CN101613483B - Bipolar membrane taking photosensitizer or photocatalytic semiconductor material as intermediate layer and preparation method thereof - Google Patents
Bipolar membrane taking photosensitizer or photocatalytic semiconductor material as intermediate layer and preparation method thereof Download PDFInfo
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- CN101613483B CN101613483B CN2009101123281A CN200910112328A CN101613483B CN 101613483 B CN101613483 B CN 101613483B CN 2009101123281 A CN2009101123281 A CN 2009101123281A CN 200910112328 A CN200910112328 A CN 200910112328A CN 101613483 B CN101613483 B CN 101613483B
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- photosensitizers
- catalyst
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- semiconductor light
- bipolar membrane
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Abstract
The invention relates to a bipolar membrane taking photosensitizer or photocatalytic semiconductor material as an intermediate layer and a preparation method thereof. The bipolar membrane comprises an anion exchange membrane layer, a cation exchange membrane layer and the intermediate layer having hydrolytic dissociation photocatalysis function; wherein the intermediate layer is formed by cross linking or coating hydrolytic dissociation catalyst on the corresponding inner surface of the cation exchange membrane layer. When in preparation, the photosensitizer or semiconductor photocatalyst, or the paired mixture of the photosensitizer and the semiconductor photocatalyst can be conglutinated on the inner surface of the cation exchange membrane layer by adopting a chemical crosslinking or physical adsorption method; or the paired mixture of the photosensitizer and the semiconductor photocatalyst is mixed into electrolyte paste and then conglutinated on the inner surface of the cation exchange membrane layer. The prepared bipolar membrane can increase the dissociation rate of water by 5-15%, improves the permeability and the ionic mobility of the water, reduces the membrane impedance and bath voltage, has good thermal and chemical stability, excellent performance and size stability as well as long service life, and is low in price and easy to obtain.
Description
Technical field
The present invention relates to a kind of high molecular polymer PREPARATIOM OF BIPOLAR MEMBRANE of high water decomposition efficient, relating to a kind of specifically is the Bipolar Membrane in middle layer and preparation method thereof with nano-scale photosensitizers or photocatalytic semiconductor material.
Technical background
Bipolar Membrane and water decomposition technology thereof have very extensively and important use in fields such as Chemical Manufacture, separation, utilization of waste material, resource recovery and environment protection.
How to reduce the membrane impedance of Bipolar Membrane, improve water decomposition efficient and iontophoretic injection performance, the overpotential when reducing water decomposition has become the focus of Bipolar Membrane research.Amphoteric metal oxide compound, weak organic acid, weak organic bases are an ideal catalyst of water decomposition.Add the material that one deck can promote water decomposition at anode membrane and cavity block interlayer, water decomposition is become easily, under low strength of electric field, just can produce enough water decomposition speed.Discovery anode membrane layers such as Hanada are used Fe
2+, Fe
3+, Ti
4+, Sn
2+, Sn
4+, Zr
4+, Pd
2+, Ru
3+Etc. the Bipolar Membrane that makes after the heavy metal ion exchange, heavy metal ion is stayed intermediate layer with suitable form and structure, has changed the attribute of two retes and intermediate layer; Make the linkage force of water weaken; Interfacial layer is more hydrophilic, thereby has promoted dissociating of water, has reduced WV.Xu's copper literary composition etc. adopts Z 150PH (PVA) respectively, and bovine serum albumin (BSA), dendriform macromole polyamide (PAMAM) are modified intermediate layer, the dissociating of catalysis Bipolar Membrane water in intermediate layer.
Summary of the invention
One of the object of the invention, providing a kind of is the Bipolar Membrane with middle layer of water decomposition photocatalysis with nano-scale photosensitizers or semiconductor material.Described Bipolar Membrane comprises anion exchange membrane facing, cationic exchange rete with sandwiched type structure and the middle layer with water decomposition photocatalysis, and intermediate layer thickness is 5～200nm.It is characterized in that the middle layer is the photosensitizers or the semiconductor light-catalyst of nano-scale in crosslinked on the opposite inner face of cationic exchange rete and anion exchange membrane facing or coating, or photosensitizers and semiconductor light-catalyst pairing mixture.
It is the Bipolar Membrane preparation method with middle layer of water decomposition photocatalysis with photosensitizers or semiconductor material that another object of the present invention provides a kind of.Comprise its method with chemically crosslinked or physical adsorption is bonded on the internal surface of cationic exchange rete; Or with photosensitizers or semiconductor light-catalyst blend in ionogen is stuck with paste, be bonded on the internal surface of cationic exchange rete with casting method or pressure sintering then and accomplish PREPARATIOM OF BIPOLAR MEMBRANE.
For realizing that the technical scheme that the object of the invention adopts is:
1, the preparation of cationic exchange rete
Take by weighing 4g CMC 99.5 (CMC), the 2g Z 150PH is mixed with 200mL CMC-PVA solution; Stir, behind the vacuum deaerator curtain coating in smooth petridish, at room temperature air-dry film forming; Behind the chromium chloride solution immersion 30min with 9% (massfraction), use distilled water flushing, natural air drying; Promptly obtain the good jade-green Cr-CMC cationic exchange rete of light transmission, the about 50 μ m of thickness.
2, the preparation that has the middle layer of water decomposition photocatalysis
Take by weighing photosensitizers or semiconductor light-catalyst; Or photosensitizers and semiconductor light-catalyst pairing mixture; Adopt the method for chemically crosslinked or physical adsorption to be bonded on the internal surface of Cr-CMC cationic exchange rete of step (1) preparation; Or with the blend of photosensitizers and semiconductor light-catalyst pairing mixture in ionogen is stuck with paste, be bonded on the internal surface of Cr-CMC cationic exchange rete of step (1) preparation with casting method or pressure sintering then.
When adopting single semiconductor light-catalyst; Earlier 10mg～30mg semiconductor light-catalyst is scattered in 10～50ml, 10～30% Z 150PH-THF solution, in pumped vacuum systems behind the vacuum deaerator curtain coating on the Cr-CMC cationic exchange rete of step (1) preparation; When adopting single photosensitizers, take by weighing the photosensitizers of 20mg～30mg, with 10mL THF dissolving back curtain coating on the Cr-CMC cationic exchange rete of step (1) preparation; When adopting photosensitizers and semiconductor light-catalyst pairing mixture; Get semiconductor light-catalyst and the photosensitizers of 10～30mg respectively; Be scattered in 10～50ml, 10～30% Z 150PH-THF solution; Curtain coating is on the Cr-CMC cationic exchange rete of step (1) preparation behind the vacuum deaerator in pumped vacuum systems, and wherein the ratio between semiconductor light-catalyst and the photosensitizers is to make up arbitrarily.
3, PREPARATIOM OF BIPOLAR MEMBRANE
Prepare 3% polyacrylamide solution, stir, vacuum deaerator obtains water white transparency thickness film liquid, constantly stirs in 50 ℃ to add 10～30% formalins down; Regulate pH=9～10 with NaOH solution, reaction 1h adds quantitative diethylamine then; Continue reaction 3h postcooling to room temperature, add HCl and stir 1h, curtain coating is on the above-mentioned Cr-CMC/ middle layer that makes; At room temperature air-dry, promptly get Cr-CMC/ middle layer/mPMA Bipolar Membrane.
Photosensitizers of the present invention is tetraiodofluorescein, thionine, rose-red, eosin, chlorophyll, thionine, tetrazaporphin, 8-hydroxy-quinoline, anthraquinone.
Semiconductor light-catalyst of the present invention is transition-metal Fe, Co, Cu, Cr, Sn, W, Mo, Zn, Ti or its oxide compound TiO
2, SnO
2, ZnO, Fe
2O
3, Fe
3O
4, WO
3, and rare earth metal y, La, Ce, the oxide compound of Zr, Pd, Ru.
Photosensitizers of the present invention or semiconductor light-catalyst pairing mixture is meant that the combination of any one and arbitrary proportion in photosensitizers and the semiconductor light-catalyst matches, as with thionine/TiO
2, SnO
2/ TiO
2, ZnO/TiO
2, Fe
2O
3/ TiO
2Use Deng pairing, use the purpose of the wavelength of light source with raising semiconductor material quantum yield to reach change.
Photosensitizers of the present invention or semiconductor light-catalyst are ordinary method self-control or commercially available nano semiconductor material; In UW atmosphere, be scattered in the solvent during use, it be bonded on the cationic exchange rete internal surface with the method with chemically crosslinked or physical adsorption after the blend of ionogen paste.
The Bipolar Membrane that the present invention relates to is owing to having introduced photosensitizers or semiconductor light-catalyst, so under UV-light or visible light radiation, on photosensitizers or semiconductor light-catalyst surface, generate light induced electron and hole in the middle layer.Light induced electron and hole have strong redox property, can improve the dissociation yield 5～15% of water.
The Bipolar Membrane that the present invention relates to can increase the perviousness and the ionic mobility of water because photosensitizers or the semiconductor light-catalyst in the middle layer, introduced are hydrophilic material.At 120mA/cm
2Under the current density, bath voltage drops to 3～4V from 5～6V, has reduced membrane impedance and bath voltage, reaches energy-conservation effect.
The transition metal semiconductor light-catalyst TiO that the present invention introduces
2, SnO
2, ZnO, Fe
2O
3, Fe
3O
4, WO
3Have good heat and chemicalstability Deng all, can in the environment of acid or alkali environment or temperature variation, work, performance and dimensional stability are good, long service life and cheaply being easy to get, and preparation cost is low.
Description of drawings
What Fig. 1 provided amplification has matching the composition material that constitutes each other with photosensitizers or semiconductor light-catalyst or the two and having Bipolar Membrane fundamental diagram under the illumination in the 0.1mol/L metabisulfite solution in the middle layer of water decomposition photocatalysis in the middle of serving as of sandwich structure characteristic.
Among Fig. 1, water is polar molecule, and its center of positive charge is in Wasserstoffatoms one end, and center of negative charge is in Sauerstoffatom one end.Under illumination, the electronics on the semi-conductor valence band is excited on the conduction band, on valence band, stays the hole; Light induced electron and hole have extremely strong chemically reactive; They attack the positive and negative charge center that infiltrates through water in the Bipolar Membrane middle layer respectively, make that the linkage force between hydroxide radical and hydrogen ion weakens in the water, and interfacial layer is more hydrophilic; Thereby promoted dissociating of water, reduced membrane impedance and film WV.The H that generates behind the water decomposition
+Ion gets in the cathode compartment through cationic exchange membrane, makes the sodium sulfate catholyte be acid.The OH that generates behind the water decomposition
-Ion gets in the anolyte compartment through anion-exchange membrane, makes the sodium sulfate anolyte be alkalescence.Photosensitizers has bigger motivational factor under visible light, excitation electron injects (transporting) conduction band to semiconductor material, thereby has enlarged the semi-conductor excitation wavelength range, improves the utilization ratio of luminous energy.
Embodiment
Embodiment 1
Accurately take by weighing 4g CMC 99.5 (CMC), the 2g Z 150PH is mixed with 200mL CMC-PVA solution; Stir, behind the vacuum deaerator curtain coating in smooth petridish, at room temperature air-dry film forming; Behind the chromium chloride solution immersion 30min with 9% (massfraction), use distilled water flushing, natural air drying; Promptly obtain jade-green Cr-CMC cationic exchange rete, the about 50 μ m of thickness, light transmission is good.
Take by weighing the 8-hydroxy-quinoline of 20mg, on Cr-CMC cationic exchange rete, promptly casting method is injected the middle layer of 8-hydroxy-quinoline water decomposition photocatalysis with 10mL THF dissolving back curtain coating.
Prepare 3% polyacrylamide solution, stir, vacuum deaerator obtains water white transparency thickness film liquid, constantly stirs in 50 ℃ to add 10～30% formalins down; Regulate pH=9～10 with NaOH solution, reaction 1h adds quantitative diethylamine then; Continue reaction 3h postcooling to room temperature, add HCl and stir 1h, curtain coating is on the above-mentioned Cr-CMC/ 8-hydroxy-quinoline layer that makes; At room temperature air-dry, promptly get Cr-CMC/ 8-hydroxy-quinoline/mPMA Bipolar Membrane.
The different Bipolar Membrane bath voltages under the different electric flow density that at room temperature record are as shown in the table:
Embodiment 2
The preparation method of cationic exchange rete, anion exchange membrane facing is with instance 1.With nano-TiO
2Be intermediate layer material.Nano-TiO
2Be homemade.Under ultrasonic vibration, with the 15mg nano-TiO
2Be scattered in 25ml20% Z 150PH-THF solution, curtain coating is casting method and injects TiO on the cationic exchange rete that makes behind the vacuum deaerator in pumped vacuum systems
2The middle layer.
The different Bipolar Membrane bath voltages under the different electric flow density that at room temperature record are as shown in the table:
Embodiment 3
The preparation method of cationic exchange rete, anion exchange membrane facing is with instance 1.With nano-TiO
2/ 8-hydroxy-quinoline is an intermediate layer material.Nano-TiO
2All make by oneself with 8-hydroxy-quinoline.Under ultrasonic vibration, with the 30mg nano-TiO
2Be scattered in 40ml 30% Z 150PH-THF solution with the 10mg 8-hydroxy-quinoline, curtain coating is casting method and injects TiO on the cationic exchange rete that makes behind the vacuum deaerator in pumped vacuum systems
2/ 8-hydroxy-quinoline middle layer.
Different Bipolar Membrane bath voltages are as shown in the table under the different electric flow density that at room temperature records:
Embodiment 4
The preparation method of cationic exchange rete, anion exchange membrane facing is with instance 1.With nano-TiO
2/ α-Fe
2O
3Be intermediate layer material.Nano-TiO
2, α-Fe
2O
3Be self-control.Under ultrasonic vibration, with the 10mg nano-TiO
2With 10mg nanometer α-Fe
2O
3Be scattered in Z 150PH-THF solution of 10ml 10%, curtain coating is casting method and injects TiO on the cationic exchange rete that makes behind the vacuum deaerator in pumped vacuum systems
2/ α-Fe
2O
3The middle layer.
Different Bipolar Membrane bath voltages are as shown in table 4 below under the different electric flow density that at room temperature records:
Claims (8)
1. one kind is the Bipolar Membrane in middle layer with photosensitizers or photocatalytic semiconductor material; Have anionresin layer, the cationic exchange layer of sandwiched type structure and have the middle layer of water decomposition photocatalysis; It is characterized in that the middle layer is a water decomposition catalyst layer in crosslinked on the opposite inner face of yin, yang ion-exchange membrane layer or coating; The water decomposition catalyst layer in the crosslinked or coating be the photosensitizers or the semiconductor light-catalyst of nano-scale, photosensitizers and semiconductor light-catalyst match mixture.
2. one kind is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material, it is characterized in that:
1) preparation of cationic exchange rete
Take by weighing the 4g CMC 99.5, the 2g Z 150PH is mixed with 200mL CMC-PVA solution; Stir, behind the vacuum deaerator curtain coating in smooth petridish, at room temperature air-dry film forming; Using massfraction is after 9% chromium chloride solution is soaked 30min; Use distilled water flushing, natural air drying obtains Cr-CMC cationic exchange rete;
2) preparation in middle layer
Take by weighing photosensitizers or semiconductor light-catalyst; Or photosensitizers and semiconductor light-catalyst pairing mixture; Adopt the method for chemically crosslinked or physical adsorption to be bonded on the internal surface of cationic exchange rete of step 1) preparation; Or with the blend of photosensitizers and semiconductor light-catalyst pairing mixture in ionogen is stuck with paste, be bonded on the internal surface of cationic exchange rete of step 1) preparation with casting method or pressure sintering then;
3) PREPARATIOM OF BIPOLAR MEMBRANE
Prepare 3% polyacrylamide solution, stir, vacuum deaerator obtains water white transparency thickness film liquid, constantly stirs in 50 ℃ to add 10～30% formalins down; Regulate pH=9～10 with NaOH solution, reaction 1h adds quantitative diethylamine then; Continue reaction 3h postcooling to room temperature, add HCl and stir 1h, curtain coating is on the above-mentioned Cr-CMC/ middle layer that makes; At room temperature air-dry, promptly get Cr-CMC/ middle layer/mPMA Bipolar Membrane.
3. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material; When it is characterized in that adopting single semiconductor light-catalyst; Earlier 10mg～30mg semiconductor light-catalyst is scattered in 10～50ml, 10～30% Z 150PH-THF solution; Curtain coating is the middle layer that casting method is injected semiconductor light-catalyst behind the vacuum deaerator on the cationic exchange rete that makes in pumped vacuum systems.
4. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material; When it is characterized in that adopting single photosensitizers; Elder generation is with the photosensitizers of 20mg～30mg; On Cr-CMC cationic exchange rete, promptly casting method is injected the water decomposition photocatalysis middle layer of photosensitizers with 10mLTHF dissolving back curtain coating.
5. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material; When it is characterized in that adopting photosensitizers and semiconductor light-catalyst pairing mixture; Get semiconductor light-catalyst and the photosensitizers of 10～30mg respectively; Be scattered in 10～50ml, 10～30% Z 150PH-THF solution; Curtain coating is the water decomposition photocatalysis middle layer that casting method is injected photosensitizers and semiconductor light-catalyst pairing mixture behind the vacuum deaerator on the cationic exchange rete that makes in pumped vacuum systems.
6. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material, it is characterized in that described photosensitizers is tetraiodofluorescein, thionine, rose-red, eosin, chlorophyll, thionine, tetrazaporphin, 8-hydroxy-quinoline or anthraquinone.
7. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material, it is characterized in that described semiconductor light-catalyst is transition-metal Fe, Co, Cu, Cr, Sn, W, Mo, Zn, Ti or its oxide compound TiO
2, SnO
2, ZnO, Fe
2O
3, Fe
3O
4, WO
3, and rare earth metal y, La, Ce, the oxide compound of Zr, Pd, Ru.
8. according to claim 2 is the PREPARATIOM OF BIPOLAR MEMBRANE method in middle layer with photosensitizers or photocatalytic semiconductor material; It is characterized in that described photosensitizers or semiconductor light-catalyst, or the pairing mixture of the two is meant the combination of any one and arbitrary proportion in photosensitizers and the semiconductor light-catalyst.
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| CN101949047B (en) * | 2010-09-21 | 2012-12-19 | 福建师范大学 | Preparation method for bipolar membrane modified by solid polymer electrolyte |
| CN102600732A (en) * | 2012-04-06 | 2012-07-25 | 福建师范大学 | Method for preparing bipolar membrane modified by solar photocatalyst |
| CN104593819A (en) * | 2015-01-06 | 2015-05-06 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
| CN107096572B (en) * | 2017-04-24 | 2019-07-23 | 太原师范学院 | A method of preparing Bipolar Membrane surface powder state photochemical catalyst |
| CN107815706B (en) * | 2017-11-07 | 2019-07-23 | 太原师范学院 | A kind of preparation method for photoelectrocatalysis water decomposition film |
| CN109529641B (en) * | 2019-01-11 | 2021-04-20 | 天津工业大学 | Polyimide-photosensitive cobalt organic framework hybrid membrane preparation and gas separation application |
| CN110205647A (en) * | 2019-06-25 | 2019-09-06 | 武汉长兴电器发展有限公司 | A kind of Bipolar Membrane and preparation method thereof |
| CN115321723A (en) * | 2022-10-17 | 2022-11-11 | 杭州水处理技术研究开发中心有限公司 | Treatment method and system for mixed brine of wastewater zero discharge system |
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