CN104475167A - Preparation method and application of 1-3-substituted aryl ether dendritic phthalocyanine complex-modified TiO2 visible light catalyst - Google Patents
Preparation method and application of 1-3-substituted aryl ether dendritic phthalocyanine complex-modified TiO2 visible light catalyst Download PDFInfo
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- CN104475167A CN104475167A CN201410800320.5A CN201410800320A CN104475167A CN 104475167 A CN104475167 A CN 104475167A CN 201410800320 A CN201410800320 A CN 201410800320A CN 104475167 A CN104475167 A CN 104475167A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 preparation method and application of a 1-3-substituted aryl ether dendritic phthalocyanine complex-modified TiO2 visible light catalyst. The preparation method comprises the following steps: hydrolyzing a alcohol salt of titanium to prepare TiO2 solid powder, adding an N,N-dimethyl formamide solution of a 1-3-substituted aryl ether dendritic phthalocyanine complex, soaking, filtering, washing and drying so as to obtain the 1-3-substituted aryl ether dendritic phthalocyanine complex-modified TiO2 visible light catalyst. The method is moderate in reaction conditions, easy to control, simple in equipment, easily available in raw materials, and simple in synthesis process, and by using the method, the industrialized production is easy to realize; the prepared 1-3-substituted aryl ether dendritic phthalocyanine complex-modified TiO2 visible light catalyst has the performance of degrading organic matters through visible light catalysis, and can be applied to light catalysis treatment on organic pollutants in air, soil and sewage.
Description
Technical field
The invention belongs to the preparation field of catalyst, particularly 1-3 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst and application thereof.
Background technology
TiO
2be current a kind of photochemical catalyst most with application potential, it be environmentally friendly, the feature such as wide material sources, resistance to acids and bases are good, stable chemical nature, at present at generation clear energy sources, purify air, water body, the field such as antibacterial are widely used.But about TiO
2light-catalysed mechanism is still not very clear, again owing to itself having larger energy gap (anatase and brockite are 3.2 eV, and Rutile Type is 3.0 eV), therefore, can only absorb the energy of in sunshine about 5%.To TiO
2carry out modification to improve its efficiency of light energy utilization and be of great significance and value.
Phthalocyanine dye is the aromatic ring system with unique plane 18 pi-electron, stable chemical nature.Because it all has stronger absorption to sunshine middle ultraviolet band and visible region, and active oxygen can be produced, as singlet oxygen, hydroxyl radical free radical, superoxide radical etc. after absorption luminous energy.So phthalocyanine-like compound is the important sensitising agent of a class, has application, as photodynamic therapy, opto-electronic conversion, photocatalysis etc. in a lot of field.But phthalocyanine compound is easily reunited in aqueous, thus reduce the quantum yield of compound singlet oxygen and triplet oxygen.
Utilize dendritic phthalocyanine modification TiO
2multiphase photocatalysis course of reaction may be affected from the following aspects, thus improving the efficiency of photocatalytic process: structurally the most outstanding compared with the traditional phthalocyanine compound feature of dendritic phthalocyanine is the introduction of dendritic structure, dendritic structure is connected in its surrounding centered by phthalocyanine compound, and connect hydrophilic radical at periphery, make it have certain hydrophilicity, both can effectively reduce the gathering of phthalocyanine compound, improve the quantum yield of singlet oxygen and triplet oxygen.On the other hand, the access of hydrophilic radical can make itself and TiO
2better combination, dendritic phthalocyanine modification TiO
2light induced electron can be made to transfer to TiO
2molecule effectively raises the transfer efficiency of electronics.
(1) dendritic phthalocyanine is after optical excitation, absorb photons energy, by ground state transition to excitation state, the sensitising agent of excitation state transits to excited triplet state by passing through between gap, and the excited triplet state dendritic phthalocyanine with longer life can react with the oxygen molecule in air and generate singlet oxygen.
(2) dendritic phthalocyanine modification TiO
2carrying out light-catalyzed reaction can by the electro transfer of dendritic phthalocyanine generation after illumination to TiO
2form electro transfer, the electronics transferring to semiconductor conduction band can generate active oxygen with oxygen reaction further, as super positive free radical, is reacted further be mineralized into CO by the active oxygen of above-mentioned generation with the organic pollution in water body
2and H
2o.
(3) dendritic phthalocyanine surrounding molecules hydrophilic functional group can with TiO
2on-OH formed active force, be better fixed on TiO
2on.Meanwhile, the metallic atom in dendritic phthalocyanine molecule can with TiO
2form the active force between axial complexing enhancing molecule.
(4) TiO
2with play fixing after dendritic phthalocyanine molecular complex and disperse the effect of dendritic phthalocyanine molecule, the gathering between Phthalocyanine can be reduced, while Phthalocyanine be fixed on TiO
2pressed powder will be conducive to reclaim.
Summary of the invention
The object of the invention is as the light catalytic purifying processing procedure of soil, air and water quality provides a kind of 1-3 with photocatalysis degradation organic contaminant for aryl oxide dendritic phthalocyanine complex modification TiO
2visible-light photocatalyst, this photochemical catalyst both can improve TiO
2to the absorbability of visible ray, turn improve the transfer efficiency of electronics, effectively improve its visible light photocatalysis performance.
The present invention seeks to realize like this, described 1-3 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, comprises the following steps:
(1) under the condition of the acidity of pH<5 or the alkalescence of pH>7 by the hydrolysis of alkoxide of titanium, obtain homogeneous transparent TiO
2content is the TiO of 0.5 ~ 5.0 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 2 ~ 7 by dialysis
2colloidal sol, colloidal sol after drying, is calcined 1 ~ 5 h under 80 ~ 110 DEG C of conditions under 150 ~ 400 DEG C of conditions, and grinding obtains TiO
2pressed powder;
(2) to the 1-3 be dissolved in DMF for adding the obtained TiO of step (1) in aryl oxide dendritic phthalocyanine complex
2solid, the 1-3 wherein added is for the quality of aryl oxide dendritic phthalocyanine complex and TiO
2solid masses ratio is 0.33 ~ 1.33%, at room temperature floods 4 ~ 24 h, filters, washing, and obtained 1-3 is for aryl oxide dendritic phthalocyanine complex and TiO
2mixture;
(3) by 1-3 for aryl oxide dendritic phthalocyanine complex and TiO
2mixture is dried.
Described 1-3 is zinc, copper, cobalt or iron for the central atom M in aryl oxide dendritic phthalocyanine complex, and its consumption is TiO
2the 0.5-1wt% of solid consumption.
Dip time described in step (2) is 6-15 h.
PH=3 ~ 5 of described acid condition or pH=8 ~ 10 of alkali condition.
The alkoxide of described titanium refers to butyl titanate, tetraisopropyl titanate or tetraethyl titanate;
The 1-3 that the above-mentioned preparation method of the present invention obtains is for aryl oxide dendritic phthalocyanine complex modification TiO
2visible-light photocatalyst.
Described 1-3 is for aryl oxide dendritic phthalocyanine complex modification TiO
2visible-light photocatalyst can be used for the photocatalysis treatment of organic dyestuff in sewage.
Described organic pollution is the bright B of Luo Dan or methylene blue.
The concrete preparation method of catalyst of the present invention is as follows:
(1) under the condition of acid (pH<5) or alkalescence (pH>7) by the hydrolysis of alkoxide of titanium, obtain homogeneous transparent TiO
2content is the TiO of 0.5 ~ 5.0 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 2 ~ 7 by dialysis
2colloidal sol, colloidal sol after drying, is calcined 1 ~ 5 h under 80 ~ 110 DEG C of conditions under 150 ~ 400 DEG C of conditions, and grinding obtains TiO
2pressed powder.
(2) by TiO
2solid joins 1-3 in the DMF solution of aryl oxide dendritic phthalocyanine complex, wherein adds 1-3 for the quality of aryl oxide dendritic phthalocyanine complex and TiO
2the ratio of solid masses is 0.33 ~ 1.33%, at room temperature floods 4 ~ 24 h, and obtained 1-3 is for aryl oxide dendritic phthalocyanine complex and TiO
2mixture.
(3) by 1-3 for aryl oxide dendritic phthalocyanine complex and TiO
2mixture filtration, washing (distilled water washs 5 times, each 10 milliliters), oven dry.
(4) 1-3 the present invention prepared is for aryl oxide dendritic phthalocyanine complex/TiO
2visible-light photocatalyst is used for the light-catalyzed reaction under visible ray or sunlight, has the performance of photocatalysis to degrade organic matter.
Beneficial effect of the present invention:
Visible-light photocatalyst preparation method technique of the present invention is simple, and cheaper starting materials is easy to get, and is easy to control, and is suitable for suitability for industrialized production and application.The 1-3 prepared is for the TiO of aryl oxide dendritic phthalocyanine complex modification
2visible-light photocatalyst specific area is large, and visible ray utilization rate is high, can significantly improve the quantum efficiency of singlet oxygen and triplet oxygen, can be used for processing trade effluent, degradation of dye waste water etc.
Accompanying drawing explanation
Fig. 1 is that the 1-3 of embodiment 1 preparation is for aryl oxide dendritic phthalocyanine complex (M is zinc)/TiO
2the X-ray diffractogram of visible-light photocatalyst.
Fig. 2 is that the 1-3 of embodiment 1 preparation is for aryl oxide dendritic phthalocyanine complex (M is zinc)/TiO
2the UV-vis DRS figure of visible-light photocatalyst.
Fig. 3 is that the 1-3 of embodiment 1 preparation is for aryl oxide dendritic phthalocyanine complex (M is zinc)/TiO
2visible-light photocatalyst rhodamine B degradation activity figure.
Fig. 4 is that the 1-3 of embodiment 2 preparation is for aryl oxide dendritic phthalocyanine complex (M is copper, iron or cobalt)/TiO
2visible-light photocatalyst rhodamine B degradation activity figure.
Fig. 5 be 1-3 for aryl oxide dendritic phthalocyanine complex (M is copper), 1-3 for aryl oxide dendritic phthalocyanine complex (M is cobalt) and 1-3 for aryl oxide dendritic phthalocyanine complex (M is iron) modification TiO
2the comparison diagram of the bright B of degraded Luo Dan.
Detailed description of the invention
Acid solution in following embodiment preferably 98 wt% sulfuric acid configuration.Alkaline solution preferably 40 wt% NaOH configuration.
Embodiment 1
(1) by the tetrabutyl titanate hydrolysis of 10 milliliters in the acid solution of the pH=5 of 90 milliliters, obtain homogeneous transparent TiO
2content is the TiO of 2.3 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 6 by dialysis
2colloidal sol, colloidal sol is dry under 105 DEG C of conditions, and under 200 DEG C of conditions, calcine 5 h, grinding obtains TiO
2pressed powder.
(2) 0.01 g 1-3 is dissolved in the DMF solution of 50 mL for aryl oxide dendritic phthalocyanine complex (M is zinc), adds above-mentioned TiO
2pressed powder 1 g, floods 12 h.
(3) filtered by the mixed liquor obtained, washing (distilled water washs 5 times, each 10 milliliters), under 105 DEG C of conditions, drying obtains prepared 1-3 for aryl oxide dendritic phthalocyanine complex (M is zinc) modification TiO
2visible-light photocatalyst.
1-3 is for aryl oxide dendritic phthalocyanine complex (M is zinc)/TiO
2the X-ray diffractogram of visible-light photocatalyst and UV-vis DRS figure are as depicted in figs. 1 and 2.
Embodiment 2
(1) by the tetrabutyl titanate hydrolysis of 17 milliliters in the alkaline solution of the pH=8.5 of 80 milliliters, obtain homogeneous transparent TiO
2content is the TiO of 4 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 7 by dialysis
2colloidal sol, colloidal sol is dry under 105 DEG C of conditions, and under 300 DEG C of conditions, calcine 3 h, grinding obtains TiO
2pressed powder.
(2) 0.02 g 1-3 is dissolved in the DMF solution of 50 milliliters for aryl oxide dendritic phthalocyanine Zn complex (M is zinc), adds above-mentioned TiO
2pressed powder 1 g, magnetic agitation 12 h.
(3) filtered by the mixed liquor obtained, washing (distilled water washs 5 times, each 10 milliliters), under 105 DEG C of conditions, drying obtains prepared 1-3 for aryl oxide dendritic phthalocyanine Zn complex (M is zinc) modification TiO
2visible-light photocatalyst.
Embodiment 3
(1) by the tetrabutyl titanate hydrolysis of 11 milliliters in the acid solution of the pH=3 of 90 milliliters, obtain homogeneous transparent TiO
2content is the TiO of 2.8 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 6 by dialysis
2colloidal sol, colloidal sol is dry under 80 DEG C of conditions, and under 200 DEG C of conditions, calcine 5 h, grinding obtains TiO
2pressed powder.
(2) 0.01 g 1-3 is dissolved in the DMF solution of 50 milliliters respectively for aryl oxide dendritic phthalocyanine complex (M is copper, iron or cobalt), adds above-mentioned TiO
2pressed powder 1 g, magnetic agitation 12 h.
(3) filtered respectively by the mixed liquor obtained, washing (distilled water washs 5 times, each 10 milliliters), under 80 DEG C of conditions, drying obtains prepared 1-3 for aryl oxide dendritic phthalocyanine complex (M is copper, iron or cobalt)/TiO
2visible-light photocatalyst.
Embodiment 4
The light source of visible light photocatalysis reaction is for being placed in 500 W halogen tungsten lamps of double glazing chuck (logical condensed water), incident light is visible ray (420 nm< λ <800 nm), with 80 ml concns for 1 × 10 to use optical filter to ensure
-5the bright B of mol/L Luo Dan is catalytic organism object, and the 1-3 prepared with 80 mg embodiments 1 is for aryl oxide dendritic phthalocyanine complex (M is for zinc) modification TiO
2for photochemical catalyst, analyzed by ultraviolet-uisible spectrophotometer, through 3 h visible ray illumination, degradation rate is 97%.
Embodiment 5:
The light source of visible light photocatalysis reaction is for being placed in 500 W halogen tungsten lamps of double glazing chuck (logical condensed water), incident light is visible ray (420 nm< λ <800 nm), with 80 ml concns for 2 × 10 to use optical filter to ensure
-5mol/L methylene blue is catalytic organism object, and the 1-3 prepared with 80 mg embodiments 2 is for aryl oxide dendritic phthalocyanine complex (M is for zinc) modification TiO
2for photochemical catalyst, analyzed by ultraviolet-uisible spectrophotometer.Through 5 h visible ray illumination, degradation rate is 91%.
Embodiment 6:
The light source of visible light photocatalysis reaction is for being placed in 500 W halogen tungsten lamps of double glazing chuck (logical condensed water), incident light is visible ray (420 nm< λ <800 nm), with 80 ml concns for 1 × 10 to use optical filter to ensure
-5the bright B of mol/L Luo Dan is catalytic organism object, and the 1-3 prepared with 80 mg embodiments 3 is for aryl oxide dendritic phthalocyanine complex (M is copper, iron, cobalt) modification TiO
2for photochemical catalyst, analyzed by ultraviolet-uisible spectrophotometer.Through 3 h visible ray illumination, 1-3 is for aryl oxide dendritic phthalocyanine complex (M is copper) modification TiO
2degradation rate be 30%, 1-3 for aryl oxide dendritic phthalocyanine complex (M is cobalt), 1-3 for aryl oxide dendritic phthalocyanine complex (M is iron) modification TiO
2be 98%, see Fig. 5.
(note: the patent of invention " 1-3 is for aryl oxide dendritic phthalocyanine complex and its preparation method and application " (ZL200910111845.7) that the 1-3 described in above-described embodiment adopts authorize the early stage of inventor for aryl oxide dendritic phthalocyanine complex and preparation method thereof, its concrete steps are as follows:
1) Frechet synthetic method synthesis 1-3 is first adopted to be the dendrimer of end group for cyano group.Namely with 3,5-dihydroxybenzyl alcohol is branch monomeric unit, synthesizes " 1 " for alcohol: 3 to cyano group benzyl bromine and branch monomeric unit 3,5-dihydroxybenzyl alcohol in potash and acetone soln, 5-bis--(4-cyano group benzyloxy) phenmethylol (CN) 2-[G-1]-OH, is called for short material (1).This material (1) and carbon tetrabromide and triphenylphosphine are synthesized " 1 " for benzyl bromine: 3,5-bis--(4-cyano group benzyloxy) benzyl bromine (CN) 2-[G-1]-Br, be called for short material (2).This material (2) and 3,5-dihydroxybenzyl alcohol couplings are synthesized " 2 " for alcohol: 3,5-bis--[3,5-bis--(4-cyano group benzyloxy) benzyloxy] phenmethylol (CN) 4-[G-2]-OH, be called for short material (3).This material (3) and carbon tetrabromide and triphenylphosphine are synthesized " 2 " for benzyl bromine: 3,5-bis--[3,5-bis--(4-cyano group benzyloxy) benzyloxy] benzyl bromine (CN) 4-[G-2]-Br, be called for short material (4).Repeat above synthetic route, above-mentioned material (4) and 3,5-dihydroxybenzyl alcohols synthesize " 3 " for alcohol: 3,5-bis--{ 3,5-bis--[3,5-bis--(4-cyano group benzyloxy) benzyloxy] } phenmethylol (CN) 8-[G-3]-OH, is called for short material (5).
2) under potash exists, in DMF solution by " the 1 to the 3 " for alcohol (see above-mentioned material (1), material (3), material (5)) react with 4-nitrophthalonitrile respectively, synthesis is the phthalocyanine presoma of the dendrimer of end group for cyano-containing containing " the 1 to the 3 ", be respectively: 3, 5-bis--(4-cyano group benzyloxy) benzyloxy phthalonitrile, be called for short material (6) and 3, 5-bis--[3, 5-bis--(4-cyano group benzyloxy) benzyloxy] phthalonitrile, be called for short material (7) and 3, 5-bis--{ 3, 5-bis--[3, 5-bis--(4-cyano group benzyloxy) benzyloxy] } phthalonitrile, be called for short material (8).
3) with DBU (1, 8-diazacyclo [5, 4, 0] hendecene-7) be catalyst, lithium chloride, silicon tetrachloride, iron chloride, cobalt chloride, zinc acetate, copper chloride, titanium tetrachloride, alchlor is template, become corresponding " the 1 to the 3 " for the aryl oxide dendritic phthalocyanine of cyano-containing end group phthalocyanine presoma (see above-mentioned material (6)-material (the 8)) cyclization taking cyano group as the dendrimer of end group containing " the 1 to the 3 " generation, be respectively: four-[3, the sub-anisyl of 5-bis--(4-cyano group benzyloxy)-1-] phthalocyanine, be called for short material (9) four-{ 3, 5-bis--[3, the sub-anisyl of 5-bis--(4-cyano group benzyloxy)-1-] the sub-anisyl of-1-} phthalocyanine (10), be called for short material (10) and four-{ 3, 5-bis--{ 3, 5-bis--[3, the sub-anisyl of 5-bis--(4-cyano group benzyloxy)-1-] the sub-anisyl of-1-} the sub-anisyl of-1-} phthalocyanine, be called for short material (11).
In above-mentioned steps to cyano group benzyl bromine with nitrobenzyl bromine being replaced to the 1-3 that just can generate containing nitro end group for aryl oxide dendritic phthalocyanine complex, and other reactions steps is the same, is the technology that persons skilled in the art can realize.
4) by above-mentioned material (9), material (10) and material (11) be hydrolyzed in NaOH accordingly " the 1 to the 3 " with the aryl oxide branch phthalocyanine of carboxyl end groups, be respectively: four-[3, the sub-anisyl of 5-bis--(4-carboxyl benzyloxy)-1-] phthalocyanine, be called for short material (12) and four-{ 3, 5-bis--[3, the sub-anisyl of 5-bis--(4-carboxyl benzyloxy)-1-] the sub-anisyl of-1-} phthalocyanine, be called for short material (13) and four-{ 3, 5-bis--{ 3, 5-bis--[3, the sub-anisyl of 5-bis--(4-cyano group benzyloxy)-1-] the sub-anisyl of-1-} the sub-anisyl of-1-} phthalocyanine, be called for short material (14), namely 1-3 is obtained for aryl oxide dendritic phthalocyanine complex.）
1-3 described in the above embodiment of the present invention is for aryl oxide dendritic phthalocyanine complex structural formula (in formula: M is zinc, cobalt, iron or copper; In formula: R is carboxyl.) adopt the compound of the arbitrary chemical constitution shown in following three kinds of structural formulas: wherein " 1 " compound of being preferably as follows of embodiment 1, wherein M is zinc; Wherein " 2 " compound of being preferably as follows of embodiment 2, wherein M is zinc; Wherein " 3 " compound of being preferably as follows of embodiment 3, wherein M is copper, iron or cobalt." 1 " of the present invention, " 2 " and " 3 " compound concrete structure formula are respectively:
1,1 generation an aryl oxide dendritic phthalocyanine complex, it is characterized in that: " 1 " compound for following chemical constitution:
In formula: R is cyano group, nitro, carboxyl or ester group; The embodiment of the present invention 1 preferably R is carboxyl, and M is zinc.
2,2 generation an aryl oxide dendritic phthalocyanine complex, it is characterized in that: " 2 " compound for following chemical constitution:
In formula: M is hydrogen, silicon, iron, titanium, cobalt, zinc, aluminium or copper;
In formula: R is cyano group, nitro, carboxyl or ester group.The embodiment of the present invention 2 preferably R is carboxyl, and M is zinc.
3,3 generation an aryl oxide dendritic phthalocyanine complex, it is characterized in that: " 3 " compound for following chemical constitution:
In formula: R is cyano group, nitro, carboxyl or ester group.The embodiment of the present invention 3 preferably R is carboxyl, and M is copper, iron or cobalt.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (8)
1. a 1-3 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, comprises the following steps:
(1) under the condition of the acidity of pH<5 or the alkalescence of pH>7 by the hydrolysis of alkoxide of titanium, obtain homogeneous transparent TiO
2content is the TiO of 0.5 ~ 5.0 wt%
2colloidal sol, regulates obtained pH value to be the TiO of 2 ~ 7 by dialysis
2colloidal sol, colloidal sol after drying, is calcined 1 ~ 5 h under 80 ~ 110 DEG C of conditions under 150 ~ 400 DEG C of conditions, and grinding obtains TiO
2pressed powder;
(2) to the 1-3 be dissolved in DMF for adding the obtained TiO of step (1) in aryl oxide dendritic phthalocyanine complex
2solid, the 1-3 wherein added is for the quality of aryl oxide dendritic phthalocyanine complex and TiO
2solid masses ratio is 0.33 ~ 1.33%, at room temperature floods 4 ~ 24 h, filters, washing, and obtained 1-3 is for aryl oxide dendritic phthalocyanine complex and TiO
2mixture;
(3) by 1-3 for aryl oxide dendritic phthalocyanine complex and TiO
2mixture is dried.
2. 1-3 according to claim 1 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, it is characterized in that 1-3 is zinc, copper, cobalt or iron for the central atom M in aryl oxide dendritic phthalocyanine complex, its consumption is TiO
2the 0.5-1wt% of solid consumption.
3. 1-3 according to claim 1 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, is characterized in that the dip time described in step (2) is 6-15 h.
4. 1-3 according to claim 1 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, is characterized in that pH=3 ~ 5 of acid condition or pH=8 ~ 10 of alkali condition.
5. the 1-3 according to claim 1 or 2 or 3 or 4 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the preparation method of visible-light photocatalyst, is characterized in that the alkoxide of described titanium refers to butyl titanate, tetraisopropyl titanate or tetraethyl titanate.
6. the 1-3 that obtains of the arbitrary described preparation method of claim 1-5 is for aryl oxide dendritic phthalocyanine complex modification TiO
2visible-light photocatalyst.
7. the 1-3 that obtains of the arbitrary described preparation method of claim 1-5 is for aryl oxide dendritic phthalocyanine complex modification TiO
2the application of visible-light photocatalyst, is characterized in that described 1-3 is for aryl oxide dendritic phthalocyanine complex modification TiO
2visible-light photocatalyst can be used for the photocatalysis treatment of organic dyestuff in sewage.
8. application according to claim 7, is characterized in that described organic pollution is the bright B of Luo Dan or methylene blue.
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| CN107698945A (en) * | 2017-08-10 | 2018-02-16 | 福建师范大学 | A kind of PETG/ dendritic phthalocyanines load SiO with photocatalysis effect2Composite wire and preparation method thereof |
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