CN101879465A - Copper porphyrin titanium dioxide composite photocatalyst and preparation method thereof - Google Patents
Copper porphyrin titanium dioxide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN101879465A CN101879465A CN2010102164934A CN201010216493A CN101879465A CN 101879465 A CN101879465 A CN 101879465A CN 2010102164934 A CN2010102164934 A CN 2010102164934A CN 201010216493 A CN201010216493 A CN 201010216493A CN 101879465 A CN101879465 A CN 101879465A
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- titanium dioxide
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- composite photocatalyst
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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
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- 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 discloses a copper porphyrin titanium dioxide composite photocatalyst and a preparation method thereof. The specific technical scheme is that: copper porphyrin as shown by the following structure is adsorbed on the surface of a pure anatase type titanium dioxide particle, and the mass ratio of the copper porphyrin to the titanium dioxide is (0.1-1):100. The preparation method comprises the following steps of: according to the mass ratio of the copper porphyrin to the pure anatase type titanium dioxide of (0.1-1):100, dissolving the copper porphyrin by using trichloromethane or dichloromethane; adding the titanium dioxide into the copper porphyrin, and fully stirring the mixture; performing reduced pressure distillation to remove a solvent; collecting the copper porphyrin titanium dioxide composite photocatalyst; and grinding and drying the copper porphyrin titanium dioxide composite photocatalyst. The copper porphyrin titanium dioxide composite photocatalyst can be synthesized simply, has stable properties, high activity and reusability, and can degrade stable organic matters.
Description
Technical field
The present invention relates to a kind of copper porphyrin titanium dioxide composite photocatalyst and preparation method thereof, belong to the photocatalysis technology field.
Background technology
Along with the quickening of process of industrialization and the expansion of human lives's scope, problem of environmental pollution is serious day by day, the consumption and the discharging of a large amount of industrial chemicals, and the surrounding environment that makes people live goes from bad to worse.Wherein, industrial pollution with nitropheneol material and waste water from dyestuff is the most serious.The nitropheneol material is an important chemical material, be widely used in explosive, paint, pharmacy, oil, leather, papermaking, disinfectant etc., especially coke-oven plant, gasworks, oil plant, oil factory etc. produce a large amount of phenol wastewater, not only can hinder the growth and breeding of aquatic organism, the growth that also can harm the crops is also directly threatening health.Waste water from dyestuff colourity is dark, concentration is high, toxicity is big, be difficult to degrade with natural method or with microbial method.The high-level oxidation technology that grows up gradually in recent years is based in the course of reaction and forms the free radical (especially hydroxyl radical free radical) with strong oxidability pollutant is decomposed, and the sewage that is particularly suitable for containing hardly degraded organic substance is handled.Photocatalysis method is a kind of as high-level oxidation technology, the reaction condition gentleness, and consersion unit is simple, secondary pollution is little, easy operating control, and operating cost is low, being expected with sunshine is advantages such as reaction light source, is a kind of very promising water pollution control technology, more and more is subjected to extensive concern.
At present, because TiO
2Have stable chemical performance, advantage such as cheap, the photochemical catalyst that is considered to have most practical application foreground.TiO
2Catalyst has demonstrated good potentiality at aspects such as degradation of dye waste water, agricultural chemicals waste water, surfactant, halo waste water, inorganic wastewaters, in the world with TiO
2Commercialization is applied to aspects such as ceramic purifying, coating, sterilization.Although TiO
2Obtain extensive use as photochemical catalyst, but also had some problems: TiO
2Forbidden band broad (3.2eV) can only utilize the ultraviolet light of λ＜387.5nm.The content of sun middle-ultraviolet lamp is less than 5%, and this makes solar energy utilization rate very low.How to expand TiO
2Spectral response range and its photocatalysis efficiency of raising in the visible region are restriction TiO
2The key issue of photocatalysis technology.In order to improve TiO
2To the utilization rate of sunshine, various countries' researcher has all been made unremitting effort, one after another to TiO
2Carry out modification.
At present, improve TiO
2The main method of photocatalysis performance has: cation or anion doped; Semiconductor is compound; Photoactivate etc.Wherein, photoactivate has obtained the attention of vast researcher, and this is because the photoactivate technology is chosen the particular dye reactive compound that can absorb visible light, with TiO
2Form compound, as long as the electromotive force of Photoactive compounds excitation state is than the electromotive force height of semiconductor conduction band, the electronics that the excited by visible light dye sensitizing agent is produced is transported to semi-conductive conduction band by sensitizer, thereby the excitation wavelength of complex systems is expanded to visible-range.
Summary of the invention
The object of the present invention is to provide a kind of copper porphyrin sensitization titanium dioxide composite photocatalyst, widen TiO
2The spectral response range of photochemical catalyst improves the utilization rate of photochemical catalyst to sunshine, and the synthetic composite photo-catalyst that obtains has good degradation rate for the 4-nitrophenol wastewater and the waste water from dyestuff of difficult degradation.
A kind of copper porphyrin titanium dioxide composite photocatalyst, it is adsorbed with the copper porphyrin shown in the following structure by pure anatase titanium dioxide particle surface:
Contain a cashew nut phenolic group in the structural formula in the substituting group long-chain, this is a kind of byproduct in the cashew nut agricultural production, originate abundant, cheap, have crucial development and application to be worth, the present invention is applied to synthetic porphyrin with this industrial waste, has reached twice laid in the preparation catalyst.
Described titanium dioxide is pure anatase titanium dioxide, and wherein the mass ratio of copper porphyrin and TiO 2 particles is: (0.1～1): 100.
The porphyrin part is according to literature method (Giuseppe Mele, Catalysis Today, 2009,140,37-43) synthetic obtaining.
The preparation method of copper porphyrin complex is as follows: the porphyrin monomer is dissolved in an amount of solvent, to wherein adding excessive CuCl
2, stir under the room temperature, with thin-layer chromatography detection reaction process, reacted completely in about 8 hours, reactant liquor becomes pink by aubergine, stops reaction, and solution is removed by filter unreacted CuCl
2, the pressure reducing and steaming solvent, drying at room temperature obtains the peony powder and is copper porphyrin.
The copper porphyrin titanium dioxide composite photocatalyst preparation method: copper porphyrin and pure anatase titania mass ratio are (0.1～1): 100, copper porphyrin is dissolved with chloroform or carrene, adding titanium dioxide more fully stirs, the pressure reducing and steaming solvent, collect copper porphyrin titanium dioxide composite photocatalyst, grind back 80 ℃ of dryings and get final product.
Advantage of the present invention and good effect: (1) the present invention utilizes agricultural by product (anacardol) to synthesize the copper porphyrin sensitising agent, the peripheral substituent chain of porphyrin is longer, can effectively overcome the sterically hindered of molecule, help the porphyrin molecule is adsorbed on titanium dioxide granule with the monolayer form surface.(2) to have a photo and thermal stability good for this composite photo-catalyst, and degrading phenol waste water and waste water from dyestuff are active high simultaneously, can be repeatedly used, and for the organic pollution of difficult degradation good degradation effect arranged.(3) the present invention selects pure anatase titanium dioxide as load, and with other crystal formations comparisons of titanium dioxide, the easier preparation of anatase titanium dioxide and common, its photocatalytic activity is obviously higher than P25 or rutile titanium dioxide.(4) copper porphyrin titanium dioxide composite photocatalyst of the present invention is compared with pure anatase titanium dioxide particle, and copper porphyrin titanium dioxide composite photocatalyst of the present invention has absorption at visible-range.
Description of drawings
Fig. 1 is the copper porphyrin titanium dioxide composite photocatalyst stereoscan photograph for preparing;
Fig. 2 has the TiO of copper porphyrin for load
2Fixed point EDS analytical spectra;
Fig. 3 is the ultraviolet-visible diffuse reflection spectrum comparison diagram of pure anatase titanium dioxide particle and copper porphyrin titanium dioxide composite photocatalyst of the present invention;
Fig. 4 is respectively under ultraviolet light and radiation of visible light, P25, pure anatase titanium dioxide particle and copper porphyrin titanium dioxide composite photocatalyst of the present invention degraded 4-nitrophenol solution, and 4-nitrophenol solution absorbance is change curve in time;
Fig. 5 is respectively under ultraviolet light and radiation of visible light, P25, pure anatase titanium dioxide particle and copper porphyrin titanium dioxide composite photocatalyst of the present invention degraded rhodamine B solution, and the rhodamine B solution absorbance is change curve in time;
Fig. 6 is under UV-irradiation, and copper porphyrin titanium dioxide composite photocatalyst of the present invention is reused degraded 4-nitrophenols solution, the degradation rate of 4-nitrophenol solution when ultraviolet lighting 180min 6 times.
The specific embodiment
Set forth the preparation and the character thereof of copper porphyrin titanium dioxide composite photocatalyst of the present invention below by instantiation, its purpose is better to understand content of the present invention and unrestricted protection scope of the present invention.
The pure anatase titanium dioxide that the present invention uses is produced by Hunssman company.
In the single neck bottle of 100mL,, 15-triphenyl-20-[4-(2-(3-pentadecyl-8-thiazolinyl) phenoxy group) ethyoxyl with 0.01g 5,10] the phenyl copper porphyrin is dissolved in the 30mL chloroform soln, adds 1g TiO
2(pure Detitanium-ore-type), room temperature (25 ℃) stirred 24h hour.The evaporated under reduced pressure chloroform is collected the copper porphyrin titanium dioxide composite photocatalyst of preparation and be ground to Powdered in agate mortar, 80 ℃ of dryings of baking oven can obtain copper porphyrin titanium dioxide composite photocatalyst in 30 minutes.
Fig. 1 is the SEM photo of the copper porphyrin titanium dioxide composite photocatalyst for preparing, and visible titanium dioxide composite photocatalyst particle diameter is about 100～300nm, and its fixed point EDS analytical spectra shows that copper porphyrin has been attached to titanium dioxide surface (Fig. 2).
Fig. 3 is that the ultraviolet-visible diffuse reflection spectrum of pure anatase titanium dioxide particle and copper porphyrin sensitization titanium dioxide composite photocatalyst of the present invention compares.Curve (a) is pure anatase titanium dioxide particle ultraviolet-visible diffuse reflection spectrum, and curve (b) is a copper porphyrin titanium dioxide composite photocatalyst ultraviolet-visible diffuse reflection spectrum of the present invention.Curve clearlys show that the prepared copper porphyrin titanium dioxide composite photocatalyst of the present invention has absorption in visible-range.
Copper porphyrin titanium dioxide composite photocatalyst of the present invention is illustrated the effect of catalysis material below by comparison example to the degraded percentage of model pollutant in the following unit interval of Different Light.
With copper porphyrin titanium dioxide composite photocatalyst of the present invention, respectively under 250W mercury lamp and 500W xenon source (adding the 400nm filter plate), and be target solution, with pure Detitanium-ore-type TiO with 4-nitrophenol solution
2With the P25 contrast, target solution is positioned in the 150mL beaker, and beaker is vertical with light source to be placed, and beaker center and light source keep 40 centimetres, last change calculations degraded percentage (see figure 2) according to 4-nitrophenol solution absorbance behind the light source pre-irradiation.
Fig. 4 is composite photo-catalyst, P25 or the pure Detitanium-ore-type TiO that obtains with 20mg copper porphyrin sensitization titanium dioxide
2Under Different Light, degraded 100mL concentration is the 4-nitrophenol solution of 20mg/L, and the solution absorptance is change curve in time, wherein,
(a) curve is under the 250W high voltage mercury lamp radiation, pure anatase titanium dioxide degradation curve;
(b) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, pure anatase titanium dioxide degradation curve;
(c) curve is under the 250W high voltage mercury lamp radiation, the P25 degradation curve;
(d) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, the P25 degradation curve;
(e) curve is under the 250W high voltage mercury lamp radiation, the degradation curve of copper porphyrin titanium dioxide composite photocatalyst of the present invention;
(f) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, the degradation curve of copper porphyrin titanium dioxide composite photocatalyst of the present invention;
Fig. 4 as seen, under the irradiation of 250W mercury lamp, titanium dioxide (pure Detitanium-ore-type), P25 and copper porphyrin titanium dioxide composite photocatalyst of the present invention all have certain degradation effect to the 4-nitrophenol, behind the degraded 180min, almost degradable is complete, and the copper porphyrin titanium dioxide composite photocatalyst degradation efficiency is the highest; At the 500W xenon lamp (when adding the 400nm filter plate, radiation source is a visible light) light source irradiation down, the degradation effect of titanium dioxide (pure Detitanium-ore-type) and P25 is all very poor, behind the 300min that degrades, degradation rate is less than 10%, and almost degraded is complete behind the copper porphyrin titanium dioxide composite photocatalyst 300min.As seen, copper porphyrin titanium dioxide composite photocatalyst of the present invention is far superior to the degradation effect of titanium dioxide (pure Detitanium-ore-type) and P25 to the degradation effect of 4-NP under visible light.
Under 250W mercury lamp and 500W xenon lamp (adding the 400nm filter plate) light source, choosing rhodamine B is target solution, target solution is positioned in the 250mL beaker, beaker is vertical with light source to be placed, beaker center and light source keep 40 centimetres, last change calculations degraded percentage (Fig. 5) according to rhodamine B solution absorbance behind the light source pre-irradiation.
Fig. 5 is with 20mg copper porphyrin sensitization titanium dioxide composite catalyst, P25 or pure Detitanium-ore-type TiO
2Under Different Light, degraded 100mL concentration is the rhodamine B solution of 20mg/L, and the solution absorptance is change curve in time, wherein,
(a) curve is under the 250W high voltage mercury lamp radiation, pure Detitanium-ore-type TiO
2Degradation curve;
(b) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, pure Detitanium-ore-type TiO
2Degradation curve;
(c) curve is under the 250W high voltage mercury lamp radiation, the P25 degradation curve;
(d) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, the P25 degradation curve;
(e) curve is under the 250W high voltage mercury lamp radiation, the degradation curve of copper porphyrin titanium dioxide composite photocatalyst of the present invention;
(f) curve is under 500W xenon lamp (the adding the 400nm filter plate) irradiation, the degradation curve of copper porphyrin titanium dioxide composite photocatalyst of the present invention;
From Fig. 5 as seen, under the irradiation of 250W mercury lamp, titanium dioxide (pure Detitanium-ore-type), P25 and copper porphyrin titanium dioxide composite photocatalyst of the present invention all have degradation effect preferably to rhodamine B, behind the degraded 180min, almost degradable is complete, and the copper porphyrin titanium dioxide composite photocatalyst degradation efficiency is the highest; At the 500W xenon lamp (when adding the 400nm filter plate, radiation source is a visible light) light source irradiation down, titanium dioxide (pure Detitanium-ore-type) and the degradation effect of P25 are very poor, behind the 300min that degrades, degradation rate is less than 20%, and almost degraded is complete behind the copper porphyrin titanium dioxide composite photocatalyst 300min.As seen, copper porphyrin titanium dioxide composite photocatalyst of the present invention is far superior to the degradation effect of titanium dioxide (pure Detitanium-ore-type) and P25 to the degradation effect of rhodamine B under visible light.
The copper porphyrin titanium dioxide composite photocatalyst of the present invention preparation is reusable, under ultraviolet light with the unit interval in the stability of degraded percentage explanation catalysis material of 4-nitrophenols.
Copper porphyrin titanium dioxide composite photocatalyst of the present invention is repeated experiments under 250W high-pressure sodium lamp light source, after each the degraded, the degradation solution centrifugation is handled, reclaiming catalyst, reuse 6 times, is target solution with 4-nitrophenol solution, target solution is positioned in the 250mL beaker, beaker is vertical with light source to be placed, and beaker center and light source keep 40 centimetres, last change calculations degraded percentage (Fig. 6) according to 4-nitrophenol solution absorbance behind the light source pre-irradiation.
As can be seen from Figure 6, after copper porphyrin titanium dioxide composite photocatalyst of the present invention is reused 6 times, the degradation rate of 4-nitrophenol solution is still maintained more than 90%, composite photo-catalyst stable performance of the present invention is described, can be repeatedly used.
Claims (4)
1. copper porphyrin titanium dioxide composite photocatalyst, it is characterized in that: pure anatase titanium dioxide particle surface is adsorbed with the copper porphyrin shown in the following structure,
2. copper porphyrin titanium dioxide composite photocatalyst according to claim 1 is characterized in that: the mass ratio of copper porphyrin and titanium dioxide is: (0.1～1): 100.
3. the preparation method of the described copper porphyrin titanium dioxide composite photocatalyst of claim 1, it is characterized in that: copper porphyrin and pure anatase titania mass ratio are (0.1～1): 100, copper porphyrin is dissolved with chloroform or carrene, adding titanium dioxide more fully stirs, the pressure reducing and steaming solvent, collect copper porphyrin titanium dioxide composite photocatalyst, grinding, dry getting final product.
4. the application of the described copper porphyrin titanium dioxide composite photocatalyst of claim 1 in organic wastewater and dye wastewater treatment.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127958A (en) * | 2013-02-20 | 2013-06-05 | 西北大学 | Preparation and application of metal copper porphyrin/titanium dioxide composite photocatalyst |
| CN104941684A (en) * | 2015-05-21 | 2015-09-30 | 西北大学 | Preparation method of cobalt-porphyrin-based metal organic aerogel |
| CN107188295A (en) * | 2017-06-02 | 2017-09-22 | 珠海路德通环保科技有限公司 | Preprocess method before a kind of coking chemical waste water is biochemical |
| CN107308990A (en) * | 2017-06-02 | 2017-11-03 | 北京科技大学 | A kind of TiO2The preparation method of the ultra-thin heteroplasmons of/porphyrin/MOFs |
| CN107899618A (en) * | 2017-10-23 | 2018-04-13 | 中山大学 | A kind of hybrid material based on macrocyclic compound light-sensitive coloring agent and titanium dioxide and preparation method thereof and the application in photocatalysis |
| CN108579820A (en) * | 2018-04-09 | 2018-09-28 | 西北师范大学 | A kind of copper（Ⅱ）The preparation and application of tetracarboxylic phenyl porphyrin/composite titania material |
| CN108620136A (en) * | 2018-05-21 | 2018-10-09 | 西北师范大学 | The preparation and application of copper porphyrin functional metal organic frame/composite titania material |
| CN108940380A (en) * | 2018-07-27 | 2018-12-07 | 中国石油大学(华东) | A kind of preparation method of the visible light-responded photochemical catalyst based on dye-sensitized titania |
| CN109433176A (en) * | 2018-11-07 | 2019-03-08 | 山东科技大学 | A kind of titanium dioxide-montmorillonite nanometer complex preparation method of porphyrin functionalization |
| CN109433274A (en) * | 2018-11-14 | 2019-03-08 | 郑州师范学院 | A kind of cupric organometallic complex-TiO2Composite material and preparation method and application |
| CN112316984A (en) * | 2020-11-20 | 2021-02-05 | 华中科技大学 | Supported metalloporphyrin/phthalocyanine catalyst, and preparation method and application thereof |
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2010
- 2010-07-02 CN CN2010102164934A patent/CN101879465A/en active Pending
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| CN103127958A (en) * | 2013-02-20 | 2013-06-05 | 西北大学 | Preparation and application of metal copper porphyrin/titanium dioxide composite photocatalyst |
| CN103127958B (en) * | 2013-02-20 | 2015-02-04 | 西北大学 | Preparation and application of metal copper porphyrin/titanium dioxide composite photocatalyst |
| CN104941684A (en) * | 2015-05-21 | 2015-09-30 | 西北大学 | Preparation method of cobalt-porphyrin-based metal organic aerogel |
| CN104941684B (en) * | 2015-05-21 | 2017-08-29 | 西北大学 | A kind of preparation method of Cob altporphyrin Base Metal organic aerogel |
| CN107188295A (en) * | 2017-06-02 | 2017-09-22 | 珠海路德通环保科技有限公司 | Preprocess method before a kind of coking chemical waste water is biochemical |
| CN107308990A (en) * | 2017-06-02 | 2017-11-03 | 北京科技大学 | A kind of TiO2The preparation method of the ultra-thin heteroplasmons of/porphyrin/MOFs |
| CN107899618A (en) * | 2017-10-23 | 2018-04-13 | 中山大学 | A kind of hybrid material based on macrocyclic compound light-sensitive coloring agent and titanium dioxide and preparation method thereof and the application in photocatalysis |
| CN108579820B (en) * | 2018-04-09 | 2020-11-10 | 西北师范大学 | Preparation and application of copper (II) tetracarboxyphenylporphyrin/titanium dioxide composite material |
| CN108579820A (en) * | 2018-04-09 | 2018-09-28 | 西北师范大学 | A kind of copper（Ⅱ）The preparation and application of tetracarboxylic phenyl porphyrin/composite titania material |
| CN108620136A (en) * | 2018-05-21 | 2018-10-09 | 西北师范大学 | The preparation and application of copper porphyrin functional metal organic frame/composite titania material |
| CN108620136B (en) * | 2018-05-21 | 2020-11-10 | 西北师范大学 | Preparation and application of copper porphyrin functionalized metal organic framework/titanium dioxide composite material |
| CN108940380A (en) * | 2018-07-27 | 2018-12-07 | 中国石油大学(华东) | A kind of preparation method of the visible light-responded photochemical catalyst based on dye-sensitized titania |
| CN109433176A (en) * | 2018-11-07 | 2019-03-08 | 山东科技大学 | A kind of titanium dioxide-montmorillonite nanometer complex preparation method of porphyrin functionalization |
| CN109433274A (en) * | 2018-11-14 | 2019-03-08 | 郑州师范学院 | A kind of cupric organometallic complex-TiO2Composite material and preparation method and application |
| CN109433274B (en) * | 2018-11-14 | 2021-09-10 | 郑州师范学院 | Copper-containing organic metal complex-TiO2Composite material and preparation method and application thereof |
| CN112316984A (en) * | 2020-11-20 | 2021-02-05 | 华中科技大学 | Supported metalloporphyrin/phthalocyanine catalyst, and preparation method and application thereof |
| CN112316984B (en) * | 2020-11-20 | 2022-05-13 | 华中科技大学 | Supported metalloporphyrin/phthalocyanine catalyst, and preparation method and application thereof |
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Application publication date: 20101110 |