CN108866567A - Using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof - Google Patents
Using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof Download PDFInfo
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Abstract
It is a kind of using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof, the intermediate layer of the Bipolar Membrane is in anions and canons exchange film layer inner surface crosslinking or to be coated with zinc-metal-organic framework materials catalyst；The method is using layer-by-layer the tape casting, first cation-exchange membrane liquid stream is prolonged on clean glass plate, cation-exchange membrane is obtained after being air-dried at room temperature, then intermediate layer film liquid is cast using the method for chemical crosslinking or physical absorption in cation-exchange membrane surface, intermediate layer is formed after drying process, finally anion-exchange membrane liquid stream is prolonged and forms anion exchange membrane facing in intermediate interface layer surface, obtains Bipolar Membrane after drying process；The advantages that gained Bipolar Membrane water decomposition rate is high, and hydrolysis ionization voltage is low, and working current density is big, performance stabilization and long service life, is advantageously implemented the continuously operating that nitrogen is reduced to ammonia.
Description
Technical field
It is especially a kind of with zinc-metal-organic framework materials to be the present invention relates to a kind of Bipolar Membrane and preparation method thereof
Between boundary layer Bipolar Membrane and preparation method thereof.
Background technique
Bipolar Membrane is made of cation-exchange membrane layer, anion exchange membrane facing and intermediate layer, is made in DC electric field
Under, the water of intermediate layer is dissociated, and is generated hydrogen ion and hydroxide ion and is respectively enterd yin, yang pole room；Bipolar Membrane
The size of intermediate layer water decomposition efficiency be measure Bipolar Membrane performance advantage one of key factor, therefore improve in boundary
For surface layer water decomposition efficiency with regard to particularly important, document and patent report can be excellent by being modified processability to intermediate layer
Bipolar Membrane, Chen Zhen etc. reports with metal phthalocyanine derivative（Chinese invention patent, CN：101899675 B）, photosensitizer or half
Conductor catalysis material（Chinese invention patent, CN：1011613483 B）Modified Bipolar Membrane intermediate layer has greatly accelerated double
Pole film intermediate layer water decomposition；Xu's copper text etc. uses dissaving polymer（Chinese invention patent, CN：101138707 B）, tree
The complex that heavy metallic salt obtains is added in branch type polymer or its modifier（Chinese invention patent, CN：1319632 C）
Deng being modified to Bipolar Membrane intermediate layer, water decomposition is accelerated, hydrolysis ionization voltage is reduced.
Nitrogen rich in atmosphere, the overwhelming majority is with N2Form exist, it is difficult to directly absorbed by organism, need
By N2Being transformed into can just be absorbed and used containing nitrogen compound；The N that will be dissociated by photo-electrocatalytic technology2Being converted into ammonia is
One of the hot spot of photoelectrocatalysis area research at present；But due to larger (940 kJmol of N ≡ N bond energy-1), it is difficult to it is lived
Change, causes the reduction efficiency of nitrogen very low, and need to consume a large amount of H during being reduced to ammonia due to nitrogen+, so that
Cathode chamber electrolyte can gradually become alkalinity, on the one hand will lead to the reduction of cathode material catalytic activity, be unfavorable for catalysis reaction
It is lasting to carry out；On the other hand it can make H in electrolyte+Insufficient supply causes reduction rate to decline.
Summary of the invention
The present invention is big for Bipolar Membrane water decomposition low efficiency in the prior art, hydrolysis ionization voltage, and nitrogen reduction efficiency is low, mentions
For a kind of using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof.
It is a kind of using zinc-metal-organic framework materials as the Bipolar Membrane of intermediate layer, including cation-exchange membrane layer, yin from
Proton exchange layer and intermediate layer, it is characterised in that：The intermediate layer is handed in anion exchange membrane facing and cation
It changes the inner surface crosslinking of film layer or is coated with zinc-metal-organic framework materials water decomposition catalyst layer；
The water decomposition catalyst layer is to use the molecular formula of electrochemical process preparation for Zn in ionic liquid4O(BDC)3Urge
Agent layer, and by isolated secondary structure unit Zn4O is formed by independently being filled with organic ligand BDC, and phenyl ring bridging
Coordination polymer, wherein BDC=terephthalic acid (TPA) group.
Wherein, spherical or flower shape is presented in the appearance structure of the catalyst layer, and diameter is 0.5-5 μm.
It is above-mentioned a kind of for using zinc-metal-organic framework materials as the preparation method of the Bipolar Membrane of intermediate layer,
It is characterized in that：The preparation method follows these steps to carry out：
（1）According to molar ratio be to be dissolved in n,N-Dimethylformamide at 4: 3 by dried zinc nitrate and terephthalic acid (TPA), then plus
Enter the ionic liquid of 1- butyl -3- methylimidazole villaumite or 1- butyl -3- methylimidazole bromide, stirring is to being completely dissolved；
（2）Using zinc metal sheet as anode, titanium sheet or copper sheet as cathode, above-mentioned steps（1）The liquid of middle preparation as electrolyte,
It is 0.005A cm in current density-2-0.055A cm-2Under reacted；
（3）After reacting 0.5-5.5 h, there is white flock precipitate precipitation in solution, then filtering precipitating uses N, N- dimethyl methyl
Amide and chloroform wash three times drying preservation afterwards respectively.
Further, the preparation method follows these steps to carry out：
（1）The preparation of film liquid
It is 0.05-1.0 mol L that polyvinyl alcohol or polypropyleneimine, which are configured to concentration,-1Aqueous solution, then be added zinc-gold
Belong to organic framework material, obtains intermediate layer film liquid after mixing evenly；
Prepare the poly- second of carboxymethyl cellulose or cellulose acetate aqueous solution and 1.0-5.0% that mass fraction is 1.0-5.0%
Enol or aqueous povidone solution after mixing and are stirred continuously to form jelly, and standing and defoaming is made after 60-100 minutes
Obtain cation-exchange membrane liquid；
Preparing mass fraction is the chitosan of 1.0-5.0%, the aqueous solution of polyimides or benzimidazole and 1.0-5.0%
Polyvinyl alcohol or aqueous povidone solution after mixing and are stirred continuously to form jelly, and standing and defoaming 60-100 minutes
Anion exchange film liquid is made afterwards；
（2）The preparation of Bipolar Membrane
Bipolar Membrane is prepared using layer-by-layer the tape casting, is first prolonged cation-exchange membrane liquid stream on clean band frame glass plate, room
Temperature obtains cation-exchange membrane after air-drying, and is then cast intermediate layer film liquid using the method for chemical crosslinking or physical absorption
In cation-exchange membrane surface, intermediate layer is formed after drying process, finally prolongs anion-exchange membrane liquid stream in middle boundary
Facing surface forms anion exchange membrane facing, obtains Bipolar Membrane after drying process；
The cation-exchange membrane is with a thickness of 30-50 nm, and anion-exchange membrane is with a thickness of 30-60 nm, intermediate interface thickness
Degree is 0.01-5.0 nm.
Compared with prior art, the present invention has beneficial effect below：
（1）Bipolar Membrane prepared by the present invention uses zinc-metal-organic framework materials for intermediate layer catalyst, the catalyst
There is photocatalytic effect and electric catalyticing effect simultaneously, water decomposition reaction can be effectively facilitated, reduce Bipolar Membrane water decomposition and react institute
The activation energy needed, water decomposition efficiency improve 5-20%.
（2）Zinc-metal-organic framework materials are in ionic liquid using the molecular formula of electrochemical process preparation in the present invention
For Zn4O(BDC)3Spherical or flower shape catalyst, there is flexible porosity, biggish specific surface area, unsaturated coordinate bond
Etc. characteristics, have using water decomposition catalysis reaction progress.
（3）Electrochemistry prepares zinc-metal-organic framework materials catalyst in ionic liquid, and part zinc is electrochemically oxidized
It for ZnO, is doped in metal-organic framework materials, forms it into new band structure, be conducive to improve incident photon-to-electron conversion efficiency, promote
Water inlet dissociation reaction.
（4）It is prepared by the present invention to be applied to nitrogen by the Bipolar Membrane of intermediate layer of zinc-metal-organic framework materials
Fixed and reduction, amount of nitrogen fixation may be up to 300 ~ 900 μm of ol L−1 h-1, and Bipolar Membrane intermediate layer water decomposition provides company
Continue continuous H+, ammonia is reduced to for nitrogen and provides raw material, is advantageously implemented the continuously operating that nitrogen is reduced to ammonia.
Detailed description of the invention
Fig. 1 is in the specific embodiment of the invention 1, and electrochemical process is in ionic liquid 1-butyl-3-methyl imidazolium villaumite body
Chondritic is presented in the zinc-metal-organic framework materials prepared in system, and diameter is about 2 μm.
Fig. 2 is in the specific embodiment of the invention 2, and electrochemical process is in ionic liquid 1-butyl-3-methyl imidazolium bromide body
Zinc-the metal-organic framework materials prepared in system, presentation flower shape structure, about 2 μm of diameter.
Fig. 3 is that it is bipolar to contain zinc-metal-organic framework materials with intermediate layer in the specific embodiment of the invention 1
When film is as diaphragm, carries out photoelectrocatalysis fixed nitrogen and be reduced to the schematic diagram of ammonia.
Specific embodiment
Embodiment 1
The preparation of zinc-metal-organic framework materials：
Dried zinc nitrate and terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide according to molar ratio for 4: 3,1- fourth is added
The ionic liquid of base -3- methylimidazole villaumite, stirring are used as electrolyte to after being completely dissolved；Zinc metal sheet is inserted into as anode, titanium sheet
It is 0.025A cm in current density as cathode-2Under reacted；There is white flock precipitate analysis after reacting 2.5 h, in solution
Out, then filtering precipitating washs three times drying preservation afterwards with n,N-Dimethylformamide and chloroform respectively, appearance structure is shown in attached
Fig. 1.
The preparation of Bipolar Membrane：
Prepare mass fraction for 2.5% carboxymethyl cellulose aqueous solution and 2.5% polyvinyl alcohol water solution, after mixing simultaneously
Be stirred continuously to form jelly, after standing and defoaming 90 minutes be made cation-exchange membrane liquid, by cation-exchange membrane liquid stream prolong in
On clean band frame glass plate, cation-exchange membrane is obtained after being air-dried at room temperature, with a thickness of 37 nm.
It is 0.5 mol L that polyvinyl alcohol, which is configured to concentration,-1Aqueous solution, then be added zinc-metal-organic framework materials,
Intermediate layer film liquid is obtained after mixing evenly, and then intermediate layer film liquid is cast in cation-exchange membrane surface, is done
Intermediate layer is formed after dry processing, with a thickness of 2.0 nm.
Prepare mass fraction for 2.5% chitosan aqueous solution and 2.5% polyvinyl alcohol water solution, after mixing not
Disconnected stirring forms jelly, and anion exchange film liquid is made after standing and defoaming 90 minutes, anion-exchange membrane liquid stream is prolonged in
Between interface layer surfaces form anion exchange membrane facing and with a thickness of 40 nm obtain Bipolar Membrane after drying process.
Contain zinc-metal-organic framework materials Bipolar Membrane as the diaphragm of cathode chamber and anode chamber using intermediate layer,
1- butyl -3- methylimidazole villaumite ionic liquid electrolyte the solution of 100 grams per liters is prepared, solvent is n,N-Dimethylformamide.
Cathode chamber uses 50 mL min-1The N of flow velocity2It is bubbled, titanium-based oxide is as anode, Bi2O2CO3As cathode, use
D.C. regulated power supply provides 1.0 V of applied voltage, and 350 W xenon lamps are used as light source, in the case where photoelectrocatalysis acts on, nitrogen is fixed and
It is reduced to ammonia, concrete principle is shown in attached drawing 3.Experimental result is shown, is 90 mA cm in current density-2Under, using intermediate layer
Bipolar Membrane containing zinc-metal-organic framework materials Bipolar Membrane relative to unused zinc-metal-organic framework materials, tank voltage
0.4V is reduced, water decomposition efficiency improves 12.6%.In being carried out continuously experiment in 48 hours, average amount of nitrogen fixation is up to 675 μ
mol L−1 h-1。
Embodiment 2
The preparation of zinc-metal-organic framework materials：
Dried zinc nitrate and terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide according to molar ratio for 4: 3,1- fourth is added
The ionic liquid of base -3- methylimidazole bromide, stirring are used as electrolyte to after being completely dissolved；Zinc foil is inserted into as anode, copper sheet
It is 0.035A cm in current density as cathode-2Under reacted；There is white flock precipitate analysis after reacting 1.5 h, in solution
Out, then filtering precipitating washs three times drying preservation afterwards with n,N-Dimethylformamide and chloroform respectively, appearance structure is shown in attached
Fig. 2.
The preparation of Bipolar Membrane：
Preparing mass fraction is 1.5% cellulose acetate aqueous solution and 1.5% aqueous povidone solution, mixing
It afterwards and is stirred continuously to form jelly, cation-exchange membrane liquid is made in standing and defoaming after sixty minutes, by cation-exchange membrane liquid stream
Prolong on clean band frame glass plate, cation-exchange membrane is obtained after being air-dried at room temperature, with a thickness of 33 nm.
It is 0.1 mol L that polypropyleneimine, which is configured to concentration,-1Aqueous solution, then be added zinc-metal organic framework material
Material, obtains intermediate layer film liquid after mixing evenly, and then intermediate layer film liquid is cast in cation-exchange membrane surface,
Intermediate layer is formed after drying process, with a thickness of 1.0 nm.
Preparing mass fraction is 1.5% chitosan aqueous solution and 1.5% aqueous povidone solution, mixing
It afterwards and is stirred continuously to form jelly, anion exchange film liquid is made in standing and defoaming after sixty minutes, by anion-exchange membrane liquid stream
Prolong and obtains Bipolar Membrane after drying process with a thickness of 38 nm in intermediate interface layer surface formation anion exchange membrane facing.
Contain zinc-metal-organic framework materials Bipolar Membrane as the diaphragm of cathode chamber and anode chamber using intermediate layer,
1- butyl -3- methylimidazole bromide ionic liquid electrolyte the solution of 150 grams per liters is prepared, solvent is n,N-Dimethylformamide.
Cathode chamber uses 80 mL min-1The N of flow velocity2It is bubbled, Pt is as anode, MoS2As cathode, using D.C. regulated power supply
1.5 V of applied voltage is provided, nitrogen is fixed under photoelectrocatalysis effect as light source and be reduced to ammonia by 350 W xenon lamps.It is real
It tests the results show that being 90 mA cm in current density-2Under, it is double that zinc-metal-organic framework materials are contained using intermediate layer
Bipolar Membrane of the pole film relative to unused zinc-metal-organic framework materials, tank voltage reduce 0.7V, and water decomposition efficiency improves
17.2%.In being carried out continuously experiment in 48 hours, average amount of nitrogen fixation is up to 735 μm of ol L−1 h-1。
Embodiment 3
The preparation of zinc-metal-organic framework materials：
Dried zinc nitrate and terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide according to molar ratio for 4: 3,1- fourth is added
The ionic liquid of base -3- methylimidazole villaumite, stirring are used as electrolyte to after being completely dissolved；Zinc metal sheet is inserted into as anode, titanium sheet
It is 0.015A cm in current density as cathode-2Under reacted；There is white flock precipitate analysis after reacting 3.5 h, in solution
Out, then filtering precipitating washs three times drying preservation afterwards with n,N-Dimethylformamide and chloroform respectively.
The preparation of Bipolar Membrane：
Prepare mass fraction for 3.5% cellulose acetate aqueous solution and 3.5% polyvinyl alcohol water solution, after mixing not
Disconnected stirring forms jelly, and cation-exchange membrane liquid is made after standing and defoaming 80 minutes, cation-exchange membrane liquid stream is prolonged in clean
On net band frame glass plate, cation-exchange membrane is obtained after being air-dried at room temperature, with a thickness of 41 nm.
It is 0.8 mol L that polyvinyl alcohol, which is configured to concentration,-1Aqueous solution, then be added zinc-metal-organic framework materials,
Intermediate layer film liquid is obtained after mixing evenly, and then intermediate layer film liquid is cast in cation-exchange membrane surface, is done
Intermediate layer is formed after dry processing, with a thickness of 2.5 nm.
Prepare mass fraction for 3.5% polyimides aqueous solution and 3.5% polyvinyl alcohol water solution, after mixing simultaneously
Be stirred continuously to form jelly, after standing and defoaming 80 minutes be made anion exchange film liquid, by anion-exchange membrane liquid stream prolong in
Intermediate interface layer surface forms anion exchange membrane facing and obtains Bipolar Membrane after drying process with a thickness of 45 nm.
Embodiment 4
The preparation of zinc-metal-organic framework materials：
By dried zinc nitrate and terephthalic acid (TPA) according to molar ratio be 4:3 are dissolved in n,N-Dimethylformamide, and 1- fourth is added
The ionic liquid of base -3- methylimidazole bromide, stirring are used as electrolyte to after being completely dissolved；Zinc foil is inserted into as anode, copper is made
It is 0.045A cm in current density for cathode-2Under reacted；There is white flock precipitate analysis after reacting 0.5 h, in solution
Out, then filtering precipitating washs three times drying preservation afterwards with n,N-Dimethylformamide and chloroform respectively.
The preparation of Bipolar Membrane：
Prepare mass fraction for 4.5% carboxymethyl cellulose aqueous solution and 4.5% polyvinyl alcohol water solution, after mixing simultaneously
Be stirred continuously to form jelly, after standing and defoaming 90 minutes be made cation-exchange membrane liquid, by cation-exchange membrane liquid stream prolong in
On clean band frame glass plate, cation-exchange membrane is obtained after being air-dried at room temperature, with a thickness of 43 nm.
It is 1.0 mol L that polypropyleneimine, which is configured to concentration,-1Aqueous solution, then be added zinc-metal organic framework material
Material, obtains intermediate layer film liquid after mixing evenly, and then intermediate layer film liquid is cast in cation-exchange membrane surface,
Intermediate layer is formed after drying process, with a thickness of 2.5 nm.
Prepare mass fraction for 4.5% benzimidazole aqueous solution and 4.5% polyvinyl alcohol water solution, after mixing simultaneously
Be stirred continuously to form jelly, after standing and defoaming 90 minutes be made anion exchange film liquid, by anion-exchange membrane liquid stream prolong in
Intermediate interface layer surface forms anion exchange membrane facing and obtains Bipolar Membrane after drying process with a thickness of 47 nm.
Aforementioned present invention specific embodiment 1- specific embodiment 4, the one kind implemented is with zinc-metal organic framework material
Material is the Bipolar Membrane and preparation method thereof of intermediate layer, and the application of preparation is using the Bipolar Membrane as diaphragm, in photoelectricity
Under effect, the fixation and reduction of nitrogen are carried out, specific method is：Contain zinc-metal-organic framework materials with intermediate layer
Diaphragm of the Bipolar Membrane as cathode chamber and anode chamber, prepares the ionic liquid electrolyte solution of 100-200 grams per liter, and cathode chamber is adopted
With the N of 50-200 mL min-1 flow velocity2It is bubbled, metal and its oxide are as anode, semiconductor material and transition metal
Oxide provides applied voltage 0.5-2.0 V as cathode, using D.C. regulated power supply, and 350 W xenon lamps are as light source, in photoelectricity
Under catalytic action, nitrogen is fixed and is reduced to ammonia.
Wherein, the metal and its oxide are one of titanium-based oxide, Pt, Pd；The ionic liquid electrolysis
Matter solution is that 1- butyl -3- methylimidazole villaumite or 1- butyl -3- methylimidazole bromide are dissolved in n,N-Dimethylformamide
Ionic liquid；The semiconductor material and transition metal oxide is BiOCl, Bi2O2CO3, BiOBr, MoS2, MoSe2,
WS2, WSe2, ZnO, Cu2O, CuO, TiO2, WO3One or more of it is compound.
Claims (4)
1. it is a kind of using zinc-metal-organic framework materials as the Bipolar Membrane of intermediate layer, including cation-exchange membrane layer, anion
Exchange film layer and intermediate layer, it is characterised in that：The intermediate layer is to exchange in anion exchange membrane facing with cation
The inner surface of film layer is crosslinked or is coated with zinc-metal-organic framework materials water decomposition catalyst layer；
The water decomposition catalyst layer is to use the molecular formula of electrochemical process preparation for Zn in ionic liquid4O(BDC)3Catalysis
Oxidant layer, and by isolated secondary structure unit Zn4O by independently being filled with organic ligand BDC, matching for being formed and phenyl ring bridging
Position polymer, wherein BDC=terephthalic acid (TPA) group.
2. as described in claim 1 using zinc-metal-organic framework materials as the Bipolar Membrane of intermediate layer, it is characterised in that：
Spherical or flower shape is presented in the appearance structure of the catalyst layer, and diameter is 0.5-5 μm.
3. a kind of for as described in claim 1 using zinc-metal-organic framework materials as the system of the Bipolar Membrane of intermediate layer
Preparation Method, it is characterised in that：The preparation method follows these steps to carry out：
（1）In molar ratio it is to be dissolved in n,N-Dimethylformamide at 4: 3 by dried zinc nitrate and terephthalic acid (TPA), is then added
The ionic liquid of 1- butyl -3- methylimidazole villaumite or 1- butyl -3- methylimidazole bromide, stirring is to being completely dissolved；
（2）Using zinc metal sheet as anode, titanium sheet or copper sheet as cathode, above-mentioned steps（1）The liquid of middle preparation as electrolyte,
It is 0.005A cm in current density-2-0.055A cm-2Under reacted；
（3）After reacting 0.5-5.5 h, there is white flock precipitate precipitation in solution, then filtering precipitating uses N, N- dimethyl methyl
Amide and chloroform wash three times drying preservation afterwards respectively.
4. as claimed in claim 3 for using zinc-metal-organic framework materials as the preparation side of the Bipolar Membrane of intermediate layer
Method, it is characterised in that：The preparation method follows these steps to carry out：
（1）The preparation of film liquid
It is 0.05-1.0 mol L that polyvinyl alcohol or polypropyleneimine, which are configured to concentration,-1Aqueous solution, then be added zinc-metal
Organic framework material obtains intermediate layer film liquid after mixing evenly；
Prepare the poly- second of carboxymethyl cellulose or cellulose acetate aqueous solution and 1.0-5.0% that mass fraction is 1.0-5.0%
Enol or aqueous povidone solution after mixing and are stirred continuously to form jelly, and standing and defoaming is made after 60-100 minutes
Obtain cation-exchange membrane liquid；
Preparing mass fraction is the chitosan of 1.0-5.0%, the aqueous solution of polyimides or benzimidazole and 1.0-5.0%
Polyvinyl alcohol or aqueous povidone solution after mixing and are stirred continuously to form jelly, and standing and defoaming 60-100 minutes
Anion exchange film liquid is made afterwards；
（2）The preparation of Bipolar Membrane
Bipolar Membrane is prepared using layer-by-layer the tape casting, is first prolonged cation-exchange membrane liquid stream on clean band frame glass plate, room
Temperature obtains cation-exchange membrane after air-drying, and is then cast intermediate layer film liquid using the method for chemical crosslinking or physical absorption
In cation-exchange membrane surface, intermediate layer is formed after drying process, finally prolongs anion-exchange membrane liquid stream in middle boundary
Facing surface forms anion exchange membrane facing, obtains Bipolar Membrane after drying process；
The cation-exchange membrane is with a thickness of 30-50 nm, and anion-exchange membrane is with a thickness of 30-60 nm, intermediate layer thickness
For 0.01-5.0 nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548545A (en) * | 2019-09-20 | 2019-12-10 | 暨南大学 | Application of titanium-based metal organic framework material in photocatalytic nitrogen fixation |
| CN115888441A (en) * | 2023-01-06 | 2023-04-04 | 湖南沁森高科新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
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