CN103071535A - Preparation method and application of zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine - Google Patents
Preparation method and application of zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine Download PDFInfo
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- CN103071535A CN103071535A CN201310013813XA CN201310013813A CN103071535A CN 103071535 A CN103071535 A CN 103071535A CN 201310013813X A CN201310013813X A CN 201310013813XA CN 201310013813 A CN201310013813 A CN 201310013813A CN 103071535 A CN103071535 A CN 103071535A
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- squarylium cyanine
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a preparation method of a zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine. The preparation method comprises the following steps: dissolving Zn(Ac)22H2O and glucose into deionized water; carrying out ultrasonic processing to form a settled solution; after transferring the solution into a liner of a polytetrafluoroethylene autoclave, performing hydrothermal reaction for 12 to 24 hours at a temperature of 140 to 180 DEG C; after cooling to room temperature, carrying out centrifugal washing on the obtained black powder respectively with the deionized water and absolute ethyl alcohol; drying at a temperature of 60 DEG C to obtain a zinc oxide and carbon composite precursor; placing the precursor into a muffle furnace to calcine for 3 hours at a temperature of 400 to 600 DEG C, so as to obtain zinc oxide microspheres; mixing the zinc oxide microspheres and the squarylium cyanine as well as an organic solvent; at a temperature of 30 to 60 DEG C, carrying out ultrasonic processing on the mixture for 0.5 to 2 hours; then removing the organic solvent under the condition of pressure reduction; and finally, drying the obtained solid at a temperature of 60 DEG C. The zinc oxide visible-light-induced photocatalyst sensitized by the squarylium cyanine can be used for photocatalysis processing on organic pollutants in air, soil and sewage.
Description
Technical field
The invention belongs to the photocatalysis technology field, be specifically related to a kind of zinc oxide visible light catalyst preparation method and application thereof of squarylium cyanine dyes sensitization.
Background technology
Along with developing rapidly of industry, problem of environmental pollution is on the rise, so that ecological environment goes from bad to worse.National governments all with environmental pollution improvement as cardinal task, drop into one after another the research that huge fund is used for the aspects such as environmental pollution treatment technology and surrounding purifying material.The photocatalysis technology that development in recent years is got up is the environment purification technology of a green, utilizes photochemical catalyst, can be with the organic pollution permineralization under ultraviolet or radiation of visible light.Therefore photocatalysis technology has obtained general concern aspect environmental improvement, especially for the research and development of catalysis material, has become at present the focus of research both at home and abroad.
Zinc oxide is a kind of semi-conducting material with broad stopband (being about 3.3eV) of many superior functions, also is the environment-friendly materials that are widely studied at present, and, low cost and other advantages nontoxic because of it are applied to photocatalysis field.It can be used for the organic matter of difficult degradation finally is oxidized to the inorganic matters such as carbon dioxide and water by the light auxiliary catalysis, can remove organic pollution nearly all in the water.Yet now the photocatalyst of zinc oxide of report is owing to have wider forbidden band, can only be in ultra-violet (UV) band display light catalytic activity, and in the occupation rate of solar spectrum medium ultraviolet light less than 5%, wavelength is that the visible light of 400-750nm accounts for about 43%.Therefore, in order to effectively utilize sunshine, it is just very meaningful to study the catalysis material that has high efficiency photocatalysis activity under visible light.
In order to address the above problem, a lot of researchs adopt the 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 visible Optical Absorption threshold wave-length, obtained larger progress, but substantial breakthrough has not all been arranged.For example Chinese patent CN1660485 discloses a kind of photocatalyst of zinc oxide with visible light activity and preparation method thereof, makes after it is characterized in that utilizing zinc acetate dihydrate and polyvinylpyrrolidone to be dissolved in ethylene glycol.
Summary of the invention
The present invention provides the zinc oxide visible light catalyst of the squarylium cyanine dyes sensitization that a kind of sunshine utilization rate is high, photocatalysis efficiency is high in order to overcome above-mentioned the deficiencies in the prior art, and its component comprises squarylium cyanine dyes and zinc oxide.
The present invention also provides a kind of preparation method of zinc oxide visible light catalyst of squarylium cyanine dyes sensitization, and this visible light catalyst carries out according to following step:
Take by weighing the Zn that mass ratio is 1:2～3 (Ac)
2.2H
2O and glucose are dissolved in the deionized water, ultrasonic formation settled solution, after changing over to solution in the polytetrafluoroethylene (PTFE) autoclave inner bag, 140～180 ℃ of hydro-thermal reaction 12～24h, after being cooled to room temperature, the black powder that obtains is carried out repeatedly centrifuge washing with deionized water and absolute ethyl alcohol respectively, and the dry composite precursor that obtains zinc oxide and carbon under 60 ℃ of conditions places 400～600 ℃ of calcinings of Muffle furnace 3h namely to get ZnO microsphere the presoma that makes afterwards.
The above-mentioned nano zine oxide microballoon that obtains is mixed with squarylium cyanine dyes and organic solvent, the mass ratio of organic solvent and zinc oxide is about 2:1, then under 30～50 ℃ temperature, with the ultrasonic processing of said mixture 0.5～2 hour, then organic solvent is removed under reduced pressure, with the solids oven dry under 60 ℃ that obtains, can obtain the zinc oxide visible light catalyst of squarylium cyanine dyes sensitization at last.
The mass ratio of wherein said zinc oxide and squarylium cyanine dyes is 100:0.5～5.
Wherein said organic solvent is a kind of in methyl alcohol, ethanol, 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 one 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.
The zinc oxide visible light catalyst of described squarylium cyanine dyes sensitization, this 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.
Dye sensitization is a kind of method of expanding the semiconductor light response range, by selecting suitable photosensitizer, make its method by 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, then excitation state photolytic activity molecule with electronic injection to semi-conductive conduction band, thereby widened the scope of semiconductor excitation wavelength, made it to utilize the Visible Light Induced Photocatalytic organic matter.
Squarylium cyanine dyes has possessed the good characteristic of square acid derivative and cyanine dyes, have good photo and thermal stability and chemical stability, and in visible and near infrared region very strong absorption band and fluorescence emission peak are arranged, can become the photosensitizer molecule for preparing the zinc oxide visible light catalyst.The present invention as sensitising agent, has implemented the preparation of zinc oxide visible light catalyst and the application of photocatalysis to degrade organic matter with a class squarylium cyanine dyes.
The present invention finds to utilize the squarylium cyanine dyes with high molar absorption coefficient that zinc oxide is carried out sensitization, will greatly improve visible Optical Absorption and utilization ratio.
Compared with prior art, beneficial effect of the present invention is:
The zinc oxide visible light catalyst of squarylium cyanine dyes sensitization under visible light or solar light irradiation, the organic wastewater pollutant such as degradation of methylene blue effectively, photocatalytic activity is high.
Visible light catalyst preparation method technique 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 scanning electron microscope (SEM) photograph of the ZnO microsphere of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope picture of the ZnO microsphere of embodiment 1 preparation.
Fig. 3 is the concentration changes with time figure of the Zinc oxide nanoparticle of preparation among the embodiment 1 and the zinc oxide visible light catalyst difference catalysis methylene blue solution that 2,3,3-trimethyl-3H indoles replaces the squarylium cyanine dyes sensitization.
The specific embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Take by weighing the Zn that mass ratio is 1 ︰ 2 (Ac)
2.2H
2O and glucose are dissolved in the deionized water, ultrasonic formation settled solution, after changing over to solution in the polytetrafluoroethylene (PTFE) autoclave inner bag, 180 ℃ of hydro-thermal reaction 12h, after being cooled to room temperature, the black powder that obtains is carried out repeatedly centrifuge washing with deionized water and absolute ethyl alcohol respectively, and the dry composite precursor that obtains zinc oxide and carbon under 60 ℃ of conditions places 600 ℃ of calcinings of Muffle furnace 3h namely to get ZnO microsphere the presoma that makes afterwards.The ESEM of the ZnO microsphere that makes and transmission electron microscope picture are as depicted in figs. 1 and 2.As seen from the figure, zinc oxide has good dispersiveness.
ZnO microsphere obtained above and 2,3,3-trimethyl-3H indoles are replaced squarylium cyanine dyes [R
1Be H, R
2Be C (CH
3)] and 40ml ethanol, join in the single port flask, wherein nano zine oxide and 2,3, the mass ratio that 3-trimethyl-3H indoles replaces squarylium cyanine dyes is 100 ︰ 0.5, under 40 ℃ temperature, ultrasonic processing 2 hours is then with the alcohol solvent evaporate to dryness, with the solids oven dry under 60 ℃ that obtains, obtain the zinc oxide visible light catalyst that 2,3,3-trimethyl-3H indoles replaces the squarylium cyanine dyes sensitization.
Embodiment 2
Take by weighing the Zn that mass ratio is 1 ︰ 3 (Ac)
2.2H
2O and glucose are dissolved in the deionized water, ultrasonic formation settled solution, after changing over to solution in the polytetrafluoroethylene (PTFE) autoclave inner bag, 140 ℃ of hydro-thermal reaction 24h, after being cooled to room temperature, the black powder that obtains is carried out repeatedly centrifuge washing with deionized water and absolute ethyl alcohol respectively, and the dry composite precursor that obtains zinc oxide and carbon under 60 ℃ of conditions places 400 ℃ of calcinings of Muffle furnace 3h namely to get ZnO microsphere the presoma that makes afterwards.
ZnO microsphere obtained above and 2,3,3-trimethyl-3-ethylindole are replaced squarylium cyanine dyes [R
1Be C
2H
5, R
2Be C (CH
3)] and 60ml methyl alcohol join in the single port flask, nano zine oxide and 2 wherein, the mass ratio that 3,3-trimethyl-3-ethylindole replaces squarylium cyanine dyes is 100 ︰ 5, under 30 ℃ temperature, with the ultrasonic processing of mixture 0.5 hour, then with the methanol solvate evaporate to dryness, the solids oven dry under 60 ℃ with obtaining obtains 2,3,3-trimethyl-3H indoles replaces the zinc oxide visible light catalyst of squarylium cyanine dyes sensitization.
Application examples
For visible light catalytic performance and the potential application of verifying squarylium cyanine dyes sensitized zinc oxide photocatalyst of the present invention, with 2,3 of preparation among the embodiment 1,3-trimethyl-3H indoles replaces the zinc oxide visible light catalyst of squarylium cyanine dyes sensitization respectively with 3 * 10
-5The methylene blue solution of mol/L is put in the photo catalysis reactor, the consumption of photochemical catalyst is every 100ml methylene blue solution 15mg, stirring and being placed on outdoor temperature is to shine under 20 ℃～23 ℃ sunshines, extracted the 4ml reactant liquor every 30 minutes with dropper, put into centrifuge centrifugal 20 minutes, survey over time situation of its absorbance after taking out, the result as shown in Figure 3.As shown in Figure 3, behind light application time 150min, methylene blue almost all is removed, so the squarylium cyanine dyes sensitized zinc oxide photocatalyst of the present invention's preparation has good visible light catalytic performance.
Claims (8)
1. the preparation method of the zinc oxide visible light catalyst of a squarylium cyanine dyes sensitization is characterized in that: comprise the steps:
The composite precursor of a, preparation zinc oxide and carbon
With Zn (Ac)
22H
2O and glucose are dissolved in the deionized water, ultrasonic formation settled solution, after changing over to solution in the polytetrafluoroethylene (PTFE) autoclave inner bag, hydro-thermal reaction 12～24h of 140～180 ℃, after being cooled to room temperature, the black powder that obtains is carried out centrifuge washing with deionized water and absolute ethyl alcohol respectively, afterwards the dry composite precursor that obtains zinc oxide and carbon under 60 ℃ of conditions;
B, preparation ZnO microsphere
The presoma that above-mentioned steps is made places 400～600 ℃ of calcinings of Muffle furnace 3h namely to get ZnO microsphere;
C, the cyanine dye-sensitized zinc oxide visible light catalyst of preparation acid
The ZnO microsphere that above-mentioned steps is made mixes with squarylium cyanine dyes and organic solvent, under 30～50 ℃ temperature, with the ultrasonic processing of said mixture 0.5～2 hour, then organic solvent is removed under reduced pressure, with the solids oven dry under 60 ℃ that obtains, namely get the zinc oxide visible light catalyst of required squarylium cyanine dyes sensitization at last.
2. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 1 is characterized in that: Zn among the step a (Ac)
22H
2The mass ratio of O and glucose is 1:2～3.
3. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 1, it is characterized in that: the mass ratio of organic solvent and zinc oxide is 2:1 among the step b.
4. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 1, it is characterized in that: the mass ratio that zinc oxide and squarylium cyanine dyes are arranged among the step c is 100:0.5～5.
5. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 1, it is characterized in that: described organic solvent is selected: a kind of in methyl alcohol, ethanol, the chloroform.
6. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 1, it is characterized in that: the structure of described squarylium cyanine dyes is shown in structural formula (1):
Structural formula (1).
7. the preparation method of the zinc oxide visible light catalyst of a kind of squarylium cyanine dyes sensitization according to claim 6 is characterized in that: substituent R in the described structural formula (1)
1For H ,-(CH
2)
iM ,-(CH
2)
iC
6H
4Z, C
1～C
12Alkyl in any one 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 group among O, halogen Cl, Br, the I, i are 1～12 positive integer.
8. according to claim 1 to 7 each described preparation methods, the zinc oxide visible light catalyst of the squarylium cyanine dyes sensitization of its preparation is characterized in that: this photochemical catalyst can be used for the photocatalysis treatment of organic pollution in air, soil and the sewage.
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| US20170065504A1 (en) * | 2015-09-03 | 2017-03-09 | International Business Machines Corporation | Implementing organic materials in sunscreen applications |
| 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 |
| US9883993B2 (en) | 2015-09-03 | 2018-02-06 | International Business Machines Corporation | Notch filter coatings for use in sunscreen applications |
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| US9993402B2 (en) | 2015-09-03 | 2018-06-12 | International Business Machines Corporation | Sunscreen additives for enhancing vitamin D production |
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Application publication date: 20130501 |