 2016-06-15 | 天津大学 | SPEEK/MIL101 loaded phosphotungstic acid hybrid membrane, preparation and application |
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| CN105789668A (en) * | 2016-03-03 | 2016-07-20 | 中国科学院化学研究所 | Preparation method of metal-organic framework material/polymer composite proton exchange membrane |
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| CN112221358A (en) * | 2020-09-14 | 2021-01-15 | 湖北工程学院 | Polyether-ether-ketone composite membrane of modified carbon nanotube and metal organic framework composite material and preparation method and application thereof |
| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313013A (en) * | 2005-11-25 | 2008-11-26 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Polymer electrolyte membrane comprising coordination polymer |
-
2014
- 2014-04-17 CN CN201410154739.8A patent/CN104037432A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313013A (en) * | 2005-11-25 | 2008-11-26 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Polymer electrolyte membrane comprising coordination polymer |
Non-Patent Citations (3)
| Title |
|---|
| G. FEREY ET AL.: "A Chromium Terephthalate–Based Solid with Unusually Large Pore Volumes and Surface Area", 《SCIENCE》, vol. 309, 18 November 2005 (2005-11-18) * |
| ZHEN LI ET AL.: "Enhanced proton conductivity of proton exchange membranes by incorporating sulfonated metal-organic frameworks", 《JOURNAL OF POWER SOURCES》, vol. 262, 15 April 2014 (2014-04-15), pages 372 - 379, XP029025978, DOI: doi:10.1016/j.jpowsour.2014.03.123 * |
| 张凤等: "金属有机框架膜的制备及应用", 《中国科学：化学》, vol. 43, no. 12, 31 December 2013 (2013-12-31) * |
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