CN104009123B - Visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity - Google Patents

Visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity Download PDF

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CN104009123B
CN104009123B CN201410225850.1A CN201410225850A CN104009123B CN 104009123 B CN104009123 B CN 104009123B CN 201410225850 A CN201410225850 A CN 201410225850A CN 104009123 B CN104009123 B CN 104009123B
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visible light
responded
tio
electrode
photocathode
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CN104009123A (en
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周保学
曾庆意
黄可
李雪瑾
魏冉
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
    • 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
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • 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
    • Y02E60/50—Fuel cells
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A kind of visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity, including visible light-responded Bi2S3The TiO of sensitization2Nano-pipe array thin film light anode, visible light-responded platinum modify silicon cell photocathode, electrolyte, visible light source, quartz reaction pond and quartz discharge, the material of light anode and photocathode all has good visible absorption performance, and it is inserted simultaneously into 0.1～0.5M Na2In the electrolyte solution of S, and by external circuit UNICOM, opening visible light source and irradiate light anode and photocathode respectively, there is electrode reaction and form loop by external circuit in light anode and photocathode, it is achieved automatic bias photoelectrocatalysis produces hydrogen and generating respectively.The invention also discloses the preparation method of described system.The present invention can be applied to solar hydrogen making and generate electricity simultaneously, has visible light-responded, product hydrogen and the advantage of excellent in power generation efficiency, good stability and low cost, and the exploitation to solar hydrogen making and generation technology is significant.

Description

Visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity
Technical field
The present invention relates to solar energy utilization system, be specifically related to a kind of visible light-responded automatic bias photoelectrocatalysis and decompose Aquatic product hydrogen also The system of generating, belongs to technical field of new energies.
Background technology
Due to the fast development of World Economics, the demand of the energy is increased by the mankind day by day.But, showing based on fossil energy Foundry industry, be faced with this non-renewable energy resources will exhausted the fact.Solar hydrogen making based on photoelectrocatalysis, is one Plant and have promising new technique.Photoelectrocatalysis hydrogen production by water decomposition system, based on bipolar electrode, by by the photoproduction electricity of optoelectronic pole Son or photohole are guided to, to electrode, promote the separation of photogenerated charge, and realize photoelectrocatalysis hydrogen production by water decomposition by external circuit. But existing photoelectrocatalysis decomposes Aquatic product hydrogen system, it is single optoelectronic pole and accepts light and irradiate, and need to provide additional inclined Voltage, i.e. provides extra energy, thus limits the absorption of light and the application of hydrogen production by water decomposition thereof；In addition develop visible ray to ring Optoelectronic pole material that answer, efficient is also always the focus of this area research.
2008, Heli Wang etc. proposed employing N-shaped light anode, p-type GaInP2Photoelectrocatalysis as photocathode decomposes Water hydrogen manufacturing system (J.Electrochem.Soc.2008,155, F91), constructs double optoelectronic pole photoelectrocatalysis hydrogen production by water decomposition system, It is compared with monochromatic light electrode system, can improve the system utilization for sunlight.But the photoelectrocatalysis decomposition water system reported Hydrogen system, under the conditions of AM1.5, in the case of without external biasing voltage, H2-producing capacity is the most weak, and this is owing to this system is adopted Conduction band positions p-GaInP to be compared with electrode N-shaped light anode2Valence band location corrigendum, under illumination condition, the Fermi of light anode Energy level is corrected than the fermi level of photocathode, thus is difficult in the case of without external biasing voltage, the photoproduction electricity of light anode Son spontaneous entrance photocathode and realize the process of Auto-decomposition Aquatic product hydrogen.2012, Chen etc. reported use N-shaped WO3Electricity Pole is as light anode, and p-type platinum modifies the silicon cell electrode photoelectrocatalysis hydrogen production by water decomposition system (ChemSusChem as negative electrode 2013,6,1276), due to this system N-shaped WO3The conduction band positions of electrode light anode modifies silicon cell electrode than p-type platinum Valence band location is low, it is thus achieved that automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen under visible light conditions.Yet with by N-shaped WO3 The restriction of electrode material fermi level, n-type electrode self-deflection voltage interelectrode with p-type is the least, and WO3Electrode material is also There is obvious photo-generated carrier to be combined, these problems cause the degraded performance of the photocatalysis Decomposition Aquatic product hydrogen of its system, Under the conditions of AM1.5, its H2-producing capacity only has 0.204 μm ol h-1cm-2, additionally use WO3Electrode absorbing wavelength can only be less than 420 The black light of nm, limits it and makes full use of visible sunlight.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of light visible light-responded, that there is efficient automatic bias Electrocatalytic decomposition Aquatic product hydrogen the system generated electricity, to realize being changed into solar energy the purpose of Hydrogen Energy and electric energy.
The present invention is achieved by the following technical solutions:
A kind of visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity, including light anode, photocathode, electricity Xie Zhi, visible light source, quartz reaction pond and quartz discharge, it is characterised in that described light anode is visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode, the platinum modification silicon cell electrode that described time is the most visible light-responded, Described electrolyte is the Na of 0.1～0.5M2S solution；Described light anode and photocathode are inserted simultaneously into described quartz anti- In the described electrolyte of Ying Chizhong, and by external circuit UNICOM；Open described visible light source and irradiate described light sun respectively Pole and photocathode, there is electrode reaction respectively and by external circuit formation loop in now described light anode and photocathode, thus reality Existing automatic bias photoelectrocatalysis produces hydrogen and generating.
Further, described visible light source is simulated solar irradiation, and light intensity is 100mW cm-2。
Another technical scheme of the present invention is:
A kind of above-mentioned visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the preparation method of system generated electricity, and it specifically walks Suddenly include:
1) the visible light-responded Bi described in preparation2S3The TiO of sensitization2Nano-tube array film electrode, its method is: first will The metallic titanium plate cleaned, as anode, is placed in the aqueous solution containing 0.5% Fluohydric acid., and with platinum electrode for electrode, regulation voltage is 20V, carries out anodic oxidation 60 minutes to metallic titanium plate, obtains by Titanium and the TiO on titanium surface2The titanio TiO constituted2Receive Mitron array material, then this titanio TiO2Nano-tube array material, after 500 DEG C of high temperature sinterings 1 hour, obtains having sharp titanium The TiO of ore deposit phase2Nano-pipe array thin film material；With this, there is the TiO of Anatase2Nano-pipe array thin film material as substrate, By the way of rotary coating, alternately to the Bi (NO of this substrate dropping 0.5ml50mM3)3Na with 100mM2S solution, Wherein, described Bi (NO3)3The acetum of solution employing 1M is as solvent, every time at 3000rpm rotating speed after dropping Lower coating 20s, is alternately repeated 30 times, obtains Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, by this Bi2S3 The titanio TiO of sensitization2Nano-pipe array thin film material through 300 DEG C of high temperature sinterings 1 hour, obtains described visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode；
2) the visible light-responded platinum described in known method preparation is used to modify silicon cell electrode；
3) by step 1) prepared by visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode as light anode, Using step 2) prepared by visible light-responded platinum modify silicon cell electrode as photocathode, insert respectively described in quartz anti- 0.1～the 0.5M Na of Ying Chizhong2In S electrolyte solution, described smooth anode and photocathode connected by external circuit and by described can See that radiant irradiates and produces photogenerated charge.
The another technical scheme of the present invention is:
A kind of above-mentioned visible light-responded automatic bias photoelectrocatalysis decomposition Aquatic product hydrogen the system generated electricity at solar hydrogen making and are sent out simultaneously Application in electricity.
Visible light-responded automatic bias photoelectrocatalysis decomposition Aquatic product hydrogen of the present invention the system generated electricity have good stablizing Property, photoelectric efficiency is high, and hydrogen generation efficiency is high, and visible light part in sunlight is all had response.Compared with prior art, achieve Good technique effect, is embodied in:
(1) present invention employs there is the Bi of good visible absorption performance2S3The TiO of sensitization2Nano-tube array film electrode is made For light anode, it is possible to overcome and include WO3Absorbing wavelength the black light of 420nm can only be less than not at interior existing smooth anode Foot, thus realize automatic bias photoelectrocatalysis decomposition water system and solar spectrum is made full use of.
(2) the light anode material of the present invention is Bi2S3The TiO of sensitization2Nano-tube array film electrode, owing to its substrate is TiO2 Nano-tube array material, thus this electrode material has the performance of good transfer charge, can overcome WO3Electrode photo-generated carrier The deficiency that recombination rate is high, it is achieved effective utilization of photo-generated carrier.
(3) Bi that the present invention uses2S3The TiO of sensitization2Nano-tube array film electrode, its TiO2Nano-tube array substrate material The conduction band positions WO to be compared of material3The conduction band positions of electrode bears about 0.3V, it is thus possible to improves the automatic bias of system, thus enters One step promotes separation and the transfer of photo-generated carrier.
(4) method that the present invention uses rotary coating to be combined with ion exchange sedimentary facies prepares Bi2S3The TiO of sensitization2Nanotube battle array Row membrane electrode, sensitizing layer is incorporated into TiO equably2The tube wall of nanotube, has good visible light-responded and photocatalysis performance, Good mechanical stability and service life are long.
(5) the visible light-responded automatic bias photoelectrocatalysis described in decomposes Aquatic product hydrogen the system generated electricity and other photoelectrocatalysis body System compares, and has without realizing the notable performance producing hydrogen under the conditions of applying bias, and is capable of the most externally power generation performance.
Accompanying drawing explanation
Fig. 1 is structure and the fundamental diagram of the present invention；
In figure, 1 is light anode, and 2 is photocathode, and 3 is quartz discharge, and 4 is hydrogen.
Fig. 2 is the absorption spectrum curve of several optoelectronic poles in the present invention；
In figure, A is titanio TiO2The absorption spectrum curve of nano-pipe array thin film material；B is visible light-responded Bi2S3Quick The TiO changed2The absorption spectrum curve of nano-tube array film electrode；C is the suction that visible light-responded platinum modifies silicon cell electrode Receive the curve of spectrum.
Fig. 3 is that the embodiment of the present invention is at simulated solar irradiation AM1.5 (100mW/cm2) under the conditions of irradiation, in 0.25M Na2S electricity H2-producing capacity and produce the current density plot during hydrogen in electrolyte solution；
In figure, D is the time dependent curve of electric current density；E is the time dependent curve of hydrogen output.
Fig. 4 is that the present invention is at simulated solar irradiation AM1.5 (100mW/cm2) under the conditions of irradiation, in 0.25M Na2S electrolyte Cell performance curve in solution；
Figure designates short-circuit current value, open-circuit voltage values, electricity conversion value and fill factor, curve factor.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated, but should not limit the scope of the invention with this.
First referring to Fig. 1, Fig. 1 is that visible light-responded automatic bias photoelectrocatalysis of the present invention decomposes Aquatic product hydrogen and generates electricity The structure of system and fundamental diagram.As seen from the figure, described system includes light anode 1, photocathode 2, electrolyte, visible ray light Source, quartz reaction pond and quartz discharge 3.Described light anode 1 is visible light-responded Bi2S3The TiO of sensitization2Nanotube Array film electrode, described photocathode 2 is that visible light-responded platinum modifies silicon cell electrode, described light anode 1 and light Negative electrode 2 inserts in the electrolyte that described quartz reaction pond is contained within respectively, and this electrolyte is the Na of 0.1～0.5M2S solution, And connected by external circuit；Described light anode 1 and photocathode 2 are visible-light response type semi-conducting material, it is possible to directly Responding to visible light irradiates and produces photogenerated charge, opens described visible light source and irradiates described light anode and photocathode respectively, should Visible light source is simulated solar irradiation, and light intensity is 100mW cm-2, now described light anode and photocathode all can produce photoproduction Electronics and hole, the described photohole in light anode is by the S in described electrolyte2-Oxidation, the photoproduction of described photocathode Electronics is by the H in described electrolyte+It is reduced to H2, and there is electrode reaction respectively and pass through dispatch from foreign news agency in described light anode and photocathode Formation loop, road, it is achieved visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the purpose externally generated electricity.
Under visible light-responded automatic bias photoelectrocatalysis of the present invention decomposes Aquatic product hydrogen and the preparation method of system that generates electricity includes Row concrete steps:
1) the visible light-responded Bi described in preparation2S3The TiO of sensitization2Nano-tube array film electrode, its method is: first will The metallic titanium plate cleaned, as anode, is placed in the aqueous solution containing 0.5% Fluohydric acid., and with platinum electrode for electrode, regulation voltage is 20V, carries out anodic oxidation 60 minutes to metallic titanium plate, obtains by Titanium and the TiO on titanium surface2The titanio TiO constituted2Receive Mitron array material, then this titanio TiO2Nano-tube array material, after 500 DEG C of high temperature sinterings 1 hour, obtains having sharp The TiO of titanium ore phase2Nano-pipe array thin film material；With this, there is the TiO of Anatase2Nano-pipe array thin film material is as base The end, by the way of rotary coating, alternately to the Bi (NO of this substrate dropping 0.5ml50mM3)3Na with 100mM2S Solution, wherein, described Bi (NO3)3The acetum of solution employing 1M is as solvent, at 3000rpm every time after dripping It is coated with 20s under rotating speed, is alternately repeated 30 times, obtains Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, should Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, through 300 DEG C of high temperature sinterings 1 hour, obtains described visible ray and rings The Bi answered2S3The TiO of sensitization2Nano-tube array film electrode；
2) the visible light-responded platinum described in known method preparation is used to modify silicon cell electrode；
3) by step 1) prepared by visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode is as light anode 1, using step 2) prepared by visible light-responded platinum modify silicon cell electrode as photocathode 2, insert described stone respectively In English reaction tank 0.1～the Na of 0.5M2In S electrolyte solution, described smooth anode 1 and photocathode 2 are by external circuit even Lead to and irradiated by described visible light source and produce photogenerated charge.
Present disclosure is illustrated below with embodiment.
Embodiment 1
First using clean metallic titanium plate as anode, it is placed in the aqueous solution containing 0.5% Fluohydric acid., adjusts for electrode with platinum electrode Economize on electricity pressure is 20V, metallic titanium plate carries out anodic oxidation 60 minutes, obtains by Titanium and the TiO on titanium surface2The titanium constituted Base TiO2Nano-tube array material, then described titanio TiO2Nano-tube array material after 500 DEG C of high temperature sinterings 1 hour, Obtain the TiO with Anatase2Nano-pipe array thin film material, has the TiO of Anatase with this2Nano-pipe array thin film material Material is as substrate, by the way of rotary coating, alternately to the Bi (NO of this substrate dropping 0.5ml50mM3)3And 100mM Na2S solution, wherein said Bi (NO3)3The acetum of solution employing 1M is as solvent, 3000 every time after dripping It is coated with 20s under rpm rotating speed, is alternately repeated 30 times, obtains Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, will This Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, through 300 DEG C of high temperature sinterings 1 hour, obtains described visible ray The Bi of response2S3The TiO of sensitization2Nano-tube array film electrode.In accompanying drawing 2, curve A and curve B gives prepared titanium Base TiO2Nano-pipe array thin film material and visible light-responded Bi2S3The TiO of sensitization2The ultraviolet of nano-tube array film electrode- Visible absorption spectra, therefrom can draw, prepared visible light-responded Bi2S3The TiO of sensitization2Nano-pipe array thin film electricity Extremely wavelength all there is absorption less than the light of 900nm, say, that it is all of visible that this electrode material can absorb in sunlight Light.
The back surface field of the business-like silicon cell cleaned up is welded copper conductor, then the back surface field of this silicon cell is insulated Epoxy sealing, after sealing, with this silicon cell as working electrode, is placed in containing 10mM K2PtCl6With 0.1M sodium sulfate In 1M sulfuric acid solution, with platinum electrode for electrode, control running voltage is-0.5V, and electrodeposition time is 30min, carries out silicon The platinum of cell piece is modified, and the silicon cell distilled water after being modified by platinum soaks removal surface residue repeatedly, then dries, i.e. Obtain visible light-responded platinum and modify silicon cell electrode.In accompanying drawing 2, curve C gives described visible light-responded platinum and modifies silicon The uv-visible absorption spectra of cell piece electrode, it shows that this electrode all has absorption to the visible ray of more than 400nm.
By prepared visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode is as light anode 1, by prepared Visible light-responded platinum modification silicon cell electrode, as photocathode 2, inserts respectively containing 0.25M Na2In S electrolyte solution, Described light anode 1 and photocathode 2 are connected by outer lead.(light intensity is 100mW cm to open simulated solar light source-2) Irradiating light anode 1 and photocathode 2, the light induced electron that now photocathode 2 produces is by the H in electrolyte+It is reduced to H2, electrolyte In S2-Being aoxidized by photohole on light anode 1, the light induced electron that light anode 1 produces is transferred to time by external circuit Pole 2 is also combined with its photohole, realizes Photocatalyzed Hydrogen Production and generating simultaneously.Accompanying drawing 3 gives product hydrogen with this understanding And can produce the current density plot during hydrogen, in figure, curve E shows that the hydrogen generation rate of the present embodiment is 45.5 μm ol h-1cm-2, curve D shows that in external circuit, current value is 1.5mAcm-2, and current value described during producing hydrogen is the most substantially Reduction and fluctuation.Accompanying drawing 4 gives the cell performance curve of the present embodiment under the conditions of this, shows the photoelectricity of the present embodiment in figure Transformation efficiency is 0.718%, and open-circuit voltage is 0.766V, and short circuit current is 1.55mAcm-2, fill factor, curve factor is 0.602.This A little results show, system of the present invention has good product hydrogen and power generation performance under visible light, has good stablizing simultaneously Property.
The effect of embodiment 1 is described with 2 reference examples below.
Reference examples 1
As comparison, in the case of other condition of embodiment 1 is constant, by Bi prepared in embodiment 12S3The TiO of sensitization2 Nano-tube array film electrode, as light anode, using platinized platinum as to electrode, irradiates this comparison with the light source described in embodiment 1 Light anode in example 1, it is 0.32 μm ol h that measurement obtains its hydrogen-producing speed-1cm-2, only the 1/142 of embodiment 1；Photoelectricity turns Changing efficiency is 0.00316%, only the 1/227 of embodiment 1；Open-circuit voltage is only 0.173V；Short circuit current is only 0.079 mAcm-2,；Fill factor, curve factor is only 0.231.
Reference examples 2
As comparison, in the case of other condition of embodiment 1 is constant, platinum prepared in embodiment 1 is modified silicon cell Electrode, as photocathode, using platinized platinum as to electrode, irradiates the photocathode in this reference examples 2 with the light source described in embodiment 1, It is 16.1 μm ol h that measurement obtains its hydrogen-producing speed-1cm-2, it is only about the 1/3 of embodiment 1；Electricity conversion is 0.0485%, It is only the 1/15 of embodiment 1；Open-circuit voltage is only 0.602V；Short circuit current is only 0.759mAcm-2,；Fill factor, curve factor is only 0.106。
Embodiment 2
With visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode is as light anode 1, it is seen that the platinum of photoresponse is repaiied Decorations silicon cell electrode, as photocathode 2, inserts respectively containing 0.1M Na2In S electrolyte solution, and by outer lead even Connect.(light intensity is 100mW cm to open simulated solar light source-2) irradiate light anode 1 and photocathode 2, now photocathode 2 produces Light induced electron by the H in electrolyte+It is reduced to H2, S in electrolyte2-Light anode 1 is aoxidized by photohole, light The light induced electron that anode 1 produces is transferred to photocathode 2 by external circuit and is combined with its photohole, realizes photocatalysis simultaneously Produce hydrogen and generating.The hydrogen generation rate of the present embodiment is 43.1 μm ol h-1cm-2, in external circuit, current value passes through electrochemical operation The result that test of standing obtains is 1.42mAcm-2, and described current value the most significantly reduces and fluctuates during product hydrogen；This The electricity conversion of embodiment is 0.673%, and open-circuit voltage is 0.764V, and short circuit current is 1.47mAcm-2, fill factor, curve factor It is 0.601.These results indicate that described system has good product hydrogen and power generation performance under visible light, have good simultaneously Stability.
Embodiment 3
With visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode is as light anode 1, it is seen that the platinum of photoresponse is repaiied Decorations silicon cell electrode, as photocathode 2, inserts respectively containing 0.5M Na2In S electrolyte solution, and by outer lead even Connect.(light intensity is 100mW cm to open simulated solar light source-2) irradiate light anode 1 and photocathode 2, now photocathode 2 produces Light induced electron by the H in electrolyte+It is reduced to H2, S in electrolyte2-Light anode 1 is aoxidized by photohole, light The light induced electron that anode 1 produces is transferred to photocathode 2 by external circuit and is combined with its photohole, realizes photocatalysis simultaneously Produce hydrogen and generating.The hydrogen generation rate of the present embodiment is 46.7 μm ol h-1cm-2, in external circuit, current value passes through electrochemical operation The result that test of standing obtains is 1.54mAcm-2, and described current value the most significantly reduces and fluctuates during product hydrogen；This The electricity conversion of embodiment is 0.723%, and open-circuit voltage is 0.768V, and short circuit current is 1.57mAcm-2, fill factor, curve factor It is 0.599.These results indicate that described system has good product hydrogen and power generation performance under visible light, have good simultaneously Stability.
The present invention can be applied to solar hydrogen making and generate electricity simultaneously, have visible light-responded, produce hydrogen and excellent in power generation efficiency, steady The qualitative good and advantage of low cost, the exploitation to solar hydrogen making and generation technology is significant.

Claims (4)

1. visible light-responded automatic bias photoelectrocatalysis decomposes Aquatic product hydrogen the system generated electricity, including light anode, photocathode, Electrolyte, visible light source, quartz reaction pond and quartz discharge, it is characterised in that described light anode is visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode, the platinum modification silicon cell electricity that described time is the most visible light-responded Pole, described electrolyte is the Na of 0.1～0.5M2S solution；Described light anode and photocathode are inserted simultaneously into described stone In described electrolyte in English reaction tank, and connected by external circuit；Open described visible light source and irradiate described respectively Light anode and photocathode, there is electrode reaction respectively and by external circuit formation loop in now described light anode and photocathode, from And realize automatic bias photoelectrocatalysis and produce hydrogen and generating.
Visible light-responded automatic bias photoelectrocatalysis the most according to claim 1 decomposes Aquatic product hydrogen the system generated electricity, and it is special Levying and be, described visible light source is simulated solar irradiation, and light intensity is 100mW cm-2。
3. the visible light-responded automatic bias photoelectrocatalysis described in a claim 1 decomposes Aquatic product hydrogen the preparation of system generated electricity Method, it is characterised in that the concrete steps of described preparation method include:
1) the visible light-responded Bi described in preparation2S3The TiO of sensitization2Nano-tube array film electrode, its method is: first will The metallic titanium plate cleaned, as anode, is placed in the aqueous solution containing 0.5% Fluohydric acid., and with platinum electrode for electrode, regulation voltage is 20V, carries out anodic oxidation 60 minutes to metallic titanium plate, obtains by Titanium and the TiO on titanium surface2The titanio TiO constituted2Receive Mitron array material, then this titanio TiO2Nano-tube array material, after 500 DEG C of high temperature sinterings 1 hour, obtains having sharp titanium The TiO of ore deposit phase2Nano-pipe array thin film material；With this, there is the TiO of Anatase2Nano-pipe array thin film material as substrate, By the way of rotary coating, alternately to the Bi (NO of this substrate dropping 0.5ml 50mM3)3Na with 100mM2S solution, Wherein, described Bi (NO3)3The acetum of solution employing 1M is as solvent, every time at 3000rpm rotating speed after dropping Lower coating 20s, is alternately repeated 30 times, obtains Bi2S3The titanio TiO of sensitization2Nano-pipe array thin film material, by this Bi2S3 The titanio TiO of sensitization2Nano-pipe array thin film material through 300 DEG C of high temperature sinterings 1 hour, obtains described visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode；
2) using the visible light-responded platinum described in known method preparation to modify silicon cell electrode, this known method is: cleaning Clean silicon cell back surface field welding copper conductor, then seals back surface field insulating epoxy, after sealing, with this silicon cell For working electrode, it is placed in containing 10mM K2PtCl6With in the 1M sulfuric acid solution of 0.1M sodium sulfate, with platinum electrode for electrode, Control running voltage is-0.5V, and at silicon cell surface platinum electrodeposition, electrodeposition time is 30min, is modified by electrodeposited platinum After silicon cell distilled water repeatedly soak removal surface residue, dry, obtain described visible light-responded platinum and modify silicon Cell piece electrode；
3) by step 1) prepared by visible light-responded Bi2S3The TiO of sensitization2Nano-tube array film electrode as light anode, Using step 2) prepared by visible light-responded platinum modify silicon cell electrode as photocathode, insert respectively described in quartz anti- 0.1～the 0.5M Na of Ying Chizhong2In S electrolyte solution, described smooth anode and photocathode connected by external circuit and by described can See that radiant irradiates and produces photogenerated charge.
4. the visible light-responded automatic bias photoelectrocatalysis described in a claim 1 decomposes Aquatic product hydrogen the body belonging to TAI YANG syndrome generated electricity Application in energy hydrogen manufacturing simultaneously generating.
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