CN100404127C - Artificial anitibody type composite photocatalyst and its prepn. method - Google Patents
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- CN100404127C CN100404127C CNB2006100194534A CN200610019453A CN100404127C CN 100404127 C CN100404127 C CN 100404127C CN B2006100194534 A CNB2006100194534 A CN B2006100194534A CN 200610019453 A CN200610019453 A CN 200610019453A CN 100404127 C CN100404127 C CN 100404127C
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Abstract
The present invention relates to an artificial antibody type composite photocatalyst and a preparation method thereof, which uses titanium dioxide (TiO2) as a substance, and a molecular engram modified layer of organic pollutants as a molecular recognizing layer. The preparation method comprises the following steps that functional monomers and target pollutants are mixed and react to generate precursors which have a polyreaction and are coated on the surface of the substance TiO2. The present invention has the advantages that the photocatalyst of the present invention can high-selectively recognize and degrade toxic organic pollutants so as to effectively control the toxic organic pollutants with low concentration and high toxicity, and the catalyst application has a broad range of pH values, high catalysis efficiency and repeated use.
Description
Technical field
The present invention is a kind of with titanium dioxide (TiO
2) be artificial anitibody type composite photocatalyst of molecule recognition layer and preparation method thereof as matrix, with organic pollutant molecule trace modified layer.
Technical background
The processing method of environmental wastewater is a lot, wherein microbial method be use in disposing of sewage at present at most, the widest and reasonable a kind of method of effect.But along with development of science and technology, organic kind is on the increase, and wherein a lot of organic pollutants adopt traditional physics, chemical method to be difficult to handle.Particularly some the poisonous persistence organic pollutants in the sewage more may cause microorganism all dead when microbial method is disposed of sewage.Therefore, at these hardly degraded organic substances, need seek a kind of effective processing method.
Semiconductor light-catalyst has tempting prospect at aspects such as photocatalysis conversion and the processing of organic matter contaminated environment.TiO wherein
2Because of it has the extremely people's favor of optical stability and high efficiency, it has high activity, safety, advantage such as pollution-free as photochemical catalyst in addition, is one of environmental type photochemical catalyst that has most DEVELOPMENT PROSPECT.But mainly there is following weak point in photochemical catalyst at present: the one, and narrow to the absorbing wavelength scope of light, the absorbing wavelength scope is mostly in the ultra-violet (UV) band, and sunshine proportion of utilization low (only accounting for 3%～5%) is difficult to the industrial wastewater that treating capacity is big and concentration is high.The 2nd, carrier recombination probability height, quantum efficiency is lower, is about 4%, the highlyest is no more than 10%.This causes TiO
2Be used for sewage disposal and not only cost an arm and a leg, and speed is slower.The 3rd, the non-selectivity of light-catalyzed reaction process.Light-catalysed non-selectivity will make the component of big (often toxicity is lower) of its preferential those concentration of degraded, makes the low persistence organic pollutant of concentration can not get effective improvement, does not reach the purpose of sewage disposal.
At these deficiencies, the researcher is to general T iO
2Photochemical catalyst has carried out a large amount of modification work: Yao Jiannian, bang plum (number of patent application CN02120037.8) is with the titanate esters hydrolysis, under the irradiation of ultraviolet light the titanium colloidal sol that obtains is worn out, solvent flashing, roasting then obtains having the TiO that light is sent out catalytic activity at visible wavelength range
2Powder.High Lian, Liu Hongyan etc. (number of patent application CN200410016013.4) are raw material and TiCl with thiocarbamide, lanthanum nitrate or lanthanum chloride, polyethylene glycol or polyvinyl alcohol
4Aqueous solution hydro-thermal synthesizing visible light catalyst, this visible light catalyst effective degradation of dye methylene blue (its degradation rate can reach 98.4%) under radiation of visible light; Tang and clear wait (number of patent application CN200510018393) have developed a kind of with homemade commercially available TiO
2Be matrix, coat one deck Fe (OH) on its surface
3, Cu (OH)
2Deng the composite photocatalyst of hydroxide, this catalyst is degradation of dye methyl orange effectively, and its degradation rate can reach 100%.
Though these technology can improve TiO
2The ability of photocatalyst for degrading organic pollution, but some highly toxic organic pollutions of can not optionally degrading, promptly when the high toxicity pollutant coexistence of the low toxicity pollutant of pollution system middle and high concentration and low concentration, existing TiO
2Photochemical catalyst can't be administered the low persistence toxic pollutant of concentration effectively.Therefore, how realizing that the high selectivity of highly toxic organic pollution is preferentially degraded, is one of difficult problem of needing to be resolved hurrily of environmental science.The present invention is exactly a kind of photochemical catalyst that proposes at the preferential degraded of the high selectivity of highly toxic organic pollution specially and preparation method thereof.
Summary of the invention
The purpose of this invention is to provide a kind of artificial anitibody type composite photocatalyst that can the highly selective photocatalysis degradation organic contaminant.The Preparation of catalysts method is that function monomer is mixed in the aqueous solution of certain pH value with target contaminant, and makes it to take place chemical reaction and generate presoma, with the presoma of gained polymerization reaction take place and be coated on nano-TiO under outer field actions such as electricity, magnetic and light
2Matrix surface.
TiO of the present invention
2The basic structure of composite photo-catalyst as shown in Figure 1, its internal layer is TiO
2Matrix, its skin are to be skeleton, to be the artificial anitibody type TiO of artificial antibody's modified layer of preparing of marking molecule (antigen) with target contaminant to be degraded with the conducting polymer composite that the function monomer polymerization obtains
2Composite photo-catalyst, this TiO
2Composite catalyst can produce photohole under UV-irradiation, have the photocatalytic degradation ability, simultaneously, because its surface has coated one deck artificial anitibody type polymer, and has the ability of selectivity degradable organic pollutant.
Above-mentioned function monomer is selected from: thiophene and derivative class thereof, pyrroles and derivative class thereof or aniline and derivative class thereof.
Thiophene and derivative class thereof specifically are meant: thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-(2-methyl butyl) thiophene, (s)-(+)-3-(2-first butyl) thiophene or 3,4-dibromo thiophene;
Pyrroles and derivative class thereof specifically are meant: pyrroles, N-methylpyrrole, pyrrolidones or N-vinyl pyrrolidone;
Aniline and derivative class thereof specifically are meant: aniline, o-toluidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, 2-chloroaniline, o-phenylenediamine or p-phenylenediamine (PPD).
Above-mentioned target contaminant is selected from: one of chlorophenols, nitropheneol.
Chlorophenols specifically is meant: orthomonochlorphenol, parachlorphenol, 2,4-two chlorophenols, 2,6-two chlorophenols, pentachlorophenol, 2,4,6-trichlorophenol or 2,4,5-trichlorophenol;
Nitropheneol specifically is meant: paranitrophenol, ortho-nitrophenol and 2,4-dinitrophenol dinitrophenolate or 2,4,6-picric acid.
Artificial anitibody type TiO of the present invention
2Concrete preparation method's step of composite photo-catalyst is as follows:
1. in reactor, add function monomer: a kind of in thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and the derivative class thereof; Target contaminant: a kind of in chlorophenols, the nitropheneol; The mol ratio of target contaminant and function monomer is 0.005%～200%, extraordinarily go into distilled water by 20～200 of function monomer quality again, in temperature is 25 ℃～70 ℃ stirring reactions 10～50 minutes, makes target contaminant and function monomer form compound type presoma with chemical bond;
2. be that 0.002%～100% ratio adds TiO in reactor in function monomer and titanium atom mol ratio
2, ultrasonic dispersion 5～15min makes suspension;
3. regulate above-mentioned pH of suspension value to 2～6 with 6mol/L hydrochloric acid, control solution temperature in 25 ℃～70 ℃ scopes, stirring reaction 5～48 hours;
4. collecting particle after the modification by suction filtration, is 7～11 Na with the pH value
2CO
3Solution washing particle 5～6 times washs particle 5～6 times with distilled water again;
5. at last with the particle drying, grind, record last TiO by transmission electron microscope with mortar
2Powdered artificial anitibody type photochemical catalyst, its particle diameter is 10～80nm.
The function monomer that 1. step of said method adds in reactor: be two to three kinds arbitrarily in thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and the derivative class thereof; General function monomer and titanium atom mol ratio are 0.002%～100%, and the ratio between two to three kinds of function monomers of adding is arbitrarily.
Because various function monomer structure differences, the structure of the polymer that forms is also inequality with relevant physicochemical properties, multiple monomer carries out copolymerization, can be in structure and play complementary effect in nature, help to improve the selectivity of photochemical catalyst, the efficient of catalyst, widen the absorbing wavelength scope of photochemical catalyst, the ultraviolet-visible diffuse reflection figure of catalyst such as accompanying drawing 2 to sunshine.
Artificial anitibody type TiO of the present invention
2Composite photo-catalyst can be directly with commercially available TiO
2Be base material, do not need high-temperature calcination to handle, preparation technology is simple.The present invention has improved the selectivity of light-catalyzed reaction, its low high toxicity organic pollution of concentration of preferentially degrading; It is wide that it uses pH value scope, and especially the catalytic selectivity of such catalyst is good under the condition of faintly acid and neutrality, catalytic efficiency is high, and is little to equipment corrosion; Catalyst is reusable; The polymer that coats has been widened the absorbing wavelength scope of photochemical catalyst to sunshine.These advantages, particularly its special molecule distinguishability can guarantee catalyst highly selective identification toxic organic pollutant, thereby effectively administer the environmental pollution that is caused by these pollutants.
With the prepared artificial anitibody type TiO that the 4-chlorophenol is had specific selectivity of embodiment
2Composite photo-catalyst is degraded under the uviol lamp of 9W, and (concentration is respectively 2ppm, 50ppm for 4-chlorophenol and 2-chlorophenol mixed liquor; PH6～7; Catalyst amount is 0.025g/L), both concentration residue percentage variation diagram such as accompanying drawings 3 in the degradation process.The 4-chlorophenol is at artificial anitibody type TiO
2Degradation rate on the composite photo-catalyst is 2～3 times on P25; And the 2-chlorophenol is at artificial anitibody type TiO
2Degradation rate on the composite photo-catalyst than the degradation rate on P25 slow 15%.
With the prepared artificial anitibody type TiO that the 4-nitrophenol is had specific selectivity of embodiment
2Composite photo-catalyst is degraded under the uviol lamp of 9W, and (concentration is respectively 1.8ppm, 50ppm for the mixed liquor of 4-nitrophenol and bisphenol-A; PH6～7; Catalyst amount is 0.025g/L), both concentration residue percentage variation diagram such as accompanying drawings 4 in the degradation process.The 4-nitrophenol is at artificial anitibody type TiO
2Degradation rate on the composite photo-catalyst is 2～3 times on P25; And bisphenol-A is at artificial anitibody type TiO
2Degradation rate on the composite photo-catalyst is slower 2.5～3 times than the degradation rate on P25.
Description of drawings
The basic structure of Fig. 1 artificial anitibody type composite photocatalyst
The basic structure of artificial anitibody type composite photocatalyst is core-shell structure: matrix TiO
2For nuclear, the macromolecule modified layer of molecular engram are shell.
The ultraviolet-visible diffuse reflection figure of Fig. 2 artificial anitibody type composite photocatalyst
With the 4-nitrophenol is that the synthetic artificial anitibody type photochemical catalyst of antigen has very strong absorption more than the 400nm wavelength, and its maximum absorption band is at the 420nm place; The P25 photochemical catalyst does not absorb more than the 400nm wavelength basically.
Ordinate reflectivity (%), abscissa are wavelength (nm).
Pollutant remains mark variation diagram in time in the process of Fig. 3 selectivity degraded 4-chlorophenol
Adopt the P25 photochemical catalyst respectively and be the synthetic artificial anitibody type photochemical catalyst of antigen with the 4-chlorophenol, the degraded original concentration is respectively 2ppm 4-chlorophenol and 50ppm 2-chlorophenol mixed liquor;
On behalf of 2-chlorophenol and 4-chlorophenol concentration on p25, curve 1,3 remain mark variation diagram in time respectively, and curve 2,4 is represented 2-chlorophenol and the 4-chlorophenol concentration residue mark on artificial anitibody type composite photocatalyst variation diagram in time respectively.
Ordinate is pollutant residue mark (C/C
0), abscissa is time (min).
In the process of Fig. 4 selectivity degraded 4-nitrophenol pollutant residue mark in time variation diagram adopt the P25 photochemical catalyst respectively and be the synthetic artificial anitibody type photochemical catalyst of antigen with the 4-nitrophenol, the degraded original concentration is respectively 1.8ppm 4-nitrophenol and 50ppm bisphenol-A mixed liquor.On behalf of 4-nitrophenol and bisphenol-A concentration on p25, curve 1,3 remain mark variation diagram in time respectively, and curve 2,4 is represented 4-nitrophenol and the bisphenol-A concentration residue mark on artificial anitibody type composite photocatalyst variation diagram in time respectively.
Ordinate is pollutant residue mark (C/C
0), abscissa is time (min).
The specific embodiment
Example 1: the monomer o-phenylenediamine and 5 * 10 that in the beaker of 100mL, adds 0.2mol
-4The 4-chlorophenol of mol adds 30mL distilled water again, is 65 ℃ of stirring reaction 30min in temperature.In beaker, add 2gTiO
2, ultrasonic dispersion 15min makes suspension, and the pH value of regulator solution is 2.3, and the temperature of control solution is 65 ℃, stirring reaction 6h.With the nano particle suction filtration after the modification, with the Na of 0.025mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 5 times.Nano particle at 86 ℃ of dry 2h, is ground with mortar, obtain a kind of poly-o-phenylenediamine/TiO that the 4-chlorophenol is had specific selectivity at last
2Powdered artificial anitibody type composite photocatalyst.
Example 2: the monomer aniline and 3 * 10 that in the beaker of 100mL, adds 0.3mol
-5The 4-nitrophenol of mol adds 40mL distilled water again, is 25 ℃ of stirring reaction 30min in temperature.In beaker, add 1.8gTiO
2, ultrasonic dispersion 10min makes suspension, and the pH value of regulator solution is 5, and the temperature of control solution is 30 ℃, stirring reaction 10h.With the nano particle suction filtration after the modification, with the Na of 0.025mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 5 times.Nano particle at 86 ℃ of dry 2h, is ground with mortar, obtain a kind of polyaniline/TiO that the 4-nitrophenol is had specific selectivity at last
2Powdered artificial anitibody type composite photocatalyst.
Example 3: in the beaker of 100mL, add the monomer o-phenylenediamine of 0.25mol and the monomer pyrroles and 5 * 10 of 0.05mol
-32 of mol, 6-two chlorophenols add 50mL distilled water again, are 35 ℃ of stirring reaction 30min in temperature.In beaker, add 1.5gTiO
2, ultrasonic dispersion 10min makes suspension, and the pH value of regulator solution is 5.5, and the temperature of control solution is 70 ℃, stirring reaction 48h.With the nano particle suction filtration, with the Na of 0.025mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 5 times.Nano particle at 86 ℃ of dry 2h, is ground with mortar, obtain a kind ofly to 2 at last, 6-two chlorophenols have o-phenylenediamine, the co-pyrrole copolymer/TiO of specific selectivity
2Powdered artificial anitibody type composite photocatalyst.
Example 4: in the beaker of 500mL, add 2 * 10
-2The monomer p-phenylenediamine (PPD) and 1 * 10 of mol
-6The pentachlorophenol of mol adds 200mL distilled water again, is 35 ℃ of stirring reaction 11min in temperature.In beaker, add 1.6g TiO
2, ultrasonic dispersion 15min makes suspension, regulator solution pH value to 3.3, and the control solution temperature is 55 ℃, stirring reaction 46h.With the nano particle suction filtration after the modification, with the Na of 0.005mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 5 times.Nano particle at 86 ℃ of dry 2h, is ground with mortar, obtain a kind of poly-p-phenylenediamine (PPD)/TiO that pentachlorophenol is had specific selectivity at last
2Powdered artificial anitibody type composite photocatalyst.
Example 5: in the beaker of 5mL, add 10
-4The monomer 3,3 of mol '-dimethoxy benzidine and 2 * 10
-42,4 of mol, the 6-trichlorophenol adds 2mL distilled water again, is 45 ℃ of stirring reaction 50min in temperature.In beaker, add 0.8gTiO
2, ultrasonic dispersion 15min makes suspension, the pH value to 2.3 of regulator solution, and the temperature of control solution is 65 ℃, stirring reaction 6h.With the nano particle suction filtration after the modification, with the Na of 0.5mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 6 times.Nano particle at 85 ℃ of dry 2h, is ground with mortar, obtain at last a kind of to 2,4, the 6-trichlorophenol have specific selectivity poly-3,3 '-dimethoxy benzidine/TiO
2Powdered artificial anitibody type composite photocatalyst.
Example 6: in the beaker of 100mL, add 1 * 10
-2The monomer N-vinyl pyrrolidones and 1 * 10 of mol
-32 of mol, the 4-dinitrophenol dinitrophenolate adds 40mL distilled water again, is 35 ℃ of stirring reaction 20min in temperature.In beaker, add 2.5gTiO
2, ultrasonic dispersion 8min makes suspension, and the pH value of regulator solution is 4.3, and the temperature of control solution is 36 ℃, stirring reaction 36h.With the nano particle suction filtration after the modification, with the Na of 0.0001mol/L
2CO
3Solution washing nano particle 6 times is again with distilled water washing 6 times.Nano particle at 86 ℃ of dry 2h, is ground with mortar, obtain a kind ofly to 2 at last, the 4-dinitrophenol dinitrophenolate has the poly N-vinyl pyrrolidone/TiO of specific selectivity
2Powdered artificial anitibody type composite photocatalyst.
Example 7: in the beaker of 100mL, add the monomer 3 of 0.25mol, 4-dibromo thiophene and 5 * 10
-42,4 of mol, the 5-trichlorophenol adds 60mL distilled water again, is 65 ℃ of stirring reaction 30min in temperature.In beaker, add 2gTiO
2, ultrasonic dispersion 12min makes suspension, and the pH value of regulator solution is 5.3, and the temperature of control solution is 31 ℃, stirring reaction 37h.With the nano particle suction filtration after the modification, with the Na of 0.028mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 6 times.Nano particle at 82 ℃ of dry 2h, is ground with mortar, obtain a kind ofly to 2,4 at last, the 5-trichlorophenol has the poly-3 of specific selectivity, 4-dibromo thiophene/TiO
2Powdered artificial anitibody type composite photocatalyst.
Example 8: in the beaker of 100mL, add 2 * 10
-5The monomer aniline of mol and 2mol o-toluidine and 5 * 10
-4The 2-chlorophenol of mol mol adds 50mL distilled water again, is 70 ℃ of stirring reaction 50min in temperature.In beaker, add 20gTiO
2, ultrasonic dispersion 15min makes suspension, and the pH value of regulator solution is 2.3, and the temperature of control solution is 47 ℃, stirring reaction 26h.With the nano particle suction filtration after the modification, with the Na of 0.0013mol/L
2CO
3Solution washing nano particle 6 times is again with distilled water washing 5 times.Nano particle at 80 ℃ of dry 2h, is ground with mortar, obtain a kind of aniline and 2 o-toluidine copolymer/TiO that the 2-chlorophenol had specific selectivity at last
2Powdered artificial anitibody type composite photocatalyst.
Example 9: the monomer N-methylpyrrole and 2 * 10 that in the beaker of 100mL, adds 2mol
-4MolN-vinyl pyrrolidone and 5 * 10
-4The ortho-nitrophenol of mol adds 40mL distilled water again, is 65 ℃ of stirring reaction 16min in temperature.In beaker, add 2.8gTiO
2, ultrasonic dispersion 9min makes suspension, and the pH value of regulator solution is 6, and the temperature of control solution is 25 ℃, stirring reaction 6h.With the nano particle suction filtration after the modification, with the Na of 0.025mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 5 times.Nano particle at 83 ℃ of dry 2h, is ground with mortar, obtain a kind of N-methylpyrrole and N-vinylpyrrolidone copolymer/TiO that the 4-chlorophenol is had specific selectivity at last
2Powdered artificial anitibody type composite photocatalyst.
Example 10: in the 100mL beaker, add 2mol monomer aniline, 0.02mol o-toluidine and 2 * 10
-4Mol3,3 '-dimethoxy benzidine and 5 * 10
-42 of mol, the 4-dinitrophenol dinitrophenolate adds 40mL distilled water again, is 55 ℃ of stirring reaction 30min in temperature.In beaker, add 2gTiO
2, ultrasonic dispersion 15min makes suspension, and the pH value of regulator solution is 4.5, and the temperature of control solution is 52 ℃, stirring reaction 24h.With the nano particle suction filtration after the modification, with the Na of 0.75mol/L
2CO
3Solution washing nano particle 6 times is again with distilled water washing 5 times.Nano particle at 84 ℃ of dry 2h, is ground with mortar, obtain at last a kind of to 2, the 4-dinitrophenol dinitrophenolate have the aniline, o-toluidine and 3,3 of specific selectivity '-dimethoxy benzidine copolymer/TiO
2Powdered artificial anitibody type composite photocatalyst.
Example 11: in the beaker of 100mL, add 2 * 10
-43,3 of mol monomer aniline, 0.2mol o-toluidine and 2mol '-dimethoxy benzidine and 5 * 10
-42 of mol, the 4-dinitrophenol dinitrophenolate adds 50mL distilled water again, is 44 ℃ of stirring reaction 21min in temperature.In beaker, add 3gTiO
2, ultrasonic dispersion 13min makes suspension, and the pH value of regulator solution is 3.7, and the temperature of control solution is 53 ℃, stirring reaction 44h.With the nano particle suction filtration after the modification, with the Na of 0.056mol/L
2CO
3Solution washing nano particle 5 times is again with distilled water washing 6 times.Nano particle at 82 ℃ of dry 2h, is ground with mortar, obtain at last a kind of to 2, the 4-dinitrophenol dinitrophenolate have the aniline, o-toluidine and 3,3 of specific selectivity '-dimethoxy benzidine copolymer/TiO
2Powdered artificial anitibody type composite photocatalyst.
Claims (4)
1. titanium dioxide composite photocatalyst, it is characterized in that with titanium dioxide being matrix, skin is to be skeleton, to be the titanium dioxide composite photocatalyst of artificial antibody's modified layer of preparing of marking molecule with target contaminant to be degraded with the conducting polymer composite that the function monomer polymerization obtains; Said function monomer is to be selected from: thiophene and derivative class thereof, pyrroles and derivative class thereof or aniline and derivative class thereof;
Thiophene and derivative class thereof specifically are meant: thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-(2-methyl butyl) thiophene, (s)-(+)-3-(2-first butyl) thiophene, 3,4-dibromo thiophene;
Pyrroles and derivative class thereof specifically are meant: pyrroles, N-methylpyrrole, pyrrolidones or N-vinyl pyrrolidone;
Aniline and derivative class thereof specifically are meant: aniline, o-toluidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, 2-chloroaniline, o-phenylenediamine or p-phenylenediamine (PPD);
Said target contaminant is to be selected from: chlorophenols, nitropheneol a kind of
Chlorophenols specifically is meant: orthomonochlorphenol, parachlorphenol, 2,4-two chlorophenols, 2,6-two chlorophenols, pentachlorophenol, 2,4,6-trichlorophenol or 2,4,5-trichlorophenol;
Nitropheneol specifically is meant: paranitrophenol, ortho-nitrophenol and 2,4-dinitrophenol dinitrophenolate or 2,4,6-picric acid.
2. the preparation method of the said titanium dioxide composite photocatalyst of claim 1 is characterized in that concrete preparation process is:
1. in reactor, add function monomer: a kind of in thiophene and derivative class thereof, pyrroles and derivative class thereof or aniline and the derivative class thereof; Target contaminant: a kind of in chlorophenols, the nitropheneol; The mol ratio of target contaminant and function monomer is 0.005%～200%, extraordinarily goes into distilled water by 20～200 of function monomer quality again, is 25 ℃～70 ℃ stirring reactions 10～50 minutes in temperature;
2. be that 0.002%～100% ratio adds titanium dioxide in reactor in function monomer and titanium atom mol ratio, ultrasonic dispersion 5～15min makes suspension;
3. regulate above-mentioned pH of suspension value to 2～6 with 6mol/L hydrochloric acid, control solution temperature in 25 ℃～70 ℃ scopes, stirring reaction 5～48 hours;
4. collecting particle after the modification by suction filtration, is 7～11 Na with the pH value
2CO
3Solution washing particle 5～6 times washs particle 5～6 times with distilled water again;
5. at last with the particle drying, grind, obtain product titanium dioxide powder powder artificial anitibody type photochemical catalyst with mortar.
3. according to the preparation method of the said titanium dioxide composite photocatalyst of claim 3, the step of said method 1., the function monomer that in reactor, adds: be selected from any two to three kinds in thiophene and derivative class thereof, pyrroles and derivative class thereof, aniline and the derivative class thereof; General function monomer and titanium atom mol ratio are 0.002%～100%, and the ratio between two to three kinds of function monomers of adding is arbitrarily.
4. according to the preparation method of claim 3 or 4 said titanium dioxide composite photocatalysts, 1. said thiophene of the step of said method and derivative class thereof specifically are meant: thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-(2-methyl butyl) thiophene, (s)-(+)-3-(2-first butyl) thiophene or 3,4-dibromo thiophene;
Pyrroles and derivative class thereof specifically are meant: pyrroles, N-methylpyrrole, pyrrolidones or N-vinyl pyrrolidone;
Aniline and derivative class thereof specifically are meant: aniline, o-toluidine, 3,3 '-dimethoxy benzidine, 3,3 '-dimethylbenzidine, 2-chloroaniline, o-phenylenediamine or p-phenylenediamine (PPD);
Said chlorophenols specifically is meant: orthomonochlorphenol, parachlorphenol, 2,4-two chlorophenols, 2,6-two chlorophenols, pentachlorophenol, 2,4,6-trichlorophenol or 2,4,5-trichlorophenol;
Nitropheneol specifically is meant: paranitrophenol, ortho-nitrophenol and 2,4-dinitrophenol dinitrophenolate or 2,4,6-picric acid.
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| CN103120962B (en) * | 2012-12-10 | 2014-10-29 | 江苏大学 | Preparation method and application of molecularly imprinted polymer modified titanium dioxide composite photocatalyst |
| CN103785475B (en) * | 2014-01-08 | 2016-01-20 | 江苏大学 | A kind of preparation method of Conjugate ferrite conductive traces composite photo-catalyst |
| CN106324050B (en) * | 2015-07-10 | 2018-08-24 | 同济大学 | A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods |
| CN105289726B (en) * | 2015-10-28 | 2018-02-27 | 江苏大学 | Magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation and preparation method thereof |
| CN106587282B (en) * | 2016-12-08 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof |
| CN109126823B (en) * | 2018-10-23 | 2021-08-17 | 江西理工大学 | Method for preparing aniline by selective hydrogenation of nitrobenzene under catalysis of catalyst |
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| JP2002361097A (en) * | 2001-06-12 | 2002-12-17 | Furukawa Co Ltd | Visible light excitation type titanium dioxide photocatalyst and method for producing the same |
| CN1459331A (en) * | 2002-05-21 | 2003-12-03 | 中国科学院化学研究所 | Prepn. method for producing titanium dioxide having visible light catalytic activation |
| CN1557539A (en) * | 2004-01-19 | 2004-12-29 | 中国科学院上海硅酸盐研究所 | Titanium oxide photocatalyst stimulated by visible light and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002361097A (en) * | 2001-06-12 | 2002-12-17 | Furukawa Co Ltd | Visible light excitation type titanium dioxide photocatalyst and method for producing the same |
| CN1459331A (en) * | 2002-05-21 | 2003-12-03 | 中国科学院化学研究所 | Prepn. method for producing titanium dioxide having visible light catalytic activation |
| CN1557539A (en) * | 2004-01-19 | 2004-12-29 | 中国科学院上海硅酸盐研究所 | Titanium oxide photocatalyst stimulated by visible light and synthesis method thereof |
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