CN107099815B - A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction - Google Patents
A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction Download PDFInfo
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- CN107099815B CN107099815B CN201710272849.8A CN201710272849A CN107099815B CN 107099815 B CN107099815 B CN 107099815B CN 201710272849 A CN201710272849 A CN 201710272849A CN 107099815 B CN107099815 B CN 107099815B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of Bipolar Membrane surface powder state photochemical catalyst is in CO2Application in reduction is the diaphragm using the light-catalysed Bipolar Membrane of area load powdered form as cathode chamber and anode chamber, the cation-exchange membrane area load P-type semiconductor photocatalyst powder of the Bipolar Membrane；The anion-exchange membrane area load N-type semiconductor photocatalyst powder of the Bipolar Membrane, using P-type semiconductor photocatalyst powder as cathode, using N-type semiconductor photocatalyst powder as anode, using xenon lamp as light source, applied voltage effect is lower to carry out photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.Bipolar Membrane intermediate layer water decomposition is not only CO2Reduction provides continuously H+, and will not be due to H+Excessive concentration and evolving hydrogen reaction occurs, while ionic liquid improves CO2Solubility and proton delivery rate, improve CO2Reduction efficiency.
Description
Technical field
The present invention relates to a kind of bipolar film catalysts in CO2Application in reduction, specifically, being that one kind is attached with powder
State catalyst restores CO in photoelectrocatalysis2The technical solution of middle application.
Background technique
Semiconductor photoelectrocatalysielectrode technology is a kind of effective technology means for converting solar energy into chemical energy, to the solution energy
In short supply, reduction pollution pressure is of great significance.By the exploration and accumulation of scientists from all over the world's many years, the research in the field
Greater advance is achieved, but on the whole, it is still relatively low using solar photoelectric catalytic efficiency.One of main cause is
It is again compound since photo-generate electron-hole fails to efficiently separate, cause photoelectric catalytically active to decline.Domestic and foreign scholars use
Various methods separate photo-generate electron-hole, such as：Fan etc. is by TiO2It is compound with the progress of BiOCl catalyst, make BiOCl conduction band
Electronics transfer is to TiO2On conduction band, TiO2The hole of valence band is transferred in BiOCl valence band, to effectively separate electron-hole
(CrystEngComm, 2014, 16: 820-825)；Zhang etc. is prepared for BiOCl nucleocapsid structure photochemical catalyst, this structure
Photo-generate electron-hole can be efficiently separated, to improve photocatalytic activity（CrystEngComm, 2012, 14: 700-
707）.As it can be seen that improving photo-generate electron-hole separative efficiency is still that key in the urgent need to address during photoelectrocatalysis is asked
Topic.
In photoelectrocatalysis actual application, there are difficult recycling after easy to reunite and reaction for semiconductor powder state catalyst
Problem.Therefore, the immobilization of photochemical catalyst is extremely important to the functionization of photocatalysis technology.For example, Noorjahan etc. utilizes spray
TiO has been made in the technology of splashing2- HZSM-5 laminated film, this film have the degradation of phenol and organic acid toxic in waste water very high
Activity（Appl. Catal., B: Environmental, 2004, 47: 209-213）；Garc í a etc. is with glass microsphere
For carrier, supported titanium is prepared for using dip-coating method2Photochemical catalyst is for degrade simulating pollution object and municipal sewage treatment
Sewage (the Appl. Catal., B of factory: Environmental, 2011, 103:294-301), good result is achieved.
As it can be seen that the functionization in order to really realize photocatalysis technology, the immobilization of photochemical catalyst seem particularly important, up for into
One step research.
The method of traditional photoelectrocatalysis water decomposition hydrogen manufacturing is by N-type semiconductor light anode and P-type semiconductor photocathode string
Yin, yang pole room is split by connection, centre using the gas separation membrane of light transmission.But with the lasting progress of reaction, anode chamber by
In oxygen evolution reaction can gradually souring, cathode chamber is since evolving hydrogen reaction can gradually become alkali, and most of anode material prefers neutrality
Or slight alkali environment, most of cathode material prefer slant acidity environment, therefore strongly limit holding for water decomposition reaction
It is continuous to carry out.
The present invention proposes for P-type semiconductor photocatalyst powder and N-type semiconductor photocatalyst powder to be attached respectively to double
The surface of pole film two sides, and as the diaphragm of yin, yang pole room, it carries out photoelectrocatalysis and restores CO2It is based on considered below：①
Under photoelectric action, Bipolar Membrane intermediate layer occurs water decomposition and generates H+ And OH-Ion, H+Ion penetrates cation-exchange membrane
Into cathode chamber, CO is participated in2Reduction is consumed, OH-Ion enters anode chamber through anion-exchange membrane, and occurs at anode
Water oxidation reaction is consumed.Theoretically, Bipolar Membrane water decomposition generates H+Rate be equal to cathode CO2Reduction consumption H+Speed
Therefore rate can not only guarantee continuously H+Supply, and will not be excessively high due to hydrogen ion concentration and that liberation of hydrogen occurs is anti-
It answers.Equally, Bipolar Membrane water decomposition generates OH-Rate be equal to anodic oxidation reactions consume OH-Rate, therefore anode chamber can
It is always maintained at alkaline condition, is conducive to the progress of water oxidation reaction.2. using ionic liquid as catholyte, can not only play
The effect of " carbon sequestration " improves CO2Solubility in the reaction system, and can be used as co-catalyst, with semiconductor catalyst
Powder concerted catalysis CO2Reduction, while the delivery rate of proton in reaction system can also be improved.3. being fixed with half using surface
Diaphragm of the Bipolar Membrane of conductor photocatalyst powder as yin, yang pole room, can be by cathode catalysis CO2It restores anti-with Oxygen anodic evolution
It answers effective Ground Split in two pole rooms, while carrying out cathode CO2Reduction and anode water oxidation reaction, the two are mutually promoted, and are improved
Photoelectrocatalysis efficiency.
Summary of the invention
Problem of the invention is that be difficult to recycle after semiconductor light-catalyst powder is easy to reunite in the prior art and reaction
The problem of problem, semiconductor light-catalyst photo-generate electron-hole low separation efficiency, semiconductor light-catalyst cannot stablize, efficiently,
The problem of continuing working, and Bipolar Membrane surface powder state photochemical catalyst is provided in CO2Application in reduction.
To solve the above-mentioned problems, Bipolar Membrane surface powder state photochemical catalyst provided by the present invention is in CO2In reduction
Using the application is the diaphragm for being attached with the light-catalysed Bipolar Membrane of powdered form using surface as cathode chamber and anode chamber, described
The cation-exchange membrane surface of Bipolar Membrane is to be attached with P-type semiconductor photocatalyst powder；The anion exchange of the Bipolar Membrane
Film surface is to be attached with N-type semiconductor photocatalyst powder, and using P-type semiconductor photocatalyst powder as cathode, N-type is partly led
For body photocatalyst powder as anode, catholyte is imidazoles or pyridine ionic liquid, anolyte be KOH or
NaOH, using xenon lamp as light source, applied voltage is under 0.5 ~ 2.0 V effect, and cathode chamber carries out photoelectrocatalysis CO2Reduction, sun
Pole room carries out water oxidation reaction.
The additional technical feature of above scheme is as follows.
The P-type semiconductor photocatalyst powder is Ag2O、NiO、Cu2O, one of CoO and SnO or combinations thereof.
The N-type semiconductor photocatalyst powder is for ZnO, TiO2、Fe2O3, CdS and SnO2One of or its group
It closes.
The imidazoles or pyridine ionic liquid are 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- butyl -3- methyl miaow
Azoles hexafluorophosphate, chlorination 1- butyl -3- methylimidazole, N- ethylpyridine hexafluorophosphate, N- ethylpyridine tetrafluoroborate,
One of bromination N- ethylpyridine or combinations thereof.
Realize the present invention it is above-mentioned provided by a kind of Bipolar Membrane surface powder state photochemical catalyst in CO2Application in reduction,
Compared with prior art, surface of the present invention is attached with the light-catalysed Bipolar Membrane of powdered form as cathode chamber and anode chamber
Diaphragm, which carries out photoelectrocatalysis CO under sunlight and electric field action2Reduction, efficiently solves conductor photocatalysis
After agent powder is easy to reunite and reaction the problem of difficult recycling；Meanwhile utilizing the fixation anionic group and yin in cation-exchange membrane
Fixed cation group efficiently separates hole-electron respectively to the sucking action in hole and electronics in amberplex, solves
The problem of photo-generate electron-hole low separation efficiency during semiconductor photoelectrocatalysielectrode of having determined；Importantly, boundary in Bipolar Membrane
Surface layer occurs water decomposition and generates H+ And OH-Ion, H+Ion enters cathode chamber and participates in CO2Reduction reaction not only guarantees successive
H+Supply, and evolving hydrogen reaction will not occur since hydrogen ion concentration is excessively high；OH-Ion enters anode chamber and water oxygen occurs
Reaction, maintains the alkaline condition of anode chamber, is conducive to the progress of water oxidation reaction.Catholyte is used ionic liquid as, no
It can only play the role of " carbon sequestration ", improve CO2Solubility in the reaction system, and can be used as co-catalyst, with half
Conductor catalyst powder concerted catalysis CO2Reduction, while the delivery rate of proton in reaction system can also be improved.The invention benefit
Use the Bipolar Membrane of area load semiconductor light-catalyst powder as the diaphragm of yin, yang pole room, it can be by cathode catalysis CO2Reduction
Effective Ground Split is reacted with Oxygen anodic evolution in two pole rooms, while carrying out cathode CO2Reduction and anode water oxidation reaction, the two phase
Mutually promote, improve photoelectrocatalysis efficiency, realizes semiconductor powder state photochemical catalyst and carry out cathode CO2Reduction is aoxidized with anode water
Efficient, the continuous operation of reaction.
Specific advantage and good effect concentrated reflection are as follows.
The present invention solves the problems, such as that semiconductor light-catalyst powder is easy to reunite and recycles with difficult after reaction.
The present invention utilizes cation fixed in the fixation anionic group and anion-exchange membrane in cation-exchange membrane
To the sucking action in hole and electronics, hole-electron is efficiently separated respectively for group, during solving semiconductor photoelectrocatalysielectrode
The problem of photo-generate electron-hole low separation efficiency.
The present invention occurs water decomposition using Bipolar Membrane intermediate layer and generates H+And OH-Ion maintains yin, yang pole room pH
Stabilization, solve the problems, such as semiconductor light-catalyst cannot stablize, efficiently, continue working.
The present invention occurs water decomposition using Bipolar Membrane intermediate layer and generates H+ And OH-Ion, H+Ion enters cathode chamber
Participate in CO2Reduction reaction not only guarantees continuously H+Supply, and liberation of hydrogen will not occur since hydrogen ion concentration is excessively high
Reaction；OH-Ion enters anode chamber and water oxidation reaction occurs, and maintains the alkaline condition of anode chamber, is conducive to water oxidation reaction
Progress.
The present invention uses ionic liquid as catholyte, can not only play the role of " carbon sequestration ", improves CO2In reactant
Solubility in system, and can be used as co-catalyst, with semiconductor catalyst powder concerted catalysis CO2Reduction, while may be used also
To improve the delivery rate of proton in reaction system.
The present invention is fixed with the Bipolar Membrane of semiconductor light-catalyst powder as the diaphragm of yin, yang pole room using surface, can
With by cathode catalysis CO2Reduction reacts effective Ground Split with Oxygen anodic evolution in two pole rooms, while carrying out cathode CO2Reduction and sun
Pole water oxidation reaction, the two are mutually promoted, and photoelectrocatalysis efficiency is improved, and are realized semiconductor powder state photochemical catalyst and are carried out cathode
CO2Efficient, the continuous operation of reduction and anode water oxidation reaction.
Detailed description of the invention
Fig. 1 is the schematic diagram of Bipolar Membrane both side surface load powdery photocatalyst of the present invention.In figure：1- anion exchange
Film；2- cation-exchange membrane；3-P type semiconductor light-catalyst powder；4-N type semiconductor light-catalyst powder；Cation exchange
Film and anion-exchange membrane is compound obtains Bipolar Membrane.
Fig. 2 is the sodium carboxymethylcellulose crosslinking schematic diagram that the present invention prepares cation-exchange membrane.
Fig. 3 is the chitosan and glutaraldehyde cross-linking schematic diagram that the present invention prepares anion-exchange membrane.
Fig. 4 is the Cross Section Morphology figure of Bipolar Membrane in the present invention, and lower left corner illustration presents Bipolar Membrane with good light transmission
Performance is conducive to preferably absorb sunlight；Upper right corner illustration is that Bipolar Membrane impregnates the picture after 48 hours, table in distilled water
Bright Bipolar Membrane is not soluble in water, is conducive to it and steadily works in aqueous solution.
Fig. 5 is the device that the present invention carries out photoelectrocatalysis experiment using the Bipolar Membrane of area load semiconductor catalyst powder
Schematic diagram.
Fig. 6 is in the embodiment of the present invention 1, and the two sides of preparation load powdery photocatalyst Bipolar Membrane respectively and urge with unsupported
The contact angle of agent powder Bipolar Membrane.In figure, the cation-exchange membrane surface contact angle of (a)-unsupported catalyst fines；(b)-
The anion-exchange membrane surface contact angle of unsupported catalyst fines Bipolar Membrane；(c)-area load Cu2O powder photocatalyst
Cation-exchange membrane surface contact angle；(d)-area load TiO2The anion-exchange membrane surface contact angle of powder photocatalyst；
Loading powdery photocatalyst Bipolar Membrane has smaller contact angle, shows that its hydrophily is more preferable, promotes boundary in Bipolar Membrane
Surface layer water decomposition is conducive to the pH gradient for maintaining yin, yang pole room stable.
Fig. 7 is in the embodiment of the present invention 1, and the voltage drop (IR) of load powdery photocatalyst Bipolar Membrane changes over time song
Line chart.
Fig. 8 is that the tank voltage of powdery photocatalyst Bipolar Membrane is loaded in the embodiment of the present invention 1 with current density change song
Line chart.
Fig. 9 is to load the AC impedance curve graph of powdery photocatalyst Bipolar Membrane in the embodiment of the present invention 1.
Figure 10 is in the embodiment of the present invention 1, and photoelectrocatalysis restores CO2Current efficiency figure.
Figure 11 is in the embodiment of the present invention 1, and photoelectrocatalysis restores CO under different current densities2Energy conversion efficiency
Figure.
Specific embodiment
A specific embodiment of the invention is further illustrated below.
Embodiment 1
The light-catalysed Bipolar Membrane of powdered form is attached with as the diaphragm of cathode chamber and anode chamber using surface（Wherein, it constitutes double
The cation-exchange membrane surface of pole film is attached with Ag2O semiconductor light-catalyst powder constitutes the anion-exchange membrane table of Bipolar Membrane
Face is attached with TiO2Semiconductor light-catalyst powder）, by Ag2O semiconductor light-catalyst dusty material is as cathode, by TiO2Half
For conductor photocatalyst powder material as anode, catholyte material is 1- butyl -3- methyl imidazolium tetrafluoroborate ion
Liquid, anolyte are 0.5 M KOH, using xenon lamp as simulated solar radiant, under applied voltage acts on for 0.5 V,
Cathode chamber carries out photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.
After experiment, catholyte is collected, the CO content generated using chromatography of gases calibration, by light is calculated
Electro-catalysis restores CO2Current efficiency be 65.5%, energy conversion efficiency 26.8%.
Embodiment 2
The light-catalysed Bipolar Membrane of powdered form is attached with as the diaphragm of cathode chamber and anode chamber using surface（Wherein, it constitutes double
The cation-exchange membrane surface of pole film is attached with Ag2O semiconductor light-catalyst powder constitutes the anion-exchange membrane table of Bipolar Membrane
Face is attached with Fe2O3Semiconductor light-catalyst powder）, by Ag2O semiconductor light-catalyst dusty material is as cathode, by Fe2O3Half
For conductor photocatalyst powder material as anode, catholyte material is chlorination 1- butyl -3- methylimidazole ionic liquid, sun
Pole electrolyte be 1.0 M KOH, using xenon lamp be used as simulated solar radiant, applied voltage be 0.8 V act under, cathode chamber into
Row photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.
After experiment, catholyte is collected, the CO content generated using chromatography of gases calibration, by light is calculated
Electro-catalysis restores CO2Current efficiency be 65.2%, energy conversion efficiency 30.2%.
Embodiment 3
The light-catalysed Bipolar Membrane of powdered form is attached with as the diaphragm of cathode chamber and anode chamber using surface（Wherein, it constitutes double
The cation-exchange membrane surface of pole film is attached with CoO semiconductor light-catalyst powder, constitutes the anion-exchange membrane table of Bipolar Membrane
Face is attached with ZnO semiconductor light-catalyst powder）, using CoO semiconductor light-catalyst dusty material as cathode, ZnO is partly led
For body photocatalyst powder material as anode, catholyte material is N- ethylpyridine hexafluorophosphoric acid ionic liquid, anode
Electrolyte be 0.5 M NaOH, using xenon lamp be used as simulated solar radiant, applied voltage be 1.0 V act under, cathode chamber into
Row photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.
After experiment, catholyte is collected, the CO content generated using chromatography of gases calibration, by light is calculated
Electro-catalysis restores CO2Current efficiency be 66.6%, energy conversion efficiency 25.8%.
Embodiment 4
The light-catalysed Bipolar Membrane of powdered form is attached with as the diaphragm of cathode chamber and anode chamber using surface（Wherein, it constitutes double
The cation-exchange membrane surface of pole film is attached with Cu2O semiconductor light-catalyst powder constitutes the anion-exchange membrane table of Bipolar Membrane
Face is attached with CdS semiconductor light-catalyst powder）, by Cu2O semiconductor light-catalyst dusty material is partly led as cathode, by CdS
For body photocatalyst powder material as anode, catholyte material is N- ethylpyridine tetrafluoroborate ion liquid, anode
Electrolyte be 1.0 M NaOH, using xenon lamp be used as simulated solar radiant, applied voltage be 1.5 V act under, cathode chamber into
Row photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.
After experiment, catholyte is collected, the CO content generated using chromatography of gases calibration, by light is calculated
Electro-catalysis restores CO2Current efficiency be 68.3%, energy conversion efficiency 28.8%.
Embodiment 5
The light-catalysed Bipolar Membrane of powdered form is attached with as the diaphragm of cathode chamber and anode chamber using surface（Wherein, it constitutes double
The cation-exchange membrane surface of pole film is attached with NiO semiconductor light-catalyst powder, constitutes the anion-exchange membrane table of Bipolar Membrane
Face is attached with SnO2Semiconductor light-catalyst powder）, using NiO semiconductor light-catalyst dusty material as cathode, by SnO2Partly lead
For body photocatalyst powder material as anode, catholyte material is chlorination 1- butyl -3- methyl miaow and N- ethylpyridine six
The ionic liquid of fluorophosphate, anolyte is 2.0 M NaOH, using xenon lamp as simulated solar radiant, applied voltage
For under 2.0 V effect, cathode chamber carries out photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction.
After experiment, catholyte is collected, the CO content generated using chromatography of gases calibration, by light is calculated
Electro-catalysis restores CO2Current efficiency be 56.3%, energy conversion efficiency 28.4%.
Specific embodiment 1 ~ 5 described in aforementioned present invention, a kind of provided powdered form of bipolar film surface attachment are urged
Agent is in CO2The preparation method of application in reduction, the bipolar film surface attaching powder state photochemical catalyst of the application is as follows：
（1）Prepare carboxymethyl cellulose that mass fraction is 2.0 ~ 5.0% or cellulose acetate aqueous solution and 2.0 ~
5.0% polyvinyl alcohol or aqueous povidone solution after mixing and is stirred continuously to form jelly, standing and defoaming 30 ~ 60
Minute, it is cast on clean band frame glass plate, the cation-exchange membrane with a thickness of 30 ~ 60 μm is obtained after being air-dried at room temperature.
（2）Weigh 0.5 ~ 2.0g P-type semiconductor photocatalyst powder, be scattered under ultrasonic oscillation 100 mL water or
In dehydrated alcohol, continues concussion and be uniformly dispersed for 2.0 hours, the cation-exchange membrane surface of above-mentioned preparation is poured into, using metal
Ion carries out crosslinking 5 ~ 15 minutes, and after 30 ~ 60 °C of drying, P-type semiconductor photocatalyst powder is attached to cation-exchange membrane table
Face.
（3）By step（2）In cation-exchange membrane top and bottom it is reverse, be tightly attached to the surface of supported catalyst and soaked
Glass plate on, another surface（The surface of i.e. unsupported catalyst）Upward.
（4）Prepare mass fraction be 2.0 ~ 5.0% chitosan, polyimides or benzimidazole aqueous solution and 2.0 ~
5.0% polyvinyl alcohol or aqueous povidone solution after mixing and is stirred continuously to form jelly, standing and defoaming 30 ~ 60
Minute, it is cast in step（3）In cation-exchange membrane surface, obtained after being air-dried at room temperature with a thickness of 30 ~ 60 μm anion hand over
Change film.
（5）Weigh 0.5 ~ 2.0g N-type semiconductor photocatalyst powder, be scattered under ultrasonic oscillation 100 mL water or
In dehydrated alcohol, continues concussion and be uniformly dispersed for 2.0 hours, the anion exchange film surface of above-mentioned preparation is poured into, using aldehydes
Crosslinking agent carries out crosslinking 5 ~ 15 minutes, and after 30 ~ 60 °C of drying, N-type semiconductor photocatalyst powder is attached to anion-exchange membrane
Surface.
Wherein, the P-type semiconductor photocatalyst powder is Ag2O、NiO、Cu2O, one of CoO and SnO
Or combinations thereof；The metal ion is Fe3+、Sn2+And Ti4+One of；The N-type semiconductor photocatalyst powder is
ZnO、TiO2、Fe2O3, CdS and SnO2One of or combinations thereof；The aldehyde crosslinking agent is in glutaraldehyde and butanedial
It is a kind of；The Bipolar Membrane is combined by cation-exchange membrane, anion-exchange membrane.
The Bipolar Membrane area load powdery photocatalyst of above-mentioned preparation is by P-type semiconductor photocatalyst powder and N-type
Semiconductor light-catalyst powder is attached respectively to the both side surface of Bipolar Membrane, this film translucency is good and can effectively absorb the sun
Light, anionic group and cation group are fixed in Bipolar Membrane has sucking action to hole and electronics respectively, can be by hole-electricity
Son efficiently separates；Bipolar Membrane intermediate layer occurs water decomposition and generates H+And OH-Ion maintains the stabilization of yin, yang pole room pH,
By Photocatalitic Technique of Semiconductor in conjunction with Bipolar Membrane water decomposition technology, while carrying out cathode CO2Reduction and anode water oxidation reaction,
The two is mutually promoted, and photoelectrocatalysis efficiency is improved, and is realized semiconductor powder state photochemical catalyst and is carried out cathode CO2Reduction and anode
Efficient, the continuous operation of water oxidation reaction.
Claims (4)
1. a kind of Bipolar Membrane surface powder state photochemical catalyst is in CO2Application in reduction, the application are with area load powdered form
Diaphragm of the Bipolar Membrane of photochemical catalyst as cathode chamber and anode chamber, the cation-exchange membrane area load p-type of the Bipolar Membrane
Semiconductor light-catalyst powder；The anion-exchange membrane area load N-type semiconductor photocatalyst powder of the Bipolar Membrane, by P
Type semiconductor light-catalyst powder is as cathode, and using N-type semiconductor photocatalyst powder as anode, catholyte is imidazoles
Or pyridine ionic liquid, anolyte are KOH or NaOH, using xenon lamp as light source, applied voltage is 0.5 ~ 2.0 V work
Under, cathode chamber carries out photoelectrocatalysis CO2Reduction, anode chamber carry out water oxidation reaction, are applied to CO2Reduction reaction；
The preparation method of the Bipolar Membrane area load powdery photocatalyst of its application is as follows：
（1）Prepare the carboxymethyl cellulose or cellulose acetate aqueous solution and 2.0 ~ 5.0% that mass fraction is 2.0 ~ 5.0%
Polyvinyl alcohol or aqueous povidone solution after mixing and are stirred continuously to form jelly, and standing and defoaming 30 ~ 60 minutes,
It is cast on clean band frame glass plate, the cation-exchange membrane with a thickness of 30 ~ 60 μm is obtained after being air-dried at room temperature；
（2）0.5 ~ 2.0g P-type semiconductor photocatalyst powder is weighed, 100 mL water or anhydrous are scattered under ultrasonic oscillation
In ethyl alcohol, continues concussion and be uniformly dispersed for 2.0 hours, the cation-exchange membrane surface of above-mentioned preparation is poured into, using metal ion
Carry out crosslinking 5 ~ 15 minutes, after 30 ~ 60 °C of drying, P-type semiconductor photocatalyst powder is attached to cation-exchange membrane surface；
（3）By step（2）In cation-exchange membrane top and bottom it is reverse, so that the surface of supported catalyst is tightly attached to the glass soaked
In glass plate, another surface is upward；
（4）Prepare the chitosan that mass fraction is 2.0 ~ 5.0%, the aqueous solution and 2.0 ~ 5.0% of polyimides or benzimidazole
Polyvinyl alcohol or aqueous povidone solution, after mixing and be stirred continuously to form jelly, 30 ~ 60 points of standing and defoaming
Clock is cast in step（3）In cation-exchange membrane surface, the anion exchange with a thickness of 30 ~ 60 μm is obtained after being air-dried at room temperature
Film；
（5）0.5 ~ 2.0g N-type semiconductor photocatalyst powder is weighed, 100 mL water or anhydrous are scattered under ultrasonic oscillation
In ethyl alcohol, continues concussion and be uniformly dispersed for 2.0 hours, be poured into the anion exchange film surface of above-mentioned preparation, be crosslinked using aldehydes
Agent carries out crosslinking 5 ~ 15 minutes, and after 30 ~ 60 °C of drying, N-type semiconductor photocatalyst powder is attached to anion exchange film surface.
2. Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 is in CO2Application in reduction, the P-type semiconductor
Photocatalyst powder is Ag2O、NiO、Cu2O, one of CoO and SnO or combinations thereof.
3. Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 is in CO2Application in reduction, the N-type semiconductor
Photocatalyst powder is for ZnO, TiO2、Fe2O3, CdS and SnO2One of or combinations thereof.
4. Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 is in CO2Application in reduction, the imidazoles or pyrrole
Pyridine class ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- butyl -3- methylimidazole hexafluorophosphate, chlorination 1-
Butyl -3- methylimidazole, N- ethylpyridine hexafluorophosphate, N- ethylpyridine tetrafluoroborate, in bromination N- ethylpyridine
One kind or combinations thereof.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710272849.8A CN107099815B (en) | 2017-04-24 | 2017-04-24 | A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction |
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| CN201710272849.8A CN107099815B (en) | 2017-04-24 | 2017-04-24 | A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction |
Publications (2)
| Publication Number | Publication Date |
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