CN104009123A - Visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system - Google Patents
Visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system Download PDFInfo
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Abstract
The invention provides a visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system. The visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system comprises a visible-light response type Bi2S3 sensitized TiO2 nanotube array film photo-anode, a visible-light response type silicon cell photo-cathode decorated with platinum, an electrolyte, a visible-light source, a quartz reaction tank and a quartz gas collecting tube. The materials of the photo-anode and the materials of the photo-cathode are both high in visible-light absorption performance. The photo-anode and the photo-cathode are inserted into a 0.1-0.5 M Na2S electrolyte solution at the same time and are connected through an external circuit. The visible-light source is switched on to irradiate the photo-anode and the photo-cathode, the photo-anode and the photo-cathode respectively generate an electrode reaction and then form a loop through the external circuit, and therefore automatic-bias photoelectrical catalytic hydrogen production and electricity generation are achieved. The invention further discloses a preparation method of the visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system. The visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system can be applied to solar hydrogen production and electricity generation at the same time and has the advantages of visible-light response, efficient hydrogen production and electricity generation, good stability and low cost. The visible-light response type automatic-bias photoelectrical catalytic water decomposition hydrogen production and electricity generation system and the preparation method of the system have an important significance in developing the solar hydrogen production and electricity generation technology.
Description
Technical field
The present invention relates to solar energy utilization system, be specifically related to the system that a kind of visible light-responded automatic bias photoelectrocatalysis decomposes aquatic products hydrogen generating, belong to technical field of new energies.
Background technology
Due to the fast development of World Economics, the mankind increase day by day to the demand of the energy.Yet, take fossil energy as basic modern industry, be faced with this non-renewable energy resources and be about to the exhausted fact.Take photoelectrocatalysis as basic solar hydrogen making, is the promising new technology of a kind of tool.Photoelectrocatalysis hydrogen production by water decomposition system, take bipolar electrode as basis, by the light induced electron of optoelectronic pole or photohole are guided to electrode by external circuit, promotes the separation of photogenerated charge, and realizes photoelectrocatalysis hydrogen production by water decomposition.But existing photoelectrocatalysis decomposes aquatic products hydrogen system, is independent optoelectronic pole and accepts irradiation, and additional bias-voltage need to be provided, and extra energy is provided, thereby has limited the absorption of light and the application of hydrogen production by water decomposition thereof; In addition develop visible light-responded, optoelectronic pole material is also the focus of this area research always efficiently.
2008, Heli Wang etc. proposed employing N-shaped light anode, p-type GaInP
2photoelectrocatalysis hydrogen production by water decomposition system (J.Electrochem.Soc.2008 as photocathode, 155, F91), built two optoelectronic pole photoelectrocatalysis hydrogen production by water decomposition systems, it is compared with monochromatic light electrode system, can improve system for the utilization of sunlight.But the photoelectrocatalysis hydrogen production by water decomposition system of reporting, under AM1.5 condition, without external biasing voltage in the situation that, product hydrogen performance is very weak, and this is because this system adopts the conduction band position of electrode N-shaped light anode than p-GaInP
2valence band location corrigendum, under illumination condition, the Fermi level of light anode is than the Fermi level corrigendum of photocathode, thereby is difficult to realize without external biasing voltage in the situation that, and the light induced electron of light anode is spontaneous to be entered photocathode and realize the process of Auto-decomposition aquatic products hydrogen.2012, Chen etc. reported use N-shaped WO
3electrode is as light anode, and p-type platinum is modified silicon cell electrode as the photoelectrocatalysis hydrogen production by water decomposition system (ChemSusChem2013,6,1276) of negative electrode, due to this system N-shaped WO
3the valence band location that silicon cell electrode is modified than p-type platinum in the conduction band position of electrode light anode is low, thereby has realized automatic bias photoelectrocatalysis under visible ray condition and decomposed aquatic products hydrogen.Yet owing to being subject to N-shaped WO
3the restriction of electrode material Fermi level, N-shaped electrode and the interelectrode self-deflection voltage of p-type are still less, and WO
3it is compound that electrode material also exists obvious photo-generated carrier, and these problems cause the performance of photocatalysis Decomposition aquatic products hydrogen of its system low, and under AM1.5 condition, it produces hydrogen performance and only has 0.204 μ mol h
-1cm
-2, use in addition WO
3electrode can only absorbing wavelength be less than the black light of 420nm, has limited its making full use of visible sunlight.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of photoelectrocatalysis visible light-responded, that there is efficient automatic bias to decompose the system of aquatic products hydrogen generating, to realize the object that solar energy is changed into Hydrogen Energy and electric energy.
The present invention is achieved by the following technical solutions:
Visible light-responded automatic bias photoelectrocatalysis decomposes a system for aquatic products hydrogen generating, comprises light anode, photocathode, electrolyte, visible light source, quartz reaction pond and quartzy discharge, it is characterized in that, described light anode is visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode, described time,, very visible light-responded platinum was modified silicon cell electrode, the Na that described electrolyte is 0.1～0.5M
2s solution; Described light anode and photocathode are inserted in the described electrolyte in described quartz reaction pond simultaneously, and by external circuit UNICOM; Open described visible light source and irradiate respectively described light anode and photocathode, now described light anode and the generating electrodes reaction of photocathode difference also forms loop by external circuit, thereby realize 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:
Above-mentioned visible light-responded automatic bias photoelectrocatalysis decomposes a preparation method for the system of aquatic products hydrogen generating, and its concrete steps comprise:
1) the described visible light-responded Bi of preparation
2s
3the TiO of sensitization
2nano-tube array film electrode, its method is: first using clean metallic titanium plate as anode, be placed in the aqueous solution containing 0.5% hydrofluoric acid, take platinum electrode as to electrode, regulation voltage is 20V, and metallic titanium plate is carried out to anodic oxidation 60 minutes, obtains the TiO by Titanium and titanium surface
2the titanium base TiO forming
2nano-tube array material, then this titanium base TiO
2nano-tube array material after 1 hour, obtains having the TiO of Anatase through 500 ℃ of high temperature sinterings
2nano-pipe array thin film material; With this, there is the TiO of Anatase
2nano-pipe array thin film material, as substrate, by the mode of rotary coating, alternately drips the Bi (NO of 0.5ml50mM to this substrate
3)
3na with 100mM
2s solution, wherein, described Bi (NO
3)
3solution adopts the acetum of 1M as solvent, after dropwising, under 3000rpm rotating speed, is coated with 20s at every turn, alternately repeats 30 times, obtains Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, by this Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, through 300 ℃ of high temperature sinterings 1 hour, obtains described visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode;
2) adopt the described visible light-responded platinum of known method preparation to modify silicon cell electrode;
3) by step 1) prepared visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode is as light anode, using step 2) prepared visible light-responded platinum modifies silicon cell electrode as photocathode, inserts respectively the 0.1～0.5M Na in described quartz reaction pond
2in S electrolyte solution, described smooth anode and photocathode are communicated with by external circuit and are irradiated and produced photogenerated charge by described visible light source.
Another technical scheme of the present invention is:
The application of the system of a kind of above-mentioned visible light-responded automatic bias photoelectrocatalysis decomposition aquatic products hydrogen generating in solar hydrogen making generating simultaneously.
The system that visible light-responded automatic bias photoelectrocatalysis of the present invention decomposes aquatic products hydrogen generating has good stability, and photoelectric efficiency is high, and hydrogen generation efficiency is high, and visible light part in sunlight is all had to response.Compared with prior art, obtained good technique effect, be embodied in:
(1) the present invention has adopted the Bi with good visible absorption performance
2s
3the TiO of sensitization
2nano-tube array film electrode, as light anode, can overcome and comprise WO
3at interior existing smooth anode, can only absorbing wavelength be less than the deficiency of the black light of 420nm, thereby realize automatic bias photoelectrocatalysis decomposition water system making full use of solar spectrum.
(2) smooth anode material of the present invention is Bi
2s
3the TiO of sensitization
2nano-tube array film electrode, because its substrate is TiO
2nano-tube array material, thereby this electrode material has the performance of good transfer charge, can overcome WO
3the deficiency that electrode photo-generated carrier recombination rate is high, realizes effective utilization of photo-generated carrier.
(3) Bi that the present invention adopts
2s
3the TiO of sensitization
2nano-tube array film electrode, its TiO
2the conduction band position of nano-tube array base material is than WO
3about conduction band location negative 0.3V of electrode, thereby can improve the automatic bias of system, thus further promote the separated of photo-generated carrier and shift.
(4) the present invention adopts the method that rotary coating is combined with ion-exchange sedimentary facies to prepare Bi
2s
3the TiO of sensitization
2nano-tube array film electrode, sensitizing layer is incorporated into TiO equably
2the tube wall of nanotube, has good visible light-responded and photocatalysis performance, good mechanical stability and long service life.
(5) described visible light-responded automatic bias photoelectrocatalysis decomposition aquatic products hydrogen the system of generating are compared with other photoelectrocatalytioxidation oxidation system, have without realizing the significantly performance of product hydrogen under applying bias condition, and can realize significant externally power generation performance.
Accompanying drawing explanation
Fig. 1 is structure of the present invention and fundamental diagram;
In figure, 1 is light anode, and 2 is photocathode, and 3 is quartzy discharge, and 4 is hydrogen.
Fig. 2 is the absorption spectrum curve of several optoelectronic poles in the present invention;
In figure, A is titanium base TiO
2the absorption spectrum curve of nano-pipe array thin film material; B is visible light-responded Bi
2s
3the TiO of sensitization
2the absorption spectrum curve of nano-tube array film electrode; C is the absorption spectrum curve that visible light-responded platinum is modified silicon cell electrode.
Fig. 3 is that the embodiment of the present invention is at simulated solar irradiation AM1.5 (100mW/cm
2) under illuminate condition, in 0.25M Na
2in S electrolyte solution, produce hydrogen performance and produce the current density curve in hydrogen process;
In figure, D is the time dependent curve of 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/cm
2) under illuminate condition, in 0.25M Na
2battery performance curve in S electrolyte solution;
Figure acceptance of the bid understands short-circuit current value, open-circuit voltage values, electricity conversion value and fill factor, curve factor.
Embodiment
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 refer to Fig. 1, Fig. 1 is structure and the fundamental diagram that visible light-responded automatic bias photoelectrocatalysis of the present invention decomposes the system of aquatic products hydrogen generating.As seen from the figure, described system comprises light anode 1, photocathode 2, electrolyte, visible light source, quartz reaction pond and quartzy discharge 3.Described light anode 1 is visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode, described photocathode 2 is that visible light-responded platinum is modified silicon cell electrode, described light anode 1 and photocathode 2 insert respectively in the electrolyte that described quartz reaction pond contains, the Na that this electrolyte is 0.1～0.5M
2s solution, and be communicated with by external circuit; Described light anode 1 and photocathode 2 are visible-light response type semi-conducting material, directly responding to visible light irradiates and produces photogenerated charge, open described visible light source and irradiate respectively described light anode and photocathode, this visible light source is simulated solar irradiation, and light intensity is 100mW cm
-2, now described light anode and photocathode all can produce light induced electron and hole, and the photohole in described light anode is by the S in described electrolyte
2-oxidation, the light induced electron of described photocathode is by the H in described electrolyte
+be reduced to H
2, and described light anode and photocathode difference generating electrodes are reacted and form loop by external circuit, realize the object that visible light-responded automatic bias photoelectrocatalysis decomposes aquatic products hydrogen and externally generates electricity.
The preparation method that visible light-responded automatic bias photoelectrocatalysis of the present invention decomposes the system of aquatic products hydrogen generating comprises following concrete steps:
1) the described visible light-responded Bi of preparation
2s
3the TiO of sensitization
2nano-tube array film electrode, its method is: first using clean metallic titanium plate as anode, be placed in the aqueous solution containing 0.5% hydrofluoric acid, take platinum electrode as to electrode, regulation voltage is 20V, and metallic titanium plate is carried out to anodic oxidation 60 minutes, obtains the TiO by Titanium and titanium surface
2the titanium base TiO forming
2nano-tube array material, then this titanium base TiO
2nano-tube array material after 1 hour, obtains having the TiO of Anatase through 500 ℃ of high temperature sinterings
2nano-pipe array thin film material; With this, there is the TiO of Anatase
2nano-pipe array thin film material, as substrate, by the mode of rotary coating, alternately drips the Bi (NO of 0.5ml50mM to this substrate
3)
3na with 100mM
2s solution, wherein, described Bi (NO
3)
3solution adopts the acetum of 1M as solvent, after dripping, under 3000rpm rotating speed, is coated with 20s at every turn, alternately repeats 30 times, obtains Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, by this Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, through 300 ℃ of high temperature sinterings 1 hour, obtains described visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode;
2) adopt the described visible light-responded platinum of known method preparation to modify silicon cell electrode;
3) by step 1) prepared visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode is as light anode 1, using step 2) prepared visible light-responded platinum modifies silicon cell electrode as photocathode 2, inserts respectively the Na of 0.1～0.5M in described quartz reaction pond
2in S electrolyte solution, described smooth anode 1 and photocathode 2 are communicated with by external circuit and are irradiated and produced photogenerated charge by described visible light source.
With embodiment, illustrate content of the present invention below.
Embodiment 1
First using clean metallic titanium plate as anode, be placed in the aqueous solution containing 0.5% hydrofluoric acid, take platinum electrode as being 20V to electrode regulating voltage, metallic titanium plate is carried out to anodic oxidation 60 minutes, obtain the TiO by Titanium and titanium surface
2the titanium base TiO forming
2nano-tube array material, then described titanium base TiO
2nano-tube array material after 1 hour, obtains having the TiO of Anatase through 500 ℃ of high temperature sinterings
2nano-pipe array thin film material, has the TiO of Anatase with this
2nano-pipe array thin film material, as substrate, by the mode of rotary coating, alternately drips the Bi (NO of 0.5ml50mM to this substrate
3)
3na with 100mM
2s solution, wherein said Bi (NO
3)
3solution adopts the acetum of 1M as solvent, after dripping, under 3000rpm rotating speed, is coated with 20s at every turn, alternately repeats 30 times, obtains Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, by this Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, through 300 ℃ of high temperature sinterings 1 hour, obtains described visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode.In accompanying drawing 2, curve A and curve B have provided prepared titanium base TiO
2nano-pipe array thin film material and visible light-responded Bi
2s
3the TiO of sensitization
2the uv-visible absorption spectra of nano-tube array film electrode, therefrom can draw, prepared visible light-responded Bi
2s
3the TiO of sensitization
2the light that nano-tube array film electrode is less than 900nm to wavelength all has absorption, that is to say, this electrode material can absorb all visible rays in sunlight.
By the back surface field soldering copper wire of the business-like silicon cell cleaning up, then the epoxy sealing with insulation by the back surface field of this silicon cell, after sealing, take this silicon cell as work electrode, is placed in the K containing 10mM
2ptCl
6in the 1M sulfuric acid solution of 0.1M sodium sulphate, take platinum electrode as to electrode, controlling operating voltage is-0.5V, electrodeposition time is 30min, carrying out the platinum of silicon cell modifies, silicon cell after platinum is modified soaks removal surface residue repeatedly with distilled water, then dries, and obtains visible light-responded platinum and modifies silicon cell electrode.In accompanying drawing 2, curve C has provided the uv-visible absorption spectra that described visible light-responded platinum is modified silicon cell electrode, and it shows that visible ray more than this electrode pair 400nm all has absorption.
By the visible light-responded Bi making
2s
3the TiO of sensitization
2nano-tube array film electrode, as light anode 1, is modified silicon cell electrode as photocathode 2 using the visible light-responded platinum making, and inserts and contains 0.25M Na respectively
2in S electrolyte solution, described light anode 1 is connected by outer lead with photocathode 2.(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
+be reduced to H
2, the S in electrolyte
2-on light anode 1, by photohole, be oxidized, the light induced electron that light anode 1 produces is passed to photocathode 2 by external circuit and is combined with its photohole, realizes Photocatalyzed Hydrogen Production and generating simultaneously.Accompanying drawing 3 has provided product hydrogen performance with this understanding and has produced the current density curve in hydrogen process, and in figure, curve E shows that it is 45.5 μ molh that the hydrogen of the present embodiment produces speed
-1cm
-2, curve D shows that in external circuit, current value is 1.5mAcm
-2, and significantly do not reduce and fluctuate at the current value described in product hydrogen process.Accompanying drawing 4 has provided the battery performance curve of the present embodiment under this condition, and the electricity conversion that shows the present embodiment in figure 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.These results show, system of the present invention has good product hydrogen and power generation performance under visible ray, has good stability simultaneously.
The effect of embodiment 1 is described with 2 reference examples below.
Reference examples 1
In contrast, in embodiment 1 other condition constant in the situation that, by Bi prepared in embodiment 1
2s
3the TiO of sensitization
2nano-tube array film electrode, as light anode, is usingd platinized platinum as to electrode, with the light source described in embodiment 1, irradiates the light anode in this reference examples 1, and measuring its hydrogen-producing speed is 0.32 μ mol h
-1cm
-2, be only 1/142 of embodiment 1; Electricity conversion is 0.00316%, is only 1/227 of embodiment 1; Open circuit voltage is only 0.173V; Short circuit current is only 0.079mAcm
-2; Fill factor, curve factor is only 0.231.
Reference examples 2
In contrast, in embodiment 1 other condition constant in the situation that, platinum prepared in embodiment 1 is modified to silicon cell electrode as photocathode, using platinized platinum as to electrode, with the light source described in embodiment 1, irradiate the photocathode in this reference examples 2, measuring its hydrogen-producing speed is 16.1 μ mol h
-1cm
-2, be only about 1/3 of embodiment 1; Electricity conversion is 0.0485%, is only 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 Bi
2s
3the TiO of sensitization
2nano-tube array film electrode is as light anode 1, and visible light-responded platinum is modified silicon cell electrode as photocathode 2, inserts and contains 0.1M Na respectively
2in S electrolyte solution, and connect 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
+be reduced to H
2, the S in electrolyte
2-on light anode 1, by photohole, be oxidized, the light induced electron that light anode 1 produces is passed to photocathode 2 by external circuit and is combined with its photohole, realizes Photocatalyzed Hydrogen Production and generating simultaneously.It is 43.1 μ mol h that the hydrogen of the present embodiment produces speed
-1cm
-2, in external circuit, by electrochemical workstation, to test the result obtaining be 1.42mAcm to current value
-2, and significantly do not reduce and fluctuate at the current value described in product hydrogen process; The electricity conversion of the present embodiment is 0.673%, and open circuit voltage is 0.764V, and short circuit current is 1.47mAcm
-2, fill factor, curve factor is 0.601.These results show, described system has good product hydrogen and power generation performance under visible ray, has good stability simultaneously.
Embodiment 3
With visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode is as light anode 1, and visible light-responded platinum is modified silicon cell electrode as photocathode 2, inserts and contains 0.5M Na respectively
2in S electrolyte solution, and connect 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
+be reduced to H
2, the S in electrolyte
2-on light anode 1, by photohole, be oxidized, the light induced electron that light anode 1 produces is passed to photocathode 2 by external circuit and is combined with its photohole, realizes Photocatalyzed Hydrogen Production and generating simultaneously.It is 46.7 μ mol h that the hydrogen of the present embodiment produces speed
-1cm
-2, in external circuit, by electrochemical workstation, to test the result obtaining be 1.54mAcm to current value
-2, and significantly do not reduce and fluctuate at the current value described in product hydrogen process; The electricity conversion of the present embodiment is 0.723%, and open circuit voltage is 0.768V, and short circuit current is 1.57mAcm
-2, fill factor, curve factor is 0.599.These results show, described system has good product hydrogen and power generation performance under visible ray, has good stability simultaneously.
The present invention can be applied to solar hydrogen making generating simultaneously, have advantages of visible light-responded, produce hydrogen and excellent in power generation efficiency, good stability and cost low, significant to the exploitation of solar hydrogen making and generation technology.
Claims (4)
1. visible light-responded automatic bias photoelectrocatalysis decomposes a system for aquatic products hydrogen generating, comprises light anode, photocathode, electrolyte, visible light source, quartz reaction pond and quartzy discharge, it is characterized in that, described light anode is visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode, described time,, very visible light-responded platinum was modified silicon cell electrode, the Na that described electrolyte is 0.1～0.5M
2s solution; Described light anode and photocathode are inserted in the described electrolyte in described quartz reaction pond simultaneously, and by external circuit UNICOM; Open described visible light source and irradiate respectively described light anode and photocathode, now described light anode and the generating electrodes reaction of photocathode difference also forms loop by external circuit, thereby realize automatic bias photoelectrocatalysis, produces hydrogen and generating.
2. visible light-responded automatic bias photoelectrocatalysis according to claim 1 decomposes the system of aquatic products hydrogen generating, it is characterized in that, described visible light source is simulated solar irradiation, and light intensity is 100mW cm
-2.
3. visible light-responded automatic bias photoelectrocatalysis claimed in claim 1 decomposes a preparation method for the system of aquatic products hydrogen generating, it is characterized in that, described preparation method's concrete steps comprise:
1) the described visible light-responded Bi of preparation
2s
3the TiO of sensitization
2nano-tube array film electrode, its method is: first using clean metallic titanium plate as anode, be placed in the aqueous solution containing 0.5% hydrofluoric acid, take platinum electrode as to electrode, regulation voltage is 20V, and metallic titanium plate is carried out to anodic oxidation 60 minutes, obtains the TiO by Titanium and titanium surface
2the titanium base TiO forming
2nano-tube array material, then this titanium base TiO
2nano-tube array material after 1 hour, obtains having the TiO of Anatase through 500 ℃ of high temperature sinterings
2nano-pipe array thin film material; With this, there is the TiO of Anatase
2nano-pipe array thin film material, as substrate, by the mode of rotary coating, alternately drips the Bi (NO of 0.5ml50mM to this substrate
3)
3na with 100mM
2s solution, wherein, described Bi (NO
3)
3solution adopts the acetum of 1M as solvent, after dropwising, under 3000rpm rotating speed, is coated with 20s at every turn, alternately repeats 30 times, obtains Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, by this Bi
2s
3the titanium base TiO of sensitization
2nano-pipe array thin film material, through 300 ℃ of high temperature sinterings 1 hour, obtains described visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode;
2) adopt the described visible light-responded platinum of known method preparation to modify silicon cell electrode;
3) by step 1) prepared visible light-responded Bi
2s
3the TiO of sensitization
2nano-tube array film electrode is as light anode, using step 2) prepared visible light-responded platinum modifies silicon cell electrode as photocathode, inserts respectively the 0.1～0.5M Na in described quartz reaction pond
2in S electrolyte solution, described smooth anode and photocathode are communicated with by external circuit and are irradiated and produced photogenerated charge by described visible light source.
4. the application of the system that a visible light-responded automatic bias photoelectrocatalysis claimed in claim 1 decomposes aquatic products hydrogen generating in solar hydrogen making generating simultaneously.
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