CN103990498A - titanium dioxide metal phthalocyanine composite nanometer powder body and preparation process thereof - Google Patents
titanium dioxide metal phthalocyanine composite nanometer powder body and preparation process thereof Download PDFInfo
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- CN103990498A CN103990498A CN201410209262.9A CN201410209262A CN103990498A CN 103990498 A CN103990498 A CN 103990498A CN 201410209262 A CN201410209262 A CN 201410209262A CN 103990498 A CN103990498 A CN 103990498A
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Abstract
The invention belongs to the technical field of preparation of inorganic-organic composite nanometer catalytic materials, and relates to a titanium dioxide metal phthalocyanine composite nanometer powder body and a preparation process thereof. The composite nanometer powder body contains a titanium dioxide nanometer powder body and metal phthalocyanine, and a mass ratio of the metal phthalocyanine to the titanium dioxide is (0.5-1.0):100. The composite nanometer powder body is prepared by adopting the following steps: mixing the titanium dioxide nanometer powder body with the metal phthalocyanine in an organic solvent in a weight ratio of 100:2, heating and stirring, filtering, washing, and heating and drying, wherein the weight ratio of the metal phthalocyanine to the titanium dioxide nanometer powder body is (0.5-1.0):100. Diffuse reflection and absorbing spectrum analysis proves that a composite is remarkably enhanced in spectrum response of a visible region and a near infrared region in comparison with a pure titanium dioxide nanometer powder body. The preparation process is simple in preparation procedure; the prepared composite catalytic material is stable in performance, high in cost performance, and suitable for large-scale production, and is used for photo-catalysis treatment of atmosphere and water body pollution.
Description
Technical field
The invention belongs to inorganic-organic hybrid nano catalytic material preparing technical field, be specifically related to the preparation method of metal phthalocyanine sensitized nano cobalt dioxide powder.
Background technology
With TiO
2for representative the agent of conventional semiconductors nano-crystalline photocatalysis be the main active function material of current light catalyzed coating, this class coating have purify air, the function such as degradation of organic substances, antibacterial, automatically cleaning, significant to solving the great society problems deeply concerned such as current pollution control, energy-saving and emission-reduction.Due to it, there is the advantages such as cost is low, spectrochemical property stable, non-secondary pollution and be subject to extensive concern.
Yet, TiO
2energy gap (3.2 eV) larger, the sunshine that can only be less than 387 nm to wavelength effectively absorbs, this part only accounts for solar spectrum gross energy less than 10%, and the visible and near-infrared radiation that all the other are accounted for to sunshine gross energy >90% cannot be utilized; Meanwhile, TiO
2the quantity of photogenerated charge of nano-crystalline photocatalysis agent minute amorph (electron-hole pair) is easy to compound, causes photo-quantum efficiency to reduce, and conventionally can not surpass 10%.These 2 make conventional Ti O
2the overall efficiency of photocatalysis technology is very limited, has limited greatly it and has applied.
Dye sensitization technology can effectively be expanded the spectral response range of semiconductor nano, improves the quantum yield of quantity of photogenerated charge separation, thereby optimizes its photocatalysis efficiency.Phthalocyanine metal complex is the organic functions dyestuff of a class excellent performance, has following feature: 1) wider spectral response range (200-700 nm) and up to 10
6molar extinction coefficient, thereby there is good extinction ability; 2) less electron recombination energy and stronger electron donation, thus the separation of charge ability at dyestuff-nanocrystalline interface can be improved, improve optical energy utilization efficiency; 3) good chemical modification performance, can carry out stable coupling by covalency or supermolecule effect and matrix; 4) higher photostability, chemical stability and heat endurance, can effectively limit photobleaching and autosensibilization degraded, guarantees longer service life and complex environment adaptability.These characteristics shows that phthalocyanines dye is particularly suitable for as TiO
2nanocrystalline sensitizer, for the preparation of composite photocatalyst functional material.
Summary of the invention
In order to address the above problem, the object of this invention is to provide a kind of succinct, method of being suitable for large-scale production, the organic and inorganic composite nano powder for the preparation of having visible and near-infrared response, is specially phthalocyanine-sensitized nano TiO 2 powder.
The said titanium dioxide metal phthalocyanine of the present invention composite nano powder is comprised of nano TiO 2 powder and metal phthalocyanine, and wherein the mass ratio of metal phthalocyanine and titanium dioxide is 0.5-1.0:100.
another object of the present invention is to providethe preparation method of above-mentioned titanium dioxide metal phthalocyanine composite nano powder, step is as follows: a certain amount of nano TiO 2 powder and excessive metal phthalocyanine are mixed, add in container, add enough organic solvents, after adding thermal agitation, filtration washing and heat drying, obtain composite granule; Wherein, the mass ratio of described nano TiO 2 powder and metal phthalocyanine is 100:2.
Described metal phthalocyanine can be sulfonated phthalocyanine cobalt or unsubstituted CuPc.
Described nano TiO 2 powder can be commercial Nano titanium dioxide, comprises rutile TiO
2p25, rutile TiO
2p15, Detitanium-ore-type TiO
2p15 etc.
Described organic solvent comprises: DMF, dimethyl sulfoxide (DMSO), pyridine, specifically according to metal phthalocyanine used, select, and sulfonated phthalocyanine cobalt is selected to DMF or DMSO, unsubstituted CuPc is selected to pyridine; Solvent load is restriction not.
Heating whipping temp, between 80-150 ℃, is specifically determined according to different solvents, is specially: DMF, 100 ℃; DMSO, 150 ℃; Pyridine, 80 ℃.
Heating mixing time is 4-6 hour, available machinery or electromagnetic agitation.
Described filtration and washing are carried out in suction filtration device with 0.45 μ m miillpore filter, and described solvent comprises DMF, dimethyl sulfoxide (DMSO), pyridine, acetone, oxolane, second alcohol and water.
Heat drying can carry out in baking oven, heating-up temperature 100-110 ℃, drying time 3-6 hour.
In the composite granule making, the mass ratio of metal phthalocyanine and titanium dioxide is generally in 0.5-1.0:100 scope.
Utilize diffuse reflection and absorption spectroanalysis to find that composite has obtained remarkable reinforcement in the spectral response of visible and near infrared region than simple nano TiO 2 powder.
Titanium dioxide/sulfonated phthalocyanine cobalt composite nano powder of preparing with this method and titanium dioxide/do not replace cyanines phthalein copper composite nano powder and TiO
2p25 comparison, finds that composite granule is very strong at the light absorpting ability in 400-800 nm region, and TiO
2p25 does not absorb in this region.
Advantage of the present invention is that preparation process is succinct, the nano composite material stable performance obtaining, and cost performance is high, is suitable for large-scale production, can be used for photocatalysis and administers atmosphere and water pollution.
Accompanying drawing explanation
Fig. 1 is the TiO representing with absorbance A bs
2the uv-visible absorption spectra comparison diagram of P25 nano TiO 2 powder and titanium dioxide sulfonated phthalocyanine cobalt composite nano powder of the present invention.
Fig. 2 is the TiO representing with reflectivity R%
2the UV-Vis DRS spectrum comparison diagram of P25 nano TiO 2 powder and titanium dioxide sulfonated phthalocyanine cobalt composite nano powder of the present invention.
The specific embodiment
Below in conjunction with specific embodiment, the preparation of metal phthalocyanine sensitized nano cobalt dioxide powder in the present invention is elaborated.
Embodiment 1
By l g TiO
2p25 nano-powder and 20 mg sulfonated phthalocyanine cobalts are put into 100 ml N, in dinethylformamide, be heated to 100 ℃, stirring reaction 6 hours, then by sample with 0.45 μ m miillpore filter at suction filtration device suction filtration, with DMF, THF and distilled water, wash successively pressed powder, until eluent is colourless, put into baking oven, be heated to 110 ℃ and be dried 3 hours, make titanium dioxide/sulfonated phthalocyanine cobalt composite nano-powder, wherein the mass ratio of sulfonated phthalocyanine cobalt and titanium dioxide is 0.8: 100.
Fig. 1 provides TiO
2the uv-visible absorption spectra comparison of P25 nano-powder and titanium dioxide/sulfonated phthalocyanine cobalt composite nano powder.In Fig. 1, (a) curve is TiO
2the uv-visible absorption spectra of P25 nano-powder, (b) curve is the uv-visible absorption spectra of titanium dioxide/sulfonated phthalocyanine cobalt composite nano powder.From Fig. 1, can clearly be seen that, composite granule is very capable at the extinction in 400-800 nm region, and TiO
2p25 does not absorb in this region.Fig. 2 provides TiO
2the UV-Vis DRS spectrum comparison of P25 nano-powder and titanium dioxide/sulfonated phthalocyanine cobalt composite nano powder, as can be seen from Figure 2, composite granule significantly strengthens in the spectral response in Visible-to-Near InfaRed region.
Embodiment 2
By l g TiO
2p25 nano-powder and the unsubstituted CuPc of 20 mg are put into 100 ml pyridines, be heated to 80 ℃, stirring reaction 6 hours, then by sample with 0.45 μ m miillpore filter at suction filtration device suction filtration, with pyridine, acetone and distilled water, wash successively pressed powder, until eluent is colourless, put into baking oven, be heated to 100 ℃ dry 6 hours, make the substituted phthalocyanine copper nanometer composite powder of titanium dioxide/not, wherein the mass ratio of substituted phthalocyanine copper and titanium dioxide is not 0.5: 100.
Utilize diffuse reflection and absorption spectroanalysis to find that composite has obtained remarkable reinforcement in the spectral response of visible and near infrared region than simple nano TiO 2 powder.Similar to embodiment 1, the titanium dioxide of preparing with this method/not substituted phthalocyanine copper composite nano powder and TiO
2p25 comparison, finds that composite granule is very strong at the light absorpting ability in 400-800 nm region, and TiO
2p25 does not absorb in this region.
Embodiment 3
By l g TiO
2p25 nano-powder and 20 mg sulfonated phthalocyanine cobalts are put into 100 ml dimethyl sulfoxide (DMSO)s, be heated to 150 ℃, stirring reaction 4 hours, then by sample with 0.45 μ m miillpore filter at suction filtration device suction filtration, with DMSO, ethanol and distilled water, wash successively pressed powder, until eluent is colourless, put into baking oven, be heated to 110 ℃ and be dried 3 hours, make titanium dioxide/sulfonated phthalocyanine cobalt composite nano-powder, wherein the mass ratio of sulfonated phthalocyanine cobalt and titanium dioxide is 1.0: 100.
Similar to embodiment 1, utilize diffuse reflection and absorption spectroanalysis to find that composite has obtained remarkable reinforcement in the spectral response of visible and near infrared region than simple nano TiO 2 powder.
Claims (6)
1. a titanium dioxide metal phthalocyanine composite nano powder, the component of this composite nano powder contains nano TiO 2 powder and metal phthalocyanine, it is characterized in that, and the mass ratio of described metal phthalocyanine and titanium dioxide is 0.5-1.0:100.
2. composite nano powder as claimed in claim 1, is characterized in that, described metal phthalocyanine is sulfonated phthalocyanine cobalt or unsubstituted CuPc.
3. composite nano powder as claimed in claim 1, is characterized in that, described nano TiO 2 powder is rutile TiO
2p25, rutile TiO
2p15 or Detitanium-ore-type TiO
2p15.
4. a preparation method who prepares the titanium dioxide metal phthalocyanine composite nano powder as described in claim l-3 any one, is characterized in that, step is as follows:
A certain amount of nano TiO 2 powder and excessive metal phthalocyanine are mixed, add in container, add enough organic solvents, be heated to 80-150 ℃ and continue to stir suction filtration after 4-6 hour, pressed powder, by solvent wash, until eluent is colourless, after being 100-110 ℃ of heat drying 3-6 hour, temperature is obtained to the nano TiO 2 powder of metal phthalocyanine sensitization by the pressed powder after washing, wherein, the mass ratio of described nano TiO 2 powder and metal phthalocyanine is 100:2.
5. preparation method as claimed in claim 4, is characterized in that, described organic solvent comprises: DMF, dimethyl sulfoxide (DMSO) or pyridine.
6. preparation method as claimed in claim 4, it is characterized in that, described filtration and washing are carried out in suction filtration device with 0.45 μ m miillpore filter, and described solvent comprises DMF, dimethyl sulfoxide (DMSO), pyridine, acetone, oxolane, second alcohol and water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772166A (en) * | 2015-03-31 | 2015-07-15 | 嘉兴学院 | Composite floating bead photocatalyst as well as preparation method and application thereof |
| CN105170192A (en) * | 2015-10-26 | 2015-12-23 | 北京科技大学 | Preparation method for sulfonated cobalt phthalocyanine sensitized titanium dioxide compound photocatalyst |
| CN105833913A (en) * | 2016-04-13 | 2016-08-10 | 河海大学 | Chemical modified titanium dioxide photocatalyst and preparation method thereof |
| CN107715922A (en) * | 2017-11-02 | 2018-02-23 | 广州怡居节能环保科技有限公司 | A kind of long-acting photocatalyst and preparation method thereof |
| CN113731503A (en) * | 2021-09-08 | 2021-12-03 | 河南师范大学 | Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst |
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| CN1680021A (en) * | 2005-01-27 | 2005-10-12 | 浙江大学 | Water heating preparation of phthalocyanin sennsitized nano cobalt dioxide powder |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772166A (en) * | 2015-03-31 | 2015-07-15 | 嘉兴学院 | Composite floating bead photocatalyst as well as preparation method and application thereof |
| CN105170192A (en) * | 2015-10-26 | 2015-12-23 | 北京科技大学 | Preparation method for sulfonated cobalt phthalocyanine sensitized titanium dioxide compound photocatalyst |
| CN105833913A (en) * | 2016-04-13 | 2016-08-10 | 河海大学 | Chemical modified titanium dioxide photocatalyst and preparation method thereof |
| CN107715922A (en) * | 2017-11-02 | 2018-02-23 | 广州怡居节能环保科技有限公司 | A kind of long-acting photocatalyst and preparation method thereof |
| CN107715922B (en) * | 2017-11-02 | 2020-04-24 | 广州怡居节能环保科技有限公司 | Long-acting photocatalyst and preparation method thereof |
| CN113731503A (en) * | 2021-09-08 | 2021-12-03 | 河南师范大学 | Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst |
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