CN1174495C - Composite titanium-base film photoelectrode and its making process - Google Patents
Composite titanium-base film photoelectrode and its making process Download PDFInfo
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- CN1174495C CN1174495C CNB021157707A CN02115770A CN1174495C CN 1174495 C CN1174495 C CN 1174495C CN B021157707 A CNB021157707 A CN B021157707A CN 02115770 A CN02115770 A CN 02115770A CN 1174495 C CN1174495 C CN 1174495C
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Abstract
The present invention relates to a composite film optical electrode with visual light response and a making method thereof, which belongs to the technical field of the photoelectrocatalysis of a semiconductor. The film optical electrode comprises a titanium base, a doped titanium dioxide film compounded with cobalt and ruthenium is permeated and covered on the titanium base, and a titanium dioxide film layer is covered outside the doped titanium dioxide film compounded with cobalt and ruthenium. A sol-gel method is used for making the film optical electrode, and thus, the present invention has the advantages of simple technology and easy regulation of the doped density of metallic ions. The outer layer of the optical electrode is composed of titanium dioxide, forbidden band width is gradually reduced from outside to inside in favor of the order absorption of the light in different wave bands, and consequently, the spectral response range of materials is sufficiently enlarged, and the performance of the optical electrode is stable. One or more performance aspects of light absorption, photocatalysis, photoelectric conversion, etc. of the present invention are greatly superior to the optical electrode with single metallic ions with uniform phases or gradient doping. The present invention can be effectively used for the fields of solar energy utilization, photoelectric conversion, organic contaminant photocatalytic degradation, etc.
Description
Technical field
The present invention relates to the semiconductor photoelectrocatalysielectrode technical field, particularly have visible light-responded composite membrane optoelectronic pole and preparation method thereof.
Background technology
In recent years, the research of the photocatalysis performance of semi-conducting material has obtained very big progress.In the middle of numerous inorganic catalysis materials such as zinc oxide, titanium dioxide, iron oxide, cadmium sulfide etc., titanium dioxide be proved to be have the photocatalytic activity height, chemical property is stable, fast light chemical corrosion and advantage such as nontoxic, thereby utilizes field such as hydrogen manufacturing that bigger potential using value is arranged at photoelectrocatalysis, solar energy.But it is big that its weak point is an energy gap, can only absorbing wavelength less than the light of 387.5mm, thereby only can absorb very a spot of ultraviolet light in the solar spectrum, and this part sunlight that is radiated ground only accounts for about the 5-10% of global solar radiation amount, so solar energy utilization ratio is little.The spectrum that how to enlarge semiconductor catalyst utilizes scope, is the important research contents in photoelectrocatalysis field to improve solar energy utilization ratio.Adopt metal ion such as the titania-doped spectral response range that all can enlarge semiconductor catalyst in various degree such as Co, Ru, but single metal homogeneous phase doping preparation photochemical catalyst is all adopted in research mostly at present, and the performance of its photoelectrocatalysis and conversion is also desirable not to the utmost.
Theoretical and experiment shows, the energy gap of mixed semiconductor of many III-V family system is the function of its composition, and the charge transport properties of this system is better than the semiconductor system of coupled mode abrupt hetero-structures, if with the composite mixed titanium dioxide of Co, Ru and adopt method of pulling up successively can prepare the optoelectronic pole material that gradient type absorbs visible light.
Summary of the invention
Technical problem to be solved of the present invention is based on above-mentioned this thought and to propose a kind of spectral response scope bigger, composite titanium-base film photoelectrode of optoelectronic pole stable in properties and preparation method thereof.
The technical scheme of composite titanium-base film photoelectrode of the present invention is: include titanium substrate 3, its difference is to ooze in the titanium substrate and is covered with the composite mixed titanium deoxid film layer 2 of cobalt ruthenium, is covered with titanium deoxid film layer 1 again outside the composite mixed titanium deoxid film layer of cobalt ruthenium.
Press such scheme, the consisting of of the described composite mixed titanium deoxid film layer of cobalt ruthenium: Ti
1-x-yRu
xCo
yO
20＜X＜0.03 wherein, 0＜Y＜0.08, X, Y value increase to the titanium substrate gradually from the composite mixed titanium deoxid film laminar surface of described cobalt ruthenium, the concentration in gradient that is Co, Ru changes, the concentration of Co, Ru increases gradually in the composite mixed titanium deoxid film layer of ecto-entad cobalt ruthenium, and the thickness of the composite mixed titanium deoxid film layer of cobalt ruthenium is the 0.1-0.15 micron.
Preparation method's of the present invention technical scheme is:
The titanium substrate preparation: pure titanium sheet (TA1) cuts into sheet, and polishing is after acetone and washed with de-ionized water are inserted HNO
3With etching in the mixed liquor of HF, stand-by through acetone and washed with de-ionized water again;
The colloidal sol preparation: titanate esters and ethanol are mixed into A liquid with about 1: 8 proportioning of molal quantity, make serial B liquid in the mixed liquor that the ruthenium salt and the cobalt salt of difference amount joined ethanol, hydrochloric acid and water, serial B liquid is slowly dropped in the A liquid respectively, mix to such an extent that serial colloidal sol is stand-by;
The titanium substrate of handling well was immersed respectively in the metal ion dark glue of series from thick to thin 1 to several minutes according to the order of sequence, and lift with the speed of about 600mm/h and to take off liquid, in air drying about 10 minutes of calcination in 500 ℃ of temperature after a period of time, finish once and film, repeat the required number of times of filming and reach the 0.1-0.15 micron until film, finish the coating of the composite mixed titanium deoxid film layer of cobalt ruthenium, in unadulterated colloidal sol, film 2 then as stated above inferior to calcination in 600 ℃ 30 minutes, natural cooling, in back side spot welding lead, all the other are with epoxy sealings except that working portion.
Among the above-mentioned preparation method of the present invention, described ruthenium salt is chloride, and concentration of salt solution (molal quantity) is 0-0.03; Cobalt salt can be cobaltous sulfate or cobalt nitrate; Concentration of salt solution (molal quantity) is 0-0.08; Used titanate esters is butyl titanate, titanium propanolate or isopropyl titanate.HNO
3With the volumetric ratio of HF mixed liquor be 3: 1; The mol ratio of ethanol, hydrochloric acid and water is in the preparation of B liquid: ethanol: hydrochloric acid: water=4: 0.162: 1.
Advantage of the present invention is: 1, adopt sol-gel processing to prepare film photoelectric electrode, technology is simple, and is with low cost, and metal ion mixing concentration is easy to regulate; 2, the optoelectronic pole outermost layer is made up of titanium dioxide, by outward inward energy gap diminish gradually, help different-waveband light and absorb successively, thereby fully enlarged the spectral response scope of material, and the stable performance of optoelectronic pole; 3, be better than single homogeneous phase metal ion or grade doping greatly at one or more aspect of performances such as light absorption, photocatalysis, opto-electronic conversion; 4, the present invention can effectively be used in fields such as solar energy utilization, opto-electronic conversion, photocatalysis degradation organic contaminants.
Description of drawings
Fig. 1 is the deck structure generalized section of one embodiment of the invention.
Embodiment
Below further introduce the embodiment of the invention.
Embodiment 1: get titanate esters 8.5ml, ethanol 11.7ml makes A liquid in the flask mixing and stirring; 272 milligrams, 204 milligrams, 136 millimeters, 6.8 milligrams, 0 milligram ruthenium trichloride is joined respectively by in ethanol 11.7ml, hydrochloric acid 0.68ml, the water 0.9ml liquid mixture prepared, and the Cobalt monosulfate heptahydrate that respectively adds 217 milligrams simultaneously gets serial B liquid; Each drops in the A liquid with the speed that 1ml/ divides respectively with serial B liquid, and stirring 10 minutes must be colloidal sol; The titanium sheet of anticipating was immersed in the highest colloidal sol of ruthenium content 1 minute, speed with 600mm/h lifts, air drying was calcined 10 minutes in 500 ℃ after 10 minutes, finish once and film, repeat again to film to finish the doping of a serial colloidal sol from thick to thin, and make thin layer thickness reach the 0.1-0.15 micron, thereby finish the metal Ru ion concentration from thick to thin be coated with membrane process; In unadulterated colloidal sol, film at last in 600 ℃ of calcinings 30 minutes, natural cooling, in back side spot welding lead, all the other promptly get film photoelectric electrode with epoxy sealing except that working portion.
Embodiment 2: get titanate esters 8.5ml, ethanol 11.7ml makes A liquid in the flask mixing and stirring; The Cobalt monosulfate heptahydrate of 579 milligrams, 362 milligrams, 217 milligrams, 72.4 milligrams and 0 milligram is added respectively by in ethanol 11.7ml, hydrochloric acid 0.68ml, water 0.9ml liquid mixture prepared, and the ruthenium trichloride that respectively adds 136 milligrams simultaneously gets serial B liquid; Each drops in the A liquid with 1ml/ branch speed respectively with serial B liquid, stirs to get serial colloidal sol in 10 minutes; The titanium sheet of anticipating was immersed in the highest colloidal sol of cobalt content 1 minute, speed with 600mm/h lifts, air drying was calcined 10 minutes in 500 ℃ after 10 minutes, finish once and film, repeat again to film to finish the doping of a serial colloidal sol from thick to thin, and make thin layer thickness reach the 0.1-0.15 micron, thereby finish the metallic cobalt ion concentration from thick to thin be coated with membrane process; In unadulterated colloidal sol, film at last in 600 ℃ of calcinings 30 minutes, natural cooling, in back side spot welding lead, all the other promptly get film photoelectric electrode with epoxy sealing except that working portion.
Optoelectronic pole in the embodiment of the invention 1,2 is carried out photoelectric current measurement and the experiment of photoelectric catalysis degrading aniline, (the composite mixed and pure titinium dioxide film photoelectric electrode according to example 1 or 2 preparations is respectively the research electrode to photoelectric measurement in the pyrex three-electrode system, platinum filament is to electrode, saturated calomel electrode is made reference, 0.5mol dm
-3Na
2SO
4Be supporting electrolyte) carry out.Wavelength is a light source greater than the light of 460nm, and the photoelectric current under the short circuit current extra electric field is write down in short circuit or add the voltage with respect to reference electrode 0-1.0V respectively.
The aniline that adds 0-10ppm in above-mentioned system, the illumination certain hour is analyzed the aniline change in concentration.
The result shows, the photoelectric current when composite mixed film electrode photoelectric flows all much larger than single homogeneous phase metal ion mixing and the doping of single metal ion gradients; Corresponding degrading aniline speed rule is consistent therewith.
Claims (8)
1, a kind of composite titanium-base film photoelectrode includes titanium substrate (3), it is characterized in that oozing in the titanium substrate being covered with the composite mixed titanium deoxid film layer of cobalt ruthenium (2), is covered with titanium deoxid film layer (1) again outside the composite mixed titanium deoxid film layer of cobalt ruthenium.
2, by the described composite titanium-base film photoelectrode of claim 1, it is characterized in that consisting of of the described composite mixed titanium deoxid film layer of cobalt ruthenium: Ti
1-x-yRu
xCo
yO
2, 0＜X＜0.03,0＜Y＜0.08 wherein, X, Y value increase to the titanium substrate sheet gradually from the composite mixed titanium deoxid film laminar surface of described cobalt ruthenium.
3, by claim 1 or 2 described composite titanium-base film photoelectrodes, the thickness that it is characterized in that the composite mixed titanium deoxid film layer of cobalt ruthenium is the 0.1-0.15 micron.
4, a kind of preparation method of composite titanium-base film photoelectrode is characterized in that
The titanium substrate preparation: pure titanium sheet cuts into sheet, and polishing is after acetone and washed with de-ionized water are inserted HNO
3With etching in the mixed liquor of HF, stand-by through acetone and washed with de-ionized water again;
The colloidal sol preparation: titanate esters and ethanol are mixed into A liquid with about 1: 8 proportioning of molal quantity, make serial B liquid in the mixed liquor that the ruthenium salt and the cobalt salt of difference amount joined ethanol, hydrochloric acid and water, serial B liquid is slowly dropped in the A liquid respectively, mix to such an extent that serial colloidal sol is stand-by;
The titanium substrate of handling well was immersed respectively in the metal ion serial colloidal sol from thick to thin 1 to several minutes according to the order of sequence, and lift with the speed of about 600mm/h and to take off liquid, in air drying about 10 minutes of calcination in 500 ℃ of temperature after a period of time, finish once and film, repeat the required number of times of filming and reach the 0.1-0.15 micron until film, finish the coating of the composite mixed titanium deoxid film layer of cobalt ruthenium, in unadulterated colloidal sol, film 2 then as stated above inferior to calcination in 600 ℃ 30 minutes, natural cooling, in back side spot welding lead, all the other are with epoxy sealings except that working portion.
5, by the preparation method of the described composite titanium-base film photoelectrode of claim 4, it is characterized in that described ruthenium salt is chloride, the concentration of salt solution molal quantity is 0-0.03; Cobalt salt can be cobaltous sulfate or cobalt nitrate; The concentration of salt solution molal quantity is 0-0.08.
6, by the preparation method of claim 4 or 5 described composite titanium-base film photoelectrodes, it is characterized in that used titanate esters is butyl titanate, titanium propanolate or isopropyl titanate.
7, by the preparation method of claim 4 or 5 described composite titanium-base film photoelectrodes, it is characterized in that HNO
3With the volumetric ratio of HF mixed liquor be 3: 1.
8,, it is characterized in that the mol ratio of ethanol, hydrochloric acid and water in the preparation of B liquid is: ethanol: hydrochloric acid: water=4: 0.162: 1 by the preparation method of claim 4 or 5 described composite titanium-base film photoelectrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157707A CN1174495C (en) | 2002-04-27 | 2002-04-27 | Composite titanium-base film photoelectrode and its making process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157707A CN1174495C (en) | 2002-04-27 | 2002-04-27 | Composite titanium-base film photoelectrode and its making process |
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| CN1389932A CN1389932A (en) | 2003-01-08 |
| CN1174495C true CN1174495C (en) | 2004-11-03 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395895C (en) * | 2003-11-05 | 2008-06-18 | 南京大学 | Porous membrane semiconductor optical electrode having visible light response and photoelectrochemical reaction equipment and preparation thereof |
| CN100359046C (en) * | 2005-01-26 | 2008-01-02 | 上海大学 | Production of coating anode for electrolysis |
| CN101636796B (en) * | 2007-03-19 | 2013-04-10 | 旭硝子株式会社 | Process for producing electroconductor |
| TW201232792A (en) * | 2010-12-29 | 2012-08-01 | Auria Solar Co Ltd | Thin film solar cell and fabricating method thereof |
| CN107854999B (en) * | 2017-11-23 | 2019-06-11 | 江苏鸿顺合纤科技有限公司 | A kind of catalysis fibre material and preparation method for air cleaning |
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