CN107012475B - A kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition - Google Patents
A kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition Download PDFInfo
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- 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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- 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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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/55—Photoelectrolysis
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- 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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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition, the application is using the cation-exchange membrane of area load P-type semiconductor photocatalyst powder and the anion-exchange membrane of area load N-type semiconductor photocatalyst powder as Bipolar Membrane, and constitute cathode chamber and anode chamber's diaphragm, using P-type semiconductor photocatalyst powder material as cathode, using N-type semiconductor photocatalyst powder material as anode, prepare the catholyte and anolyte of 0.5 ~ 1.0 M respectively afterwards, using xenon lamp as light source, applied voltage is under 0.5 ~ 2.0 V effect, it is carried out continuously photoelectrocatalysis water decomposition hydrogen manufacturing.The catalyst of powdered form is attached to Bipolar Membrane two sides by the present invention, for photoelectrocatalysis water decomposition hydrogen manufacturing, hydrogen generation efficiency is up to 90 ~ 99.8%, hydrogen purity is up to 90% ~ 99.99%, continuous operation 10 ~ 48 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and realize efficient, the continuous operation of semiconductor powder state photochemical catalyst hydrogen production by water decomposition.
Description
Technical field
The present invention relates to a kind of application of powdered form catalyst in water decomposition, specifically, being a kind of load powdered form
The technical solution that the Bipolar Membrane of catalyst is applied in water decomposition hydrogen manufacturing.
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 greatly limit the continuous of water decomposition reaction
It carries out.
The present invention proposes for P-type semiconductor photocatalyst powder and N-type semiconductor photocatalyst powder to be individually fixed in double
The surface of pole film two sides, and as the diaphragm of yin, yang pole room, photoelectrocatalysis water decomposition hydrogen manufacturing is carried out, is examined based on following
Consider：1. Bipolar Membrane intermediate layer occurs water decomposition and generates H under photoelectric action+ And OH-Ion, H+Ion is through cation
Exchange membrane enters cathode chamber, and evolving hydrogen reaction occurs at cathode and is consumed, OH-Ion enters anode through anion-exchange membrane
Room, and oxygen evolution reaction occurs at anode and is consumed.Therefore, it is theoretically able to maintain the stabilization of cathode chamber and anode chamber pH, this
The steady operation for being conducive to semiconductor light-catalyst powder makes reaction that can continue to carry out.2. being fixed with semiconductor using surface
Oxygen anodic evolution can be reacted and react effective with cathode hydrogen evolution by diaphragm of the Bipolar Membrane of photocatalyst powder as yin, yang pole room
Ground Split avoids generated hydrogen, oxygen from intersecting, recombines generation hydrone in two pole rooms, not only increases water decomposition effect
Rate, and the higher hydrogen of purity is made.3. considering from thermodynamics, the H that Bipolar Membrane water decomposition generates+More hold than hydrone
Easily restore, and OH-It is easier that oxidation reaction occurs than hydrone, further improves water decomposition efficiency.
Summary of the invention
It is asked problem of the invention is that semiconductor light-catalyst powder is easy to reunite in the prior art with what hardly possible after reaction recycled
Topic, the problem of semiconductor light-catalyst photo-generate electron-hole low separation efficiency, semiconductor light-catalyst cannot stablize, efficiently, hold
The problem of continuous work, and a kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition is provided.
To solve the above-mentioned problems, a kind of Bipolar Membrane surface powder state photochemical catalyst provided by the present invention is in water decomposition
Application, the application is with the cation-exchange membrane of area load P-type semiconductor photocatalyst powder and area load N-type half
The anion-exchange membrane of conductor photocatalyst powder is Bipolar Membrane, and constitutes cathode chamber and anode chamber's diaphragm, by P-type semiconductor light
Catalyst powder powder material is as cathode, using N-type semiconductor photocatalyst powder material as anode, after prepare 0.5 ~ 1.0 respectively
The catholyte and anolyte of M, using xenon lamp as light source, applied voltage is to be carried out continuously under 0.5 ~ 2.0 V effect
Photoelectrocatalysis water decomposition hydrogen manufacturing.
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 ZnO, TiO2、Fe2O3, CdS and SnO2One of or combinations thereof.
The catholyte is H2SO4And HClO4One of solution, anolyte are in KOH and NaOH solution
It is a kind of.
The Bipolar Membrane is combined by cation-exchange membrane, anion-exchange membrane.
Realize the present invention it is above-mentioned provided by a kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition, with
The prior art is compared, the light-catalysed Bipolar Membrane of area load powdered form of the present invention as cathode chamber and anode chamber every
Film, the diaphragm carry out photoelectrocatalysis water decomposition hydrogen under sunlight and electric field action, efficiently solve 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 maintains the stabilization of yin, yang pole room pH, is conducive to semiconductor light-catalyst powder
Stablize, is efficient, continuing working.The invention carries out photoelectrocatalysis water decomposition hydrogen manufacturing, and hydrogen generation efficiency is up to 90 ~ 99.8%, hydrogen purity
Up to 90 ~ 99.99%, continuous operation 10 ~ 48 hours, tank voltage, hydrogen generation efficiency were held essentially constant, and realized semiconductor powder
Efficient, the continuous operation of state photochemical catalyst hydrogen production by water decomposition.
In conclusion its 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.
By Photocatalitic Technique of Semiconductor in conjunction with Bipolar Membrane water decomposition technology, concerted catalysis water decomposition hydrogen manufacturing produces the present invention
Hydrogen efficiency is up to 90 ~ 99.8%, and hydrogen purity is up to 90% ~ 99.99%, and continuous operation 10 ~ 48 hours, tank voltage, hydrogen generation efficiency base
Originally it remains unchanged, realizes efficient, the continuous operation of semiconductor powder state photochemical catalyst hydrogen production by water decomposition.
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 yin, yang pole room pH change curve in the embodiment of the present invention 1.
Figure 11 is the energy consumption figure of photoelectrocatalysis water decomposition hydrogen manufacturing in the embodiment of the present invention 1.
Figure 12 is that the production of photoelectrocatalysis water decomposition hydrogen manufacturing is carried out using supported catalyst Bipolar Membrane in the embodiment of the present invention 1
Hydrogen efficiency figure.
Figure 13 is to carry out photoelectrocatalysis water decomposition hydrogen manufacturing using unsupported catalyst Bipolar Membrane in the embodiment of the present invention 1
Hydrogen generation efficiency figure.
Specific embodiment
A specific embodiment of the invention is further illustrated below.
Embodiment 1
Using the light-catalysed Bipolar Membrane of area load powdered form as the diaphragm of cathode chamber and anode chamber（Wherein, it constitutes bipolar
The cation-exchange membrane area load Ag of film2O semiconductor light-catalyst powder, the anion exchange film surface for constituting Bipolar Membrane are negative
Carry TiO2Semiconductor light-catalyst powder）, by Ag2O semiconductor light-catalyst dusty material is as cathode, by TiO2Semiconductor light
Catalyst powder powder material is as anode, the H of 0.5 M2SO4Solution is as catholyte, and the KOH solution of 1.0 M is as anode electricity
Solve liquid；Using xenon lamp as simulated solar radiant, applied voltage is to be carried out continuously photoelectrocatalysis water decomposition under 1.0 V effect
Hydrogen manufacturing.
Hydrogen generation efficiency result is bipolar using supported catalyst under same current density as shown in attached drawing 12 and attached drawing 13
Film has bigger hydrogen generation efficiency as diaphragm than unsupported catalyst Bipolar Membrane, and especially under illumination condition, hydrogen generation efficiency is more
Height, when current density is 90 mA cm-2When, hydrogen generation efficiency is up to 98.7%；The method for utilizing chromatography of gases on-line checking simultaneously,
The purity for measuring hydrogen is 99.8%.After continuous operation 15 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and are realized and are partly led
Efficient, the continuous operation of body powdery photocatalyst hydrogen production by water decomposition.
Embodiment 2
Using the light-catalysed Bipolar Membrane of area load powdered form as the diaphragm of cathode chamber and anode chamber（Wherein, it constitutes bipolar
The cation-exchange membrane area load Ag of film2O semiconductor light-catalyst powder, the anion exchange film surface for constituting Bipolar Membrane are negative
Carry Fe2O3Semiconductor light-catalyst powder）, by Ag2O semiconductor light-catalyst dusty material is as cathode, by Fe2O3Semiconductor light
Catalyst powder powder material is as anode, the H of 0.5 M2SO4Solution is as catholyte, and the KOH solution of 0.5 M is as anode electricity
Solve liquid；Using xenon lamp as simulated solar radiant, applied voltage is to be carried out continuously photoelectrocatalysis water decomposition under 0.8 V effect
Hydrogen manufacturing.
Result of study is shown, more bipolar than unsupported catalyst using supported catalyst Bipolar Membrane under same current density
Film has bigger hydrogen generation efficiency as diaphragm, and especially under illumination condition, hydrogen generation efficiency is higher, when current density is 90 mA
cm-2When, hydrogen generation efficiency is up to 99.1%；The method for utilizing chromatography of gases on-line checking simultaneously, the purity for measuring hydrogen is 99.9%.
After continuous operation 10 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and are realized semiconductor powder state photochemical catalyst and are decomposed water
Efficient, the continuous operation of hydrogen manufacturing.
Embodiment 3
Using the light-catalysed Bipolar Membrane of area load powdered form as the diaphragm of cathode chamber and anode chamber（Wherein, it constitutes bipolar
The cation-exchange membrane area load CoO semiconductor light-catalyst powder of film, the anion exchange film surface for constituting Bipolar Membrane are negative
Carry ZnO semiconductor light-catalyst powder）, using CoO semiconductor light-catalyst dusty material as cathode, ZnO semiconductor light is urged
Agent dusty material is as anode, the H of 1.0 M2SO4Solution is as catholyte, and the KOH solution of 1.0 M is as anode electrolysis
Liquid；Using xenon lamp as simulated solar radiant, applied voltage is to be carried out continuously photoelectrocatalysis water decomposition system under 1.0 V effect
Hydrogen.
Result of study is shown, more bipolar than unsupported catalyst using supported catalyst Bipolar Membrane under same current density
Film has bigger hydrogen generation efficiency as diaphragm, and especially under illumination condition, hydrogen generation efficiency is higher, when current density is 90 mA
cm-2When, hydrogen generation efficiency is up to 99.3%；The method for utilizing chromatography of gases on-line checking simultaneously, the purity for measuring hydrogen is 99.7%.
After continuous operation 18 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and are realized semiconductor powder state photochemical catalyst and are decomposed water
Efficient, the continuous operation of hydrogen manufacturing.
Embodiment 4
Using the light-catalysed Bipolar Membrane of area load powdered form as the diaphragm of cathode chamber and anode chamber（Wherein, it constitutes bipolar
The cation-exchange membrane area load Cu of film2O semiconductor light-catalyst powder, the anion exchange film surface for constituting Bipolar Membrane are negative
Carry CdS semiconductor light-catalyst powder）, by Cu2O semiconductor light-catalyst dusty material urges CdS semiconductor light as cathode
Agent dusty material is as anode, the HClO of 0.5 M4Solution is as catholyte, and the NaOH solution of 0.5 M is as anode electricity
Solve liquid；Using xenon lamp as simulated solar radiant, applied voltage is to be carried out continuously photoelectrocatalysis water decomposition under 1.5 V effect
Hydrogen manufacturing.
Result of study is shown, more bipolar than unsupported catalyst using supported catalyst Bipolar Membrane under same current density
Film has bigger hydrogen generation efficiency as diaphragm, and especially under illumination condition, hydrogen generation efficiency is higher, when current density is 90 mA
cm-2When, hydrogen generation efficiency is up to 99.5%；The method for utilizing chromatography of gases on-line checking simultaneously, the purity for measuring hydrogen is 99.6%.
After continuous operation 16 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and are realized semiconductor powder state photochemical catalyst and are decomposed water
Efficient, the continuous operation of hydrogen manufacturing.
Embodiment 5
Using the light-catalysed Bipolar Membrane of area load powdered form as the diaphragm of cathode chamber and anode chamber（Wherein, it constitutes bipolar
The cation-exchange membrane area load NiO semiconductor light-catalyst powder of film, the anion exchange film surface for constituting Bipolar Membrane are negative
Carry SnO2Semiconductor light-catalyst powder）, using NiO semiconductor light-catalyst dusty material as cathode, by SnO2Semiconductor light is urged
Agent dusty material is as anode, the HClO of 1.0 M4Solution is as catholyte, and the NaOH solution of 1.0 M is as anode electricity
Solve liquid；Using xenon lamp as simulated solar radiant, applied voltage is to be carried out continuously photoelectrocatalysis water decomposition under 2.0 V effect
Hydrogen manufacturing.
Result of study is shown, more bipolar than unsupported catalyst using supported catalyst Bipolar Membrane under same current density
Film has bigger hydrogen generation efficiency as diaphragm, and especially under illumination condition, hydrogen generation efficiency is higher, when current density is 90 mA
cm-2When, hydrogen generation efficiency is up to 99.6%；The method for utilizing chromatography of gases on-line checking simultaneously, the purity for measuring hydrogen is 99.9%.
After continuous operation 20 hours, tank voltage, hydrogen generation efficiency are held essentially constant, and are realized semiconductor powder state photochemical catalyst and are decomposed water
Efficient, the continuous operation of hydrogen manufacturing.
Specific embodiment 1 ~ 5 described in aforementioned present invention, a kind of provided Bipolar Membrane area load powdered form catalysis
The preparation method of application of the agent in water decomposition, the Bipolar Membrane area load powdery photocatalyst 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 carried on the both side surface of Bipolar Membrane respectively, 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, concerted catalysis water decomposition hydrogen manufacturing, hydrogen generation efficiency is up to 90 ~
99.8%, hydrogen purity is up to 90% ~ 99.99%, and continuous operation 10 ~ 48 hours, tank voltage, hydrogen generation efficiency were held essentially constant, real
Efficient, the continuous operation of semiconductor powder state photochemical catalyst water decomposition hydrogen manufacturing are showed.
Claims (5)
1. a kind of application of Bipolar Membrane surface powder state photochemical catalyst in water decomposition, the application is with area load p-type half
The cation-exchange membrane of conductor photocatalyst powder and the anion-exchange membrane of area load N-type semiconductor photocatalyst powder are
Bipolar Membrane, and cathode chamber and anode chamber's diaphragm are constituted, using P-type semiconductor photocatalyst powder as cathode, by N-type semiconductor light
Catalyst fines as anode, after prepare the catholyte and anolyte of 0.5 ~ 1.0 M respectively, using xenon lamp as light
Source, applied voltage are to be carried out continuously photoelectrocatalysis water decomposition hydrogen manufacturing under 0.5 ~ 2.0 V effect.
2. application of the Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 in water decomposition, the P-type semiconductor
Photocatalyst powder is Ag2O、NiO、Cu2O, one of CoO and SnO or combinations thereof.
3. application of the Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 in water decomposition, the N-type semiconductor
Photocatalyst powder is ZnO, TiO2、Fe2O3, CdS and SnO2One of or combinations thereof.
4. application of the Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 in water decomposition, the catholyte
Liquid is H2SO4And HClO4One of solution, anolyte are one of KOH and NaOH solution.
5. application of the Bipolar Membrane surface powder state photochemical catalyst as described in claim 1 in water decomposition, the Bipolar Membrane are
It is combined by cation-exchange membrane, anion-exchange membrane.
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| CN109082677B (en) * | 2018-09-11 | 2019-09-03 | 太原师范学院 | A kind of application of the Bipolar Membrane of area load graphite alkene in photoelectrocatalysis water decomposition |
| CN111101142B (en) * | 2018-10-26 | 2021-05-18 | 中国科学院金属研究所 | Construction method of graphical integrated high-efficiency photocatalytic decomposition water system |
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