CN104762634A - Photoelectrode for producing hydrogen and oxygen by photoelectro-chemically decomposing water, preparation and application thereof - Google Patents

Photoelectrode for producing hydrogen and oxygen by photoelectro-chemically decomposing water, preparation and application thereof Download PDF

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CN104762634A
CN104762634A CN201510119013.5A CN201510119013A CN104762634A CN 104762634 A CN104762634 A CN 104762634A CN 201510119013 A CN201510119013 A CN 201510119013A CN 104762634 A CN104762634 A CN 104762634A
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oxygen
photocathode
product
hydrogen
quantum dot
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CN104762634B (en
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吴骊珠
刘宾
李旭兵
李剑
高雨季
李治军
佟振合
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Technical Institute of Physics and Chemistry of CAS
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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
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • 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
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

A photoelectrode for producing hydrogen and oxygen by photoelectro-chemically decomposing water is characterized in that the photoelectrode is composed of a photocathode and a photoanode, wherein the photocathode and a photoanode are provide with quantum dots being assembled with assistance of a double-functional molecule. The invention achieves the establishment and the application of the photoelectrode for producing hydrogen and oxygen on the basis of semiconductors, quantum dots and catalysts. The photoelectrode is high in stability, is free of a sacrificial agent, is simple in operation, is good in repeatability, is strong in universality and is high in utilization rate on visible light. In addition, the catalyst is free of requirement of noble metals, is low in cost and is easy to obtain.

Description

Photoelectrochemistry decomposes aquatic products hydrogen, the optoelectronic pole producing oxygen and Synthesis and applications thereof
Technical field
The present invention relates to photoelectrocatalysis water of decomposition field.More specifically, relate to a kind of photoelectrochemistry based on p-type and n-type semiconductor substrate, quantum dot and catalyzer and decompose aquatic products hydrogen, produce oxygen optoelectronic pole, and Synthesis and applications.
Background technology
Along with the develop rapidly of economy, the mankind increase day by day for the demand of the energy.The main energy that fossil energy consumes as the world today, once appeared remarkable contribution on the road of human industryization development.But along with the lasting exploitation of the mankind, the exhaustion of fossil energy is inevitable.Related data shows, and most fossil energy will be exploited totally within the centuries; On the other hand, the environmental problem that the consumption of fossil energy is adjoint also receives the mankind and more and more payes attention to.Therefore, development and utilization is green, continuable novel energy (as sun power, biomass energy, nuclear energy, wind energy etc.), improves its ratio in whole energy structure extremely urgent.In numerous novel energies, sun power, with its aboundresources, not only can freely to have used but also without the need to transport, and did not produce the advantages such as any environmental pollution and attracted increasing concern.Although the total resources of sun power be equivalent to current mankind utilize more than 10,000 times of the energy, its exist energy density very low, because of time and the shortcoming becoming, vary in different localities, therefore very large challenge is caused to the exploitation of sun power.Consider above-mentioned limiting factor, people are more prone to find a kind of effective approach and convert solar energy into chemical energy, electric energy etc., and are concentrated storage thus utilize.In numerous sun power path for transformation, directly converting solar energy into the photocatalytic water approach of hydrogen and the oxygen chemical energy that is carrier is one of mode of greatest concern.In the reaction of photocatalytic water, oxidising process can produce oxygen, and it is the root of current species diversity; Reduction process can produce hydrogen, and it is considered to the clean energy of the great potential of high-energy-density.With regard to China, sun power and water resources are all abundanter, and therefore sun power photocatalytic water method has very vast potential for future development.
Semiconductor nano (quantum dot) has that specific absorbance is large, band gap is adjustable, with the advantage such as solar spectrum mates, the research of the Photocatalyzed Hydrogen Production system in recent years using it as light absorbing material also achieves huge progress.But, adding a large amount of electronics sacrificial body based on all needing in the Photocatalyzed Hydrogen Production system of quantum dot at present, which greatly limits its further practical application.Photoelectrocatalysis water of decomposition provides a kind of method avoiding using sacrificial reagent.Compared to the photocatalysis Decomposition aqueous systems in solution, photoelectricity system can realize the full decomposition of water, and the generation of hydrogen and oxygen betides negative electrode and anode respectively, and no coupling product produces, and has a good application prospect for suitability for industrialized production.But still there is a lot of problem in current photoelectrocatalytioxidation oxidation system, such as its effciency of energy transfer still very low, system cost is higher, therefore is difficult to use in actual production.Therefore more deep research is carried out to photoelectrocatalysis water of decomposition system and there is very major and immediate significance.
In photoelectricity system, light anode generally uses n-type semiconductor, and wherein studying is TiO the most widely 2.Since Honda and Fujishima in 1972 utilizes TiO 2electrode, achieve the decomposition of water under the irradiation of UV-light since, the researcher of various countries utilizes TiO 2do the research of a large amount of photoelectrochemistry hydrogen production by water decomposition.But TiO 2be a kind of wide bandgap material (3.2eV), only can absorb UV-light contained little in sunlight.This character makes single TiO 2electrode phototranstormation efficiency is very low, needs to expand TiO by suitable method 2light absorption range, as doping, sensitization etc.Quantum dot is a kind of excellent sensitized material, and professor Kamat has been a large amount of quantum dot sensitized TiO 2research, by bifunctional molecule, quantum dot is connected to TiO 2on, on mensuration quantum dot, light induced electron is to TiO 2rate of injection, by adjustment quantum dot TiO 2the ligand modified function of the Charger transfer of interface and quantum point, improves device performance (J.Phys.Chem.C 2013,117,14418-14426; J.Am.Chem.Soc.2006,128,2385-2393; J.Phys.Chem.Lett.2012,3,663-672; Proc.Nat.Acad.Sci.U.S.A.2011,108,29-34).But that the work of Kamat professor is mainly paid close attention to is quantum dot sensitized TiO 2the solar cell of type, does not carry out the research of water of decomposition.2013, professor Bisquert etc. (Adv.Energy Mater.2013,3,176-182) adopted the mode of chemical thought that CdSe quantum dot is deposited to TiO 2on, constructed the light anode producing hydrogen, theoretical hydrogen-producing speed reaches 20ml/ (cm 2day 1).At present, the light anode architectures based on quantum dot is mode of so constructing (ACS Appl.Mat.Interfaces2013,5,1113-1121 mostly; Chem.Mater.2010,22,922-927; J.Phys.Chem.C 2011,115,25429-25436; J.Mater.Chem.2011,21,8749-8755 etc.), but this kind of system be all have in electrolyte solution sacrifice reagent condition under produce hydrogen, what therefore carry out is in fact the half-reaction of water of decomposition.When not sacrificing reagent, quantum dot, as light anodic oxidation water, also exists perishable, the problem of poor stability, and the progress of this respect is slower.2010, CdTe quantum is adsorbed onto on ZnO nano-wire by Thiovanic acid by Liu etc. (Angew.Chem.Int.Ed.2010,49,5966-5969), prepare the light anode of water of decomposition, but hydrogen and oxygen really do not detected in their system.Therefore, development is efficient, stable, cheap, and the real light anode decomposing aquatic products oxygen of realization is still a difficult task in the system without the need to adding sacrifice reagent.
On the other hand, photocathode generally uses p-type semiconductor material, because the kind of p-type semiconductor material is very limited, is therefore a meaningful and challenging job for the research of photocathode.At present, the work of photocathode mainly p-type silicon and Cu 2o system.P-type silicon photocathode not rarely seen (EnergyEnviron.Sci.2011,4,1690-1694; Nano Lett.2012,12,298-302; Nat.Mater.2011,10,434-438; ACS Appl.Mat.Interfaces 2014,6,12111-12118 etc.), wherein most representative, Ib Chorkendorff etc. (Nat.Mater.2011,10,434-438) modify Mo on p-type silicon 3s 4bunch photocathode the constructed sun power achieved more than 10% forwards the transformation efficiency of Hydrogen Energy to, but the manufacturing cost of p-type silicon is very high, have impact on the prospect of its large-scale application.Cu 2the problem of O photocathode is that stability is too poor, and making progress maximum in the research of enhanced stability is Switzerland professor study group.They are (Nat.Mater.2011,10,456-461; Angew.Chem.Int.Ed.2014,54,664-667) propose a kind of Cu 2o Preservation tactics, namely passes through the mode of ald at Cu 2znO and TiO of the Al doping of O upper depositing nano level thickness 2, successfully improve Cu 2the stability of O.Although protective layer inhibits Cu 2the photoetch of O, but its preparation needs higher instrument condition, operates also more complicated.Quantum dot is applied to the work (Angew.Chem.Int.Ed.2010 that photocathode starts from the people such as professors Pickett in 2010,49,1574-1577), they utilize two thiol molecule to be modified on gold electrode by InP quantum dot as connection molecule and have constructed quantum dot light cathode systems, but the cathode photo current of this system (receive peace) and photoelectrocatalysis hydrogen output (nmole) very low, the synthesis condition of photosensitizers InP is harsh simultaneously, toxicity is comparatively large, and these deficiencies all limit its further application and development.Henceforth, quantum dot light negative electrode rarely has report.Until 2013, professor Domen etc. (J.Am.Chem.Soc.2013,135,3733-3735) adopt chemical bath deposition by CdS nanoparticle deposition at p-type CuGaSe 2on semi-conductor, modify Pt further and constructed photocathode as product hydrogen promotor, this photocathode shows very high stability (more than 10 days); 2014, they reported Pt/TiO again at group 2/ CdS/CuInS 2photocathode (Angew.Chem.Int.Ed.2014,53,11808-11812).But this type of system Problems existing is CuGaSe 2or CuInS 2semi-conductor needs to adopt the mode of atomic shell evaporation to prepare, high to equipment requirements, complicated operation, and with Pt as catalyzer, cost is high.
In recent years, as a kind of cheap p-type semiconductor, NiO is subject to the people's attention gradually, due to NiO greater band gap (Eg=3.5eV), needs to adopt suitable dyestuff to carry out sensitization to expand its utilization to sunlight to it.2011, (the Chem.Commun.2012 such as Sun Licheng, 48,988-990) first organic dye (P1) is connected on NiO, and uses cobalt oxime complex as promotor, constructed the NiO photocathode of first case based on molecular photoactive agent and molecular catalyst, but the ligation of its catalyzer and NiO is more weak, in operation, easily come off from electrode, affect electrode performance.2013, (the J.Am.Chem.Soc.135 such as Wu Yiying, 32,11696-11699) bifunctional Ru title complex is adopted to make photosensitizers, achieve and be connected with the chemistry of NiO electrode and Co composition catalyst, avoid coming off of catalyzer, therefore electrode shows higher stability.Organic dye molecule is the sensitizing agent that NiO photocathode often adopts, but organic dye synthesis is complicated, with high costs, and less stable.(the ACS Catalysis 2015 such as Richard professor Eisenberg, DOI:10.1021/cs5021035) CdSe quantum dot is chemically adsorbed on NiO, prepare CdSe/NiO electrode, and carry out the H-H reaction of photoelectricity product at the cooperation produce hydrogen catalyst of cobalt or nickel, but the obvious problem that this system exists runs to need in the electrolyte solution of organic solvent acetonitrile.2014, Liu etc. (ACS Nano 2014,8,10403-10413) were by IrO xnH 2o/CdS/TiO 2light anode and NiS/CdSe/NiO photocathode are together in series, prepare the water of decomposition battery of two light absorbing zone, but the load of its quantum dot is respectively by electrochemical deposition and chemical bath deposition mode, be difficult to control the size of quantum dot and charge capacity on the semiconductor and distribution.Simultaneously when not adding passivation layer and catalyzer, the efficiency of system and less stable; In addition, this system is prepared loaded down with trivial details, IrO xcatalyzer price is high.Therefore, the photoabsorption that development preparation is simple, cheap, stable material strengthens nickel oxide or other p-type semiconductor, the photoelectricity H2-producing capacity improving photocathode also has a lot of work to do.Desirable photoelectrochemistry decomposes aquatic products hydrogen, the optoelectronic pole of product oxygen should possess the advantage that preparation is simple, efficiency is high, reproducible, stability is high, catalyzer is cheap, universality is strong.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of optoelectronic pole; it can realize photoelectric decomposition aquatic products hydrogen efficiently and stably without the need to sacrifice agent, protective layer and buffered soln, produce oxygen; realize the conversion of luminous energy to chemical energy, and there is the advantage that preparation is simple, efficiency is high, reproducible, high to the transformation efficiency of visible ray, stability is high, catalyzer is cheap, universality is strong.
For solving first technical problem, the invention provides following technical scheme:
Photoelectrochemistry is decomposed aquatic products hydrogen, is produced an optoelectronic pole for oxygen, and it is characterized in that, described optoelectronic pole comprises photocathode and light anode, and described photocathode and light anode have the quantum dot of being assisted assembling by bifunctional molecule.
Preferably, one or more in described bifunctional molecule selected from mercapto phosphoric acid, mercaptan carboxylic acid, the amino acid containing sulfydryl, the polymer containing sulfydryl, the polypeptide containing sulfydryl, two carboxyl molecule, pyridine carboxylic acid and thiophene acetic acid.Described bifunctional molecule can be used as connection molecule, and what have also can be used as electronics or hole transport relaying body.In described smooth anode, bifunctional molecule is as connection molecule, and what have also can be used as electric transmission relaying body.In described photocathode, bifunctional molecule is as connection molecule, and what have also can be used as hole transport relaying body.
Preferably, the type of described auxiliary assembling is chemisorption, and described chemisorption is realized by bifunctional molecule.
Preferably, the quantum dot of described photocathode has and produces hydrogen catalyst or produce hydrogen catalyst precursor, wherein said product hydrogen catalyst or to produce hydrogen catalyst precursor be that other non-quantum point in quantum dot itself or load produces hydrogen catalyst or product hydrogen catalyst precursor.
Preferably, the quantum dot load on described smooth anode has produces oxygen catalyst or produces oxygen catalyst precursor.
Preferably, described quantum dot is water-soluble quantum dot or oil soluble quantum dot, preferably, described quantum dot is selected from one or more in CdS, CdSe, CdTe, CdSe/ZnS, CdSe/ZnSe, CdSe/CdS, ZnSe/CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnS, CdSe/CdS/ZnS and CdTe/CdSe/CdS.
Preferably, described product hydrogen catalyst or produce in the metal-salt of hydrogen catalyst precursor chosen from Fe, cobalt, nickel, copper, molybdenum, zinc or cadmium, metal oxide, sulfide, oxyhydroxide and metal complexes one or more; Preferably, described product hydrogen catalyst or catalyst precursor are selected from Ni (OH) 2, CoCl 2, FeCl 3, NiCl 2, CuCl 2, Ni (NO 3) 2, MoS 2, one or more in hydrogenase and hydrogenase simulated compound; Wherein said hydrogenase simulated compound is iron hydrogenase simulated compound.
Preferably, described product oxygen catalyst or produce one or more of oxygen catalyst precursor chosen from Fe, cobalt, nickel, manganese, the metal oxide of copper, sulfide, oxyhydroxide and metal complexes.Preferably, described product oxygen catalyst or catalyst precursor are selected from Fe (OH) 3, Ni (OH) 2, FeOOH, NiOOH, CoOOH, Fe 2o 3, Co 2o 3with one or more in NiO.
The material of described photocathode is p-type metal-oxide semiconductor (MOS), and it is selected from NiO, CuMO 2(M=Cr, Al, Fe, Ga, In) and CuBi 2o 4in one or more.
The material of described smooth anode is n-type metal oxide semiconductor, and it is selected from TiO 2, ZnO, Fe 2o 3and WO 3in one or more.
This electrode is that the photoelectrochemistry of based semiconductor, quantum dot and catalyzer is decomposed aquatic products hydrogen, produced oxygen, and photoelectrochemistry water of decomposition can be realized within the scope of very wide pH, the performance of optoelectronic pole water of decomposition can be regulated easily by the regulation and control size of quantum dot, the kind of bifunctional molecule simultaneously.
Second technical problem that the present invention will solve is to provide a kind of photoelectrochemistry and decomposes aquatic products hydrogen, produces the preparation method of oxygen optoelectronic pole.
For solving above-mentioned second technical problem, the present invention adopts following technical proposals:
The preparation method of a kind of above-mentioned product hydrogen, product oxygen optoelectronic pole, comprise the preparation of photocathode and the preparation of light anode, the preparation method of wherein said photocathode is: first prepare one deck p-type semiconductor film, secondly bifunctional molecule auxiliary under, p-type semiconductor film is assembled one or more quantum dots, obtained photocathode; Wherein the preparation method of light anode is as follows: the film first preparing one deck n-type semiconductor, secondly bifunctional molecule auxiliary under on n-type semiconductor film, assemble one or more quantum dots, last load is over the qds produced oxygen catalyst or is produced oxygen catalyst precursor, obtained light anode.
Preferably, the quantum dot itself wherein on photocathode has the function of producing hydrogen catalyst or producing hydrogen catalyst precursor.
The preparation method of a kind of above-mentioned product hydrogen, product oxygen optoelectronic pole, comprise the preparation of photocathode and the preparation of light anode, the preparation method of wherein said photocathode is: first prepare one deck p-type semiconductor film, secondly bifunctional molecule auxiliary under, p-type semiconductor film is assembled one or more quantum dots, last load is over the qds produced hydrogen catalyst or is produced hydrogen catalyst precursor, prepares photocathode; Wherein the preparation method of light anode is as follows: the film first preparing one deck n-type semiconductor, secondly bifunctional molecule auxiliary under on n-type semiconductor film, assemble one or more quantum dots, last load is over the qds produced oxygen catalyst or is produced oxygen catalyst precursor, obtained light anode.
The preparation method of the film of described p-type semiconductor and the film of n-type semiconductor comprises silk screen printing, scrapes the skill in using a kitchen knife in cookery, sol-gel method, spin-coating method, is preferably silk screen printing; The thickness of described semiconductor film is 200nm ~ 10 μm; Preferably, described product hydrogen catalyst, the carrying method that produces hydrogen catalyst precursor, produce oxygen catalyst and produce oxygen catalyst precursor be drip paintings, dipping, chemical thought, continuous ionic layer adsorb deposit, one or more in electrochemical deposition and chemisorption.
Utilize above-mentioned product hydrogen, produce an application for oxygen optoelectronic pole hydrogen production by water decomposition, oxygen, concrete steps are as follows: first assembled battery; Secondly, described battery is placed in the electrolyte solution of certain pH; Certain bias voltage is applied to described battery, and with light source, it is irradiated; Finally, the generation of electric current and gas is detected.
Described battery is by independent photocathode or independent light anode in conjunction with reference electrode, to electrode, composition three-electrode system; Or photocathode and light anode are composed in series two electrode systems; Preferably three-electrode system executes biased scope is 0 ~-0.8V (vs. reference electrode); Preferably two electrode systems execute biased scope is 0.8 ~-0.8V (vs. is to electrode); Preferably described electrolyte solution is selected from Na 2sO 4, K 2sO 4, KNO 3, NaNO 3, Na 3pO 4, K 3pO4, K 2cO 3, Na 2cO 3, K 2hPO 4, Na 2hPO 4, KH 2pO 4and NaH 2pO 4in the aqueous solution of one or more; The scope of described pH is 1 ~ 14; Preferably, described light source is selected from sunlight, incandescent light, xenon lamp, LEDs, laser, solar simulator or high voltage mercury lamp.
Beneficial effect of the present invention is as follows:
1) photoelectrochemistry that this invention achieves based on p-type and n-type semiconductor, quantum dot and catalyzer is decomposed aquatic products hydrogen, is produced the foundation of oxygen optoelectronic pole;
2) this optoelectronic pole can water of decomposition efficiently and stably without the need to electronics sacrificial body, buffered soln;
3) even if this optoelectronic pole obtains very high photoelectric decomposition water-based energy under the condition of not additional product hydrogen catalyst;
4) this optoelectronic pole hole relaying body has fabulous separation and laser propagation effect for quantum dot photohole;
5) this optoelectronic pole simple to operate, reproducible, good stability, universality is strong, high to the utilising efficiency of visible ray; Catalyzer does not need precious metal, cheap and easy to get.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates uv-visible absorption spectra and the emmission spectrum spectrogram of CdS quantum dot.
Fig. 2 illustrates the uv-visible absorption spectra spectrogram of CdSe quantum dot and CdSe/ZnS quantum dot.
Fig. 3 illustrates the emmission spectrum spectrogram of CdSe quantum dot and CdSe/ZnS quantum dot.
Fig. 4 illustrates the shape appearance figure that CdS quantum dot is observed under high-resolution-ration transmission electric-lens (HRTEM).
Fig. 5 illustrates the shape appearance figure that CdSe/ZnS quantum dot is observed under high-resolution-ration transmission electric-lens (HRTEM).
Fig. 6 illustrates the electrode water of decomposition schematic diagram of nickel oxide/quantum dot/product hydrogen catalyst in embodiment 1.
Fig. 7 illustrates the cathodic current curve over time of embodiment 2.
Fig. 8 illustrates cathodic current curve over time in embodiment 3.
Fig. 9 illustrates the anodic current curve over time that in example 4, photocathode produces.
Figure 10 illustrates the electric current curve over time of embodiment 5 electrode.
Figure 11 is the electric current curve over time of the electrode of embodiment 6.
Figure 12 illustrates the electric current curve over time of embodiment 7.
Figure 13 illustrates the cathodic current curve over time in embodiment 9.
Figure 14 illustrates the electric current curve over time in embodiment 11.
Figure 15 is the electric current curve over time of embodiment 12.
Figure 16 illustrates the monitoring data of gas spectrum in embodiment 13.
Figure 17 illustrates the structural formula of cobalt complex in embodiment 14.
Figure 18 illustrates oxygen detection curve in embodiment 15.
Figure 19 illustrates the electric current curve over time in embodiment 17.
Figure 20 illustrates the light anode dissolution water schematic diagram in embodiment 18.
Figure 21 illustrates the electric current curve over time in embodiment 18.
Figure 22 illustrates the two optoelectronic pole water of decomposition schematic diagram in embodiment 19.
Figure 23 illustrates the electric current curve over time of the electrode in embodiment 19.
Figure 24 illustrates X-ray diffraction (XRD) collection of illustrative plates of the ZnO/CdS in embodiment 20.
Figure 25 illustrates the structural formula of embodiment 22 cobalt complex.
Figure 26 illustrates the scanning electron microscope (SEM) photograph of the ZnO nanorod in embodiment 23.
Figure 27 illustrates the scanning electron microscope (SEM) photograph of the FeOOH nanotube in embodiment 24.
Figure 28 illustrates TiO in embodiment 25 2the scanning electron microscope (SEM) photograph of nanometer rod.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
The preparation of quantum dot:
Quantum dot reference obtains.The present invention is exemplified below: to synthesize CdS quantum dot, experimental procedure comprises:
1. 0.2284g CdCl is accurately taken 25/2H 2o, in 500ml round-bottomed flask, adds 190ml deionized water and is dissolved.
2. 1ml thiohydracrylic acid is added, stirring, degasification 30min.
3. dropwise add 10M sodium hydroxide solution under fast stirring, solution can be observed and become pearl opal turbid solution from clarification, then become clarification.Then use 1M sodium hydroxide solution adjust ph to about 7.
4. 10ml 0.1M Na is added 2s solution (takes 0.24018g Na 2s9H 2o, both obtained with 10.0ml deionized water dissolving).
5. stirring at normal temperature reaction 3.5h.
Synthesis reference literature (APL Materials 2014,2 (1), 012104 of other quantum dot; J.Phys.Chem.C 2008,112,8587-8593).
Fig. 1,2,3 is uv-visible absorption spectra and the emmission spectrum spectrogram of CdS quantum dot, CdSe quantum dot and CdSe/ZnS quantum dot respectively, and excitation wavelength is all 400nm.As can be seen from the figure, the first absorption peak of CdSe quantum dot is positioned at about 430nm; First absorption peak of CdS quantum dot is positioned at about 390nm; First absorption peak of CdSe/ZnS quantum dot is positioned at about 450nm.Under 400nm optical excitation, the emission peak of CdSe quantum dot at 470nm place is its band-edge emission, and the emission peak at 600nm place is the transmitting of its defect; There is 490nm and 600nm two place emission peak in CdSe/ZnS quantum dot.
Fig. 4,5 drops in ultrathin carbon films after CdS quantum dot and CdSe/ZnS quantum dot water ultrasonic disperse, the shape appearance figure observed under HRTEM (high-resolution-ration transmission electric-lens).As can be seen from the figure, the mean sizes of CdS quantum dot is 3.0 ± 0.3nm; CdSe/ZnS quantum dot is unbodied club shaped structure.The quantum dot obtaining different-shape and structure is synthesized by controlling synthesis reaction times of quantum dot, temperature, the kind of stablizer and proportioning.
Embodiment 1
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
First screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, bifunctional molecule is Thiovanic acid; Finally utilize the method that continuous ionic layer adsorbs deposition that product hydrogen catalyst is prepared into quantum dot surface, product hydrogen catalyst is Ni (OH) 2, with this obtained photocathode.
The negative electrode prepared is connected in photoelectrochemistrpool pool, adds Na 2sO 4ionogen (pH=7), platinized platinum build photoelectrochemistry water of decomposition battery as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.3V vs. reference electrode), with the hydrogen generated in gas-chromatography (TCD thermal conductivity detector) detection reaction.The electrode water of decomposition schematic diagram of nickel oxide/quantum dot/product hydrogen catalyst that Fig. 6 obtains.
Embodiment 2
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, connection molecule is thiohydracrylic acid; With this obtained photocathode.
The photocathode prepared is connected in photoelectrochemistrpool pool, adds Na 2sO 4ionogen (pH=7), platinized platinum build photoelectrochemical cell as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.3V vs. reference electrode), with the hydrogen generated in gas-chromatography (TCD thermal conductivity detector) detection reaction.Fig. 7 is the cathodic current curve over time that nickel oxide/quantum dot electrode produces.As we can see from the figure at identical conditions, this life of nickel oxide can only produce extremely faint cathodic current; After QDs sensitization, cathodic current is sharply increased to close-60 μ A/cm 2; This result can surmount the maximum of the photocathode bibliographical information based on nickel oxide.
Embodiment 3
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, connection molecule is thiohydracrylic acid, with this obtained photocathode.
Be connected in photoelectrochemistrpool pool by the photocathode prepared, in sodium sulfate ionogen, (pH=9), platinized platinum build photoelectrochemical cell as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.3V vs. reference electrode), with the hydrogen generated in gas-chromatography (TCD thermal conductivity detector) detection reaction.Fig. 8 is the cathodic current curve over time that nickel oxide/quantum dot electrode produces.
Embodiment 4
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdS quantum dot prepared is adsorbed onto nickel oxide film surface, connection molecule is mercaptohexanoic acid, finally utilizes the method for dipping that product hydrogen catalyst is loaded to quantum dot surface, and producing hydrogen catalyst is Co (NO 3) 2, with this obtained photocathode.
The photocathode prepared is connected in photoelectrochemistrpool pool, at Na 2sO 4in ionogen, (pH=12), platinized platinum build photocathode system as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.3V vs. reference electrode).Fig. 9 is the cathodic current curve over time that in example 4, photocathode produces.The cathodic current of photocathode is about-22 μ A/cm as we can see from the figure 2.
Embodiment 5
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, connection molecule is thiohydracrylic acid; Finally utilize the method for dipping that product hydrogen catalyst is prepared into quantum dot surface, product hydrogen catalyst is CoCl 2, with this obtained photocathode,
In sodium sulfate ionogen, (pH=5), platinized platinum build photocathode system as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.3V vs. reference electrode).Figure 10 is the cathodic current curve over time that in example 5, photocathode produces.Photoelectric current is about-7 μ A/cm as we can see from the figure 2.
Embodiment 6
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Utilize screen printing technique nickel oxide nanoparticle is carried on tin dope conductive glass surface and prepares nickel oxide film, then utilize the means of chemisorption that the CdS quantum dot prepared is adsorbed onto nickel oxide film surface, connection molecule is Thiovanic acid; Finally utilize chemistry to drip the mode be coated with and product hydrogen catalyst is prepared into quantum dot surface, product hydrogen catalyst is NiCl 2, with this obtained photocathode.
At Na 2sO 4in ionogen, (pH=7), platinized platinum build photocathode system as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (-0.1V vs. reference electrode).Figure 11 is the cathodic current curve over time that in example 6, photocathode produces.Photoelectric current is about-48 μ A/cm as we can see from the figure 2.
Embodiment 7
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized titania nanoparticles to be carried on tin dope conductive glass surface and to prepare titanium deoxid film; Then utilize the means of chemisorption that the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface, bifunctional molecule is mercaptohexanoic acid, finally utilizes the method for chemical thought that product oxygen catalyst is loaded to quantum dot surface, and product oxygen catalyst is Co 2o 3nano particle.Figure 12 is the pictorial diagram of the titanium dioxide/quantum dot/catalyst film electrode prepared.
Embodiment 8
With embodiment 1, change is quantum dot is CdSe/ZnS, and bifunctional molecule is mercaptohexanoic acid.
Embodiment 9
With embodiment 6, change is applying voltage is 0V.Figure 13 is the electric current curve over time that in example 9, photocell produces.Photoelectric current is about-40 μ A/cm as can see from Figure 13 2.
Embodiment 10
With embodiment 1, change is semi-conductor is CdS, and bifunctional molecule is gsh.
Embodiment 11
With embodiment 3, in metal oxide layer, composition is CuBi 2o 4, produce the mixture (amount of substance is than being 2:1) that hydrogen catalyst is nickelous chloride and cobalt chloride.Figure 14 is the change curve of cathodic current with illumination of photocathode generation in example 11, and under this condition, cathodic current is about-11 μ A/cm as we can see from the figure 2.
Embodiment 12
With embodiment 3, in metal oxide layer, composition is CuCrO 2, quantum dot is CdS, CdSe and CdS/ZnSe (consumption 1:1:1).Figure 15 is the change curve of cathodic current with illumination of photocathode generation in example 12, and under this condition, cathodic current is about-16 μ A/cm as we can see from the figure 2.
Embodiment 13
With embodiment 6, change is product hydrogen catalyst is molybdenumdisulphide.Figure 16 is the monitoring data of gas spectrum in example 13.
Embodiment 14
With embodiment 6, change is product hydrogen catalyst is cobalt complex.Figure 17 is the structural formula of cobalt complex in example 14.
Embodiment 15
With embodiment 5, change is that in semiconductor layer, composition is CuAlO 2, producing hydrogen catalyst is the title complex of cobalt.Figure 18 is oxygen detection curve in example 15.
Embodiment 16
With embodiment 3, in metal oxide layer, composition is CuCrO 2, quantum dot is CdSe/ZnS.
Embodiment 17
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film, then utilize the means of chemisorption that the CdTe quantum prepared is adsorbed onto nickel oxide film surface, connection molecule is Thiovanic acid; Finally utilize the method for dipping that product hydrogen catalyst is prepared into quantum dot surface, product hydrogen catalyst is NiCl 2, with this obtained photocathode.
Photocathode and light anode are together in series, the TiO of light anode prepared by embodiment 7 2/ CdS electrode, with xenon lamp as light source (p=100mW/cm 2) irradiating photocathode and light anode simultaneously, applying bias voltage is 0V.Figure 19 is the electric current curve over time that in example 17, photocell produces.Photoelectric current is about-6 μ A/cm as we can see from the figure 2.
Embodiment 18
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized titania nanoparticles to be carried on tin dope conductive glass surface and to prepare titanium deoxid film; Then utilize the means of chemisorption that the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface, bifunctional molecule is mercaptohexanoic acid, finally utilizes the method for chemical thought that product oxygen catalyst is loaded to quantum dot surface, and product oxygen catalyst is Co 2o 3nano particle, obtained light anode.
Be connected in photoelectrochemistrpool pool by the light anode prepared, using pure water as solvent, platinized platinum builds photocathode system as to electrode, Ag/AgCl electrode as reference electrode.With xenon lamp as light source (p=100mW/cm 2) irradiate photocathode (working electrode) and apply certain bias voltage (0.5V vs. reference electrode).Figure 20 is light anode dissolution water schematic diagram in example 18, and Figure 21 is the anodic current curve over time that light anode produces.The anodic current of CdS quantum dot light anode is about 100 μ A/cm as we can see from the figure 2.
Embodiment 19
Decompose based on photoelectrochemistry the method that aquatic products hydrogen produces the hydrogen production by water decomposition oxygen of oxygen optoelectronic pole, comprise the following steps:
Screen printing technique is utilized nickel oxide nanoparticle to be carried on tin dope conductive glass surface and to prepare nickel oxide film; Then utilize the means of chemisorption that the CdSe quantum dot prepared is adsorbed onto nickel oxide film surface, bifunctional molecule is thiohydracrylic acid; Finally utilize the method that continuous ionic layer adsorbs deposition that product hydrogen catalyst is prepared into quantum dot surface, product hydrogen catalyst is Ni (OH) 2, with this obtained photocathode;
Utilize screen printing technique titania nanoparticles to be carried on tin dope lead glass surface and prepare titanium deoxid film; Then utilize the means of chemisorption that the CdS quantum dot prepared is adsorbed onto titanium deoxid film surface, bifunctional molecule is mercaptohexanoic acid, and finally utilize the method for dripping painting that product oxygen catalyst is loaded to quantum dot surface, product oxygen catalyst is Co 2o 3nano particle, with this obtained light anode;
Photocathode and light anode are together in series, with xenon lamp as light source (p=100mW/cm 2) irradiating photocathode and light anode simultaneously, applying bias voltage is 0V (vs. is to electrode).Figure 22 is two optoelectronic pole water of decomposition schematic diagram in example 19, and Figure 23 is the electric current curve over time produced in embodiment 19.Photoelectric current is about-10 μ A/cm as we can see from the figure 2.
Embodiment 20
With embodiment 18, the XRD spectra of change is semi-conductor to be ZnO, Figure 24 be ZnO-CdS electrode.
Embodiment 21
With embodiment 19, product oxygen catalyst is cobalt complex.Figure 25 is the structural formula of cobalt complex in example 21.
Embodiment 22
With embodiment 5, change is electrolyte solution is K 2hPO4 solution.
Embodiment 23
With embodiment 18, change is semi-conductor is ZnO.The pattern of ZnO is nanometer rod.Figure 26 is the scanning electron microscope (SEM) photograph of ZnO nanorod.As can be seen from the figure TiO 2the length of nanometer rod is about 4.5 μm, and diameter is about 350nm.
Embodiment 24
With embodiment 7, change utilizes the method for electrochemical deposition that product oxygen catalyst is loaded to quantum dot surface, and producing oxygen catalyst is hydroxyl oxidize iron nanotube.Figure 27 is the scanning electron microscope (SEM) photograph of hydroxyl oxidize iron nanotube.As can be seen from the figure FeOOH nanotube tube wall is about 30nm, and external diameter is about 150nm, and internal diameter is about 90nm.
Embodiment 25
With embodiment 7, change is that collosol and gel mode prepares TiO 2nanometer rod light anode.Figure 28 is TiO 2the scanning electron microscope (SEM) photograph of nanometer rod, as can be seen from the figure TiO 2the length of nanometer rod is about 5 μm, and diameter is about 200nm.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.

Claims (14)

1. photoelectrochemistry is decomposed aquatic products hydrogen, is produced an optoelectronic pole for oxygen, and it is characterized in that, described optoelectronic pole comprises photocathode and light anode, and described photocathode and light anode have the quantum dot of being assisted assembling by bifunctional molecule.
2. the optoelectronic pole of product hydrogen according to claim 1, product oxygen, is characterized in that, the quantum dot of described photocathode has and produces hydrogen catalyst or produce hydrogen catalyst precursor.
3. the optoelectronic pole of product hydrogen according to claim 1, product oxygen, is characterized in that, the quantum dot load on described smooth anode has produces oxygen catalyst or produces oxygen catalyst precursor.
4. the optoelectronic pole of product hydrogen according to claim 1, product oxygen, it is characterized in that, one or more in described bifunctional molecule selected from mercapto phosphoric acid, mercaptan carboxylic acid, the amino acid containing sulfydryl, the polymer containing sulfydryl, the polypeptide containing sulfydryl, two carboxyl molecule, pyridine carboxylic acid and thiophene acetic acid.
5. the optoelectronic pole of product hydrogen according to claim 1 and 2, product oxygen, it is characterized in that, the material of described photocathode is p-type metal-oxide semiconductor (MOS), and it is selected from NiO, CuMO 2(M=Cr, Al, Fe, Ga, In) and CuBi 2o 4in one or more.
6. the optoelectronic pole of the product hydrogen according to claim 1 or 3, product oxygen, it is characterized in that, the material of described smooth anode is n-type metal oxide semiconductor, and it is selected from TiO 2, ZnO, Fe 2o 3and WO 3in one or more.
7. the optoelectronic pole of product hydrogen according to claim 1, product oxygen, it is characterized in that, described quantum dot is water-soluble quantum dot or oil soluble quantum dot, preferably, described quantum dot is selected from one or more in CdS, CdSe, CdTe, CdSe/ZnS, CdSe/ZnSe, CdSe/CdS, ZnSe/CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnS, CdSe/CdS/ZnS and CdTe/CdSe/CdS.
8. the optoelectronic pole of product hydrogen according to claim 2, product oxygen, it is characterized in that, described product hydrogen catalyst or produce in the metal-salt of hydrogen catalyst precursor chosen from Fe, cobalt, nickel, copper, molybdenum, zinc or cadmium, metal oxide, sulfide, oxyhydroxide and metal complexes one or more; Preferably, described product hydrogen catalyst or product hydrogen catalyst precursor are selected from Ni (OH) 2, CoCl 2, FeCl 3, NiCl 2, CuCl 2, Ni (NO 3) 2, MoS 2, one or more in hydrogenase and hydrogenase simulated compound.
9. product hydrogen according to claim 3, produce the optoelectronic pole of oxygen, it is characterized in that, described product oxygen catalyst or produce one or more of oxygen catalyst precursor chosen from Fe, cobalt, nickel, manganese, the metal oxide of copper, sulfide, oxyhydroxide and metal complexes.Preferably, described product oxygen catalyst is selected from Fe (OH) 3, Ni (OH) 2, FeOOH, NiOOH, CoOOH, Fe 2o 3, Co 2o 3with one or more in NiO.
10. an above-mentioned product hydrogen, produce the preparation method of oxygen optoelectronic pole, comprise the preparation of photocathode and the preparation of light anode, the preparation method of wherein said photocathode is: first prepare one deck p-type semiconductor film, secondly bifunctional molecule auxiliary under, p-type semiconductor film is assembled one or more quantum dots, obtained photocathode; Wherein the preparation method of light anode is as follows: the film first preparing one deck n-type semiconductor, secondly bifunctional molecule auxiliary under on n-type semiconductor film, assemble one or more quantum dots, last load is over the qds produced oxygen catalyst or is produced oxygen catalyst precursor, obtained light anode.
11. 1 kinds of above-mentioned product hydrogen, produce the preparation method of oxygen optoelectronic pole, comprise the preparation of photocathode and the preparation of light anode, the preparation method of wherein said photocathode is: first prepare one deck p-type semiconductor film, secondly bifunctional molecule auxiliary under, p-type semiconductor film is assembled one or more quantum dots, last load is over the qds produced hydrogen catalyst or is produced hydrogen catalyst precursor, prepares photocathode; Wherein the preparation method of light anode is as follows: the film first preparing one deck n-type semiconductor, secondly bifunctional molecule auxiliary under on n-type semiconductor film, assemble one or more quantum dots, last load is over the qds produced oxygen catalyst or is produced oxygen catalyst precursor, obtained light anode.
12. 1 kinds of product hydrogen as described in claim 10 or 11, produce the preparation method of oxygen optoelectronic pole, it is characterized in that, the preparation method of the film of described p-type semiconductor and the film of n-type semiconductor comprises silk screen printing, scrapes the skill in using a kitchen knife in cookery, sol-gel method, spin-coating method, is preferably silk screen printing; The thickness of described semiconductor film is 200nm ~ 10 μm.
13. 1 kinds utilize the application of producing hydrogen, product oxygen optoelectronic pole hydrogen production by water decomposition, oxygen described in any one of claim 1-9, and it is characterized in that, concrete steps are as follows: first assembled battery; Secondly, described battery is placed in the electrolyte solution of certain pH; Certain bias voltage is applied to described battery, and with light source, it is irradiated; Finally, the generation of electric current and gas is detected.
14. product hydrogen according to claim 13, produce the application of oxygen optoelectronic pole hydrogen production by water decomposition, oxygen, it is characterized in that, described battery is by independent photocathode or independent light anode in conjunction with reference electrode, to electrode, composition three-electrode system; Or photocathode and light anode are composed in series two electrode systems; Preferably three-electrode system executes biased scope is 0 ~-0.8V (vs. reference electrode); Preferably two electrode systems execute biased scope is 0.8 ~-0.8V (vs. is to electrode); Preferably described electrolyte solution is selected from Na 2sO 4, K 2sO 4, KNO 3, NaNO 3, Na 3pO 4, K 3pO4, K 2cO 3, Na 2cO 3, K 2hPO 4, Na 2hPO 4, KH 2pO 4and NaH 2pO 4in the aqueous solution of one or more; The scope of described pH is 1 ~ 14; Preferably, described light source is selected from sunlight, incandescent light, xenon lamp, LEDs, laser, solar simulator or high voltage mercury lamp.
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