CN108823590A - TiO is carried out using electron irradiation2The modified method and its application of nano-wire array - Google Patents
TiO is carried out using electron irradiation2The modified method and its application of nano-wire array Download PDFInfo
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- CN108823590A CN108823590A CN201810631432.0A CN201810631432A CN108823590A CN 108823590 A CN108823590 A CN 108823590A CN 201810631432 A CN201810631432 A CN 201810631432A CN 108823590 A CN108823590 A CN 108823590A
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- 239000002070 nanowire Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 111
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 151
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 98
- 230000003287 optical effect Effects 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 230000005855 radiation Effects 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000012545 processing Methods 0.000 claims abstract description 26
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims description 130
- 239000000758 substrate Substances 0.000 claims description 129
- 239000000243 solution Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000010792 warming Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000002390 adhesive tape Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002071 nanotube Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000005518 electrochemistry Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
Abstract
TiO is carried out using electron irradiation the invention discloses a kind of2The modified method and its application of nano-wire array, first progress hydro-thermal method prepare TiO2Nano-wire array prepares TiO2Compacted zone simultaneously synthesizes TiO by hydro-thermal method2Then nano-wire array utilizes electron irradiation TiO2Nano-wire array obtains TiO2Nano-wire array photoelectric device.TiO prepared by the present invention2Nano-wire array photoelectric device can apply to electrochemical decomposition water process for making hydrogen, carry out the electrolytic preparation hydrogen energy source of water.The method of the present invention introduces electronic radiation method, on the one hand can controllably regulate and control lattice defect to improve TiO2Carrier concentration and mobility, to effectively improve TiO2The photo-generated carrier of optical anode material transmits and separative efficiency；On the other hand since this method is to be modified processing to material in atomic level, has exclusive compatibility, it can be combined well with the methods of other ion dopings, heterojunction structure, so as to further promote the axial transport ability of light absorption red shift and photo-generated carrier, Carrier recombination is reduced, TiO is increased substantially2The density of photocurrent of light anode device.Simple process, favorable repeatability, economy benefit are big.
Description
Technical field
The present invention relates to a kind of preparation method and applications of photoelectric device, more particularly to a kind of combination nano functional material
The preparation method and applications of the photoelectric device of material, are applied to optical electro-chemistry hydrogen production by water decomposition and solar energy trans-utilization technology is led
Domain.
Background technique
Water is referred to as electrolysis hydrogen producing process by the process of the electrolytically generated hydrogen of direct current and oxygen, and water electrolysis hydrogen production is to take
The method for preparing hydrogen fuel for the next generation of steam reformation hydrogen production.Under ideal conditions, electrolysis water generate gas flow with pass through
Electricity it is directly proportional.But under actual conditions, due to the participation of many side reactions, a certain amount of by-product can be generated, is existed at present
Technique is using upper also uneconomical.
1971, Fujishima and Honda helped electrolysis water to obtain hydrogen with titanium dioxide electrodes light, started photoelectricity
Chemical hydrogen manufacturing introduces electrolysis hydrogen producing process, has started the new method of optical electro-chemistry hydrogen production by water decomposition and luminous energy trans-utilization,
In optical electro-chemistry hydrogen production by water decomposition technique, density of photocurrent is a very important index, is mainly used for evaluating the system of material
Hydrogen Energy power.
Traditional photoelectrochemical cell is made of light anode, photocathode and electrolyte.Electrode material is usually semiconductor material
Material, light excitation can produce electron hole pair, photoelectrochemical cell formed in electrolyte solution, in the driving of light and electricity
Under, generate hydrogen and oxygen.Since the electrochemical kinetics that oxygen generates is slower, light anode semiconductor material is to influence system
The factor of the most critical of hydrogen efficiency.Semiconductor absorption limit should be made to shift to visible light part as much as possible, reduce photoproduction current-carrying
It is compound between son, and the service life of carrier is improved, and improve the utilization efficiency to solar energy.Optical anode material is studied most
That more is TiO2, TiO2As light anode, resistance to photoetch, chemical stability is good.But current TiO2The efficiency of light absorption of light anode
Also undesirable, the axial transport ability of photo-generated carrier is to be improved, and compound between photo-generated carrier needs to inhibit, TiO2Light
Anode device density of photocurrent needs to improve, and is just able to satisfy the need of the trans-utilization of heavy industrialization hydrogen manufacturing and solar energy
It wants, this becomes technical problem urgently to be resolved.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
TiO is carried out using electron irradiation2The modified method and its application of nano-wire array introduce electronic radiation method, and on the one hand energy can
Control control lattice defect improves TiO2Carrier concentration and mobility, to effectively improve TiO2The light of optical anode material
Raw carrier transport and separative efficiency；On the other hand since this method is to be modified processing to material in atomic level, tool
Standby exclusive compatibility, can be combined well with the methods of other ion dopings, heterojunction structure, so as to further promote light
The axial transport ability of red shift and photo-generated carrier is absorbed, Carrier recombination is reduced, TiO is greatly improved2Light anode device
The density of photocurrent of part, simple process, favorable repeatability, economy benefit are big.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
It is a kind of to carry out TiO using electron irradiation2The modified method of nano-wire array, includes the following steps：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. HCl solution of the mass percent concentration of 14~16 μ L not higher than 37%, 0.5~0.7mg metatitanic acid are successively taken
8~10mL the absolute alcohol of four butyl esters, purity not less than 99.9% (v/v.), which is placed in container, to be mixed, and is stirred by ultrasound
It mixes, until being sufficiently mixed uniformly, obtains TiO2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, spin coating instrument is then turned on, to be not less than
The revolving speed of 3000rmp/min, at least rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution
Liquid film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, at least the high temperature anneal of 1h is carried out at not less than 500 DEG C, makes TiO2Compacted zone solidification after with FTO glass substrate knot
It closes, is formed and combine TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. the deionization of the mass percent concentration of the 8~10mL HCl solution not higher than 37% and 8~10mL is successively taken
Water mixes in container, then puts it into magnetic force ultrasonic device, is uniformly mixed, is obtained dilute by being no less than 10min stir process
HCl solution after releasing, it is spare；
B-2. 0.2~0.4mL butyl titanate is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1 is molten
In liquid, and be uniformly mixed within no less than 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to resistance
In furnace, then reaction kettle is heated, hydro-thermal reaction is carried out at not higher than 170 DEG C and is not higher than 6h；It is preferred that carrying out hydro-thermal reaction
80~170 DEG C of temperature；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2TiO on compacted zone2The FTO glass substrate complex of nano tube/linear array film, changes compacted zone and is equivalent to one layer
Seed crystal, for growing TiO2；
B-5. there will be TiO by the growth of the step b-4 drying and processing2The FTO glass substrate of nano tube/linear array film is multiple
Zoarium is put into annelaing pot, carries out at least the high temperature anneal of 1h at not less than 500 DEG C, to obtain combining TiO2Nanometer
The optical device precursor of linear array；
(2) electron irradiation TiO2Nano-wire array is modified：
Using linac, to the combination TiO to be processed prepared in the step b-52Nano-wire array
Optical device precursor carry out electron irradiation processing, control electron accelerator electronic beam current intensity be 5~10mA, radiation resistance
For 50~300kGy, radiation environment uses room temperature and condition of normal pressure, and radiation mode uses and scans back and forth formula, TiO2Nano-wire array
After electron irradiation, TiO is obtained2Nano-wire array photoelectric device.In electron irradiation TiO2When nano-wire array is modified, preferably
Radiation resistance is 50~300kGy.
As currently preferred technical solution, TiO is carried out using electron irradiation2The modified method of nano-wire array,
In the step b-3, the thermal system that progress hydro-thermal reaction uses is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min.
The technical solution further preferred as the present invention, when carrying out hydro-thermal reaction, first when being not higher than 200min
In from room temperature to 80 DEG C, the heating-up time from 80 DEG C to 110 DEG C is 9min, and the heating-up time from 110 DEG C to 120 DEG C is
3min, the heating-up time from 120 DEG C to 130 DEG C are 3min, and the heating-up time from 130 DEG C to 150 DEG C is 6min, from 150 DEG C to
170 DEG C of heating-up time is 6min.
When carrying out hydro-thermal reaction, the heating rate for further preferably controlling thermal system is not higher than 3.34 DEG C/min.More
The heating rate of further preferably control thermal system is 0.2~3.34 DEG C/min.
The method of the present invention can improve photoelectric current with other ion dopings, heterojunction structure etc. as a preferred technical solution,
The method of density, which cooperates with, to be used, and has exclusive compatibility.
It is a kind of the present invention using electron irradiation progress TiO2The TiO of the modified method preparation of nano-wire array2Nano-wire array
The application of photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Nano-TiO of the present invention2The working principle of array photoelectric chemical breakdown water：
Electrode material TiO prepared by the present invention2Effective broadband light absorption is carried out under certain illumination condition, to produce
Raw electron-hole pair.Again respectively by the strong reducing property of the strong oxidizing property of photohole and light induced electron respectively reach analysis oxygen and
The purpose of liberation of hydrogen, to realize the electrolysis of water.The present invention utilizes TiO2The photo-generated carrier effect of material is by photocatalysis and water power
Solution is organically coupled, and the electrolysis of water is reached by the strong oxidizing property of photohole and the strong reducing property of light induced electron, most
Realize that solar energy is converted into Hydrogen Energy eventually.It can effectively change the energy pattern that current mankind faces, promote the storage of solar energy with
It utilizes.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the nano-wire array of the method for the present invention preparation can not only greatly improve the specific surface area of material, thus effectively
Raising electrode material efficiency of light absorption, moreover it is possible to effectively facilitate the axial transport ability of photo-generated carrier, it is multiple to reduce carrier
It closes；
2. the method for the present invention introduces electronic radiation method, on the one hand it can controllably regulate and control lattice defect to improve TiO2Current-carrying
Sub- concentration and mobility, to effectively improve TiO2The photo-generated carrier of optical anode material transmits and separative efficiency；Another party
Face has exclusive compatibility, can mix with other ions since this method is to be modified processing to material in atomic level
The methods of miscellaneous, heterojunction structure combines well, so as to further promote the transverse direction of light absorption red shift and photo-generated carrier
Transport capacity reduces Carrier recombination, increases substantially TiO2The density of photocurrent of light anode device promotes heavy industrialization
The trans-utilization of hydrogen manufacturing and solar energy；
3. the method for the present invention simple process, favorable repeatability, economy benefit are big.
Detailed description of the invention
Fig. 1 is that one method of the embodiment of the present invention carries out TiO before and after electron irradiation2The XRD diagram of nano-wire array.
Fig. 2 is TiO before and after the embodiment of the present invention one to five method difference fluence electron irradiation of embodiment2Nano-wire array
Density of photocurrent comparison diagram.
Fig. 3 is TiO after the embodiment of the present invention one to five method difference fluence electron irradiation of embodiment vulcanization2Nano-wire array
Density of photocurrent comparison diagram.
Fig. 4 is that one method of the embodiment of the present invention carries out controlling Intelligent box type resistance furnace heating schedule figure when hydro-thermal reaction.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one
In the present embodiment, FIG. 1 to FIG. 4 is participated in, it is a kind of to carry out TiO using electron irradiation2The modified side of nano-wire array
Method includes the following steps：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. successively take 14 μ L mass percent concentration be 37% HCl solution, 0.5mg butyl titanate (TTIP),
Purity is placed in a beaker for the 8mL absolute alcohol of 99.9% (v/v.) and is mixed, by ultrasonic agitation, until being sufficiently mixed
It is even, obtain TiO2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, is then turned on spin coating instrument, with
The revolving speed of 3000rmp/min, rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution liquid
Film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, the high temperature anneal of 1h is carried out at 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, is formed and combined
TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. the deionized water for the HCl solution and 8mL that the mass percent concentration of 8mL is 37% is successively taken to mix in container
It closes, then puts it into magnetic force ultrasonic device, be uniformly mixed by 10min stir process, the HCl solution after being diluted is spare；
B-2. 0.2mL butyl titanate (TTIP) is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1
In solution, and be uniformly mixed within 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to intelligence
In chamber type electric resistance furnace, then reaction kettle is heated, hydro-thermal reaction 6h is carried out at 80~170 DEG C；Referring to Fig. 3；
When carrying out hydro-thermal reaction, the thermal system used is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min；
When carrying out hydro-thermal reaction, first with 200min (allowing it) from room temperature to 80 DEG C, then, from 80 DEG C to
110 DEG C of heating-up time is 9min, and the heating-up time from 110 DEG C to 120 DEG C is 3min, the heating-up time from 120 DEG C to 130 DEG C
For 3min, the heating-up time from 130 DEG C to 150 DEG C is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2The FTO glass substrate complex of nano-wire array on compacted zone；
B-5. will there is surface TiO by the step b-4 drying and processing2The FTO glass of compacted zone nano-wire array
Glass liner compound body is put into annelaing pot, and the high temperature anneal of 1h is carried out at 500 DEG C, to obtain combining TiO2Nano wire
The optical device precursor of array；
(2) electron irradiation TiO2Nano-wire array is modified：
To the combination TiO prepared in the step b-52The optical device precursor of nano-wire array carries out predose point
Group is divided into 4-6 group, and every group combines TiO comprising 9 parts2The optical device precursor sample of nano-wire array；Using straight line electron plus
Fast device, to combination TiO to be processed2The optical device precursor of nano-wire array carries out electron irradiation processing, and control electronics accelerates
The electronic beam current intensity of device is 5mA, and radiation resistance 50kGy, radiation environment is using room temperature and condition of normal pressure, radiation mode use
Scan back and forth formula, TiO2Nano-wire array obtains TiO after electron irradiation2Nano-wire array photoelectric device.
Experimental test and analysis：
To TiO manufactured in the present embodiment2The carry out electronics of nano-wire array photoelectric device and the present embodiment step b-5 preparation
Combination TiO before irradiation2The optical device precursor of nano-wire array carries out thermophysical experiment performance test, carries out x-ray and spreads out
Experiment is penetrated, and tests its density of photocurrent, Fig. 1 is that the present embodiment method carries out TiO before and after electron irradiation2Nano-wire array
XRD diagram.Fig. 2 is TiO before and after the present embodiment method electron irradiation2The density of photocurrent figure of nano-wire array.From the diffraction in Fig. 1
It is found that occurring after irradiation without new diffraction maximum, intensity increases position and the peak intensity at peak.It should be the result shows that electron irradiation change it
Crystal phase, but influence can be formed on its crystallinity.As can be seen from Figure 2, the TiO after irradiation2The density of photocurrent of nano-wire array is more former
Beginning TiO2It is significantly increased.TiO manufactured in the present embodiment2The density of photocurrent of nano-wire array photoelectric device is in 1.23V
From 0.66mA/cm under vs.RHE voltage2Promote 0.85mA/cm2, increased by 29% on a year-on-year basis.This is only individually to take electron irradiation
In atomic level to TiO2The result of nano-wire array study on the modification.Due to the exclusive compatibility of this method, usually change with other
Property method collaboration use, so as to make density of photocurrent have dual promotion.Based on TiO made from step of the present invention (1)2It carries out again
Vulcanization introduces heterojunction structure and S doping simultaneously, then carries out electron irradiation, can be by density of photocurrent in 1.23V vs.RHE
From the 0.66mA/cm of most original under voltage2Promote 1.08mA/cm2, increased by 64% on a year-on-year basis.Referring to Fig. 3.
A kind of the present embodiment utilizes electron irradiation to carry out TiO2The TiO of the modified method preparation of nano-wire array2Nanometer linear array
The application of column photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Using TiO manufactured in the present embodiment2Nano-wire array photoelectric device forms optical electro-chemistry as light anode, with cathode
Decompose solar pond, TiO2The excitation of nano-wire array photoelectric device light anode light can produce electron hole pair, light anode extinction
The electronics generated on semiconductor band afterwards flows to cathode by external circuit, and the hydrogen ion in water receives electronics from cathode and generates hydrogen
Gas.TiO manufactured in the present embodiment2Nano-wire array photoelectric device light anode optical absorption edge reduces in visible light part harness
It is compound between photo-generated carrier, and the service life of carrier is improved, resistance to photoetch, chemical stability is good, and significantly improves
To the utilization efficiency of solar energy.The present embodiment introduces electronic radiation method, and TiO is greatly improved2The photoelectric current of photoelectric device
Density is conducive to heavy industrialization hydrogen manufacturing and solar energy trans-utilization, and simple process is reproducible, and economy benefit is big.
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that：
In the present embodiment, a kind of to carry out TiO using electron irradiation2The modified method of nano-wire array, including walk as follows
Suddenly：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. successively take 15 μ L mass percent concentration be 37% HCl solution, 0.6mg butyl titanate (TTIP),
Purity is placed in a beaker for the 9mL absolute alcohol of 99.9% (v/v.) and is mixed, by ultrasonic agitation, until being sufficiently mixed
It is even, obtain TiO2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, is then turned on spin coating instrument, with
The revolving speed of 3000rmp/min, rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution liquid
Film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, the high temperature anneal of 1h is carried out at 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, is formed and combined
TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. the deionized water for the HCl solution and 9mL that the mass percent concentration of 9mL is 37% is successively taken to mix in container
It closes, then puts it into magnetic force ultrasonic device, be uniformly mixed by 10min stir process, the HCl solution after being diluted is spare；
B-2. 0.3mL butyl titanate (TTIP) is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1
In solution, and be uniformly mixed within 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to intelligence
In chamber type electric resistance furnace, then reaction kettle is heated, hydro-thermal reaction 5h is carried out at 80~170 DEG C；
When carrying out hydro-thermal reaction, the thermal system used is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min；
When carrying out hydro-thermal reaction, first with 140min from room temperature to 80 DEG C, then, from 80 DEG C to 110 DEG C
Heating-up time is 9min, and the heating-up time from 110 DEG C to 120 DEG C is 3min, and the heating-up time from 120 DEG C to 130 DEG C is 3min,
Heating-up time from 130 DEG C to 150 DEG C is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2TiO on compacted zone2The FTO glass substrate complex of nano tube/linear array film；
B-5. TiO will be grown in by the step b-4 drying and processing2TiO on compacted zone2The FTO of nano tube/linear array film
Glass substrate complex is put into annelaing pot, and the high temperature anneal of 1h is carried out at 500 DEG C, to obtain combining TiO2Nanometer
The optical device precursor of linear array；
(2) electron irradiation TiO2Nano-wire array is modified：
To the combination TiO prepared in the step b-52The optical device precursor of nano-wire array carries out predose point
Group is divided into 4-6 group, and every group combines TiO comprising 9 parts2The optical device precursor sample of nano-wire array；Using straight line electron plus
Fast device, to combination TiO to be processed2The optical device precursor of nano-wire array carries out electron irradiation processing, and control electronics accelerates
The electronic beam current intensity of device is 5mA, radiation resistance 100kGy, and radiation environment uses room temperature and condition of normal pressure, and radiation mode adopts
With the formula that scans back and forth, TiO2Nano-wire array obtains TiO after electron irradiation2Nano-wire array photoelectric device.
Experimental test and analysis：
To TiO manufactured in the present embodiment2The carry out electronics of nano-wire array photoelectric device and the present embodiment step b-5 preparation
Combination TiO before irradiation2The optical device precursor of nano-wire array carries out thermophysical experiment performance test, carries out x-ray and spreads out
Experiment is penetrated, and tests its density of photocurrent, it is known that the TiO after irradiation2Change and its energy of the nano-wire array due to crystal property
The improvement of band structure, the more original TiO of density of photocurrent2It is significantly increased.This is only individually to take electron irradiation in atomic level
To TiO2The result of nano-wire array study on the modification.TiO manufactured in the present embodiment2The photoelectric current of nano-wire array photoelectric device is close
Degree is under 1.23V vs.RHE voltage from 0.66mA/cm2Promote 0.96mA/cm2, increased by 45% on a year-on-year basis.Referring to fig. 2.This is only
It is individually to take electron irradiation in atomic level to TiO2The result of nano-wire array study on the modification.Due to exclusive simultaneous of this method
Capacitive usually cooperates with use with other method of modifying, so as to make density of photocurrent have dual promotion, is based on step of the present invention
(1) TiO made from2Vulcanized again, i.e., introduces heterojunction structure and S doping simultaneously, then carry out electron irradiation, it can be by photoelectric current
Density is under 1.23V vs.RHE voltage from the 0.66mA/cm of most original2Promote 1.34mA/cm2, increased by 103% on a year-on-year basis.
Referring to Fig. 3.
A kind of the present embodiment utilizes electron irradiation to carry out TiO2The TiO of the modified method preparation of nano-wire array2Nanometer linear array
The application of column photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Using TiO manufactured in the present embodiment2Nano-wire array photoelectric device forms optical electro-chemistry as light anode, with cathode
Decompose solar pond, TiO2The excitation of nano-wire array photoelectric device light anode light can produce electron hole pair, light anode extinction
The electronics generated on semiconductor band afterwards flows to cathode by external circuit, and the hydrogen ion in water receives electronics from cathode and generates hydrogen
Gas.TiO manufactured in the present embodiment2Nano-wire array photoelectric device light anode optical absorption edge reduces in visible light part harness
It is compound between photo-generated carrier, and the service life of carrier is improved, resistance to photoetch, chemical stability is good, and significantly improves
To the utilization efficiency of solar energy.The present embodiment introduces electronic radiation method, and TiO is greatly improved2The photoelectric current of photoelectric device
Density is conducive to heavy industrialization hydrogen manufacturing and solar energy trans-utilization, and simple process is reproducible, and economy benefit is big.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of to carry out TiO using electron irradiation2The modified method of nano-wire array, including walk as follows
Suddenly：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. successively take 16 μ L mass percent concentration be 37% HCl solution, 0.7mg butyl titanate (TTIP),
Purity is placed in a beaker for the 10mL absolute alcohol of 99.9% (v/v.) and is mixed, by ultrasonic agitation, until being sufficiently mixed
Uniformly, TiO is obtained2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, is then turned on spin coating instrument, with
The revolving speed of 3000rmp/min, rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution liquid
Film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, the high temperature anneal of 1h is carried out at 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, is formed and combined
TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. successively take the deionized water for the HCl solution and 10mL that the mass percent concentration of 10mL is 37% in container
Mixing, then put it into magnetic force ultrasonic device, it is uniformly mixed by 10min stir process, the HCl solution after being diluted is standby
With；
B-2. 0.2mL butyl titanate (TTIP) is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1
In solution, and be uniformly mixed within 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to intelligence
In chamber type electric resistance furnace, then reaction kettle is heated, hydro-thermal reaction 4h is carried out at 80~170 DEG C；
When carrying out hydro-thermal reaction, the thermal system used is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min；
When carrying out hydro-thermal reaction, first with 80min from room temperature to 80 DEG C, then, the liter from 80 DEG C to 110 DEG C
The warm time is 9min, and the heating-up time from 110 DEG C to 120 DEG C is 3min, and the heating-up time from 120 DEG C to 130 DEG C is 3min, from
130 DEG C to 150 DEG C of heating-up time is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2TiO on compacted zone2The FTO glass substrate complex of nano tube/linear array film；
B-5. will there is surface TiO by the step b-4 drying and processing2The FTO glass of compacted zone nano-wire array
Glass liner compound body is put into annelaing pot, and the high temperature anneal of 1h is carried out at 500 DEG C, to obtain combining TiO2Nano wire
The optical device precursor of array；
(2) electron irradiation TiO2Nano-wire array is modified：
To the combination TiO prepared in the step b-52The optical device precursor of nano-wire array carries out predose point
Group is divided into 4-6 group, and every group combines TiO comprising 9 parts2The optical device precursor sample of nano-wire array；Using straight line electron plus
Fast device, to combination TiO to be processed2The optical device precursor of nano-wire array carries out electron irradiation processing, and control electronics accelerates
The electronic beam current intensity of device is 5mA, radiation resistance 150kGy, and radiation environment uses room temperature and condition of normal pressure, and radiation mode adopts
With the formula that scans back and forth, TiO2Nano-wire array obtains TiO after electron irradiation2Nano-wire array photoelectric device.
Experimental test and analysis：
To TiO manufactured in the present embodiment2The carry out electronics of nano-wire array photoelectric device and the present embodiment step b-5 preparation
Combination TiO before irradiation2The optical device precursor of nano-wire array carries out thermophysical experiment performance test, carries out x-ray and spreads out
Experiment is penetrated, and tests its density of photocurrent, it is known that the TiO after irradiation2Change and its energy of the nano-wire array due to crystal property
The improvement of band structure, the more original TiO of density of photocurrent2It is significantly increased.TiO manufactured in the present embodiment2Nano-wire array phototube
The density of photocurrent of part under 1.23V vs.RHE voltage density of photocurrent from 0.66mA/cm2Promote 0.74mA/cm2, on year-on-year basis
Increase 12%.Referring to fig. 2.This is only individually to take electron irradiation in atomic level to TiO2Nano-wire array study on the modification
As a result.This is only individually to take electron irradiation in atomic level to TiO2The result of nano-wire array study on the modification.Due to the party
The exclusive compatibility of method, usually cooperates with use with other method of modifying, so as to make density of photocurrent have dual promotion, based on this
TiO made from inventive step (1)2Vulcanized again, i.e., introduces heterojunction structure and S doping simultaneously, then carry out electron irradiation, it can
By density of photocurrent from the 0.66mA/cm of most original under 1.23V vs.RHE voltage2Promote 1.01mA/cm2, increase by a year-on-year basis
53%.Referring to Fig. 3.
A kind of the present embodiment utilizes electron irradiation to carry out TiO2The TiO of the modified method preparation of nano-wire array2Nanometer linear array
The application of column photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Using TiO manufactured in the present embodiment2Nano-wire array photoelectric device forms optical electro-chemistry as light anode, with cathode
Decompose solar pond, TiO2The excitation of nano-wire array photoelectric device light anode light can produce electron hole pair, light anode extinction
The electronics generated on semiconductor band afterwards flows to cathode by external circuit, and the hydrogen ion in water receives electronics from cathode and generates hydrogen
Gas.TiO manufactured in the present embodiment2Nano-wire array photoelectric device light anode optical absorption edge reduces in visible light part harness
It is compound between photo-generated carrier, and the service life of carrier is improved, resistance to photoetch, chemical stability is good, and significantly improves
To the utilization efficiency of solar energy.The present embodiment introduces electronic radiation method, and TiO is greatly improved2The photoelectric current of photoelectric device
Density is conducive to heavy industrialization hydrogen manufacturing and solar energy trans-utilization, and simple process is reproducible, and economy benefit is big.
Example IV
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of to carry out TiO using electron irradiation2The modified method of nano-wire array, including walk as follows
Suddenly：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. successively take 16 μ L mass percent concentration be 37% HCl solution, 0.7mg butyl titanate (TTIP),
Purity is placed in a beaker for the 10mL absolute alcohol of 99.9% (v/v.) and is mixed, by ultrasonic agitation, until being sufficiently mixed
Uniformly, TiO is obtained2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, is then turned on spin coating instrument, with
The revolving speed of 3000rmp/min, rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution liquid
Film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, the high temperature anneal of 1h is carried out at 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, is formed and combined
TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. successively take the deionized water for the HCl solution and 10mL that the mass percent concentration of 10mL is 37% in container
Mixing, then put it into magnetic force ultrasonic device, it is uniformly mixed by 10min stir process, the HCl solution after being diluted is standby
With；
B-2. 0.4mL butyl titanate (TTIP) is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1
In solution, and be uniformly mixed within 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to intelligence
In chamber type electric resistance furnace, then reaction kettle is heated, hydro-thermal reaction 3h is carried out at 80~170 DEG C；
When carrying out hydro-thermal reaction, the thermal system used is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min；
When carrying out hydro-thermal reaction, first with 20min from room temperature to 80 DEG C, then, the liter from 80 DEG C to 110 DEG C
The warm time is 9min, and the heating-up time from 110 DEG C to 120 DEG C is 3min, and the heating-up time from 120 DEG C to 130 DEG C is 3min, from
130 DEG C to 150 DEG C of heating-up time is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2TiO on compacted zone2The FTO glass substrate complex of nano-wire array；
B-5. will there is surface TiO by the step b-4 drying and processing2The FTO glass of compacted zone nano-wire array
Glass liner compound body is put into annelaing pot, and the high temperature anneal of 1h is carried out at 500 DEG C, to obtain combining TiO2Nano wire
The optical device precursor of array；
(2) electron irradiation TiO2Nano-wire array is modified：
To the combination TiO prepared in the step b-52The optical device precursor of nano-wire array carries out predose point
Group is divided into 4-6 group, and every group combines TiO comprising 9 parts2The optical device precursor sample of nano-wire array；Using straight line electron plus
Fast device, to combination TiO to be processed2The optical device precursor of nano-wire array carries out electron irradiation processing, and control electronics accelerates
The electronic beam current intensity of device is 10mA, radiation resistance 200kGy, and radiation environment uses room temperature and condition of normal pressure, and radiation mode adopts
With the formula that scans back and forth, TiO2Nano-wire array obtains TiO after electron irradiation2Nano-wire array photoelectric device.
Experimental test and analysis：
To TiO manufactured in the present embodiment2The carry out electronics of nano-wire array photoelectric device and the present embodiment step b-5 preparation
Combination TiO before irradiation2The optical device precursor of nano-wire array carries out thermophysical experiment performance test, carries out x-ray and spreads out
Experiment is penetrated, and tests its density of photocurrent, it is known that the TiO after irradiation2Change and its energy of the nano-wire array due to crystal property
The improvement of band structure, the more original TiO of density of photocurrent2It is significantly increased.TiO manufactured in the present embodiment2The photoelectricity of nano-wire array
Current density under 1.23V vs.RHE voltage density of photocurrent from 0.66mA/cm2Promote 0.70mA/cm2, increase by a year-on-year basis
6%.Referring to fig. 2.This is only individually to take electron irradiation in atomic level to TiO2The result of nano-wire array study on the modification.By
In the exclusive compatibility of this method, use usually is cooperateed with other method of modifying, so as to make density of photocurrent have dual promotion,
Based on TiO made from step of the present invention (1)2Vulcanized again, i.e., introduces heterojunction structure and s simultaneously2-Doping, then carry out electronics
Irradiation, can by density of photocurrent under 1.23V vs.RHE voltage from the 0.66mA/cm of most original2Promote 0.81mA/cm2, together
Than increasing 23%.Referring to Fig. 3.
A kind of the present embodiment utilizes electron irradiation to carry out TiO2The TiO of the modified method preparation of nano-wire array2Nanometer linear array
The application of column photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Using TiO manufactured in the present embodiment2Nano-wire array photoelectric device forms optical electro-chemistry as light anode, with cathode
Decompose solar pond, TiO2The excitation of nano-wire array photoelectric device light anode light can produce electron hole pair, light anode extinction
The electronics generated on semiconductor band afterwards flows to cathode by external circuit, and the hydrogen ion in water receives electronics from cathode and generates hydrogen
Gas.TiO manufactured in the present embodiment2Nano-wire array photoelectric device light anode optical absorption edge reduces in visible light part harness
It is compound between photo-generated carrier, and the service life of carrier is improved, resistance to photoetch, chemical stability is good, and significantly improves
To the utilization efficiency of solar energy.The present embodiment introduces electronic radiation method, and TiO is greatly improved2The photoelectric current of photoelectric device
Density is conducive to heavy industrialization hydrogen manufacturing and solar energy trans-utilization, and simple process is reproducible, and economy benefit is big.
Embodiment five
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of to carry out TiO using electron irradiation2The modified method of nano-wire array, including walk as follows
Suddenly：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. successively take 16 μ L mass percent concentration be 37% HCl solution, 0.7mg butyl titanate (TTIP),
Purity is placed in a beaker for the 10mL absolute alcohol of 99.9% (v/v.) and is mixed, by ultrasonic agitation, until being sufficiently mixed
Uniformly, TiO is obtained2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate
Width regions between the edge position 1~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, is made not by glue
FTO glass substrate central region with covering is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be described with dropper
The TiO of step a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, is then turned on spin coating instrument, with
The revolving speed of 3000rmp/min, rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution liquid
Film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, is obtained attached
TiO2The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot
In, the high temperature anneal of 1h is carried out at 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, is formed and combined
TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. the deionized water for the HCl solution and 9mL that the mass percent concentration of 9mL is 37% is successively taken to mix in container
It closes, then puts it into magnetic force ultrasonic device, be uniformly mixed by 10min stir process, the HCl solution after being diluted is spare；
B-2. 0.3mL butyl titanate (TTIP) is taken with liquid-transfering gun, the HCl being added to after diluting in the step b-1
In solution, and be uniformly mixed within 10 minutes in magnetic force ultrasonic device, obtains mixed reactant solution, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction of sealing
In kettle, then the mixed reactant solution obtained in the step b-2 poured into reaction kettle, then reaction kettle is set to intelligence
In chamber type electric resistance furnace, then reaction kettle is heated, hydro-thermal reaction 3.5h is carried out at 80~170 DEG C；
When carrying out hydro-thermal reaction, the thermal system used is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up at 110 DEG C and carries out second-order
Section hydro-thermal reaction 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C
Carry out fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally heat up
The 6th stage hydro-thermal reaction 48min is carried out to 160 DEG C；When carrying out hydro-thermal reaction, it is not high for controlling the heating rate of thermal system
In 5.0 DEG C/min；
When carrying out hydro-thermal reaction, first with 50min from room temperature to 80 DEG C, then, the liter from 80 DEG C to 110 DEG C
The warm time is 9min, and the heating-up time from 110 DEG C to 120 DEG C is 3min, and the heating-up time from 120 DEG C to 130 DEG C is 3min, from
130 DEG C to 150 DEG C of heating-up time is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature
When, reaction kettle is opened, takes out FTO glass substrate, then slowly rinse FTO glass substrate surface with deionized water, and dried,
It obtains being grown in TiO2TiO on compacted zone2The FTO glass substrate complex of nano-wire array；
B-5. will there is surface TiO by the step b-4 drying and processing2The FTO glass of compacted zone nano-wire array
Glass liner compound body is put into annelaing pot, and the high temperature anneal of 1h is carried out at 500 DEG C, to obtain combining TiO2Nano wire
The optical device precursor of array；
(2) electron irradiation TiO2Nano-wire array is modified：
To the combination TiO prepared in the step b-52The optical device precursor of nano-wire array carries out predose point
Group is divided into 4-6 group, and every group combines TiO comprising 9 parts2The optical device precursor sample of nano-wire array；Using straight line electron plus
Fast device, to combination TiO to be processed2The optical device precursor of nano-wire array carries out electron irradiation processing, and control electronics accelerates
The electronic beam current intensity of device is 5mA, radiation resistance 250kGy, and radiation environment uses room temperature and condition of normal pressure, and radiation mode adopts
With the formula that scans back and forth, TiO2Nano-wire array obtains TiO after electron irradiation2Nano-wire array photoelectric device.
Experimental test and analysis：
To TiO manufactured in the present embodiment2The carry out electronics of nano-wire array photoelectric device and the present embodiment step b-5 preparation
Combination TiO before irradiation2The optical device precursor of nano-wire array carries out thermophysical experiment performance test, carries out x-ray and spreads out
Experiment is penetrated, and tests its density of photocurrent, it is known that the TiO after irradiation2Change and its energy of the nano-wire array due to crystal property
The improvement of band structure, the more original TiO of density of photocurrent2It is significantly increased.TiO manufactured in the present embodiment2The photoelectricity of nano-wire array
Current density is under 1.23V vs.RHE voltage from 0.66mA/cm2Promote 0.67mA/cm2, increased by 1.5% on a year-on-year basis.Referring to figure
2.This is only individually to take electron irradiation in atomic level to TiO2The result of nano-wire array study on the modification.Since this method is only
Some compatibility usually cooperate with use with other method of modifying, so as to make density of photocurrent have dual promotion, based on the present invention
TiO made from step (1)2Vulcanized again, i.e., introduces heterojunction structure and s simultaneously2-Doping, then electron irradiation is carried out, it can incite somebody to action
Density of photocurrent is under 1.23V vs.RHE voltage from the 0.66mA/cm of most original2Promote 0.77mA/cm2, increase by a year-on-year basis
17%.Referring to Fig. 3.
A kind of the present embodiment utilizes electron irradiation to carry out TiO2The TiO of the modified method preparation of nano-wire array2Nanometer linear array
The application of column photoelectric device is applied to electrochemical decomposition water process for making hydrogen, carries out the electrolytic preparation hydrogen energy source of water.
Using TiO manufactured in the present embodiment2Nano-wire array photoelectric device forms optical electro-chemistry as light anode, with cathode
Decompose solar pond, TiO2The excitation of nano-wire array photoelectric device light anode light can produce electron hole pair, light anode extinction
The electronics generated on semiconductor band afterwards flows to cathode by external circuit, and the hydrogen ion in water receives electronics from cathode and generates hydrogen
Gas.TiO manufactured in the present embodiment2Nano-wire array photoelectric device light anode optical absorption edge reduces in visible light part harness
It is compound between photo-generated carrier, and the service life of carrier is improved, resistance to photoetch, chemical stability is good, and significantly improves
To the utilization efficiency of solar energy.The present embodiment introduces electronic radiation method, on the one hand can controllably regulate and control lattice defect to improve
TiO2Carrier concentration and mobility, to effectively improve TiO2The photo-generated carrier of optical anode material transmits and separation effect
Rate；On the other hand since this method is to be modified processing to material in atomic level, have an exclusive compatibility, energy and its
The methods of its ion doping, heterojunction structure combine well, so as to further promote light absorption red shift and photoproduction current-carrying
The axial transport ability of son reduces Carrier recombination, increases substantially TiO2The density of photocurrent of light anode device is conducive to big
Technical scale hydrogen manufacturing and solar energy trans-utilization, simple process is reproducible, and economy benefit is big.
In conclusion the nano-wire array of the above embodiment of the present invention method preparation can not only greatly improve material
Specific surface area, to effectively improve the efficiency of light absorption of electrode material, moreover it is possible to effectively facilitate the axial transport of photo-generated carrier
Ability reduces Carrier recombination；The above embodiment of the present invention method introduces electronic radiation method, on the one hand can controllably regulate and control lattice
Defect improves TiO2Carrier concentration and mobility, to effectively improve TiO2The photo-generated carrier of optical anode material passes
Defeated and separative efficiency；On the other hand since this method is to be modified processing to material in atomic level, have exclusive simultaneous
Capacitive can be combined well with the methods of other ion dopings, heterojunction structure, so as to further promote light absorption red shift with
And the axial transport ability of photo-generated carrier, Carrier recombination is reduced, TiO is increased substantially2The photoelectric current of light anode device is close
Degree promotes the trans-utilization of heavy industrialization hydrogen manufacturing and solar energy；The above embodiment of the present invention method and process is simple, can weigh
Renaturation is good, and economy benefit is big.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
TiO is carried out using electron irradiation without departing from the present invention2The technical principle of the modified method and its application of nano-wire array and
Inventive concept belongs to protection scope of the present invention.
Claims (9)
1. a kind of carry out TiO using electron irradiation2The modified method of nano-wire array, which is characterized in that include the following steps：
(1) hydro-thermal method prepares TiO2Nano-wire array：
A. TiO is prepared2Compacted zone：
A-1. HCl solution of the mass percent concentration of 14~16 μ L not higher than 37%, 0.5~0.7mg metatitanic acid, four fourth are successively taken
8~10mL the absolute alcohol of ester, purity not less than 99.9% (v/v.), which is placed in container, to be mixed, by ultrasonic agitation, directly
To being sufficiently mixed uniformly, TiO is obtained2Compacted zone solution；
A-2. using FTO glass substrate as substrate, since FTO glass substrate edge and distance FTO glass substrate edge 1
Width regions between the position~1.5cm stick adhesive tape, and FTO glass substrate edge is covered with adhesive tape, makes not covered by adhesive tape
The FTO glass substrate central region of lid is spare as region to be coated；
A-3. will by the step a-2, treated that FTO glass substrate is fixed on spin coater, will be in the step with dropper
The TiO of a-1 preparation2Compacted zone solution is dripped in the central area of FTO glass substrate, spin coating instrument is then turned on, to be not less than
The revolving speed of 3000rmp/min, at least rotary coating 30s uniformly coat TiO in FTO glass substrate central region2Compacted zone solution
Liquid film；
A-4. after the step a-3 coating processing, the adhesive tape pasted at FTO glass substrate edge is removed, obtains attachment TiO2
The FTO glass substrate of compacted zone liquid film, then will adhere to TiO2The FTO glass substrate of compacted zone liquid film is put into annelaing pot,
At least the high temperature anneal of 1h is carried out at not less than 500 DEG C, makes TiO2After compacted zone solidification in conjunction with FTO glass substrate, shape
At in conjunction with TiO2The FTO glass substrate of compacted zone；
B. hydro-thermal method synthesizes TiO2Nano-wire array：
B-1. successively take the deionized water of the HCl solution of the mass percent concentration of 8~10mL not higher than 37% and 8~10mL in
It mixes, then is put it into magnetic force ultrasonic device in container, is uniformly mixed by being no less than 10min stir process, after obtaining dilution
HCl solution, it is spare；
B-2. 0.2~0.4mL butyl titanate is taken with liquid-transfering gun, the HCl solution being added to after diluting in the step b-1
In, and be uniformly mixed within no less than 10 minutes in magnetic force ultrasonic device, mixed reactant solution is obtained, it is spare；
B-3. the combination TiO that will be prepared in the step a-42The FTO glass substrate of compacted zone is put into the reaction kettle of sealing,
The mixed reactant solution obtained in the step b-2 is poured into reaction kettle again, then reaction kettle is set in resistance furnace,
Reaction kettle is heated again, hydro-thermal reaction is carried out at not higher than 170 DEG C and is not higher than 6h；
B-4. in the step b-3 after hydro-thermal reaction, stop heating, when the temperature of reaction kettle is cooled to room temperature, beat
Reaction kettle is opened, FTO glass substrate is taken out, then slowly rinse FTO glass substrate surface with deionized water, and dried, obtains
Growth has TiO2The FTO glass substrate complex of nano tube/linear array film；
B-5. there will be TiO by the growth of the step b-4 drying and processing2The FTO glass substrate complex of nano tube/linear array film is put
Enter in annelaing pot, carry out at least the high temperature anneal of 1h at not less than 500 DEG C, to obtain combining TiO2Nano-wire array
Optical device precursor；
(2) electron irradiation TiO2Nano-wire array is modified：
Using linac, to the combination TiO to be processed prepared in the step b-52The optics of nano-wire array
Device precursor carries out electron irradiation processing, and the electronic beam current intensity for controlling electron accelerator is 5~10mA, and irradiation fluence rate is 5
~35kGy/s, radiation environment use room temperature and condition of normal pressure, and radiation mode uses and scans back and forth formula, TiO2Nano-wire array warp
After crossing electron irradiation, TiO is obtained2Nano-wire array photoelectric device.
2. carrying out TiO using electron irradiation according to claim 12The modified method of nano-wire array, it is characterised in that：?
In the step b-3,80~170 DEG C of temperature of hydro-thermal reaction are carried out.
3. carrying out TiO using electron irradiation according to claim 22The modified method of nano-wire array, it is characterised in that：?
In the step b-3, the thermal system that progress hydro-thermal reaction uses is as follows for multistep step temperature heating method：
It is warming up to progress first stage hydro-thermal reaction 20min at 80 DEG C first；Then it is warming up to progress second stage water at 110 DEG C
Thermal response 15min；Then it is warming up to progress phase III hydro-thermal reaction 10min at 120 DEG C；Then it is warming up at 130 DEG C and carries out
Fourth stage hydro-thermal reaction 15min；Then it is warming up to the 5th stage hydro-thermal reaction 15min of progress at 150 DEG C；Finally it is warming up to
The 6th stage hydro-thermal reaction 48min is carried out at 160 DEG C；Carry out hydro-thermal reaction when, control thermal system heating rate be not higher than
5.0℃/min。
4. carrying out TiO using electron irradiation according to claim 32The modified method of nano-wire array, it is characterised in that：?
In the step b-3, when carrying out hydro-thermal reaction, it is being not higher than in the 200min time from room temperature to 80 DEG C, from 80 DEG C first
It is 9min to 110 DEG C of heating-up times, the heating-up time from 110 DEG C to 120 DEG C is 3min, when heating from 120 DEG C to 130 DEG C
Between be 3min, the heating-up time from 130 DEG C to 150 DEG C is 6min, and the heating-up time from 150 DEG C to 170 DEG C is 6min.
5. carrying out TiO using electron irradiation according to any one of claim 2~42The modified method of nano-wire array,
It is characterized in that：In the step b-3, when carrying out hydro-thermal reaction, control the heating rate of thermal system not higher than 3.34 DEG C/
min。
6. carrying out TiO using electron irradiation according to claim 52The modified method of nano-wire array, it is characterised in that：?
In the step b-3, when carrying out hydro-thermal reaction, the heating rate for controlling thermal system is 0.2~3.34 DEG C/min.
7. carrying out TiO using electron irradiation described according to claim 1~any one of 42The modified method of nano-wire array,
It is characterized in that：In the step (2), in electron irradiation TiO2When nano-wire array is modified, irradiation fluence rate is 8~
35kGy/s。
8. carrying out TiO using electron irradiation according to claim 12The modified method of nano-wire array, it is characterised in that：Energy
The method for improving density of photocurrent with other ion dopings, heterojunction structure etc. cooperates with use, has exclusive compatibility.
9. carrying out TiO using electron irradiation described in a kind of claim 12The TiO of the modified method preparation of nano-wire array2Nanometer
The application of linear array photoelectric device, it is characterised in that：Applied to electrochemical decomposition water process for making hydrogen, the electrolytic preparation hydrogen of water is carried out
The energy.
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| CN101794670A (en) * | 2010-04-06 | 2010-08-04 | 东华大学 | Preparation method of photo anode of dye-sensitized solar cell with optical gradient |
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| CN101794670A (en) * | 2010-04-06 | 2010-08-04 | 东华大学 | Preparation method of photo anode of dye-sensitized solar cell with optical gradient |
| CN101976611A (en) * | 2010-08-25 | 2011-02-16 | 广东工业大学 | TiO2 nanowire array film light anode and preparation method thereof |
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