CN109524698A - One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof - Google Patents

One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof Download PDF

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CN109524698A
CN109524698A CN201811159089.0A CN201811159089A CN109524698A CN 109524698 A CN109524698 A CN 109524698A CN 201811159089 A CN201811159089 A CN 201811159089A CN 109524698 A CN109524698 A CN 109524698A
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preparation
thiocarbamide
proton exchange
exchange membrane
carboxylic acids
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梁茜
刘畅
王诚
穆怀萍
张向东
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Hydrogen Energy Technology Co Ltd Of China Energy Engineering Group
Tsinghua University
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Hydrogen Energy Technology Co Ltd Of China Energy Engineering Group
Tsinghua 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
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    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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    • C08G83/008—Supramolecular polymers
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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    • 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
    • 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
    • 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
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention relates to a kind of thiocarbamide carboxylic acids metal-organic framework material/Nafion hydridization proton exchange membrane and preparation method thereof that can be used for fuel cell.The method of the present invention is first prepared with proton conductive metal organic frameAgain wherein by the doping of perfluorinated sulfonic resin Nafion solution, the proton exchange membrane of ghiourea group carboxylic acids metal organic frame/Nafion polymer hybrid is madeThe hybrid proton exchange membrane has excellent proton-conducting, electrochemical stability and mechanical stability, not only increases the conductivity of perfluorinated sulfonic acid class proton exchange membrane, and the problem for being greatly reduced that its preparation cost is excessively high, environmental pollution is big etc..This method preparation condition is mild, simple process and low cost, is easy to produce in batches, have broad application prospects.

Description

One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid matter Proton exchange and preparation method thereof
Technical field
The invention belongs to technical field of membrane, and in particular to it is a kind of can be applied to fuel cell based on ghiourea group carboxylic acid eka-gold Belong to organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof.
Background technique
Power of the energy as the national economic development, and measure overall national strength, degree of national civilization and people's lives Horizontal important indicator.From the last century 90's mid-term, with the rapidly development of human civilization, come into being many energy Source problem, as urban air pollution is got worse, global warming is accelerated, the demand of low emission or zero emission vehicle persistently increases Add etc..Meanwhile along with increasingly surging global energy cry in short supply, many countries all come into effect energy diversification war Slightly, the R&D intensity of new energy is increased, the clean energy technology for replacing the fossil fuels such as petroleum is explored.Fuel cell is as a kind of All solid state energy conversion device, high conversion efficiency is environmental-friendly pollution-free, directly can convert electric energy for chemical energy, is recognized For the important directions for being future automobile industrial sustainable development.
Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC) is a kind of green Color, efficient, high-energy density energy conversion device, directly can convert electric energy for chemical energy.The groundwork temperature of PEMFC Degree is at 80 DEG C, and it is fast to there is starting, No leakage, advantages of environment protection, transfer efficiency up to 40%, be mainly used in automobile, The fields such as submarine and Mobile portable power supply.But due to Proton Exchange Membrane Fuel Cells higher cost, its quotient is limited Industryization development.Primarily focusing at present for the research of fuel cell, which reduces cost, improves in stability.
Metal organic frame (MOFs) porosity with higher, biggish specific surface area and adjustable changeable duct knot The features such as structure, has been applied to molecular recognition, gas stores or the fields such as separation, electric transducer, catalysis.It has recently been found that logical The MOFs crossed after carrying out specific modification or functionalization to gained target product possesses more advantages, such as: efficient electric conductivity, Good stability, strong corrosion resistance and the active site being evenly distributed etc., in proton conduction and electro-catalysis direction institute table Reveal the great attention that the potentiality come have caused people.But since proton transfer is limited by MOFs solid phase and crystal boundary, make The proton transmitting channel obtained in MOFs is discontinuous.In order to which application of the MOFs in terms of proton conduction is better achieved, will have The MOFs of special groups be capable of providing the polymer-doped of proton transfer space, obtained the hydridization matter of high proton conductivity Proton exchange." ACS application material and surface " (ACS Appl.Mater.Interfaces 2017,9 (27): 22597- 22603) it reports functionalization MOF-NH2(UIO-66-NH2) and MOF-SO3H (UIO-66-SO3H) codope is to Nafion In polymer ,-NH has been obtained2/-SO3The polymer hybrid proton exchange membrane of the metal organic frame modified synergic of H functionalization UiO-66-NH2+UiO-66-SO3H/Nafion, the proton conductivity under 90 DEG C and 95%RH are up to 0.256Scm-1, exhibition The proton conduction property much higher than pure Nafion membrane is showed." membrane science " (Journal of Membrane Science 533 (2017) 160-170) it reports UIO-66-NH2It is first strapped in the surface graphene oxide (GO), then is mixed with Nafion matrix It is miscellaneous, GO@UIO-66-NH has been made2/ Nafion modified polymer hybrid proton exchange membrane, the composite membrane is in 90 DEG C, 95% Conductivity under RH is 0.303Scm-1, but its conductivity 3.403 × 10 under low humidity or anhydrous condition-3 S·cm-1And It is less desirable.Therefore, ideal MOFs material how is constructed for combining preparation hydridization proton exchange with polymer substrate Film is still a huge challenge.
The present invention has the ghiourea group carboxylic acids metal organic frame of proton conductive by preparationAgain By it in conjunction with polymer Nafion, it has been made a kind of based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid Proton exchange membrane.Due to the O-H ... O or N-H ... O or O-H ... S hydrogen bond contained in the MOF structure, so that hybridized film is in height Proton conductivity under humidity is obviously improved.Meanwhile and due to having the N atom for having neither part nor lot in coordination in the MOF frame, so that MOF In-NH- and Nafion in-SO3H can form continuous acid-base pair proton channel, be conducive to proton in low humidity or anhydrous Under the conditions of effectively transmitted along acid-base pair channel, thus more effectively promoted hybridized film proton conductivity.Therefore, by this hair It is bright to be preparedThe proton conductivity of hybrid proton exchange membrane is much higher than Nafion proton exchange Film.In addition, hybrid proton exchange membrane obtained has lower fuel permeability and fabulous stability, to guarantee hybridized film High proton conductivity, stability and durability, can be used in fuel cell.
Summary of the invention
That the purpose of the present invention is to provide a kind of stability is good, fuel permeability is low, high performance thiocarbamide carboxylic acid metalloid Organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof.
The present invention is first prepared for proton-conducting metal organic frameAgain by perfluorinated sulfonic acid Resin Nafion solution adulterates wherein, obtainsHybrid proton exchange membrane.Hydridization prepared by the present invention Film be based on hydrophilic molecule, O-H ... O or N-H ... O or the O-H ... S contained in the MOF structure the hydrogen bond network constructed and its - the SO in-NH- and Nafion in structure3H-shaped at acid-base pair (- NH- ...-SO3H) proton channel makes the film high and low wet Excellent proton conductivity, low fuel permeability and preferable stability are all had under degree.
The proton exchange membrane of ghiourea group carboxylic acids metal organic frame/Nafion polymer hybrid provided by the inventionIt can be prepared by the following method, specifically includes the following steps:
1) metal salt hydrates are dissolved in water and organic solvent；
2) by thiocarbamide carboxylic acids ligandIt is dissolved in organic solvent；
It 3) will be obtained by step 2)Metal salt solution obtained by step 1) is slowly added in solution, ultrasound makes It is sufficiently dissolved, and forms precursor solution；
4) the precursor solution standing that step 3) obtains is placed on centrifuge tube to be centrifuged, supernatant is taken after centrifugation；
5) it is sealed the merging beaker of supernatant obtained by step 4) and with the preservative film with pinprick, using solution-evaporation, Standing at room temperature after a week has bulk crystals precipitation；
6) bulk crystals obtained by step 5) are separated by filtration out, are successively repeatedly washed with organic solvent, water, finally true It is dry in empty baking oven, obtain ghiourea group carboxylic acids metal-organic framework material
It 7) will be obtainedIt is added in polymer Nafion solution, and ultrasound keeps its evenly dispersed Obtain film liquid；
8) gained film liquid is cast on clean matrix or coating carries out film process, film forming is placed on baking oven；It obtains Hybridized film；
9) finally, the hybridized film is impregnated in certain density acid solution, thiocarbamide carboxylic acids metal organic frame is obtained Material/polymer hybrid proton exchange membrane
Further, metal salt described in step 1) is the acetate M (OAc) of transition metaln·mH2One of O, or The mixture of a variety of salt.
Further, the ligand of thiocarbamide carboxylic acids described in step 2) is sulphonyl-amino thiocarbamide: benzoylalanine sulphur Urea, benzoyl-glycine thiocarbamide, benzoyl-glutamic acid thiocarbamide, benzoyl-histidine thiocarbamide, benzoyl-silk ammonia One of sour thiocarbamide, naphthoyl-amion acetic acid thiourea compound or a variety of mixtures.
Further, step 1), 2), 6) described in reaction organic solvent be CH3OH、CH3CH2OH、 CH3In CN, DMF One or several kinds of mixtures.
Further, the molar ratio of metal salt described in step 3) and ligand is 1:20~20:1, preferably 1:3~3:1； The step 3) and 7) in ultrasonic power 400W, time 1h.
Further, centrifugal rotational speed described in step 4) is 12000rpm/min.
Further, the coordination not being occupied is contained in the metal-organic framework of ghiourea group carboxylic acids described in step 6) Point and hydrone, and the drying temperature of vacuum drying oven is 15~40 DEG C, 1~3h of retention time.
Further, the concentration of polymer Nafion solution described in step 7) is 0.5wt%~40wt%.
Further, oven temperature described in step 8) is first 15~50 DEG C, keeps 2~5h；Then, by oven temperature liter Up to 50~100 DEG C, keep 2~5h.
Further, acid described in step 9) is HCl, H of 1~3mol/L2SO4Or H3PO4One kind or in which several Mixture.
Compared to commercialized Nafion proton exchange membrane, the present invention is first prepared for proton-conducting metal organic frameIt adulterates, obtains with perfluorinated sulfonic resin Nafion solution againHydridization matter Proton exchange.Due in the hydrophilic molecule, hydrogen bond network and the structure that contain in ghiourea group carboxylic acids metal organic frame- - SO in NH- and Nafion3H-shaped at acid-base pair (- NH- ...-SO3H) proton channel has the film under high and low humidity There are excellent proton conductivity, low fuel permeability and preferable stability.Simultaneously as ghiourea group carboxylic acid metalloid is organic Frame is to the controllability in aperture, so that fuel permeability significantly reduces；Skeleton stability due to MOF, chemical stability again, So that hybrid proton exchange membrane also has preferable stability.
This method preparation condition is mild, and simple process, production cost is low, is easy to produce in batches, before wide application Scape.
Detailed description of the invention
Fig. 1 is ghiourea group carboxylic acids metal organic frame of the present inventionHybrid proton exchange membrane ((Nafion doping accounts for 0.5wt%, 1.0wt%, 1.5wt% respectively) under the conditions of 90%RH, Nafion proton exchange membrane The comparison diagram of temperature vs. proton conductivity.
Fig. 2 is the present inventionHybrid proton exchange membrane (Nafion doping accounts for 1.0wt%) exists Under the conditions of 30 DEG C, Nafion proton exchange membrane H2The comparison diagram of permeability.
Fig. 3 is the present inventionHybrid proton exchange membrane (Nafion doping accounts for 1.0wt%) exists 90 DEG C, the conductivity under the conditions of 90%RH changes with time figure.
Specific embodiment
In order to illustrate more clearly of the purpose of the present invention and technical solution, this hair is described in detail below by specific embodiment The proton exchange membrane of bright ghiourea group carboxylic acids metal organic frame/Nafion polymer hybrid's Preparation, proton conductivity, fuel permeability and its stability.Following embodiment is only to provide explanation rather than limits this hair It is bright.
Embodiment 1
1,2mmol Cu (OAc) is weighed respectively2·4H2O is dissolved in 1.5mL water and 2.5mL methanol, stirring, by 1mmol Thiocarbamide carboxylic acids ligandMethanol (3mL) solution be slowly added to l Cu (OAc)2In solution, ultrasound makes it Sufficiently dissolution is formedPrecursor solution is stood and is placed in centrifuge tube, takes supernatant to be placed in after centrifugation In beaker, standing has bulk crystals precipitation after a week, and reaction product is isolated by filtration out, successively uses CH3OH, water are continuous Washing is placed in 25 DEG C of vacuum drying oven dry 1.5h finally to get ghiourea group carboxylic acids metal-organic framework material is arrived
It 2, will be above-mentioned obtainedIt is added in the Nafion solution of 0.5wt%, 2 h of ultrasound make it Form uniform film liquid.The film liquid is cast on the clean smooth surface of solids (such as glass plate), and is quickly placed into 50 DEG C of bakings 3h is kept in case；Temperature is then raised slowly to 100 DEG C and keeps 4h.Finally, being removed film with tweezers, it is immersed in It is acidified 10h at room temperature in the HCl of 1mol/L, film is converted to H+Type can be obtainedHydridization matter Proton exchange.
3, proton conductivity of the Cu-MOF material of embodiment preparation at 90 DEG C, 90%RH is 1.15 × 10-3S· cm-1, being adulterated the proton conductivity of hybrid proton exchange membrane obtained at 90 DEG C, 90%RH after Nafion is 0.178S·cm-1, the proton conductivity under 110 DEG C, anhydrous condition is 3.47 × 10-3 S·cm-1.Under the same conditions, should Hybridized film is (0.042Scm higher than pure Nafion proton exchange membrane-1With 3.25 × 10-3S·cm-1).In addition, the hydridization matter After proton exchange keeps 40h under the conditions of 90 DEG C, 90%RH, proton conductivity of phosphoric acid does not decrease.Meanwhile the hydridization H of the proton exchange membrane at 30 DEG C2Permeability is 5.655 × 10-8·cm2·s-1, reduced than pure Nafion proton exchange membrane About 64% (8.78 × 10-8 cm2·s-1)。
Embodiment 2
1,2mmol Cu (OAc) is weighed respectively2·4H2O is dissolved in 1.5mL water and 2.5mL methanol, stirring, by 1mmol Thiocarbamide carboxylic acids ligandMethanol (3mL) solution be slowly added thereto, ultrasound makes it sufficiently dissolve formationPrecursor solution is stood and is placed in centrifuge tube, is taken in supernatant merging beaker, is stood after centrifugation There is bulk crystals precipitation after a week, reaction product is isolated by filtration out, successively uses CH3OH, water constantly wash, most postposition 1.5h is dried in 25 DEG C of vacuum drying oven to get ghiourea group carboxylic acids metal-organic framework material is arrived
It 2, will be above-mentioned obtainedIt is added in the Nafion solution of 1.0wt%, 2 h of ultrasound make it Form uniform film liquid.The film liquid is cast on the clean smooth surface of solids (such as glass plate), and is quickly placed into 50 DEG C of bakings 3h is kept in case；Temperature is then raised slowly to 100 DEG C and keeps 4h.Finally, being removed film with tweezers, it is immersed in It is acidified 10h at room temperature in the HCl of 1mol/L, film is converted to H+Type can be obtainedHydridization matter Proton exchange.
3, proton conductivity of the Cu-MOF material of embodiment preparation at 90 DEG C, 90%RH is 1.15 × 10-3S· cm-1, being adulterated the proton conductivity of hybrid proton exchange membrane obtained at 90 DEG C, 90%RH after Nafion is 0.247S·cm-1, the proton conductivity under 110 DEG C, anhydrous condition is 6.72 × 10-3 S·cm-1.Under the same conditions, should Hybridized film is (0.042Scm higher than pure Nafion proton exchange membrane-1With 3.25 × 10-3S·cm-1).In addition, the hydridization matter After proton exchange keeps 40h under the conditions of 90 DEG C, 90%RH, proton conductivity is almost without decline.Meanwhile the hydridization matter H of the proton exchange at 30 DEG C2Permeability is 2.51 × 10-8·cm2·s-1, reduced about than pure Nafion proton exchange membrane 71% (8.78 × 10-8cm2·s-1)。
Embodiment 3
1,2mmol Cu (OAc) is weighed respectively2·4H2O is dissolved in 1.5mL water and 2.5mL methanol, stirring, by 1mmol Thiocarbamide carboxylic acids ligandMethanol (3mL) solution be slowly added thereto, ultrasound makes it sufficiently dissolve formationPrecursor solution is stood and is placed in centrifuge tube, is taken in supernatant merging beaker after centrifugation, is stood one Zhou Houyou bulk crystals are precipitated, and reaction product is isolated by filtration out, successively uses CH3OH, water constantly wash, and are finally placed in 1.5h is dried in 25 DEG C of vacuum drying oven to get ghiourea group carboxylic acids metal-organic framework material is arrived
It 2, will be above-mentioned obtainedIt is added in the Nafion solution of 1.5wt%, 2 h of ultrasound make it Form uniform film liquid.The film liquid is cast on the clean smooth surface of solids (such as glass plate), and is quickly placed into 50 DEG C of bakings 3h is kept in case；Temperature is then raised slowly to 100 DEG C and keeps 4h.Finally, being removed film with tweezers, it is immersed in It is acidified 10h at room temperature in the HCl of 1mol/L, film is converted to H+Type can be obtainedHydridization matter Proton exchange.
3, proton conductivity of the Cu-MOF material of embodiment preparation at 90 DEG C, 90%RH is 1.15 × 10-3S· cm-1, being adulterated the proton conductivity of hybrid proton exchange membrane obtained at 90 DEG C, 90%RH after Nafion is 0.218S·cm-1, the proton conductivity under 110 DEG C, anhydrous condition is 4.16 × 10-3 S·cm-1.Under the same conditions, should Hybridized film is (0.042Scm higher than pure Nafion proton exchange membrane-1With 3.25 × 10-3S·cm-1).In addition, the hydridization matter After proton exchange keeps 40h under the conditions of 90 DEG C, 90%RH, proton conductivity is almost without decline.Meanwhile the hydridization matter H of the proton exchange at 30 DEG C2Permeability is 4.03 × 10-8·cm2·s-1, reduced about than pure Nafion proton exchange membrane 54% (8.78 × 10-8cm2·s-1)。
Embodiment 4
1,1mmol Cu (OAc) is weighed respectively2·4H2O is dissolved in 1.5mL water and 2.5mL methanol, stirring, by 1mmol Thiocarbamide carboxylic acids ligandMethanol (3mL) solution be slowly added thereto, ultrasound makes it sufficiently dissolve shape AtPrecursor solution is stood and is placed in centrifuge tube, is taken in supernatant merging beaker after centrifugation, quiet Setting after a week has bulk crystals precipitation, and reaction product is isolated by filtration out, successively uses CH3OH, water constantly wash, finally Dry 1.5h is placed in 25 DEG C of vacuum drying oven to get ghiourea group carboxylic acids metal-organic framework material is arrived
It 2, will be above-mentioned obtainedIt is added in the Nafion solution of 1.0wt%, ultrasonic 2h makes it Form uniform film liquid.The film liquid is cast on the clean smooth surface of solids (such as glass plate), and is quickly placed into 50 DEG C of bakings 3h is kept in case；Temperature is then raised slowly to 100 DEG C and keeps 4h.Finally, being removed film with tweezers, it is immersed in It is acidified 10h at room temperature in the HCl of 1mol/L, film is converted to H+Type can be obtainedHydridization matter Proton exchange.
3, proton conductivity of the Cu-MOF material of embodiment preparation at 90 DEG C, 90%RH is 8.37 × 10-4S· cm-1, being adulterated the proton conductivity of hybrid proton exchange membrane obtained at 90 DEG C, 90%RH after Nafion is 0.196S·cm-1, the proton conductivity under 110 DEG C, anhydrous condition is 4.86 × 10-3 S·cm-1.Under the same conditions, should Hybridized film is (0.042Scm higher than pure Nafion proton exchange membrane-1With 3.25 × 10-3S·cm-1).In addition, the hydridization matter After proton exchange keeps 40h under the conditions of 90 DEG C, 90%RH, proton conductivity is almost without decline.Meanwhile the hydridization matter H of the proton exchange at 30 DEG C2Permeability is 5.24 × 10-8cm2·s-1, about 40% is reduced than pure Nafion proton exchange membrane (8.78×10-8cm2·s-1)。

Claims (11)

1. a kind of preparation method of the proton exchange membrane of thiocarbamide carboxylic acids metal-organic framework material/Nafion hydridization, feature It is, includes the following steps:
1) metal salt hydrates are dissolved in water and organic solvent；
2) by thiocarbamide carboxylic acids ligandIt is dissolved in organic solvent；
It 3) will be obtained by step 2)Metal salt solution obtained by step 1) is slowly added in solution, ultrasound fills it Divide dissolution, forms precursor solution；
4) the precursor solution standing that step 3) obtains is placed on centrifuge tube to be centrifuged, supernatant is taken after centrifugation；
5) supernatant obtained by step 4) is placed in beaker and is sealed with the preservative film with pinprick, using solution-evaporation, room temperature Lower standing has bulk crystals precipitation after a week；
6) bulk crystals obtained by step 5) are separated by filtration out, are successively repeatedly washed with organic solvent, water, finally dried in vacuum It is dry in case, obtain ghiourea group carboxylic acids metal-organic framework material
It 7) will be obtainedIt is added in polymer Nafion solution, and ultrasound makes its evenly dispersed obtain film Liquid；
8) gained film liquid is cast or is coated film forming, film forming is placed on baking oven, obtains hybridized film；
9) hybridized film is impregnated in acid solution, obtains thiocarbamide carboxylic acids metal-organic framework material/polymer hybrid Proton exchange membrane
2. preparation method according to claim 1, which is characterized in that metal salt described in step 1) is transition metal acetic acid Salt M (OAc)n·mH2The mixture of one of O or a variety of salt.
3. preparation method according to claim 1, which is characterized in that the ligand of thiocarbamide carboxylic acids described in step 2) is acyl Base-thiosemicarbazides: benzoyl-alanine thiocarbamide, benzoyl-glycine thiocarbamide, benzoyl-glutamic acid thiocarbamide, benzene first One of acyl group-histidine thiocarbamide, benzoyl-serine thiocarbamide, naphthoyl-amion acetic acid thiourea compound is a variety of Mixture.
4. preparation method according to claim 1, which is characterized in that step 1), 2), 6) described in organic solvent be CH3OH、CH3CH2OH、CH3One of CN, DMF or several mixtures.
5. preparation method according to claim 1, which is characterized in that mole of metal salt described in step 3) and ligand Than for 1:20~20:1；Step 3) and 7) described in ultrasonic power be 400W, time 1h.
6. according to preparation method described in claim 1, which is characterized in that in step 4), the revolving speed of the centrifugation is 12000rpm/ min。
7. preparation method according to claim 1, which is characterized in that ghiourea group carboxylic acid metalloid described in step 6) has Containing the coordination site and hydrone not being occupied in machine frame structure, and the drying temperature of vacuum drying oven is 15~40 DEG C, keeps 1~3h of time.
8. preparation method according to claim 1, which is characterized in that polymer Nafion solution described in step 7) Concentration is 0.5wt%~40wt%.
9. preparation method according to claim 1, it is characterised in that: oven temperature described in step 8) is first 15~50 DEG C, keep 2~5h；Then, oven temperature is increased to 50~100 DEG C, keeps 2~5h.
10. preparation method according to claim 1, it is characterised in that: acid described in step 9) is 1~4mol/L's HCl、H2SO4Or H3PO4One kind or in which several mixtures.
11. a kind of any preparation method of claim 1-10 obtains poly- based on thiocarbamide carboxylic acids metal organic frame/Nafion Close the proton exchange membrane of object hydridization.
CN201811159089.0A 2018-09-30 2018-09-30 One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof Pending CN109524698A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111957299A (en) * 2020-08-19 2020-11-20 江西理工大学 Functionalized copper-based MOFs material and preparation method and application thereof
CN113078343A (en) * 2021-03-25 2021-07-06 郑州大学 MOF (metal organic framework) based laminated composite proton exchange membrane as well as preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289733A (en) * 2015-10-28 2016-02-03 西南大学 Preparation method of hydrogen evolution electric catalyst based on metal-organic framework compound
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
CN106188590A (en) * 2016-07-14 2016-12-07 复旦大学 Polymer hybrid PEM that metallo-organic framework is modified and preparation method thereof
CN106380614A (en) * 2016-09-05 2017-02-08 复旦大学 Functionalized metal-organic framework synergistically modified polymer hybrid proton exchange membrane and production method thereof
CN106876759A (en) * 2017-01-07 2017-06-20 复旦大学 Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof
CN108376792A (en) * 2018-02-05 2018-08-07 成都新柯力化工科技有限公司 A kind of fuel battery proton exchange film and preparation method of metal-organic phase modification

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289733A (en) * 2015-10-28 2016-02-03 西南大学 Preparation method of hydrogen evolution electric catalyst based on metal-organic framework compound
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
CN106188590A (en) * 2016-07-14 2016-12-07 复旦大学 Polymer hybrid PEM that metallo-organic framework is modified and preparation method thereof
CN106380614A (en) * 2016-09-05 2017-02-08 复旦大学 Functionalized metal-organic framework synergistically modified polymer hybrid proton exchange membrane and production method thereof
CN106876759A (en) * 2017-01-07 2017-06-20 复旦大学 Modified polymer hybrid PEM of the bar-shaped metal organic framework of amino functional and preparation method thereof
CN108376792A (en) * 2018-02-05 2018-08-07 成都新柯力化工科技有限公司 A kind of fuel battery proton exchange film and preparation method of metal-organic phase modification

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KUN CAI等: ""An acid-stable hexaphosphate ester based metal-organic framework and its polymer composite as proton exchange membrane"", 《J. MATER. CHEM. A》 *
梁茜: "" 由咪唑二羧酸及酰基硫脲羧酸配体构筑的金属有机框架的电化学性能研究"", 《万方学位论文》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111957299A (en) * 2020-08-19 2020-11-20 江西理工大学 Functionalized copper-based MOFs material and preparation method and application thereof
CN111957299B (en) * 2020-08-19 2022-08-23 江西理工大学 Functionalized copper-based MOFs material and preparation method and application thereof
CN113078343A (en) * 2021-03-25 2021-07-06 郑州大学 MOF (metal organic framework) based laminated composite proton exchange membrane as well as preparation method and application thereof

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