CN102688782A - Squarylium cyanine dye sensitized titanium dioxide visible light catalyst, and preparation method and application thereof - Google Patents

Squarylium cyanine dye sensitized titanium dioxide visible light catalyst, and preparation method and application thereof Download PDF

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Publication number
CN102688782A
CN102688782A CN2012101848998A CN201210184899A CN102688782A CN 102688782 A CN102688782 A CN 102688782A CN 2012101848998 A CN2012101848998 A CN 2012101848998A CN 201210184899 A CN201210184899 A CN 201210184899A CN 102688782 A CN102688782 A CN 102688782A
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titanium dioxide
visible light
squarylium cyanine
cyanine dyes
preparation
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CN2012101848998A
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李忠玉
房永玲
徐松
钱健
吴春晖
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CHANGZHOU EXPANSION NEW STUFF TECHNOLOGY Co Ltd
Changzhou University
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CHANGZHOU EXPANSION NEW STUFF TECHNOLOGY Co Ltd
Changzhou 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to the technical field of photocatalysis, particularly a squarylium cyanine dye sensitized titanium dioxide visible light catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: mixing titanium dioxide with squarylium cyanine dye and an organic solvent, carrying out ultrasonic treatment on the mixture at 20-40 DEG C for 0.5-6 hours, wherein the ultrasonic frequency is 20-100kHz, and the ultrasonic power is 400-4000W; and drying the organic solvent by distillation to obtain the squarylium cyanine dye sensitized titanium dioxide visible light catalyst. The squarylium cyanine dye sensitized titanium dioxide visible light catalyst under the irradiation of visible light or sunlight can effectively degrade methylene blue and other organic wastewater pollutants, has high photocatalytic activity, and solves the technical problems of low visible light utilization ratio and low catalytic activity in the existing titanium dioxide photocatalyst. The preparation method provided by the invention has the advantage of simple technique, is easy to control and is suitable for industrial production and application.

Description

Squarylium cyanine dyes sensitization titanium dioxide visible light catalyzer, preparation method and application
 
Technical field
The invention belongs to the photocatalysis technology field; Be specifically related to a kind of preparation and application of titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization; This visible light catalyst can effectively utilize the visible light in the sunshine, thereby improves the photocatalysis quantum efficiency and widen spectral response.
Background technology
Nano-TiO 2Photochemical catalyst is the desirable catalysis material of generally acknowledging at present because of catalytic activity is high, chemical property is stable and nontoxic, aspect environmental pollution improvement, has broad application prospects.Yet, present TiO 2Photocatalysis oxidation technique mainly is in laboratory simulation to be handled on the level, does not drop into large-scale practical application as yet, and this mainly is because TiO 2The bottleneck that self can't break through is arranged in the practicability process: (1) greater band gap (3.2eV), can only absorbing wavelength response be arranged, and the ultraviolet light of wavelength only accounts for about 4% of sunshine like this less than the ultraviolet light of 387 nm, make TiO 2Utilization rate to sunshine is low; (2) light induced electron-hole is short to the life-span, and the photocatalytic process quantum efficiency is low.Therefore, in order to improve utilization rate to sunshine, just must be to TiO 2Carry out modification and handle, make it have visible light-responded photocatalysis performance.In addition, TiO 2The extinction ability strong more, the electron-hole pair that illumination produces is many more, the probability that separated electronics and hole induce reaction is just big more, catalyst activity will be high more.
In order to address the above problem; A lot of researchs adopt methods such as containing transition metal ions, noble metal loading, semiconductor are compound to attempt to improve its photocatalysis efficiency; And make it to the red shift of absorption of visible light threshold wave-length, obtained bigger progress, but substantial breakthrough has not all been arranged.Dye sensitization is a kind of method of expanding the optical semiconductor response range, through selecting suitable photosensitizer, makes its method through chemistry or physical absorption be adsorbed in catalyst surface; Under radiation of visible light; Behind the ADSORPTION STATE photolytic activity molecule absorption photon, the generation free electron that is excited, excitation state photolytic activity molecule is injected into electronics on the semi-conductive conduction band then; Thereby widened the scope of semiconductor excitation wavelength, made it to utilize the visible light degradation of organic substances.Patent CN1680021A and CN1680022A have proposed to prepare with phthalocyanine dye sensitization titanium dioxide the method for visible light catalyst, have improved the activity of photochemical catalyst.But phthalocyanine dye exists production cost high, is difficult to shortcomings such as purification, be unfavorable for actual applying, so choice structure is suitable, is easy to synthesize, and the sensitizer dyestuff of function admirable is the key of preparation titanium dioxide visible light catalyzer.
Squarylium cyanine dyes has possessed the good characteristic of square acid derivative and cyanine dyes; Have favorable photo-thermal stability and chemical stability; And, can become the photosensitizer molecule of preparation titanium dioxide visible light catalyzer it is thus clear that very strong absorption band and fluorescence emission peak are arranged with the near infrared region.The present invention as sensitising agent, has implemented the preparation of titanium dioxide visible light catalyzer and the application of photocatalysis to degrade organic matter with one type of squarylium cyanine dyes.
Summary of the invention
The present invention is in order to overcome the deficiency of above-mentioned prior art; The titanium dioxide visible light catalyzer of the squarylium cyanine dyes sensitization that a kind of sunshine utilization rate is high, photocatalysis efficiency is high is provided; Its component comprises squarylium cyanine dyes and titanium dioxide, and wherein the mass ratio of squarylium cyanine dyes and titanium dioxide is for being 100:0.5～10.
The present invention also provides the preparation method of the titanium dioxide visible light catalyzer of above-mentioned a kind of squarylium cyanine dyes sensitization; Carry out according to following step: titanium dioxide is mixed with squarylium cyanine dyes and organic solvent; The mass ratio of organic solvent and titanium dioxide is about 2:1, under 30 ℃～40 ℃ temperature, is 20～100kHz with said mixture in frequency then; Ultrasonic power is to handle 0.5～6 hour under the condition of 400～4000W; With the organic solvent evaporate to dryness, at last the solids that obtains is dried down at 60 ℃, can obtain the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization.
The mass ratio of wherein said titanium dioxide and squarylium cyanine dyes is 100:0.5～10.
Wherein said organic solvent is a kind of in methyl alcohol, ethanol, oxolane, the chloroform.
The structure of wherein said squarylium cyanine dyes is shown in structural formula (1):
Structural formula (1)
Substituent R in the structural formula (1) 1For H ,-(CH 2) iM ,-(CH 2) iC 6H 4Z, C 1～C 12Alkyl in any group, wherein M is any one group among COOH, OH, the H, C 6H 4Be phenyl ring, Z is COOH, OH, NO 2, CH 3Any one groups such as O, halogen Cl, Br, I, i is 1～12 positive integer.
Substituent R in the structural formula (1) 2Be O, S, Se, C (CH 3) in any group.
Substituent X is H or SO in the structural formula (1) 3H, COOH, NO 2, CH 3Any one groups such as O, halogen Cl, Br, I.
Described titanium dioxide can be commercially available prod Nano titanium dioxide P25, also can be the nano titanium oxide of existing method preparation.
The titanium dioxide visible light catalyzer of described squarylium cyanine dyes sensitization is characterized in that, light-catalyzed reaction can be carried out under visible light or sunshine, can be used for the photocatalysis treatment of organic pollution in air, soil and the sewage.
The present invention finds to utilize the squarylium cyanine dyes with high molar absorption coefficient that titanium dioxide is carried out sensitization, will improve greatly absorption of visible light and utilization ratio.Compared with prior art, the present invention has following advantage:
The titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization is under visible light or solar light irradiation; Organic wastewater pollutant such as degradation of methylene blue effectively; Photocatalytic activity is high; It is not high to the visible light utilization rate to have solved at present existing titanium dioxide optical catalyst, the technical barrier that catalytic activity is low.
Visible light catalyst preparation method technology of the present invention is simple, is easy to control, is suitable for suitability for industrialized production and application.
Description of drawings
Fig. 1 is the sem photograph of the titania nanoparticles of embodiment 1 preparation.
Fig. 2 is the abosrption spectrogram of titanium dioxide visible light catalyzer of titania nanoparticles and the squarylium cyanine dyes sensitization of embodiment 1 preparation.
Fig. 3 is the titania nanoparticles and 2,3 of preparation among the embodiment 1, and 3-trimethyl-3H indoles replaces the concentration changes with time figure of the titanium dioxide visible light catalyzer difference catalysis methylene blue solution of squarylium cyanine dyes sensitization.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to embodiment.
Embodiment 1
With 15ml butyl titanate and 45ml absolute ethyl alcohol fully mix solution A.Other gets 32 ml absolute ethyl alcohols, behind nitric acid adjusting pH to 2～3, is added drop-wise in the mixed liquor of above-mentioned butyl titanate and absolute ethyl alcohol; Stir and made it abundant mixing in 1 hour, obtain the titanium dioxide vitreosol, with vitreosol with after 6g phenol mixes; Join in the normal heptane decentralized medium, under fully stirring, drip the 8ml formalin, be warming up to 70 ℃ and react; Obtain milky colloidal liquid behind about 1.5h, after 80 ℃ of oven dry, through 400 ℃ of calcination process; Promptly obtain titania nanoparticles, the sem photograph of this nano particle is as shown in Figure 1.
Said method is made nano titanium oxide and 2,3, and 3-trimethyl-3H indoles replaces squarylium cyanine dyes [R 1Be H, R 2Be C (CH 3), X is H] and 40ml ethanol, join in the single port flask; Nano titanium oxide and 2,3 wherein, the mass ratio that 3-trimethyl-3H indoles replaces squarylium cyanine dyes is 100:0.5; Under 40 ℃ temperature, be 40kHz with mixture in frequency, ultrasonic power is to handle 2 hours under the condition of 4000W; With the alcohol solvent evaporate to dryness, the solids that obtains 60 ℃ of oven dry down, is obtained 2 then; 3,3-trimethyl-3H indoles replaces the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization, and the absorption spectrum of the titanium dioxide visible light catalyzer of gained nano titanium oxide and squarylium cyanine dyes sensitization is as shown in Figure 2.Can know that by Fig. 2 the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization has the visible absorption wavelength of broad, so squarylium cyanine dyes can be used as a kind of sensitising agent of function admirable.
Embodiment 2
With Nano titanium dioxide P25 and 2,3,3-trimethyl-3-ethylindole replaces squarylium cyanine dyes [R 1Be C 2H 5, R 2Be C (CH 3), X is H] and 60ml methyl alcohol join in the single port flask nano titanium oxide and 2,3 wherein; The mass ratio that 3-trimethyl-3-ethylindole replaces squarylium cyanine dyes is 100:10, under 30 ℃ temperature, is 20kHz with mixture in frequency; Ultrasonic power is to handle 0.5 hour under the condition of 1000W, then with the methanol solvate evaporate to dryness, with the solids that obtains 60 ℃ of oven dry down; Obtain 2,3,3-trimethyl-3H indoles replaces the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization.
Embodiment 3
Embodiment 1 is made nano titanium oxide and N-methylbenzothiazole replacement squarylium cyanine dyes [R 1Be CH 3, R 2Be S, X is H] and the 40ml chloroform join in the single port flask, wherein to replace the mass ratio of squarylium cyanine dyes be 100:2 for nano titanium oxide and N-methylbenzothiazole; Under 40 ℃ temperature; Is 30kHz with mixture in frequency, and ultrasonic power is to handle 5 hours under the condition of 500W, then with the chloroform solvent evaporate to dryness; The solids that obtains 60 ℃ of oven dry down, is obtained the titanium dioxide visible light catalyzer that the N-methylbenzothiazole replaces the squarylium cyanine dyes sensitization.
Embodiment 4
Just Nano titanium dioxide P25 and 5-nitro-N-methylbenzothiazole replaces squarylium cyanine dyes [R 1Be CH 3, R 2Be S, X is NO 2] and the 50ml oxolane join in the single port flask; Wherein the mass ratio of nano titanium oxide and 5-nitro-N-methylbenzothiazole replacement squarylium cyanine dyes is 100:3, under 30 ℃ temperature, is 40kHz with mixture in frequency; Ultrasonic power is to handle 3 hours under the condition of 2000W; With the tetrahydrofuran solvent evaporate to dryness, the solids that obtains 60 ℃ of oven dry down, is obtained the titanium dioxide visible light catalyzer that 5-nitro-N-methylbenzothiazole replaces the squarylium cyanine dyes sensitization then.
Application examples
For visible light catalytic performance and the potential application of verifying squarylium cyanine dyes sensitization titanium dioxide optical catalyst of the present invention; Titania nanoparticles and 2 with preparation among the embodiment 1; 3,3-trimethyl-3H indoles replaces the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization respectively with 3 * 10 -5The methylene blue solution of mol is put in the photo catalysis reactor; The consumption of photochemical catalyst is every 100ml methylene blue solution 20mg, and stirring and be placed on outdoor temperature is irradiation under 20 ℃～23 ℃ sunshines, whenever extracts the 4ml reactant liquor at a distance from 30 minutes with dropper; Put into centrifuge centrifugal 20 minutes; Take out the back and survey its absorbance situation over time, the change calculations of above-mentioned photochemical catalyst solution absorbance before and after the catalytic degradation methylene blue solution is obtained degradation rate, the result is as shown in Figure 3.Can know that by Fig. 3 the visible light catalytic performance of squarylium cyanine dyes sensitization titanium dioxide optical catalyst of the present invention is higher than the titanium dioxide optical catalyst of not sensitization far away.

Claims (6)

1. squarylium cyanine dyes sensitization titanium dioxide visible light catalyzer is characterized in that its component is made up of squarylium cyanine dyes and titanium dioxide, and wherein the mass ratio of squarylium cyanine dyes and titanium dioxide is for being 100:0.5～10.
2. the preparation method of the titanium dioxide visible light catalyzer of the described squarylium cyanine dyes sensitization of claim 1; It is characterized in that carrying out: titanium dioxide is mixed with squarylium cyanine dyes and organic solvent according to following step; The mass ratio of organic solvent and titanium dioxide is 2:1, under 30 ℃～40 ℃ temperature, is 20～100kHz with said mixture in frequency then; Ultrasonic power is to handle 0.5～6 hour under the condition of 400～4000W; With the organic solvent evaporate to dryness, at last the solids that obtains is dried down at 60 ℃, can obtain the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization.
3. the preparation method of the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization according to claim 2, the mass ratio that it is characterized in that wherein said titanium dioxide and squarylium cyanine dyes is 100:0.5～10.
4. the preparation method of the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization according to claim 2 is characterized in that wherein said organic solvent is a kind of in methyl alcohol, ethanol, oxolane, the chloroform.
5. the preparation method of the titanium dioxide visible light catalyzer of squarylium cyanine dyes sensitization according to claim 2, the structure that it is characterized in that wherein said squarylium cyanine dyes is shown in structural formula (1):
Structural formula (1)
Substituent R in the structural formula (1) 1For H ,-(CH 2) iM ,-(CH 2) iC 6H 4Z, C 1～C 12Alkyl in any group, wherein M is any one group among COOH, OH, the H, C 6H 4Be phenyl ring, Z is COOH, OH, NO 2, CH 3Any one groups such as O, halogen Cl, Br, I, i is 1～12 positive integer;
Substituent R in the structural formula (1) 2Be O, S, Se, C (CH 3) in any group;
Substituent X is H or SO in the structural formula (1) 3H, COOH, NO 2, CH 3Any one groups such as O, halogen Cl, Br, I.
6. the application of the titanium dioxide visible light catalyzer of the described squarylium cyanine dyes sensitization of claim 1 can be used for the photocatalysis treatment of organic pollution in air, soil and the sewage.
CN2012101848998A 2012-06-06 2012-06-06 Squarylium cyanine dye sensitized titanium dioxide visible light catalyst, and preparation method and application thereof Pending CN102688782A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN103055943A (en) * 2012-12-18 2013-04-24 华南理工大学 Dye-sensitization photocatalysis and application thereof in catalytic degradation of ionic liquid under the present of visible light
CN103071535A (en) * 2013-01-15 2013-05-01 常州浩瀚万康纳米材料有限公司 Preparation method and application of zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine
CN104974354A (en) * 2014-04-04 2015-10-14 东北林业大学 Method for degrading lignin using visible-light response composite catalyst
CN107115893A (en) * 2017-06-06 2017-09-01 常州大学 A kind of preparation method of the sour cyanines composite visible light catalyst in indium sulfide tin/side
CN108144596A (en) * 2017-12-29 2018-06-12 常州大学 A kind of controllable 3DOM-TiO of window2Photochemical catalyst preparation method
CN109205731A (en) * 2018-11-12 2019-01-15 内蒙古民族大学 A kind of method of new bio photosensitive fuel Degradation of Organo-pollutants in Water with Photo-catalysis in conjunction with titanium dioxide
CN111097541A (en) * 2018-10-25 2020-05-05 中国科学院上海硅酸盐研究所 Dye-sensitized black titanium dioxide and preparation method and application thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055943A (en) * 2012-12-18 2013-04-24 华南理工大学 Dye-sensitization photocatalysis and application thereof in catalytic degradation of ionic liquid under the present of visible light
CN103055943B (en) * 2012-12-18 2015-06-03 华南理工大学 Dye-sensitization photocatalysis and application thereof in catalytic degradation of ionic liquid under the present of visible light
CN103071535A (en) * 2013-01-15 2013-05-01 常州浩瀚万康纳米材料有限公司 Preparation method and application of zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine
CN104974354A (en) * 2014-04-04 2015-10-14 东北林业大学 Method for degrading lignin using visible-light response composite catalyst
CN107115893A (en) * 2017-06-06 2017-09-01 常州大学 A kind of preparation method of the sour cyanines composite visible light catalyst in indium sulfide tin/side
CN108144596A (en) * 2017-12-29 2018-06-12 常州大学 A kind of controllable 3DOM-TiO of window2Photochemical catalyst preparation method
CN111097541A (en) * 2018-10-25 2020-05-05 中国科学院上海硅酸盐研究所 Dye-sensitized black titanium dioxide and preparation method and application thereof
CN109205731A (en) * 2018-11-12 2019-01-15 内蒙古民族大学 A kind of method of new bio photosensitive fuel Degradation of Organo-pollutants in Water with Photo-catalysis in conjunction with titanium dioxide
CN109205731B (en) * 2018-11-12 2021-06-18 内蒙古民族大学 Method for photocatalytic degradation of organic pollutants in water by combining biological photosensitive dye and titanium dioxide

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Application publication date: 20120926