CN101462073B - Heteronuclear cobalt-zinc metallophthalocyanine/nano titanic oxide composite film and preparation method - Google Patents
Heteronuclear cobalt-zinc metallophthalocyanine/nano titanic oxide composite film and preparation method Download PDFInfo
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- CN101462073B CN101462073B CN2009101160312A CN200910116031A CN101462073B CN 101462073 B CN101462073 B CN 101462073B CN 2009101160312 A CN2009101160312 A CN 2009101160312A CN 200910116031 A CN200910116031 A CN 200910116031A CN 101462073 B CN101462073 B CN 101462073B
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Abstract
The invention relates to a heteronuclear metal cobalt-zinc phthalocyanine/nanometer titanium dioxide composite film and a preparation method thereof. The heteronuclear metal cobalt-zinc phthalocyanine/nanometer titanium dioxide composite film comprises a nanometer titanium dioxide film and heteronuclear metal cobalt-zinc phthalocyanine which is evenly immobilized on the nanometer titanium dioxidefilm; and a central metal element of the heteronuclear metal cobalt-zinc phthalocyanine is bivalent cobalt and bivalent zinc, and an R substituent on a phthalocyanine ring is a sulfonic group or a carboxyl group. The preparation method comprises the steps of: preparing the heteronuclear metal cobalt-zinc phthalocyanine, and preparing the heteronuclear metal cobalt-zinc phthalocyanine into a wateror alcohol solution with a mol concentration of between 3*10<-4> and 5*10<-4>mol.L<-1>; and using distilled water to wash after the nanometer titanium dioxide film is immersed for 24 hours, and air-drying the nanometer titanium dioxide film. The heteronuclear metal cobalt-zinc phthalocyanine is immobilized on the nanometer titanium dioxide film to be prepared into the composite film, which improves the photocatalytic property of titanium dioxide to a greater extent; at the same time, the nanometer titanium dioxide composite film also has higher catalytic activity under dark conditions, and has the characteristics of high degradation rate to organisms in wastewater, low cost, simple and convenient method, easy recovery and reutilization and the like.
Description
Technical field
The present invention relates to a kind of the degrading waste water organic matter all to be had the nano titania coextruded film of high catalytic activity under visible light and dark condition, exactly is a kind of heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film.
Background technology
In numerous environmental wastewater processing methods, photocatalysis technology is that the water with broad prospect of application that grows up gradually nineteen seventies pollutes treatment technology.Find titanium dioxide semiconductor after can the phenomenon of decomposition water under the UV-irradiation continue Fujishima in 1972, develop into the environment-friendly type catalysis material of the tool exploitation future in environment pollution treatment field because of advantages such as its safety non-toxic, chemical property are stable gradually.Yet titanium dioxide (anatase) energy gap is 3.2eV, can only absorb＜the 380nm ultraviolet light, and this part light is less than 10% of sunshine.Therefore, photocatalysis efficiency is low is difficult to reclaim the key issue of the need solution that becomes the titanium dioxide practical application with powder titanium dioxide.
Metal phthalocyanine is the big molecule in plane with π-electron system of height conjugation, and good light, heat endurance are arranged, and at 320～370nm, 600～800nm scope has strong absorption; Simultaneously, metal phthalocyanine cobalt and its derivative have good catalytic activity, find expression in the reduction of its center metal pair molecular oxygen, so metal phthalocyanine is widely used in numerous areas such as catalyst, photocell, are called as the new material of 21st century.Metal phthalocyanine is immobilized on titanium dioxide as sensitising agent, can widen titanium dioxide spectrum response range, further improve its catalytic activity.The immobilized research that relates to metal phthalocyanine sensitization titanium dioxide and titanium dioxide is more, and about the immobilized research that forms the laminated film catalyst on nano-titanium dioxide film of heteronuclear metal phthalocyanine cobalt zinc is not also had report.
Summary of the invention
It is simple that the present invention aims to provide a kind of technology, and stability is high, recyclablely utilizes again, the degrading waste water organic matter all had the nano titania coextruded film of high catalytic activity under visible light and dark condition.
Concrete technical solution is as follows:
Heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film comprises nano-titanium dioxide film, the even immobilized heteronuclear metal phthalocyanine cobalt zinc that has on the described nano-titanium dioxide film;
The central metal element of described heteronuclear metal phthalocyanine cobalt zinc is divalence cobalt and divalent zinc, and the R substituting group on the heteronuclear metal phthalocyanine cobalt zinc phthalocyanine ring is sulfonic group or carboxyl, and its structure is
The preparation method of heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film comprises following operating procedure:
The first step, with 3g 4-sulfonic acid phthalic acid three salt or 2g trimellitic acid salt, the 0.8g cobalt chloride, the 0.7g pyromellitic dianhydride, 0.03g ammonium molybdate and about 8g urea evenly mix, and after 2 hours, obtain black-and-blue solid product (a) 240 ℃ of reactions;
Second step took by weighing 3g solid product (a), zinc chloride 0.2g, and ammonium molybdate 0.02g, urea 8g evenly mixes, and 240 ℃ of reactions 2～4 hours, obtains the blue-green solid product, i.e. heteronuclear metal phthalocyanine cobalt zinc;
In the 3rd step, heteronuclear metal phthalocyanine cobalt zinc is mixed with 3～5 * 10
-4MolL
-1The aqueous solution;
In the 4th step, nano-titanium dioxide film is immersed 3～5 * 10
-4MolL
-1The heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is 24 hours, uses distilled water flushing, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
In view of titanium dioxide has photocatalytic activity under UV-irradiation, heteronuclear metal phthalocyanine cobalt zinc is sensitization titanium dioxide and can be firmly immobilized on nano-titanium dioxide film and the catalytic oxidation activity of heteronuclear metal phthalocyanine cobalt zinc with chemical bond effectively, thereby prepare the recyclable laminated film with high catalytic activity that utilizes again.
By Comparative Examples to prepared heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film in the invention under visible light and dark condition, the degradation rate of organic matter model in the waste water is illustrated that the catalytic effect of heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film is as follows:
With the methylene blue solution is target solution, utilize heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film, heteronuclear metal phthalocyanine cobalt manganese/nano titania coextruded film, heteronuclear metal phthalocyanine zinc-manganese/nano titania coextruded film, with nuclear metal phthalocyanine cobalt/nano titania coextruded film, with nuclear metal phthalocyanine zinc/nano titania coextruded film, with nuclear metal phthalocyanine manganese/nano titania coextruded film, under radiation of visible light and dark condition, carry out the catalytic degradation experiment respectively with nano-titanium dioxide film: with different heteronuclear metal phthalocyanine/nano-titanium dioxide films, be positioned in the 100mL graduated cylinder with the 50mL target solution respectively with nuclear metal phthalocyanine/nano-titanium dioxide film and nano-titanium dioxide film, vertically be placed under the incandescent lamp or the lucifuge reaction, get methylene blue solution at regular intervals and measure its UV absorption, calculate degradation rate.Under the visible light condition, nano-titanium dioxide film is with different heteronuclear metal phthalocyanine/nano-titanium dioxide films and with nuclear metal phthalocyanine/nano-titanium dioxide film degradation of methylene blue solution, degradation rate is over time as Fig. 1, under dark condition, nano-titanium dioxide film is with different heteronuclear metal phthalocyanine/nano-titanium dioxide films and with nuclear metal phthalocyanine/nano-titanium dioxide film degradation of methylene blue solution, and degradation rate is over time as Fig. 2.
In sum, heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film of the present invention, difference with the prior art is for to combine heteronuclear metal phthalocyanine cobalt zinc with nano-titanium dioxide film, be about to the immobilized laminated film that on nano-titanium dioxide film, is prepared into of heteronuclear metal phthalocyanine cobalt zinc, thereby at the photocatalysis performance that has improved titanium dioxide to a greater extent, simultaneously, nano titania coextruded film also has advantages of high catalytic activity under dark condition, have the degradation effect of organic compound height in the waste water, cost is low, method is easy, is easy to characteristics such as recycling.
Description of drawings
Fig. 1 is under the visible light condition, and nano-titanium dioxide film is with different heteronuclear metal phthalocyanine/nano-titanium dioxide films and with nuclear metal phthalocyanine/nano-titanium dioxide film degradation of methylene blue solution, and degradation rate is schemed over time.
Fig. 2 is under dark condition, and nano-titanium dioxide film is with different heteronuclear metal phthalocyanine/nano-titanium dioxide films and with nuclear metal phthalocyanine/nano-titanium dioxide film degradation of methylene blue solution, and degradation rate is schemed over time.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
Heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film comprises nano-titanium dioxide film and heteronuclear metal phthalocyanine, the even immobilized heteronuclear metal phthalocyanine cobalt zinc that has on the described nano-titanium dioxide film;
The central metal element of described heteronuclear metal phthalocyanine cobalt zinc is divalence cobalt and divalent zinc, and the R substituting group on the heteronuclear metal phthalocyanine cobalt zinc phthalocyanine ring is sulfonic group or carboxyl, and its structure is
The preparation method of heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film comprises following operating procedure:
The first step, with 3g 4-sulfonic acid phthalic acid three salt or 2g trimellitic acid salt, the 0.8g cobalt chloride, the 0.7g pyromellitic dianhydride, 0.03g ammonium molybdate and about 8g urea evenly mix, and after 2 hours, obtain black-and-blue solid product (a) 240 ℃ of reactions;
Second step took by weighing 3g solid product (a), zinc chloride 0.2g, and ammonium molybdate 0.02g, urea 8g evenly mixes, and 240 ℃ of reactions 2～4 hours, obtains the blue-green solid product, i.e. heteronuclear metal phthalocyanine cobalt zinc;
In the 3rd step, heteronuclear metal phthalocyanine cobalt zinc is mixed with 3～5 * 10
-4MolL
-1The heteronuclear phthalocyanine cobalt zinc aqueous solution or ethanolic solution;
The 4th step prepared nano-titanium dioxide film with spraying process on glass substrate, nano-titanium dioxide film is immersed 3～5 * 10
-4MolL
-1The carboxyl heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is 24 hours, uses distilled water flushing, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Embodiment 2:
On glass substrate, prepare nano-titanium dioxide film with dip-coating method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1The carboxyl heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is used distilled water flushing after being 24 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Embodiment 3:
On glass substrate, prepare nano-titanium dioxide film with silk screen print method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1The carboxyl heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is used distilled water flushing after being 24 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Embodiment 4:
On glass substrate, prepare nano-titanium dioxide film with silk screen print method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1Carboxyl heteronuclear phthalocyanine cobalt zinc ethanolic solution in, dip time is used distilled water flushing after being 24 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Embodiment 5:
On glass substrate, prepare nano-titanium dioxide film with silk screen print method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1Sulfonic group heteronuclear phthalocyanine cobalt zinc ethanolic solution in, dip time is used distilled water flushing after being 24 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Embodiment 6:
On glass substrate, prepare nano-titanium dioxide film with silk screen print method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1The sulfonic group heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is used distilled water flushing after being 24 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Embodiment 7:
On glass substrate, prepare nano-titanium dioxide film with silk screen print method, the nano-titanium dioxide film for preparing is immersed 3～5 * 10
-4MolL
-1The sulfonic group heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is used distilled water flushing after being 48 hours, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
Other is with embodiment 1.
Claims (2)
1. heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film comprises nano-titanium dioxide film, it is characterized in that: the even immobilized heteronuclear metal phthalocyanine cobalt zinc that has on the described nano-titanium dioxide film;
The central metal element of described heteronuclear metal phthalocyanine cobalt zinc is divalence cobalt and divalent zinc, and the R substituting group on the heteronuclear metal phthalocyanine cobalt zinc phthalocyanine ring is sulfonic group or carboxyl, and its structure is
2. the preparation method of heteronuclear metal phthalocyanine cobalt zinc/nano titania coextruded film according to claim 1 is characterised in that to comprise following operating procedure:
The first step, with 3g 4-sulfonic acid phthalic acid three salt or 2g trimellitic acid salt, the 0.8g cobalt chloride, the 0.7g pyromellitic dianhydride, 0.03g ammonium molybdate and 8g urea evenly mix, and after 2 hours, obtain black-and-blue solid product (a) 240 ℃ of reactions;
Second step took by weighing 3g solid product (a), zinc chloride 0.2g, and ammonium molybdate 0.02g, urea 8g evenly mixes, and 240 ℃ of reactions 2～4 hours, obtains the blue-green solid product, i.e. heteronuclear metal phthalocyanine cobalt zinc;
In the 3rd step, heteronuclear metal phthalocyanine cobalt zinc is mixed with 3～5 * 10
-4MolL
-1The aqueous solution;
In the 4th step, nano-titanium dioxide film is immersed 3～5 * 10
-4MolL
-1The heteronuclear phthalocyanine cobalt zinc aqueous solution in, dip time is 24 hours, uses distilled water flushing, dries promptly to get heteronuclear metal phthalocyanine cobalt zinc/nano-titanium dioxide film.
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| CN102513078A (en) * | 2011-11-29 | 2012-06-27 | 西安理工大学 | Preparation method of cobalt protoporphyrin sensitization titanium dioxide hollow microsphere photochemical catalyst |
| CN105585100B (en) * | 2015-12-16 | 2018-07-17 | 广东睿洁环保工程有限公司 | A kind of visible light light urges oxidation water processing reactor |
| CN105481048A (en) * | 2015-12-16 | 2016-04-13 | 无锡吉进环保科技有限公司 | Improved visible light photocatalytic oxidation water treatment reactor |
| CN105709828B (en) * | 2016-01-20 | 2018-01-02 | 辽宁大学 | A kind of cobalt phthalocyanine functionalization Janus composites and its preparation method and application |
| CN108246124B (en) * | 2017-12-17 | 2020-08-18 | 浙江理工大学 | Preparation method of PVDF (polyvinylidene fluoride) membrane with catalytic self-cleaning function |
| CN111855779B (en) * | 2020-07-31 | 2024-08-30 | 南京市同亮科技有限公司 | Preparation and application of nitrogen-doped graphene-heteronuclear copper phthalocyanine vanadyl electrochemical sensor |
| CN111855773B (en) * | 2020-07-31 | 2024-05-31 | 浙江丰能医药科技有限公司 | Preparation and application of nitrogen-doped graphene-heteronuclear manganese-nickel phthalocyanine electrochemical sensor |
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