CN104340957B - Photosynthetical system two and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas - Google Patents
Photosynthetical system two and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas Download PDFInfo
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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
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a kind of method of photosynthetical system II and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, unified with nature circle photosynthetical system II high efficiency photocatalysis decompose the property of the semi-conducting material photochemical catalyzing hydrogen producing of aquatic products oxygen and carrying metal co-catalyst, it is achieved that using the full decomposition water hydrogen producing of visible ray and oxygen.In the hybrid systems of the present invention electron transmission between photosynthetical system II and semi-conducting material by iron complex, cobalt complex, 2, the reduction of 6 dichloropheno-lindophenols or quinones and oxidation cycle process are realizing, under visible light conditions, decomposition water hydrogen producing amount can reach 4075 μm of ol (being calculated as 91mL hydrogen by standard state) per hour for 1 μm of ol photosynthetical system II semiconductor hybrids system, and quantum efficiency is 0.11%.The present invention is for providing a new way using solar energy production clean fuel hydrogen.
Description
Technical field
The invention belongs to solar energy chemical conversion production clean fuel technical field, and in particular to a kind of photosynthetical system two
（II）Method with semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas.
Background technology
Growing with human society, the energy crisis and environmental problem brought by traditional Fossil fuel consumption is tight
The sustainable development of the mankind is threatened again, and the regenerative resource for developing cleaning is extremely urgent.In the middle of many clean energy resource forms,
Solar energy has the advantages that inexhaustible, cleaning is pollution-free, widely distributed, is translated into the clean fuel that can be stored and transport
It will be one of approach of Solar use.And Hydrogen Energy has heats of combustion value and zero-emission as another kind of clean energy resource form
Advantage.Therefore, it is a kind of regenerative resource of most prospect to produce clean hydrogen fuel using solar energy by photochemical catalyzing
Technology.
The oxidation of water and two processes of reduction of proton, wherein water are included using the full hydrogen production by water decomposition gas bag of solar energy photocatalytic
Oxidation be the thermodynamically reaction of energy climbing and be related to the transfer of 4 electronics, be therefore considered as current photocatalysis Decomposition
Water needs one of bottleneck problem for solving.And in nature, higher plant, algae and cyanobacteria are carried out photosynthetic using solar energy
Effect, realizes oxidation and the carbon dioxide reduction of water under mild conditions, converts solar energy into chemical energy and be stored in life
In material.At present, artificial exploitation photosynthetical system enzyme includes photosynthetical system II (abbreviation PSII) and photosynthetical system I is (referred to as
PSI) come realize solar energy conversion have potential using value.
PSII be in nature uniquely can efficiently using the biology enzyme of sun optical drive water oxygen, be higher plant,
Algae and the important component part of cyanobacteria, content are enriched very much.But, water reduction can not be produced hydrogen by photosynthesis
Gas.Therefore, sun photooxidation water is absorbed using PSII and produce oxygen and proton, proton reduction is produced by artificial catalysis material
Hydrogen is to build the desirable route that solar energy changes into Hydrogen Energy.
At present, PSII is coupled with electrode material Optical Electro-Chemistry decomposition water is realized it has been reported that for example：
(1) a kind of patent US20100200049A1 of Kufryk et al. applications, it was recently reported that electrode hybrid based on PSII
It is the method that produces photogenerated current and hydrogen.
(2) Rao et al. reports, will be quick to dyestuff for the electron transmission of PSII with from the detached PSII of spinach as water oxidation material
The TiO of change2In light anode, it is that electrode is generated under the bias and illumination condition of relative saturation calomel electrode 0.2V with platinized platinum
35μA cm-2Photoelectric current (Rao, K.K.;Hall,D.O.;Vlachopoulos,N.;M.;Evans,M.C.W.;
Seibert,M.Journal of Photochemistry and Photobiology B:Biology1990,5,379-
389.).
(3) Kato et al. reports a kind of light anode hybrid material of water oxygen, by the PSII and mesoporous ITO of cyanobacteria
Electro-conductive glass is constituted, and under red light irradiation, water oxygen galvanic current is 1.6 ± 0.3 μ A cm-2(Kato,M.;Cardona,T.;
Rutherford,A.W.;Reisner,E.Journal of the American Chemical Society2012,134,
8332-8335.).
But, conventional report is all the structure that Optical Electro-Chemistry decomposes aqueous systems, and illumination in the presence of outer biasing is produced
Generated photo-current, produces hydrogen on negative electrode.The following problem of the method generally existing：
(1) need additional certain bias to promote separation of charge and increase to put hydrogen potential, cause the loss of electric energy；
(2) PSII electrodes hybrid material effectively can not produce oxygen by decomposition water, and side reaction is serious, causes material to lose quickly
Living；
(3) cause the electronics can not effectively to the table of electrode material as PSII is shifted in cross-film mode by the electronics on side
Face is transmitted, so that decomposition water is less efficient；
(4) preparation of PSII electrodes hybrid material is complicated, photoelectric current is low, working life is very poor.
In sum, PSII active high, prepare simple, abundance and pollution-free the advantages of, be to utilize the sun
How the ideal material of water oxygen efficiently can be coupled full decomposition hydrogen producing and oxygen that PSII and semi-conducting material enter water-filling
Many difficult problems are still suffered from, and need to build hybrid systems Efficient Conversion solar energy to be realized into Hydrogen Energy with thinking from new angle
Target.
Content of the invention
It is an object of the invention to provide a kind of photosynthetical system II and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas
Method.
The present invention is by photosynthetical system II（Abbreviation PSII）With semiconductor light-catalyst direct-coupling and it is dispersed in containing electronics
In the cushioning liquid of carrier, under visible ray illumination, it is not necessary to applying bias and be not added with any sacrifice reagent in the case of, realize
The full hydrogen production by water decomposition gas of photocatalysis and oxygen.Wherein water oxygenization produces the reaction of oxygen and proton and is completed by PSII, proton also
Originating in raw hydrogen is carried out at semiconductor light-catalyst end, and the electro transfer between PSII and semiconductor is come in fact by electron carrier
Existing.Its basic process is：
PSII absorbs light： H2O→O2+H+
Semiconductor absorber light： H+→H2
Overall reaction： H2O→H2+O2
The invention provides a kind of method of photosynthetical system II and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, will
The semiconductor light-catalyst of carrying metal co-catalyst is dispersed in cushioning liquid, under weaker nonactive optical condition, is added
Certain density electron carrier, adds photosynthetical system II, closed system to take out in the state of stirring true after electron carrier dissolving
Sky, it is 5～35 DEG C to adjust reaction temperature using temperature control device, and the full hydrogen production by water decomposition gas of photocatalysis and oxygen are realized in then illumination.
The gas of generation is by online gas chromatographic detection content.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided, the light
Syzygy system II is prepared with Leaves of The Higher Plants, algae or cyanobacteria as raw material separation.These raw materials are in different pH value
Cushioning liquid in by clasmatosis, be centrifuged at a high speed or chromatography, detergent cutting protection etc. step obtain light
Syzygy system II.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided, described half
Conductor photochemical catalyst is sulfide, oxide, nitride, selenides, elemental silicon, oxysulfide or nitrogen oxides.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided, the gold
Category co-catalyst is the one kind or several in the sulfide of Pt, Pd, Ru, Rh, Ni, Mo, Cd, Pb, Co, Au, Ag and these metals
Kind.Deposited or impregnated by photo-reduction reduction to be prepared from.Loading of the co-catalyst on semiconductor light-catalyst be 0.1～
1.0wt%.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided, the electricity
Subcarrier be iron complex, cobalt complex, 2,6- dichloropheno-lindophenols and quinones one or more.The electron carrier
Concentration is 0.01～50mM；Specially iron complex（0.1～50mM）, cobalt complex（0.1～50mM）, 2,6- dichloropheno-lindophenols
（0.1～30mM）Or quinones（0.01～20mM）.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided, the iron
Complex compound is ferrocene, the potassium ferricyanide, the one kind in potassium ferrocyanide；Cobalt complex is six amino cobalt chlorides, benzyltriphenylphosphonium chloride
One kind in cobalt, terpyridyl cobalt chloride；Quinones be methyl-p-benzoquinone, phenyl-p- benzoquinones, 2,6- dichloro quinones, 2,
One or more in 6- phlorones, duroquinone.
Photosynthetical system II and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas that the present invention is provided are described slow
Rush solution for phosphate, citrate, succinate, boric acid, 4- (2- ethoxys) piperazine -1- ethyl sulfonic acids, 4- morpholino b acids,
The aqueous solution of one or more in three (methylol) aminomethane hydrochloride；Its concentration is 5～100mM.The pH of cushioning liquid
For 5.0～9.0.
The present invention provide photosynthetical system II and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas method, described can
Any one in the light and sunshine that light sends is seen for xenon lamp, Halogen lamp LED, solar simulator；Its wave-length coverage be more than
420nm.
The present invention by photosynthetical system II and semi-conducting material direct-coupling and is dispersed in the cushioning liquid containing electron carrier
In, under conditions of visible ray illumination, it is not necessary to applying bias and sacrifice reagent, using the full hydrogen production by water decomposition gas of solar energy and oxygen
The method of gas, will not be to environment.
Description of the drawings
X-ray powder diffraction spectrograms of the Fig. 1 for CdS photochemical catalysts；
Fig. 2 is SrTiO3:The X-ray powder diffraction spectrogram of Rh photochemical catalysts；
Fig. 3 is PSII-Ru/SrTiO3:The optical microscopy map of Rh hybrid systems；
Fig. 4 is PSII-Ru2S3The photochemical catalyzing activity time curve map of/CdS hybrid systems；
Fig. 5 is PSII-Ru/SrTiO3:The photochemical catalyzing activity time curve map of Rh hybrid systems；
Fig. 6 is PSII-Ru/SrTiO3:The photochemical catalyzing activity time curve map of Rh hybrid systems；
Fig. 7 is PSII-Ru/SrTiO under low light intensity3:The photochemical catalyzing activity time curve map of Rh hybrid systems；
Fig. 8 is PSII-Pt/SrTiO3:The photochemical catalyzing activity time curve map of Rh hybrid systems；
Photochemical catalyzing activity time curve maps of the Fig. 9 for PSII-PdS/CdS hybrid systems；
Figure 10 is PSII-Ru/SrTiO under different pH value3:The photochemical catalyzing activity time curve of Rh hybrid systems
Figure；
Figure 11 is PSII-Ru/Sm2Ti2S2O5The photochemical catalyzing activity time curve map of hybrid systems；
Photochemical catalyzing activity time curve maps of the Figure 12 for PSII-Ni/CdSe hybrid systems；
Figure 13 is PSII-Co/LaTiO2The photochemical catalyzing activity time curve map of N hybrid systems.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
This example demonstrates that the step of separating PSII from spinach dish leaf：
Fresh spinach is cleaned up, removes petiole, leave intact greenery, a certain amount of greenery are taken according to 1mL:1g's
Ratio adds solution（50mM HEPES-NaOH,400mM NaCl,2mM MgCl2,1mM EGTA,2mg/ml BSA,pH7.5）,
With juice extractor cutting greenery to sufficiently fine to form slurries, slurries through filtered through gauze, filtrate be sub-packed in 250mL centrifugal bottles from
The heart, adds appropriate solution to sediment（20mM MES-NaOH,150mM NaCl,4mM MgCl2,pH6.0）After be homogenized, slurries
Taking precipitate after 12000G centrifugations, adds appropriate solution（50mM MES-NaOH,15mM NaCl,5mM MgCl2,pH6.0）
After be homogenized, be slowly added to Triton X-100 detergents and sway 30 minutes, slurries through 50000G be centrifuged, the green of taking precipitate
Part, uses solution（50mM MES-NaOH,15mM NaCl,400mM Sucrose,pH6.0）It is centrifuged after cleaning sediment repeatedly,
Finally obtain certain density PSII.
Embodiment 2
The present embodiment evaluates decomposition aquatic products oxygen activities of the PSII in different pH value cushioning liquid.
Take 100mL cushioning liquid to be placed in reactor, under the conditions of weaker green glow, add certain density electron carrier
Stirring dissolves which, is then slowly added into a certain amount of PSII, and stirring makes which be uniformly dispersed, vacuumizes, make under the conditions of lucifuge
The temperature that reaction system is controlled with water circulating pump, carries out illumination using xenon lamp, and incident using optical filter and the control of optical filtering water jacket
The wave-length coverage of light, reacts the hydrogen and oxygen that produce by gas-chromatography on-line checking content.
Its reaction result such as table 1：
Table 1
In above-mentioned reaction, cushioning liquid is 50mM dibastic sodium phosphates-sodium dihydrogen phosphate and 5mM potassium hydrogen phosphates-biphosphate
Aqueous solutions of potassium；Electron carrier is the potassium ferricyanide, and concentration is 5mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；
Xenon source wavelength X>420nm, luminous intensity are 250mW cm-2.
Embodiment 3
This example demonstrates that the preparation process of CdS photochemical catalysts used by PSII and semiconductor hybrid system：
CdS semiconductor photochemical catalyst is synthesized using precipitation hydro-thermal method, by the Na of 0.14M under stirring2The S aqueous solution delays
The Cd (OAc) of 0.14M is added drop-wise to slowly2After the aqueous solution forms precipitation, stand 24h after continuing stirring 24h again and then filter, by filter cake
Load water heating kettle hydro-thermal process 72h at 200 DEG C, be vacuum dried after filtration washing and CdS samples are obtained（Its crystalline state is as schemed
1）.
Embodiment 4
This example demonstrates that co-catalyst is supported on CdS photochemical catalysts：
Using the method supported co-catalyst of light deposition, in the Na of 0.5M2RuCl is added after dispersion CdS in the S aqueous solution3Water
Solution, the loading of Ru are 0.2wt% relative to CdS, dry Ru is obtained after evacuations → illumination → be washed with deionized2S3/
CdS;Na in 0.5M2PdCl is added after dispersion CdS in the S aqueous solution2The aqueous solution, the loading of Pd is 0.2wt% relative to CdS,
Prepared PdS/CdS is dried after evacuation → illumination → be washed with deionized.
Embodiment 5
This example demonstrates that SrTiO used in PSII and semiconductor hybrid system3:The preparation process of Rh photochemical catalysts：
Semiconductor SrTiO3:Rh photochemical catalysts are synthesized using high temperature solid-state method.By SrCO3、TiO2And Rh2O3With 1.03:
0.99:0.01 ratio is well mixed, and synthesizes to obtain SrTiO in 1100 DEG C of roasting temperature 10h3:Rh（Its crystalline state such as Fig. 2）.
Embodiment 6
This example demonstrates that SrTiO3:On Rh photochemical catalysts, co-catalyst supports：
Using light deposition method supported co-catalyst in situ, disperse SrTiO in the methanol aqueous solution of 20v%3:Add after Rh
Enter H2PtCl6·6H2The loading of O, Pt is relative to SrTiO3:Rh is 0.3wt%, after evacuation → illumination → be washed with deionized
Dry prepared Pt/SrTiO3:Rh；Disperse SrTiO in the methanol aqueous solution of 20v%3:RuCl is added after Rh3, the loading phase of Ru
For SrTiO3:Rh is 0.5wt%, dries prepared Ru/SrTiO after evacuation → illumination → be washed with deionized3:Rh.
Embodiment 7
The present embodiment evaluates the Photocatalyzed Hydrogen Production gas activity of the semiconductor light-catalyst of carrying metal co-catalyst.
Take 100mL cushioning liquid to be placed in reactor, adding the semiconductor light-catalyst ultrasound of certain mass and stirring makes
Which is dispersed in the solution, under the conditions of weaker green glow, adds certain density electron carrier stirring to dissolve which, is keeping away
Vacuumize under optical condition, the temperature for controlling reaction system using water circulating pump carries out illumination using xenon lamp, and using optical filter and
Optical filtering water jacket controls the wave-length coverage of incident light, reacts the hydrogen and oxygen that produce by gas-chromatography on-line checking content.
Its reaction result such as table 2：
Table 2
| Semiconductor light-catalyst | Hydrogen producing activity (μm ol/h) |
| Ru2S3/CdS | 68.6 |
| PdS/CdS | 81.4 |
| Pt/SrTiO3:Rh | 54.2 |
| Ru/SrTiO3:Rh | 47.5 |
In above-mentioned reaction, cushioning liquid is 10mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM dibastic sodium phosphates-phosphorus
Acid dihydride sodium water solution, pH=7.0；The quality of semiconductor light-catalyst is 0.1g；Electron carrier is potassium ferrocyanide, and concentration is
5mM；Temperature is maintained at 25 DEG C；Xenon source wavelength X>420nm, luminous intensity are 250mW cm-2.
Embodiment 8
The present embodiment evaluates PSII-Ru2S3Photocatalysis of/CdS the hybrid systems with the potassium ferricyanide and duroquinone as electron carrier point
Solution water activity.
Take 100mL cushioning liquid to be placed in reactor, adding the semiconductor light-catalyst ultrasound of certain mass and stirring makes
Which is dispersed in the solution, under the conditions of weaker green glow, adds certain density electron carrier stirring to dissolve which, then
A certain amount of PSII is slowly added to, stirring makes which be uniformly dispersed, vacuumizes under the conditions of lucifuge, using water circulating pump control reaction
The temperature of system, then carries out illumination, and using optical filter and the wave-length coverage of optical filtering water jacket control incident light, reaction is produced
Hydrogen and oxygen pass through gas-chromatography on-line checking content.Its reaction result such as Fig. 4.
In above-mentioned reaction, cushioning liquid is tri- (methylol) aminomethane hydrochlorides of 10mM and 5mM boric acid aqueous solutions, pH
=8.0；Semiconductor light-catalyst Ru2S3The quality of/CdS is 0.1g；Electron carrier is that the potassium ferricyanide and duroquinone, concentration are respectively
20mM and 0.5mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Xenon source wavelength X>420nm, luminous intensity
For 250mW cm-2.
Embodiment 9
The present embodiment evaluates PSII-Ru/SrTiO using the scheme of embodiment 83:Rh hybrid systems with phenyl-p- benzoquinones and
Photochemical catalyzing activity of the methyl-p-benzoquinone for electron carrier.Its reaction result such as Fig. 5, form such as Fig. 3 of hybrid systems.
In above-mentioned reaction, cushioning liquid is 10mM4- morpholino b acids and 5mM disodium succinates, pH=5.5；Semiconductor
Photochemical catalyst Ru/SrTiO3:The quality of Rh is 0.1g；Electron carrier is that phenyl-p- benzoquinones and methyl-p-benzoquinone, concentration are respectively
1.0mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Halogen light source wavelength X>420nm, luminous intensity is
250mW·cm-2.
Embodiment 10
The present embodiment evaluates PSII-Ru/SrTiO using the scheme of embodiment 83:Rh hybrid systems are with 2,6- Dichlorophenol indigo
Phenol and benzyltriphenylphosphonium chloride cobalt are active for the photochemical catalyzing of electron carrier.Its reaction result such as Fig. 6.
In above-mentioned reaction, cushioning liquid is 15mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM sodium citrates-lemon
Lemon acid potassium, pH=6.5；Semiconductor light-catalyst Ru/SrTiO3:The quality of Rh is 0.1g；Electron carrier is 2,6- dichloropheno-lindophenols
With benzyltriphenylphosphonium chloride cobalt, concentration respectively 1.0mM and 10mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；
Halogen light source wavelength X>420nm, luminous intensity are 250mW cm-2.
Embodiment 11
Scheme of the present embodiment using embodiment 8, evaluates PSII-Ru/SrTiO under solar simulator illumination3:Rh is miscellaneous
The photochemical catalyzing activity of change system.Its reaction result such as Fig. 7.
In above-mentioned reaction, cushioning liquid is 15mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM sodium citrates-lemon
Lemon acid potassium, pH=6.5；Semiconductor light-catalyst Ru/SrTiO3:The quality of Rh is 0.1g；Electron carrier is 2,6- dichloropheno-lindophenols
With benzyltriphenylphosphonium chloride cobalt, concentration respectively 1.0mM and 10mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；
Solar simulator optical source wavelength λ>420nm, luminous intensity are less than 100mW cm-2.
Embodiment 12
The present embodiment evaluates PSII-Pt/SrTiO using the scheme of embodiment 83:The photochemical catalyzing of Rh hybrid systems
Activity.Its reaction result such as Fig. 8.
In above-mentioned reaction, cushioning liquid is 10mM4- morpholino b acids and 5mM disodium succinates, pH=5.5；Semiconductor
Photochemical catalyst Pt/SrTiO3:The quality of Rh is 0.1g；Electron carrier is that phenyl-p- benzoquinones and methyl-p-benzoquinone, concentration are respectively
1.0mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Sunshine optical source wavelength λ>420nm.
Embodiment 13
Photochemical catalyzing activity of the present embodiment using the scheme evaluation PSII-PdS/CdS hybrid systems of embodiment 8.
Its reaction result such as Fig. 9.
In above-mentioned reaction, cushioning liquid is that tri- (methylol) aminomethane hydrochlorides of 15mM and 10mM boric acid are water-soluble
Liquid, pH=8.5；The quality of semiconductor light-catalyst PdS/CdS is 0.1g；Electron carrier is six amino cobalt chlorides and 2,6- dichloros
Benzoquinones, concentration are respectively 20mM and 0.5mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Xenon source ripple
Long λ>420nm, luminous intensity are 250mW cm-2.
Embodiment 14
The present embodiment evaluates PSII-Ru/SrTiO using the scheme of embodiment 83:Rh hybrid systems with phenyl-p- benzoquinones and
Methyl-p-benzoquinone is electron carrier photochemical catalyzing activity at various ph values.Its reaction result such as Figure 10.
In above-mentioned reaction, cushioning liquid be respectively [10mM4- morpholino b acids and 10mM disodium succinates, pH=6.0],
[10mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM dibastic sodium phosphates-biphosphate sodium water solution, pH=7.0], [10mM tri-
(methylol) aminomethane hydrochloride and 10mM sodium dihydrogen phosphates-potassium dihydrogen phosphate aqueous solution, pH=7.5]；Conductor photocatalysis
Agent Ru/SrTiO3:The quality of Rh is 0.1g；Electron carrier is phenyl-p- benzoquinones and methyl-p-benzoquinone, and concentration is respectively 1.0mM；
The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Xenon source wavelength X>420nm, luminous intensity are 250mW cm-2.
Embodiment 15
The present embodiment evaluates PSII-Ru/Sm using the scheme of embodiment 82Ti2S2O5The photochemical catalyzing of hybrid systems
Activity.Its reaction result such as Figure 11.
In above-mentioned reaction, cushioning liquid is 15mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM sodium citrates-lemon
Lemon acid potassium, pH=6.5；Semiconductor light-catalyst Ru/Sm2Ti2S2O5Quality be 0.1g；Electron carrier is 2,6- dichloropheno-lindophenols
With 2,6- phlorones, concentration is respectively 1.0mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Xenon lamp
Source wavelength λ>420nm, luminous intensity are 250mW cm-2.
Embodiment 16
Photochemical catalyzing activity of the present embodiment using the scheme evaluation PSII-Ni/CdSe hybrid systems of embodiment 8.
Its reaction result such as Figure 12.
In above-mentioned reaction, cushioning liquid is 10mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM dibastic sodium phosphates-phosphorus
Acid dihydride sodium water solution, pH=7.0；The quality of semiconductor light-catalyst Ni/CdSe is 0.1g；Electron carrier is the potassium ferricyanide, dense
Degree is 5mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；Xenon source wavelength X>420nm, luminous intensity is
250mW·cm-2.
Embodiment 17
The present embodiment evaluates PSII-Co/LaTiO using the scheme of embodiment 82The photochemical catalyzing of N hybrid systems is lived
Property.Its reaction result such as Figure 13.
In above-mentioned reaction, cushioning liquid is 10mM4- (2- ethoxys) piperazine -1- ethyl sulfonic acids and 5mM dibastic sodium phosphates-phosphorus
Acid dihydride sodium water solution, pH=7.0；Semiconductor light-catalyst Co/LaTiO2The quality of N is 0.1g；Electron carrier is 2,6- dichloros
Phenol indophenols and 2,6- phlorone, concentration are respectively 1.0mM；The corresponding 1mg chlorophyll of the consumption of PSII；Temperature is maintained at 25 DEG C；
Halogen light source wavelength X>420nm, luminous intensity are 250mW cm-2.
Claims (9)
1. a kind of method of photosynthetical system II and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, it is characterised in that：By light
The semi-conducting material direct-coupling of syzygy system II and carrying metal co-catalyst is simultaneously dispersed in the cushioning liquid containing electron carrier
In, under conditions of visible ray illumination, it is not necessary to applying bias, realize the full hydrogen production by water decomposition gas of photocatalysis and oxygen.
2. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The photosynthetical system II is that raw material separation is prepared by higher plant, algae or cyanobacteria.
3. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The metal promoters are the sulphur of Pt, Pd, Ru, Rh, Ni, Mo, Cd, Pb, Co, Au, Ag and these metals
One or more in compound.
4. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The semi-conducting material is sulfide, oxide, nitride, selenides, elemental silicon, oxysulfide or nitrogen oxygen
Compound.
5. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The electron carrier be iron complex, cobalt complex, 2,6- dichloropheno-lindophenols and quinones in one kind or
Several.
6. according to photosynthetical system II described in claim 5 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The concentration of the electron carrier is 0.01mM～50mM.
7. in the method according to photosynthetical system II described in claim 5 and semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas
Electron carrier, it is characterised in that：The iron complex is ferrocene, the potassium ferricyanide, the one kind in potassium ferrocyanide；
Cobalt complex is six amino cobalt chlorides, benzyltriphenylphosphonium chloride cobalt, the one kind in terpyridyl cobalt chloride；
Quinones be methyl-p-benzoquinone, phenyl-p- benzoquinones, 2,6- dichloro quinones, 2,6- phlorones, in duroquinone one
Plant or several.
8. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The cushioning liquid is phosphate, citrate, succinate, boric acid, 4- (2- ethoxys) piperazine -1- second sulphurs
Acid, 4- morpholino b acids, the aqueous solution of one or more in three (methylol) aminomethane hydrochloride.
9. according to photosynthetical system II described in claim 1 and the method for semiconductor hybrid system photocatalytic hydrogen production by water decomposition gas, its
It is characterised by：The visible ray is any one in the light that xenon lamp, Halogen lamp LED, solar simulator send and sunshine；
Its wave-length coverage is more than 420nm.
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| BE1023865B1 (en) * | 2016-02-23 | 2017-08-24 | H2Win S.A. | PHOTO-CATALYTIC DEVICE FOR THE PRODUCTION OF HYDROGEN GAS |
| CN106179410A (en) * | 2016-07-01 | 2016-12-07 | 上海电力学院 | A kind of photocatalyst of photocatalytic hydrogen production by water decomposition and preparation method thereof |
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| CN108100993B (en) * | 2018-01-16 | 2021-03-26 | 河北工业大学 | Method for generating hydrogen by photolyzing water by combining blue algae with p-n composite catalyst |
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