CN101320630A - Preparation method of metallic ion coupled dye sensitization photocatalyst and optoelectronic pole - Google Patents

Preparation method of metallic ion coupled dye sensitization photocatalyst and optoelectronic pole Download PDF

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CN101320630A
CN101320630A CNA2008101069456A CN200810106945A CN101320630A CN 101320630 A CN101320630 A CN 101320630A CN A2008101069456 A CNA2008101069456 A CN A2008101069456A CN 200810106945 A CN200810106945 A CN 200810106945A CN 101320630 A CN101320630 A CN 101320630A
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dyestuff
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optoelectronic pole
metal ion
dye
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CN101320630B (en
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李越湘
郭苗苗
彭邵琴
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Nanchang University
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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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a manufacturing method of a dye sensitized photocatalyst and a photoelectrode coupled by metallic ions. Used materials thereof comprise semiconductor or insulator substrate (sensitized substrate), dyes of multi-coordination atom and metal ions. The metal ions couple the semiconductor or the insulator with the dyes, and couple the dyes by coordination function to form three-dimensional, bi-dimensional or one-dimensional polymers with a multilayer structure. Merits of the invention comprise: utilization per cent of visible light of the manufactured photocatalyst and photoelectrode is improved, and efficiency for transferring electric charges to catalytic materials and surface of photoelectrode is further improved.

Description

A kind of metallic ion coupled dye sensitization photocatalyst and the preparation method of optoelectronic pole
Technical field
The present invention relates to the preparation method of a kind of dye sensitization photocatalyst and optoelectronic pole, relate in particular to a kind of metallic ion coupled dye sensitization photocatalyst and the preparation method of optoelectronic pole.
Background technology
Photocatalysis is to utilize solar energy to solve one of best method of energy shortage and environmental pollution.TiO 2, wide band gap semiconducter such as ZnO is as photochemical catalyst, at aspects such as photocatalytic hydrogen production by water decomposition, degradation of contaminant and automatically cleanings good application prospects arranged.Yet these wide band gap semiconducters are ability display light catalytic activity and photoelectric conversion efficiency under UV-irradiation only.Sunlight medium ultraviolet light only accounts for about 5%, and visible light accounts for 45%.Making wide band gap semiconducter have visible light activity by dye sensitization is one of their most important method of modifying.Absorb visible light photoactivated TiO by dyestuff 2Deng wide band gap semiconducter, can realize visible light catalytic hydrogen manufacturing, degradation of contaminant.Dyestuff absorbs visible light photoactivated TiO 2Can realize the opto-electronic conversion of visible light. Type Optical Electro-Chemistry solar cell is the novel solar cell (Nature, 353 (24) 737-740,1991) that a kind of technology is simple, cheap and have the higher-energy conversion efficiency.The TiO of dye sensitization 2The nano-porous films optoelectronic pole is one of its important component part (work electrode).
Usually, the dye sensitization of semiconductor surface monolayer adsorption is all very low to the light results efficient of any wavelength; The sensitization of multilayer absorbing dye because: 1) the self-quenching effect of dyestuff, 2) excitation electron shifts problems such as difficulty, efficient is not high yet.Therefore, the electricity conversion of the activity of dye sensitization photocatalyst and optoelectronic pole is not high.
Figure A20081010694500042
Deng by improving the semiconductor nano roughness of film, improved light results efficient and electricity conversion, but TiO 2Nano thin-film optoelectronic pole preparation process is long and complicated.Be adsorbed on the adsorbance that semiconductor surface can improve dyestuff earlier by metal ion, simultaneously also promoted electronics from the charge transfer effciency of dyestuff to sensitization matrix, thereby improved activity of such catalysts (Journal of Colloid andInterface Science 265,428-431,2003; Functional material, 38 (03), 362-365,2007).But the absorption of this dyestuff remains monolayer adsorption, has limited light results efficient, the activity of photochemical catalyst and the raising of optoelectronic pole electricity conversion.
Summary of the invention
The object of the present invention is to provide a kind of metallic ion coupled dye sensitization photocatalyst and the preparation method of optoelectronic pole, by metal ion the absorption of semiconductor surface and with the dyestuff effect, increase the absorption (multilayer absorption) of dyestuff and the absorption efficiency of light; With dyestuff and dye-coupling, improve dyestuff photogenerated charge transfer efficiency by metal ion.
The present invention is achieved like this, and its process step is:
1, semiconductor powder or film are put into metal ion solution adsorption of metal ions is reached capacity, the needed time, metal salt concentrations should be higher than its saturated adsorption concentration between 0.5-12 hour;
2, dyestuff adds in the above-mentioned solution with pure solid or liquid form, and stirs fast. and dyestuff is adsorbed on the metal surface on the one hand in the process of dissolving, on the other hand two or more dye molecule couplings are got up.Slaine and dyestuff mol ratio are 3.0-0.30 preferably, are preferably in 0.5-2.0.Can form three-dimensional, two dimension, a dimensional polymers between metal and the dyestuff;
3, obtain photochemical catalyst and optoelectronic pole by filtration or simple physics separation.
The present invention also can be achieved like this, and its process step is:
1, semiconductor powder or film being put into metal ion solution reaches capacity adsorption of metal ions, the needed time is between 0.5-12 hour, filter or the simple physics separation powder of water or ethanol or acetone and other organic solvent carrying out washing treatment or film, drying;
2, above-mentioned semiconductor powder or film dyestuff are put into dye solution, after the absorption that reaches capacity, filter or the simple physics separation powder of water or ethanol, acetone and other organic solvent carrying out washing treatment or film, drying;
3, repeating step 1 and 2, number of times is 2-50 time preferably, best number of times is 2-10 time.Repeating step 1 and 2 o'clock, the slaine of employing, their concentration of dye well can be identical, also can be different.
In the inventive method, used is TiO by sensitization matrix 2, ZnO, SnO 2And BaTiO 3Deng wide band gap semiconducter and Al 2O 3, SiO 2Powder or film Deng insulator.
In the methods of the invention, used metal ion is meant: 2-4 main group metal ion such as Al 3+, Pb 2+Deng, transition metal ions such as Fe 2+, Fe 3+, Co 2+, Cu 2+, Zn 2+Deng and rare earth metal ion such as La 3+, Ce 3+Deng, used metal ion adopts nitrate, chloride, sulfate, acetate etc., common solvents such as they are water-soluble, ethanol.
In the methods of the invention, metal ion is with semiconductor or insulator and dyestuff, and dyestuff and dye-coupling get up, and forms sandwich construction.
In the methods of the invention, constitute the used metal ion of multilayer dyestuff absorption and can be one or more, used dyestuff also can be one or more.
In the methods of the invention, semiconductor or insulator film can adopt sol-gel, hydrolysis, and methods such as hydro-thermal, solvent thermal, thermal decomposition make nano-powder, make in glass, electro-conductive glass, pottery, frosting load by czochralski method, blade method etc. then.Also preparation such as available vapour deposition process.Nano-powder among the present invention can adopt said method to make.
In the methods of the invention, used organic dyestuff is meant: the natural separation and the artificial synthetic organic dye molecule that contain two or more coordination atoms, they can absorb visible light, or they itself do not absorb visible light but and metal ion can absorb visible light after cooperating, for example eosin dyestuff, cyanine dyes, chlorophyll etc., used inorganic dyestuff is meant: the inorganic metal ion complex that contains two or more coordination atoms, for example, the hydroxyl bipyridyl ruthenium, dye strength is preferably 1.0 * 10 -5-6.0 mol, best is 1.0 * 10 -3-0.10 mol.
Advantage of the present invention is: the photochemical catalyst of preparation and the visible light of optoelectronic pole results efficient improve, and improve to catalysis material and optoelectronic pole surface transfer charge efficient.
Embodiment
Embodiment one:
With the 0.50g nano-TiO 2(KY-TiO 2-01, Detitanium-ore-type, average grain diameter≤20nm, specific surface=124m 2/ g, content 〉=99.5%, Industrial Co., Ltd. is praised in last Haikang), add 20ml 5.0 * 10 -3Mol/l Fe (NO 3) 3The aqueous solution under agitation adds the water-soluble Eosin Y of 0.10mmol dyestuff (2,4,5,7-eosin sodium salt) solid, stirs 6-12h, suction filtration, 80-100 ℃ of drying.
Obtained photochemical catalyst is in the presence of triethanolamine, and as light source, (light intensity is 18.05mw/cm to remove ultraviolet and infrared light with 420nm filter plate and water cooling chuck with the metal halide lamp of 400W 2), light application time is 2h, uses H 2PtCl 6Original position supporting Pt amount 1.0wt%, the photocatalysis hydrogen production quantum efficiency is 12.8% (no Fe 3+The pure TiO for preparing when existing, under the similarity condition 2Absorption Eosin Y (replaces above-mentioned Fe (NO with distilled water 3) 3The aqueous solution) maximum quantum efficiency is 5.3%).
Embodiment two:
With the 0.50g nano-TiO 2(KY-TiO 2-01, Detitanium-ore-type, average grain diameter≤20nm, specific surface=124m 2/ g, content 〉=99.5%, Industrial Co., Ltd. is praised in last Haikang), add 20ml 1.0 * 10 -2Mol/l Fe (NO 3) 3The aqueous solution under agitation adds the water-soluble Eosin Y of 0.20mmol dyestuff (2,4,5,7-eosin sodium salt) solid, stirs 6-12h, suction filtration, 80-100 ℃ of drying.
Obtained photochemical catalyst is in the presence of triethanolamine, and as light source, (light intensity is 18.05mw/cm to remove ultraviolet and infrared light with 420nm filter plate and water cooling chuck with the metal halide lamp of 400W 2), light application time is 2h, uses H 2PtCl 6Original position supporting Pt amount 1.0wt%, the photocatalysis hydrogen production quantum efficiency is 19.0%.
Embodiment three:
With the 0.50g nano-TiO 2(KY-TiO 2-01, Detitanium-ore-type, average grain diameter≤20nm, specific surface=124m 2/ g, content 〉=99.5%, Industrial Co., Ltd. is praised in last Haikang), add 20ml 5.0 * 10 -3Mol/l Fe (NO 3) 3Ethanolic solution under agitation adds the water-soluble Eosin Y of 0.10mmol dyestuff (2,4,5,7-eosin sodium salt) solid, stirs 6-12h, suction filtration, and 80-100 ℃ of drying makes photochemical catalyst.
Embodiment four:
With butyl titanate is raw material, and preparation colloidal sol prepares glass-loaded TiO with this colloidal sol czochralski method 2Gel film obtains TiO at 450 ℃ of calcining 1h 2Film. multiple layer metal ion and dyestuff absorption preparation catalyst and optoelectronic pole preparation process: 1) this sheet glass is put into 5.0 * 10 -3Mol/l Fe (NO 3) 3Aqueous solution 2h takes out and washes 2 times with small amount of ethanol; 2) put into 5.0 * 10 after the drying -3Mol/l Eosin Y aqueous solution 2h takes out and washes 2 times with small amount of ethanol; 3) repeating step 1; 4) repeating step 2, but replace Eosin Y with same concentration bipyridine.80-100 ℃ of drying makes film photocatalyst.

Claims (8)

1, a kind of metallic ion coupled dye sensitization photocatalyst and the preparation method of optoelectronic pole is characterized in that the process step is:
(1) with semiconductor powder or film is put into the metal ion aqueous solution or polar organic solvent makes metal ion reach capacity in its surface adsorption, the needed time, metal salt concentrations should be higher than its saturated adsorption concentration between 0.5-12 hour;
(2) dyestuff adds in the above-mentioned solution with pure solid or liquid form, and stir fast, dyestuff is in the process of dissolving water or polar organic solvent, be adsorbed on the metal surface on the one hand, on the other hand two or more dye molecule couplings are got up, slaine and dyestuff mol ratio are 3.0-0.30 preferably, be preferably in 0.5-2.0, can form three-dimensional, two dimension, a dimensional polymers between metal and the dyestuff;
(3) obtain photochemical catalyst and optoelectronic pole by filtration or simple physics separation.
2, a kind of dye sensitization photocatalyst that the described preparation of claim 1 is metallic ion coupled and another kind of preparation method of optoelectronic pole of realizing is characterized in that the process step is:
(1) with semiconductor powder or film is put into the metal ion aqueous solution or polar organic solvent reaches capacity adsorption of metal ions, the needed time is between 0.5-12 hour, filter or the simple physics separation powder of water or ethanol or acetone and other organic solvent carrying out washing treatment or film, drying;
(2) above-mentioned semiconductor powder or film dyestuff are put into dye solution, after the absorption that reaches capacity, filter or the simple physics separation powder of water or ethanol, acetone and other organic solvent carrying out washing treatment or film, drying;
(3) repeating step 1 and 2, number of times is 2-50 time preferably, best number of times is 2-10 time.Repeating step 1 and 2 o'clock, the slaine of employing, their concentration of dye well can be identical, also can be different.
3. according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that used is TiO by sensitization matrix 2, ZnO, SnO 2And BaTiO 3Deng wide band gap semiconducter and Al 2O 3, SiO 2Powder or film Deng insulator.
4, according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that semiconductor or insulator film can adopt sol-gel, methods such as hydrolysis, hydro-thermal, solvent thermal, thermal decomposition make nano-powder, make at area loads such as glass, electro-conductive glass, pottery, plastics by czochralski method, blade method then, also preparation such as available vapour deposition process, semiconductor among the present invention or insulator nano-powder also adopt said method to make.
5, according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that used organic dyestuff is meant: the natural separation and the artificial synthetic organic dye molecule that contain two or more coordination atoms, they can absorb visible light, or they itself do not absorb visible light but and metal ion can absorb visible light after cooperating, eosin dyestuff for example, cyanine dyes, chlorophyll etc., used inorganic dyestuff is meant: the inorganic metal ion complex that contains two or more coordination atoms, for example, the hydroxyl bipyridyl ruthenium, dye strength is preferably 1.0 * 10 -5-6.0 mol, best is 1.0 * 10 -3-0.10 mol.
6, according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that used metal ion is meant: 2-4 main group metal ion such as Al 3+, Pb 2+Deng, transition metal ions such as Fe 2+, Fe 3+, Co 2+, Cu 2+, Zn 2+Deng and rare earth ion such as La 3+, Ce 3+Deng, used metal ion adopts nitrate, chloride, sulfate, acetate etc., common solvents such as they are water-soluble, ethanol.
7. according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that metal ion with semiconductor or insulator and dyestuff, dyestuff and dye-coupling get up, and form sandwich construction.
8. according to claims 1 or the 2 described a kind of metallic ion coupled dye sensitization photocatalysts and the preparation method of optoelectronic pole, it is characterized in that constituting the used metal ion of multilayer dyestuff absorption and can be one or more, used dyestuff also can be one or more.
CN2008101069456A 2008-06-25 2008-06-25 Preparation method of metallic ion coupled dye sensitization photocatalyst and optoelectronic pole Expired - Fee Related CN101320630B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103868900A (en) * 2014-03-13 2014-06-18 同济大学 Application and method of series of organic dyestuffs in visible-light photocatalyst Ru(bpy)3Cl2 fluorescence quenching
CN107649159A (en) * 2017-08-30 2018-02-02 浙江工业大学 A kind of organic dyestuff is modified carbonitride graphene composite material and its application
CN109759069A (en) * 2019-03-18 2019-05-17 福州大学 A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100544054C (en) * 2007-06-26 2009-09-23 武汉大学 The preparation method of modified polymer electrolyte dye-sensitized nano-crystalline solar battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103868900A (en) * 2014-03-13 2014-06-18 同济大学 Application and method of series of organic dyestuffs in visible-light photocatalyst Ru(bpy)3Cl2 fluorescence quenching
CN107649159A (en) * 2017-08-30 2018-02-02 浙江工业大学 A kind of organic dyestuff is modified carbonitride graphene composite material and its application
CN109759069A (en) * 2019-03-18 2019-05-17 福州大学 A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide
CN109759069B (en) * 2019-03-18 2021-04-27 福州大学 Preparation and application of perovskite material for photocatalytic reduction of carbon dioxide

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