CN106876759A - Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof - Google Patents

Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof Download PDF

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CN106876759A
CN106876759A CN201710014444.4A CN201710014444A CN106876759A CN 106876759 A CN106876759 A CN 106876759A CN 201710014444 A CN201710014444 A CN 201710014444A CN 106876759 A CN106876759 A CN 106876759A
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饶壮
汤蓓蓓
武培怡
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Fudan University
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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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
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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
    • H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention belongs to technical field of membrane, modified polymer hybrid PEM of the bar-shaped metal organic framework of specially a kind of amino functional and preparation method thereof.The present invention is first obtained the bar-shaped metal organic framework of amino functional（R‑MOF‑NH2）, then be doped in polymer, obtain the modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional.The PEM it is high and low it is wet under the conditions of be respectively provided with excellent proton conductivity, meanwhile, its methanol permeability is low, and stability in use is fabulous.The inventive method operating process is simple, and preparation condition is gentle, and production cost is relatively low, is easy to mass, large-scale production, with the basic and wide application prospect of good industrialized production.

Description

The modified polymer hybrid proton exchange of the bar-shaped metal organic framework of amino functional Film and preparation method thereof
Technical field
The invention belongs to technical field of membrane, and in particular to a kind of polymer hybrid PEM and preparation method thereof, especially It is related to the bar-shaped metal organic framework of amino functional（R-MOF-NH2）Modified polymer hybrid PEM and its system Preparation Method.
Background technology
Fuel cell has pollution-free and efficient advantage, and it gradually shows to replace the great potential of internal combustion engine.Directly It is the 6th Replacing fuel battery to connect methanol fuel cell, and it possesses, and operating condition is gentle, energy density is high, pre-process dress without fuel Put and the significant advantage such as long service life.Therefore, it enjoys the extensive concern of many aspects such as industrial quarters and academia.Proton Exchange membrane is the one of its core group point, and it is not only that proton provides the passage of migration and transmission, and effectively intercepts fuel Infiltration from anode to negative electrode.It is that acquisition high-performance is direct to prepare high proton conductivity, the PEM of low fuel permeability The effective means of methanol fuel cell.
Metal organic framework（MOFs）Easily adjusted with structure, the characteristics of high porosity and high-specific surface area.Therefore, it The aspects such as gas absorption, catalysis, load medicine, separation show preferable application prospect.Recently, MOFs is in terms of proton conduction Using receiving highest attention.Research shows that the hydrogen bond network or functional site in MOFs holes can effectively transmit proton.Cause This, increasing MOFs modified proton exchange films are developed.But, the modified protons of MOFs that the overwhelming majority is developed Exchange membrane only shows the lifting of obvious proton conductivity under high humility or low-moisture conditions.Such as：《Chemical communication》 （Chemical Communication, 2013, 49, 143-145）Report Fe-MIL-101-NH2Sulfonation 2 is added to, 6- dimethyl poly-p-phenylene oxides（SPPO）In be obtained Fe-MIL-101-NH2/ SPPO hybridized films, the film is in 90 DEG C, 80% RH（Relatively Humidity）Under conditions of proton conductivity be 0.25 S/cm, the lifting of more unmodified SPPO films is obvious, but it is in low humidity conditions Lower proton conductivity lifting is not obvious.《Membrane science》（Journal of Membrane Science 458 (2014) 86-95） Reporting will be packaged with 1- (3- aminopropyls) imidazoles（NAPI）Fe-MIL-101-NH2It is added to prepared (NAPI- in SPPO Fe-MIL-101-NH2)-SPPO hybridized films, at 160 DEG C, the proton conductivity under the conditions of 0.15% RH is 0.04 S/ to the film Cm, more unmodified SPPO films are obviously improved, but it under conditions of high humidity proton conductivity lifting it is limited.《Chemical science》 （Chemical Science 2013, 4, 983-992）Report chirality two dimension MOF { [Ca (D-Hpmpc) (H2O)2]· 2HO0.5}nIt is added to polyvinylpyrrolidone（PVP）In be obtained { [Ca (D-Hpmpc) (H2O)2]·2HO0.5}n/ PVP hydridization Film, at 24.85 DEG C, the proton conductivity under the conditions of ~ 53% RH is 2.8 × 10 to the film-5S/cm, the PVP films of particle are not added Have and largely lifted, but its proton conductivity lifting under relatively low and higher levels of humidity is little.《The energy》（Journal of Power Sources 262 (2014) 372-379）Report in sulfonated polyether-ether-ketone（SPEEK）Middle doped sulfonated MIL (101) Cr is obtained MIL (101) Cr/SPEEK hybridized films, and it is in 75 DEG C, the proton conductivity under the conditions of 100% RH 0.306 S/cm is reached, more unmodified SPEEK films lifting is notable, but its proton conductivity under low moisture conditions is improved very It is few.《Chemical material A》（Journal of Materials Chemistry A 2015, 3, 15838-15842）Reporting will The compound ZIF-8@GO of GO and ZIF-8 are obtained ZIF-8@GO/Nafion hybridized films in being doped to perfluorinated sulfonic resin Nafion, , at 120 DEG C, the proton conductivity under the conditions of 40% RH reaches 0.28 S/cm for it, and more unmodified Nafion membrane lifting is very big, But the lifting of its proton conductivity under low moisture conditions is undesirable.So, preparation is respectively provided with excellent proton in high and low wet condition The modified hybrid proton exchange membranes of the MOF of conductivity, are particularly significant and urgent.
Bar-shaped metal organic framework by preparing amino functional of the invention（R-MOF-NH2）, then add it to gather A kind of modified polymer hybrid PEM of bar-shaped metal organic framework based on amino functional has been obtained in compound.By Cause that hybridized film proton conductivity under conditions of high humidity is obviously improved in the high-hydrophilic of the MOF.Again because the MOF is in Gao Lian Continue the bar-shaped of property so that its-NH2With-SO in polymer3H can form continuous acid-base pair passage, and proton is in low humidity conditions Under can effectively be transmitted in these continuous acid-base pair passages so that hybridized film under low moisture conditions proton conduction Rate has greatly raising.And obtained hybrid proton exchange membrane has very low fuel permeability and fabulous stability.That is, The polymer hybrid proton exchange that the bar-shaped metal organic framework that high performance amino functional has been obtained by the present invention is modified Film.
The content of the invention
It is low it is an object of the invention to provide a kind of fuel permeability, it is high and low it is wet under the conditions of be respectively provided with excellent proton Conductivity, high-performance proton exchange membrane of good stability and preparation method thereof.
The PEM that the present invention is provided, is the bar-shaped metal organic framework based on amino functional（R-MOF-NH2） , especially by the bar-shaped metal organic framework that amino functional is first obtained（R-MOF-NH2）, then be doped in polymer And obtain.The bar-shaped metal organic framework of obtained amino functional of the invention（R-MOF-NH2）Modified polymer hybrid matter Proton exchange it is high and low it is wet under the conditions of be respectively provided with excellent proton conductivity, fuel permeability is low, while having fabulous use Stability.
The above-mentioned bar-shaped metal organic framework based on amino functional that the present invention is provided（R-MOF-NH2）Modified polymerization The preparation method of thing hybrid proton exchange membrane, concretely comprises the following steps：
（1）By in the part addition reaction dissolvent of slaine and amino functional, ultrasound makes it fully dissolve, and forms presoma molten Liquid, gained precursor solution is carried out solvent thermal reaction 4-74 h under conditions of 50 ~ 280 DEG C, and centrifugation goes out product, After products therefrom is first cleaned repeatedly with reaction dissolvent, then cleaned with low boiling point solvent repeatedly, dried in 30 ~ 140 DEG C of vacuum 0.5 ~ 30 h is dried in case, that is, obtains the bar-shaped metal organic framework of amino functional, be designated as R-MOF-NH2；
（2）The desired amount of R-MOF-NH is added toward polymer solution2, and ultrasound makes it be uniformly dispersed to obtain casting solution, by this It is placed in 50 ~ 80 DEG C of baking ovens after casting solution coating film forming, is warming up to 110 ~ 150 DEG C, 12 ~ 36 h is then kept again； Finally the hybridized film just obtains R-MOF-NH through hydrogen peroxide solution and acid soak2Modified polymer hybrid PEM.
In the present invention, described slaine is the one kind in transition metal salt or lanthanide metal salt, or wherein several mixed Compound, part is the one kind in amino aromatic carboxylic acids or amino nitrogen-containing heterocycle compound, or wherein several mixtures, slaine It is 1 with the mol ratio of part:16~16:1, preferred molar ratio is 1:4~4:1.
In the present invention, step（1）Described in reaction dissolvent be DMF, N, N- DEFs, One kind in tetrahydrofuran, pyrrolidones, dimethyl sulfoxide, or wherein several mixed solvents.
In the present invention, step（1）Described in low boiling point solvent be CH3OH、C2H5OH、CHCl3、CH2Cl2、CH3Cl, third One kind in ketone, butanone, or wherein several mixtures.
In the present invention, step（2）Described in polymer solution for perfluorinated sulfonic resin, sulfonated polyether-ether-ketone, sulfonation gather One kind in the homogeneous phase solution of benzimidazole or sulfonated polyimide, the concentration of described polymer solution is 1 wt% ~ 40 Wt%, the solvent of described polymer solution is the solvent for above-mentioned polymer is formed homogeneous phase solution.
In the present invention, step（2）Described in heating rate be less than 0.5 DEG C/min（It is preferred that 0.1 ~ 0.5 DEG C/min）.
In the present invention, step（2）Described in through hydrogen peroxide solution and acid soak, the concentration of hydrogen peroxide is 2 ~ 10 Wt%, one kind of the sour hydrochloric acid, sulfuric acid or phosphoric acid for being 1 ~ 4 mol/L, or wherein several mixtures.
Compared with the polymer hybrid proton exchange membrane process that traditional MOF is modified, the method comprises the steps of firstly, preparing amino work( The bar-shaped metal organic framework of energyization（R-MOF-NH2）, then be doped in polymer that the bar-shaped of amino functional is obtained Metal organic framework（R-MOF-NH2）Modified polymer hybrid PEM.Because the bar-shaped metal of amino functional has Machine skeleton（R-MOF-NH2）High-hydrophilic, continuity high so that the water holding capacity of hybrid proton exchange membrane is strong, and metal is organic - the NH of skeleton structure2With-the SO in polymer3H-shaped into acid-base pair channel height it is continuous so that hybrid proton exchange membrane It is high and low it is wet under the conditions of proton conductivity be significantly increased.Further, since capture of the hole of MOF to fuel is acted on so that combustion Material permeability is effectively reduced.Again due to the bar-shaped metal organic framework of amino functional（R-MOF-NH2）Chemistry, water, heat it is steady Qualitative and structural stability is high so that hybrid proton exchange membrane has fabulous stability in use.
Additionally, operating process of the present invention is extremely simple, production cost is relatively low, and preparation condition is gentle, it is easy to mass, scale Metaplasia is produced, with the basic and wide application prospect of good industrialized production.
Brief description of the drawings
Fig. 1 is MIL-68 (In)-NH2Hybrid proton exchange membrane（Doping accounts for the 0.4 of Nafion matrix quality respectively, 0.8 and 1.2 wt%）With the temperature-independent proton conductivity comparison diagram of non-hybrid proton exchange membrane（95% RH）.
Fig. 2 is MIL-68 (In)-NH2Hybrid proton exchange membrane（Doping accounts for the 0.4 of Nafion matrix quality respectively, 0.8 and 1.2 wt%）With non-hybrid proton exchange membrane at 120 DEG C, the proton conductivity comparison diagram under anhydrous condition.
Fig. 3 is MIL-68 (In)-NH2Hybrid proton exchange membrane（Contained mass particle accounts for Nafion matrix quality in film 0.8wt%）At 90 DEG C, the stability test figure under 95% RH.
Specific embodiment
The bar-shaped metal organic framework of amino functional of the invention is further described by the following examples（R- MOF-NH2）Modified polymer hybrid PEM and its property in terms of proton transfer, fuel obstruct and stability in use Energy.However, the embodiment is merely possible to provide explanation rather than the restriction present invention.
Embodiment 1
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 1.29 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.4wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.112 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 20.87 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 1.38 and 4.73 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C is 6.28×10-8 cm2 s-1, ~ 61.8% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）. At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 2
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 1.29 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.8wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.258 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 28.96 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 4.49 and 6.96 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C is 2.12×10-8 cm2 s-1, ~ 87.1% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）. At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 3
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 1.29 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.2wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.221 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 23.92 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 3.70 and 5.57 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 4.39 × 10-8 cm2 s-1, ~ 73.3% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 4
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 2.58mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.4 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.101 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 18.63 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 1.15 and 4.12 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 6.48 × 10-8 cm2 s-1, ~ 60.6% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 5
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 2.58mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.8 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.241 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 25.95 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 4.13 and 6.13 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 2.45 × 10-8 cm2 s-1, ~ 85.1% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 6
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 2.58mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.2 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.202 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 21.03 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 3.30 and 4.78 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 4.82 × 10-8 cm2 s-1, ~ 70.7% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 7
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 5.16mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.4 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.091 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 16.61 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 0.94 and 3.56 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 6.86 × 10-8 cm2 s-1, ~ 58.2% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 8
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 5.16mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 0.8 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.219 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 23.14 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 3.66 and 5.36 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 2.79 × 10-8 cm2 s-1, ~ 83.0% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 9
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 5.16 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.2 wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and make its dispersion equal It is even；The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is slowly heated up after 2 h since 70 DEG C To 120 DEG C and keep 24 h.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.181 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 18.74 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 2.85 and 4.15 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 5.26 × 10-8 cm2 s-1, ~ 68.0% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 10
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 1.29 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.6wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.186 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 20.17 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 2.96 and 4.54 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 5.13 × 10-8 cm2 s-1, ~ 68.8% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 11
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 2.58 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.6wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.173 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 17.92 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 2.68 and 3.92 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 5.79 × 10-8 cm2 s-1, ~ 64.8% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.
Embodiment 12
1. 3.84 mmolIn (NO are weighed respectively3)3·xH2O and 5.16 mmol 2- amino terephthalic acid (TPA)s, add it to 12.4 mL DMFs（DMF）In, ultrasound makes it be dispersed into uniform MIL-68 (In)-NH2Precursor solution, In transferring them to the polytetrafluoroethyllining lining of 30 mL, cover lid and sealing is tight in being put into reactor, be subsequently placed in 125 DEG C constant temperature oven in the h of sustained response 5, by product by centrifugation out, it is first constantly clear with fresh DMF solvent Wash, then with fresh CH3OH solvent soakings 3 days, change CH fresh twice daily3OH solvents, the product after immersion is placed in 50 DEG C Baking oven in keep 6 h, that is, obtain a kind of bar-shaped metal organic framework of amino functional（MIL-68(In)-NH2）.
2. the commercially available Nafion solutions of 5mL are taken, 1.5mL DMF is added after removing about half solvent through revolving, and continue rotation Steam 10 min.MIL-68 (In)-NH of 1.6wt% is added toward above-mentioned Nafion solution2, and ultrasound 1h and it is uniformly dispersed； The dispersion liquid is carefully poured into mould and is quickly placed into 70 DEG C of baking ovens, is to slowly warm up to after 2 h since 70 DEG C 120 DEG C and 24 h of holding.Finally, by the film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, then uses 1M H2SO4 1 h is acidified at 80 DEG C film is converted into H+Type, finally can obtain MIL-68 (In)-NH2Hybrid proton exchange membrane.
At 90 DEG C, the proton conductivity under 95% RH is up to 0.160 S/ to the PEM that the embodiment is prepared Cm, at 120 DEG C, the proton conductivity under anhydrous condition is 16.19 × 10-4S/cm, respectively than unmodified Nafion matter Proton exchange is high about 2.40 and 3.45 times（0.047 S/cm and 3.64 × 10-4 S/cm）.Methanol permeability at 40 DEG C It is 6.13 × 10-8 cm2 s-1, ~ 62.7% is have dropped than unmodified Nafion PEMs（16.43×10-8 cm2 s-1）.At 90 DEG C, constant about 3250 min under 95% RH, proton conductivity is not almost reduced.

Claims (7)

1. the preparation side of the modified polymer hybrid PEM of a kind of bar-shaped metal organic framework based on amino functional Method, it is characterised in that concretely comprise the following steps：
（1）By in the part addition reaction dissolvent of slaine and amino functional, ultrasound makes it fully dissolve, and forms presoma Solution；Gained precursor solution is carried out solvent thermal reaction 4-74 h under conditions of 50 ~ 280 DEG C, centrifugation is produced Thing, products therefrom is first cleaned with reaction dissolvent, then cleaned with low boiling point solvent；Then in 30 ~ 140 DEG C of vacuum drying oven The h of middle drying 0.5 ~ 30, that is, obtain the bar-shaped metal organic framework of amino functional, is designated as R-MOF-NH2；
（2）R-MOF-NH is added toward polymer solution2, ultrasound makes it be uniformly dispersed and obtains casting solution, by casting solution coating It is placed in after film forming in 50 ~ 80 DEG C of baking ovens, is warming up to 110 ~ 150 DEG C, 12 ~ 36 h is then kept again；The last hydridization Film obtains R-MOF-NH through hydrogen peroxide solution and acid soak2Modified polymer hybrid PEM；
Wherein, described slaine is the one kind in transition metal salt or lanthanide metal salt, or wherein several mixtures, amino The part of functionalization is the one kind in amino aromatic carboxylic acids or amino nitrogen-containing heterocycle compound, or wherein several mixtures, gold The mol ratio of category salt and part is 1:16~16:1.
2. preparation method according to claim 1, it is characterised in that step（1）Described in reaction dissolvent be N, N- bis- NMF, N, the one kind in N- DEFs, tetrahydrofuran, pyrrolidones, dimethyl sulfoxide, or it is wherein several mixed Bonding solvent.
3. preparation method according to claim 1, it is characterised in that step（1）Described in low boiling point solvent be CH3OH、 C2H5OH、CHCl3、CH2Cl2、CH3One kind in Cl, acetone, butanone, or wherein several mixtures.
4. preparation method according to claim 1, it is characterised in that step（2）Described in polymer solution be perfluor One kind in the homogeneous phase solution of sulfonate resin, sulfonated polyether-ether-ketone, sulfonate polybenzimidazole or sulfonated polyimide, described is poly- The concentration of polymer solution is 1 wt% ~ 40 wt%, and the solvent of described polymer solution is to cause that above-mentioned polymer is formed homogeneously The solvent of solution.
5. preparation method according to claim 1, it is characterised in that step（2）Described in heating rate be less than 0.5 ℃/min。
6. preparation method according to claim 1, it is characterised in that step（2）Described in through hydrogen peroxide solution and acid Immersion, the concentration of hydrogen peroxide is 2 ~ 10 wt%, one kind of the sour hydrochloric acid, sulfuric acid or phosphoric acid for being 1 ~ 4 mol/L, or wherein several The mixture planted.
7. a kind of bar-shaped metal organic framework based on amino functional prepared by one of claim 1-6 preparation method Modified polymer hybrid PEM.
CN201710014444.4A 2017-01-07 2017-01-07 Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof Pending CN106876759A (en)

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Application publication date: 20170620