CN101195094B - Visible light activated titanium dioxide porphyrin nano composite catalyst and method for producing the same - Google Patents
Visible light activated titanium dioxide porphyrin nano composite catalyst and method for producing the same Download PDFInfo
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- CN101195094B CN101195094B CN2007103003035A CN200710300303A CN101195094B CN 101195094 B CN101195094 B CN 101195094B CN 2007103003035 A CN2007103003035 A CN 2007103003035A CN 200710300303 A CN200710300303 A CN 200710300303A CN 101195094 B CN101195094 B CN 101195094B
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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
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Abstract
The invention relates to a titanium dioxide and porphyrin nanometer compounded catalyst which can be activated by visible light and progress for preparation, belonging to the technical field of catalytic materials which are used to degrade contaminants of dye waste water. The titanium dioxide and porphyrin nanometer compounded catalyst of the invention is obtained after mixing particles of titanium dioxide nanometers and four-carboxyl porphyrin or four-hydroxyl porphrin or four-carboxyl porphyrin or four (dimethylin) porphyrin in solvent according to a proportion, heating, refluxing, filtering, washing and drying, wherein the mass ratio between the porphyrin and the titanium dioxide nanometers is 0.05-0.5: 100. The material which can be activated by visible light and prepared by the invention has the advantages of simple compound, stable performance, wide light visible using wavelength and high visible light photo-catalysis activity. The invention can be used as environmental cleaning materials for photo-catalysis treating organics.
Description
Technical field
The invention belongs to the catalysis material technical field of degradation of dye waste water pollutant, particularly a kind of visible light photoreactivation Catalysts and its preparation method.
Background technology
Along with socioeconomic fast development, environmental pollution is also serious further, has become the focal issue of direct threat human survival and development, even has hindered expanding economy in some aspects, and wherein waste water from dyestuff pollutes particularly serious.The colourity of waste water from dyestuff is dark, concentration is high, toxicity is big, is difficult to degrade under field conditions (factors) or degrade with microbial method.In recent years, organic pollution provides new approaches for the improvement of this pollutant waste water in the photocatalytic degradation water.Dyestuff contaminant in the photocatalytic method degrading waste water, required chemicals is few, can utilize sunshine, non-secondary pollution, thereby broad prospect of application is arranged.
In the research of photocatalysis at present, studying material maximum, that also be regarded as the best simultaneously is titanium dioxide (TiO
2).Based on TiO
2No matter the photocatalysis technology of nano particle is to substitute as a kind of new green energy resource, or as a kind of effective cleaning technological service in the environmental problem that receives publicity day by day, all shown powerful competitiveness.In the world, begun at external wall based on the catalysis material and the equipment of the ultraviolet light composition in ultraviolet light or the sunshine, household electrical appliance, and be applied on the deep purifying of water.But, because TiO
2Forbidden band broad (Eg=3.2eV), can only be by of the optical excitation of sunshine medium wavelength less than the 387.5nm interval, accounting in the sunshine 95% visible light can't be used, and makes TiO
2Effective utilization to sunshine is greatly limited.Based on this point, development and Design can effectively be utilized the TiO of the solar energy of longer wavelength
2Photochemical catalyst makes it to have visible light activity, improves the total utilization ratio to sunshine, has very important application value, is pursuing one's goal of numerous researchers.
Develop several approach at present, improved TiO
2Photocatalytic activity and stability, for example: the nitrogen doping (CN1267186C, CN1507943A); Semiconductor alloy ion doping (CN1116927C); (CN1311900C, CN1775348A) etc. method is to TiO for photoactivate
2Carry out modification.By change particle structure and surface nature, thereby enlarge the photoresponse scope, improve TiO
2Photocatalytic activity.In these methods, be subjected to researcher's extensive concern based on the photocatalysis technology of dye sensitization, this is because some dye compositions all have good absorption at whole visible region and even near infrared region, and the utilization of visible region and near infrared region is become possibility.
Summary of the invention
The objective of the invention is to, a kind of novel visible-light photocatalysis material that is used for the degradation of dye waste water pollutant is provided, improve visible-light photocatalysis material spectrum utilization rate, especially improve utilization rate visible light longer wavelength zone and near infrared region.
The said visible-light activated titanium dioxide porphyrin nano composite catalyst of the present invention is made up of titanium dioxide nano-particle and porphyrin.The structural formula of porphyrin is
In the structural formula R be-COOH (carboxyl) ,-OH (hydroxyl) ,-NO
2(nitro) or-N (CH
3)
2A kind of in (dimethylamino),
The mass ratio of its mesoporphyrin and titanium dioxide nano-particle is 0.05～0.5: 100.
A kind of preparation method of visible-light activated titanium dioxide porphyrin nano composite catalyst presses mass ratio with titanium dioxide nano-particle and porphyrin and 100: 1～2 mixes and solvent places container, adds hot reflux 5～10 hours; Then with the sample suction filtration, and colourless with solvent wash to eluent, again with distillation washing 5～10 times; Oven dry back grind up powder object.
Suction filtration can carry out in the frosted funnel; Can use the homogeneous solvent of dissolving titanium dioxide nano-particle and porphyrin to wash with solvent wash.
Oven dry can be carried out in baking oven.
Described porphyrin can be selected for use following any: tetracarboxylic porphyrin, tetrahydroxy porphyrin, tetranitro porphyrin, four dimethylamino porphyrins.Described titanium dioxide nano-particle is commodity Nano titanium dioxide TiO by name preferably
2P25.
Described solvent can be selected a kind of in the following solvent for use: organic acid, N, dinethylformamide, dimethyl sulfoxide (DMSO).Organic acid wherein can be formic acid, acetate, propionic acid etc.
The use amount of solvent does not have special restriction.
Described grind up powder object, the caking after will drying exactly pulverizes, to use when the degradation of dye waste water pollutant; In the object that makes, the mass ratio of porphyrin and titanium dioxide nano-particle is generally 0.05～0.5: 100 scopes.
With titanium dioxide tetracarboxylic porphyrin nano composite catalyst of the present invention and titanium dioxide tetranitro porphyrin nano composite catalyst is example, with titanium dioxide nano-particle P25 relatively, show that titanium dioxide porphyrin nano composite catalyst of the present invention has absorption in visible-range.
The characteristics of maximum of the present invention are, the visible-light photocatalysis material of design and preparation has that photo and thermal stability is good, specific area big, visible light utilizes wavelength wide, has very high advantages such as visible light photocatalysis active simultaneously.Can be used as the catalyst of photocatalysis to degrade organic matter pollutant.
Description of drawings
Fig. 1 is the ultraviolet-visible diffuse reflection spectrum comparison diagram of P25 titanium dioxide nano-particle and titanium dioxide porphyrin nano composite catalyst of the present invention.
Fig. 2 is under Different Light, P25 titanium dioxide nano-particle and titanium dioxide tetracarboxylic porphyrin nano composite catalyst of the present invention degraded acid chrome blue K solution, and the solution absorptance is change curve in time.
The specific embodiment
Be described further below by the preparation of specific embodiment to titanium dioxide porphyrin nano composite catalyst among the present invention, its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
With 1g TiO
2(commodity in use is called Nano titanium dioxide TiO
2P25) nano particle and tetracarboxylic porphyrin 10mg put into the 100ml dimethyl formamide solution, added hot reflux 5 hours, then with sample suction filtration in the frosted funnel, and use the dimethyl formamide solution elution samples, colourless until eluent, again with distillation washing 5～10 times, put into baking oven, after the oven dry sample is taken out from baking oven, with the inkstone alms bowl with its grind up powder, make titanium dioxide tetracarboxylic porphyrin nano composite catalyst, the mass ratio of its mesoporphyrin and titanium dioxide nano-particle is 0.5: 100.
The ultraviolet-visible diffuse reflection spectrum that Fig. 1 provides P25 titanium dioxide nano-particle and titanium dioxide tetracarboxylic porphyrin nano composite catalyst compares.(a) among Fig. 1 is P25 titanium dioxide nano-particle ultraviolet-visible diffuse reflection spectrum, (b) is titanium dioxide tetracarboxylic porphyrin nano composite catalyst ultraviolet-visible diffuse reflection spectrum.From the comparison of Fig. 1, clearly show that the prepared titanium dioxide tetracarboxylic porphyrin nano composite catalyst of the present invention has absorption in visible-range.
Embodiment 2
With 1g TiO
2(P25) nano particle and tetrahydroxy porphyrin 20mg put into the 100ml dimethyl formamide solution, added hot reflux 5 hours, then with sample suction filtration in the frosted funnel, and use the dimethyl formamide solution elution samples, colourless until eluent, again with distillation washing 5～10 times, put into 100 ℃ of baking ovens, after the oven dry sample is taken out from baking oven, with the inkstone alms bowl with its grind up powder, make titanium dioxide tetrahydroxy porphyrin nano composite catalyst, the mass ratio of porphyrin and titanium dioxide nano-particle is 0.05: 100.
In embodiment 1,2, also can substitute dimethyl formamide and make solvent with dimethyl sulfoxide (DMSO).
Embodiment 3
With 1g TiO
2(P25) nano particle and tetranitro porphyrin 20mg put into the 100ml dimethyl sulphoxide solution, added hot reflux 10 hours, then with sample suction filtration in the frosted funnel, and use the dimethyl sulphoxide solution elution samples, colourless until eluent, again with distillation washing 5～10 times, put into 100 ℃ of baking ovens, after the oven dry sample is taken out from baking oven, with the inkstone alms bowl with its grind up powder, make titanium dioxide tetranitro porphyrin nano composite catalyst, the mass ratio of porphyrin and titanium dioxide nano-particle is 0.10: 100.
The ultraviolet-visible diffuse reflection spectrum that Fig. 1 provides P25 titanium dioxide nano-particle and titanium dioxide tetranitro porphyrin nano composite catalyst compares.(a) among Fig. 1 is P25 titanium dioxide nano-particle ultraviolet-visible diffuse reflection spectrum, (c) is titanium dioxide tetranitro porphyrin nano composite catalyst ultraviolet-visible diffuse reflection spectrum.From the comparison of Fig. 1, clearly show that the prepared titanium dioxide tetranitro porphyrin nano composite catalyst of the present invention has absorption in visible-range.
Embodiment 4
With 1g TiO
2(P25) nano particle and four dimethylamino porphyrin 20mg put into the 100ml acetic acid solution, added hot reflux 10 hours, then with sample suction filtration in the frosted funnel, and use the acetic acid solution elution samples, colourless until eluent, again with distillation washing 5～10 times, put into 100 ℃ of baking ovens, after the oven dry sample is taken out from baking oven, use the inkstone alms bowl its grind up powder, make titanium dioxide porphyrin nano composite catalyst, the mass ratio of porphyrin and titanium dioxide nano-particle is 0.15: 100.
The acetate that substitutes present embodiment with formic acid or propionic acid is made solvent, also can realize the preparation of titanium dioxide four dimethylamino porphyrin nano composite catalysts.
Comparative Examples 1
Below by Comparative Examples to the titanium dioxide porphyrin nano composite catalyst for preparing among the present invention under visible light with the unit interval in to the effect of the degraded percentage explanation catalysis material of model pollutant.
In order to verify the potential application of titanium dioxide porphyrin nano composite catalyst, the inventor is with itself and TiO
2(P25) under the Different Light radiation, do a series of contrasts.With acid chrome blue K solution is target solution, and the light source that the photocatalysis experiment is adopted is 450W high pressure mercury fluorescent lamp or 200W incandescent lamp.Target solution is positioned in the 100ml beaker, and beaker is vertical with lamp to be placed, and beaker center and lamp spacing are from remaining on 15 centimetres.Change calculations according to dyestuff absorbance before and after the illumination obtains the percentage of degrading at last, and their comparison diagram is seen Fig. 2.
Fig. 2 is with 50mg titanium dioxide tetracarboxylic porphyrin nano composite catalyst or 50mg TiO
2(P25) 50 milliliters of 10mg/L acid chrome blue K solution of degraded are under Different Light, and the solution absorptance is change curve in time.Wherein,
(a) curve is at black out condition, TiO
2(P25) exist down;
(b) curve is in the black out condition, and titanium dioxide tetracarboxylic porphyrin nano composite catalyst is left;
(c) curve is at 450W high pressure mercury fluorescent lamp illuminate condition, TiO
2(P25) exist down;
(d) curve is at 450W high pressure mercury fluorescent lamp illuminate condition, and titanium dioxide tetracarboxylic porphyrin nano composite catalyst exists down;
(e) curve is at the incandescent lamp irradiation condition of 200W, TiO
2(P25) exist down;
(f) curve is in the incandescent lamp irradiation condition of 200W, and titanium dioxide tetracarboxylic porphyrin nano composite catalyst exists down.
We can find under the black out condition from Fig. 2, TiO
2(P25) and titanium dioxide tetracarboxylic porphyrin nano composite catalyst all acid chrome blue K is had certain absorption.With the 450W high pressure mercury fluorescent lamp is within the light source 15 minutes, TiO
2(P25) percent of decolourization is less than 50%, and the almost all degradeds of titanium dioxide tetracarboxylic porphyrin nano composite catalyst.Change the lower 200W incandescent lamp irradiation of power, the degradation rate of titanium dioxide tetracarboxylic porphyrin nano composite catalyst is that light source slightly reduces than the 450W high pressure mercury fluorescent lamp, after 15 minutes, still almost all degradeds, its degradation rate is far superior to commercialization titanium dioxide (P25).As seen our product of invention is under the irradiation of the minimum incandescent lamp of luminous efficiency, still to obtain higher photocatalysis efficiency at light source.
Claims (3)
1. visible-light activated titanium dioxide porphyrin nano composite catalyst, component has titanium dioxide nano-particle, it is characterized in that, and component also has porphyrin, and the structural formula of porphyrin is
In the formula substituent R be-COOH ,-OH ,-NO
2Or-N (CH
3)
2In a kind of.
2. visible-light activated titanium dioxide porphyrin nano composite catalyst as claimed in claim 1 is characterized in that, the mass ratio of porphyrin and titanium dioxide nano-particle is 0.05～0.5: 100.
3. the preparation method of the visible-light activated titanium dioxide porphyrin nano composite catalyst of a claim 1 is characterized in that, titanium dioxide nano-particle and porphyrin is pressed mass ratio 100: 1～2 mix and solvent places container, adds hot reflux 5～10 hours; Then with the sample suction filtration, and colourless with solvent wash to eluent, again with distillation washing 5～10 times; Oven dry back grind up powder object; Said solvent is organic acid, N, dinethylformamide or dimethyl sulfoxide (DMSO).
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| CN102008980A (en) * | 2010-11-02 | 2011-04-13 | 浙江理工大学 | Metalloporphyrin-sensitized titanium dioxide photocatalyst and preparation method thereof |
| CN102408744B (en) * | 2011-08-10 | 2013-06-12 | 中北大学 | Photosensitive fuel for dye-sensitized solar cell and preparation method thereof |
| CN102408745B (en) * | 2011-11-25 | 2014-06-18 | 北京科技大学 | Asymmetrical dye molecule adopting tetraphenylporphin as core, and preparation method thereof |
| CN103788101B (en) * | 2012-10-31 | 2017-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Cross-linked metalloporphyrin nanocrystal and preparation method thereof, and manufacturing method for optical detector |
| CN104022227A (en) * | 2014-05-19 | 2014-09-03 | 西北师范大学 | Composite material of titanium dioxide and tetracarboxyl phenyl porphyrin and preparation method and application thereof |
| CN104028309B (en) * | 2014-06-26 | 2016-01-20 | 浙江理工大学 | A kind of compound visible light catalyst and preparation method thereof |
| CN106732786B (en) * | 2015-11-19 | 2019-04-16 | 南京理工大学 | A kind of aluminium oxide/silver-PORPHYRIN IRON composite photo-catalyst and preparation method thereof |
| CN106001600B (en) * | 2016-06-02 | 2018-02-13 | 河南大学 | A kind of method that one-dimensional hollow Ag nanostructureds are prepared using photocatalytic method in situ |
| CN107377004A (en) * | 2017-07-28 | 2017-11-24 | 盐城市龙强机械制造有限公司 | A kind of baking finish for car paint house catalyst for treating waste gas |
| CN108625155B (en) * | 2018-03-21 | 2021-01-12 | 浙江理工大学 | Preparation method of fiber for generating photocurrent by using sunlight |
| CN109529825A (en) * | 2018-11-26 | 2019-03-29 | 中南民族大学 | One kind being based on sylphon shape TiO2Nano bionic Photoreactor and its preparation method and application |
| KR20230123615A (en) * | 2022-02-17 | 2023-08-24 | 충남대학교산학협력단 | Composition for decomposition and removal of spray-type contaminants |
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