CN103464213B - Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof - Google Patents
Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof Download PDFInfo
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- CN103464213B CN103464213B CN201310267295.4A CN201310267295A CN103464213B CN 103464213 B CN103464213 B CN 103464213B CN 201310267295 A CN201310267295 A CN 201310267295A CN 103464213 B CN103464213 B CN 103464213B
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- ferrite
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Abstract
The invention discloses a polypyrrole-TiO2 magnetically supported photocatalytic composite material and a preparation method thereof, belongs to the field of magnetically supported photocatalytic material technology, and relates to a ferrite magnetically supported photocatalytic composite material. The polypyrrole-TiO2 magnetically supported photocatalytic composite material comprises a magnetic substrate and a photocatalyst; the magnetic substrate is obtained by subjecting ferrite to surface organic modification with a silane coupling agent, and the photocatalyst is prepared by subjecting TiO2 to surface photosensitization with polypyrrole; and the polypyrrole-TiO2 magnetically supported photocatalytic composite material is of a multi-layer core-shell structure comprising ferrite, the silane coupling agent, TiO2 and polypyrrole from inside to outside. The polypyrrole-TiO2 magnetically supported photocatalytic composite material is capable of increasing magnetic property and acid stability of ferrite; inhibiting recombination of TiO2 carriers; enlarging spectral response range of TiO2; and improving utilization ratio of sunlight.
Description
Technical field
The invention belongs to magnetic carrier catalysis material technical field, relate to ferrite magnetic and carry optic catalytic composite material, be specifically related to a kind of polypyrrole-TiO
2magnetic photocatalyst composite and preparation method thereof.
Background technology
At present, magnetic photocatalyst material is formed primarily of magnetic matrix and catalysis material.The magnetic matrix overwhelming majority is ferrite, and catalysis material is modal is TiO
2, the two direct combination forms the composite of nucleocapsid structure, and this composite not only has photocatalysis performance but also have the performance utilizing the separable recovery of externally-applied magnetic field.But, be that composite photocatalyst material prepared by raw material exists the defect that magnetic reduces and acid resistance is more weak with ferrite, affect recovery and the recycling of composite; Meanwhile, in the nucleocapsid structure that direct combination is formed, ferrite makes TiO
2the Carrier recombination rate of photochemical catalyst improves, and can reduce photocatalysis efficiency; Not modified TiO
2photochemical catalyst band gap is wide, lower to the utilization rate of sunshine.Due to above-mentioned defect, general magnet carried photocatalyst is restricted in the application.
How to improve ferritic magnetic property and absolute acid stability energy, inhibit TiO simultaneously
2the compound of carrier, improves the utilization rate to sunshine, is current magnetic carrier catalysis material technical field urgent problem.
Summary of the invention
The object of this invention is to provide a kind of polypyrrole-TiO
2magnetic photocatalyst composite, to solve that the existing ferrite magnetic performance as magnetic matrix reduces, acid resistance is weak and as the TiO of photocatalysis part
2the problem that photocatalytic degradation efficiency is low.
Another object of the present invention is to provide polypyrrole-TiO
2the preparation method of magnetic photocatalyst composite.
Invention thinking of the present invention is: by silane coupler γ-r-chloropropyl trimethoxyl silane to ferritic surface organic modification, improves ferritic magnetic property and absolute acid stability energy; By polypyrrole to TiO
2carry out photoactivate, inhibit TiO
2the compound of carrier, has expanded TiO
2spectral response range, improve the utilization rate to sunshine; By with Modified Iron oxysome for core, coated appropriate TiO successively
2and polypyrrole, form the magnet carried photocatalyst of multilayer coating structure.
A kind of polypyrrole-TiO
2magnetic photocatalyst composite, comprises magnetic matrix and photochemical catalyst, and described magnetic matrix is the ferrite being carried out surface organic modification by silane coupler, and described photochemical catalyst is the TiO being carried out surface sensitization process by polypyrrole
2, be respectively ferrite, silane coupler, TiO from inside to outside
2, polypyrrole multi-layer core-shell structure.
Described ferrite is Fe
3o
4, or Mn
0.4zn
0.6fe
2o
4.
Described silane coupler is the silane coupler containing hydrolysising group alkoxyl, comprise silane resin acceptor kh-550 (3-aminopropyl triethoxysilane), KH-792 [N-(β mono-aminoethyl)-γ-aminopropyl front three (second) TMOS], or γ-r-chloropropyl trimethoxyl silane NQ-54 γ-r-chloropropyl trimethoxyl silane, silane coupler containing hydrolysising group alkoxyl, the silanol formed after hydrolyzing and ferrite surfaces hydroxyl generation chemical action, modification is carried out to ferrite, silane resin acceptor kh-550 (3-aminopropyl triethoxysilane), its hydrolysising group is three ethyoxyls, silanol can be generated after hydrolysis modification is carried out to ferrite surfaces, silane coupler KH-792 [N-(β mono-aminoethyl)-γ-aminopropyl front three (second) TMOS], hydrolysising group is methoxy or ethoxy, in like manner can carry out modification to ferrite.
Above-mentioned polypyrrole-TiO
2magnetic photocatalyst composite is achieved through the following technical solutions:
Polypyrrole-TiO
2the preparation method of magnetic photocatalyst composite, comprise the following steps: use silane coupler to carry out organically-modified to ferrite, make silane coupler cover ferrite surfaces, the ferrite of obtained surface modification, by the ferrite of surface modification by the coated amorphous TiO of sol-gel process
2, after high-temperature calcination, obtain TiO
2magnetic photocatalyst composite, then by in-situ oxidizing-polymerizing method, at TiO
2magnetic photocatalyst composite material surface coated with conductive polymer poly pyrroles, obtains polypyrrole-TiO
2magnetic photocatalyst composite.
Further, when using silane coupler to carry out organically-modified to ferrite, joined by silane coupler in ethanol water, the volume ratio shared by silane coupler is 1.51%, then adds ferrite, reacts and obtain the ferrite of surface modification.
In described ethanol water, the volume ratio of distilled water and absolute ethyl alcohol is 100:30.
Described at TiO
2during magnetic photocatalyst composite material surface coated with conductive polymer poly pyrroles, the addition of pyrrole and TiO
2the ratio of amount of substance be 0.069.
The present invention to ferritic surface organic modification, improves ferritic magnetic property and absolute acid stability energy by silane coupler; By polypyrrole to TiO
2carry out photoactivate, inhibit TiO
2the compound of carrier, has expanded TiO
2spectral response range, improve the utilization rate to sunshine; By with Modified Iron oxysome for core, coated appropriate TiO successively
2and polypyrrole, form the magnet carried photocatalyst of multilayer coating structure, overcome that existing magnetic photocatalyst material is low as the ferrite magnetic performance of magnetic matrix, acid resistance is weak and TiO
2the deficiency that photocatalytic degradation efficiency is low.
Accompanying drawing explanation
Fig. 1 is that silane coupler acts on ferritic schematic diagram;
Fig. 2 is polypyrrole-TiO
2magnetic photocatalyst composite structure schematic diagram;
Fig. 3 is the degradation rate curve of each sample photo-catalytic degradation of methyl-orange under uviol lamp;
Fig. 4 is the degradation rate curve of each sample photo-catalytic degradation of methyl-orange under sunshine;
Fig. 5 is TiO
2, PPy-TiO
2/ M-Fe
3o
4and PPy-TiO
2/ M-Mn
0.4zn
0.6fe
2o
4sample is Recovery curve repeatedly.
Detailed description of the invention
below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
Coprecipitation is used to prepare magnetic matrix Fe
3o
4: take FeSO
47H
2o 3.00g, Fe
2(SO
4)
34.00g is dissolved in 250mL distilled water, and in 55 DEG C of water-baths, magnetic agitation is all dissolved to solid; In solution, drip the NaOH solution 42mL that concentration is 2mol/L, continue afterwards to be warming up to 60 DEG C of sustained response 6h, after magnetic settlement, remove supernatant liquor, successively with distillation washing 5 times, ethanol washes 2 times; Sample, after the process of drying at room temperature mode, obtains Fe through grinding
3o
4magnetic matrix.
Use silane coupler γ-r-chloropropyl trimethoxyl silane (NQ-54) to Fe
3o
4-R and carry out modification.Measure 2.0mL silane coupler to join in ethanol water (100mL distilled water+30mL absolute ethyl alcohol), the volume ratio shared by silane coupler is 1.51%; In sample, drip glacial acetic acid regulates solution ph to be 3 ~ 4, and magnetic agitation is transparent to solution; Above-mentioned solution is moved in there-necked flask, adds 1.00g Fe wherein
3o
4magnetic matrix, stirs 1.3h under 80 DEG C of waters bath with thermostatic control, and Separation of Solid and Liquid after room temperature cooling, washs more than 5 times with ethanol; After washing completely at 100 DEG C dry 2h, grinding obtains modified M-Fe
3o
4magnetic matrix.Silane coupler NQ-54 in acid condition can stepwise hydrolysis, reacts as follows:
The easy dehydrating condensation of the silanol that hydrolysis generates generates oligomer, for tripolymer, in FIG, hydroxyl after silane coupler hydrolysis and the hydroxyl of ferrite surfaces generate hydrogen bond, after further heating, will be there is dehydration and form covalent bond in the hydrogen bond between ferrite surfaces and siloxane oligomer, silane coupler will cover magnetic material surface.
TiO
2compound magnet carried photocatalyst synthesizes: accurately measure 5mL butyl titanate and be dissolved in 7.5mL absolute ethyl alcohol, magnetic agitation makes it to mix, and adds the M-Fe that quality is 1.00g wherein
3o
4sample, ultrasonic disperse 30min, is called A liquid; Accurately measure 2.5mL absolute ethyl alcohol, 2.5mL distilled water, 2.5mL glacial acetic acid mixes, and is called B liquid, is slowly added dropwise in A liquid by B liquid under ultrasonic disperse condition, drips off rear continuation ultrasonic disperse until form gel, at 80 DEG C of freeze-day with constant temperature 24h, and grinding; Ambient temperatare enters in Muffle furnace to be calcined, calcining at constant temperature 2h after being warming up to 550 DEG C, obtained TiO
2/ M-Fe
3o
4compound magnet carried photocatalyst.
Adopt in-situ oxidizing-polymerizing legal system for polypyrrole-TiO
2compound magnet carried photocatalyst: the TiO obtained by previous step
2/ M-Fe
3o
4the round-bottomed flask that 100mL 1.0mol/L hydrochloric acid is housed put into by sample, adds the pyrrole monomer ultrasonic disperse 30min of 0.06mL; In 0 ~ 3 DEG C of ice-water bath, the concentration slowly dripping corresponding amount under vigorous stirring is 0.1 mol/L FeCl
3solution (pyrroles and FeCl
3the ratio of amount of substance be 1 ︰ 1), drip off rear continuation stirring reaction 12h in ice-water bath; After reaction terminates, first use 50mL absolute ethanol washing, more repeatedly wash to neutrality with distilled water; Dry at 50 DEG C, obtain PPy-TiO after grinding
2/ M-Fe
3o
4composite photocatalyst material.
Polypyrrole-the TiO of preparation
2magnetic photocatalyst composite is nucleocapsid structure, and structural representation is shown in Fig. 2, with Modified Iron oxysome for core, is coated with TiO successively from inside to outside
2and polypyrrole.
Embodiment 2
Sol-gel process is used to prepare magnetic matrix Mn
0.4zn
0.6fe
2o
4: take Zn (NO
3)
26H
2o0.89g, Fe (NO
3)
39H
2o4.04g is dissolved in the distilled water of 60mL, adds thermal agitation and makes it to dissolve completely; Dropwise add the Mn (NO that mass fraction is 50%
3)
2solution 0.46mL, then add compounding ingredient tartaric acid 2.25g, constant temperature 60 DEG C continues heating and is stirred to and dissolves completely, add mass fraction be 25% ammoniacal liquor regulate pH to be 7, at 80 DEG C, constant temperature stirs 2h, forms colloidal sol; Continue to place under about 80 DEG C to make formation gel, dry at 110 DEG C, put into Muffle furnace at 550 DEG C and calcine 2h, through grinding to obtain Mn
0.4zn
0.6fe
2o
4magnetic matrix.
Use silane coupler γ-r-chloropropyl trimethoxyl silane (NQ-54) to Mn
0.4zn
0.6fe
2o
4carry out modification.Measure 2.0mL silane coupler to join in ethanol water (100mL distilled water+30mL absolute ethyl alcohol), the volume ratio shared by silane coupler is 1.51%; In sample, drip glacial acetic acid regulates solution ph to be 3 ~ 4, and magnetic agitation is transparent to solution; Above-mentioned solution is moved in there-necked flask, adds 1.00g Mn wherein
0.4zn
0.6fe
2o
4magnetic matrix, stirs 1.3h under 80 DEG C of waters bath with thermostatic control, and Separation of Solid and Liquid after room temperature cooling, washs more than 5 times with ethanol; After washing completely at 100 DEG C dry 2h, grinding obtains modified M-Mn
0.4zn
0.6fe
2o
4magnetic matrix.Silane coupler NQ-54 in acid condition can stepwise hydrolysis, reacts as follows:
The easy dehydrating condensation of the silanol that hydrolysis generates generates oligomer, for tripolymer, in FIG, hydroxyl after silane coupler hydrolysis and the hydroxyl of ferrite surfaces generate hydrogen bond, after further heating, will be there is dehydration and form covalent bond in the hydrogen bond between ferrite surfaces and siloxane oligomer, silane coupler will cover magnetic material surface.
TiO
2compound magnet carried photocatalyst synthesizes: accurately measure 5mL butyl titanate and be dissolved in 7.5mL absolute ethyl alcohol, magnetic agitation makes it to mix, and adding quality is wherein 1.00g's or M-Mn
0.4zn
0.6fe
2o
4sample, ultrasonic disperse 30min, is called A liquid; Accurately measure 2.5mL absolute ethyl alcohol, 2.5mL distilled water, 2.5mL glacial acetic acid mixes, and is called B liquid, is slowly added dropwise in A liquid by B liquid under ultrasonic disperse condition, drips off rear continuation ultrasonic disperse until form gel, at 80 DEG C of freeze-day with constant temperature 24h, and grinding; Ambient temperatare enters in Muffle furnace to be calcined, calcining at constant temperature 2h after being warming up to 550 DEG C, obtained TiO
2/ M-Mn
0.4zn
0.6fe
2o
4compound magnet carried photocatalyst.
Adopt in-situ oxidizing-polymerizing legal system for polypyrrole-TiO
2compound magnet carried photocatalyst: the TiO obtained by previous step
2/ M-Mn
0.4zn
0.6fe
2o
4the round-bottomed flask that 100mL 1.0mol/L hydrochloric acid is housed put into by sample, adds pyrrole monomer (pyrroles and the TiO of 0.06mL
2the ratio of amount of substance be 0.069), ultrasonic disperse 30min; In 0 ~ 3 DEG C of ice-water bath, the concentration slowly dripping corresponding amount under vigorous stirring is 0.1 mol/L FeCl
3solution (pyrroles and FeCl
3the ratio of amount of substance be 1 ︰ 1), drip off rear continuation stirring reaction 12h in ice-water bath; After reaction terminates, first use 50mL absolute ethanol washing, more repeatedly wash to neutrality with distilled water; Dry at 50 DEG C, obtain PPy-TiO after grinding
2/ M-Mn
0.4zn
0.6fe
2o
4composite photocatalyst material.
Polypyrrole-the TiO of preparation
2magnetic photocatalyst composite is nucleocapsid structure, and structural representation is shown in Fig. 2, with Modified Iron oxysome for core, is coated with TiO successively from inside to outside
2and polypyrrole.
Embodiment 3
Analyze and research the PPy-TiO prepared
2/ M-Fe
3o
4ability and the separating for several times of sample photo-catalytic degradation of methyl-orange under uviol lamp and under sunshine reclaim ability.Concrete steps are as follows:
The experiment of research photo-catalytic degradation of methyl-orange
Get obtained PPy-TiO
2/ M-Fe
3o
4it is in 6mg/L methyl orange solution that sample 0.1g is scattered in 50mL mass concentration respectively, ultrasonic disperse 20min.Carry out photocatalysis test under sample being placed on respectively uviol lamp and sunshine, under uviol lamp (18W), light source is 10cm apart from sample.Every 30min sampling, centrifugation 10min under rotating speed is 3000r/min, gets supernatant liquor and surveys its absorbance, and wavelength is set to methyl orange maximum absorbance 463nm.Calculate degradation rate and analyze photo-catalysis capability, formula is as follows:
In formula, η is photodegradation rate; A
0for processing the absorbance of front methyl orange; A is the absorbance of methyl orange after process.
Degradation rate and the relation of time of the photo-catalytic degradation of methyl-orange of experiment gained are as shown in the table:
Known PPy-TiO is shown by experimental result
2/ M-Fe
3o
4under uviol lamp and sunshine, 96.24% and 89.21% are reached respectively to the photocatalytic activity of methyl orange in sample 180min, demonstrate good photo-catalysis capability.
Research separating for several times recovery experiment:
Take appropriate PPy-TiO
2/ M-Fe
3o
4sample dispersion, in methyl orange solution, utilizes magnetic to carry TiO
2magnetic property by its separation and recovery from methyl orange solution, be positioned over by reactant liquor on disk, catalyst sample can very fast sedimentation, is removed by supernatant liquid, repeatedly with distillation washing, dry after the sample that must reclaim.Sample after reclaiming is weighed, calculates the rate of recovery.
Rate of recovery computing formula is as follows:
In formula, R is catalyst recovery yield; m
0for catalyst initial mass; m
nfor using the loss quality of n rear catalyst.
Experiment gained PPy-TiO
2/ M-Fe
3o
4sample rate of recovery after recovery five times can reach 97.91%, and separation and recovery ability is stronger.
Embodiment 4
Analyze and research the PPy-TiO prepared
2/ M-Mn
0.4zn
0.6fe
2o
4ability and the separating for several times of sample photo-catalytic degradation of methyl-orange under uviol lamp and under sunshine reclaim ability.Concrete steps are as follows:
The experiment of research photo-catalytic degradation of methyl-orange
Get obtained PPy-TiO
2/ M-Mn
0.4zn
0.6fe
2o
4it is in 6mg/L methyl orange solution that sample 0.1g is scattered in 50mL mass concentration respectively, ultrasonic disperse 20min.Carry out photocatalysis test under sample being placed on respectively uviol lamp and sunshine, under uviol lamp (18W), light source is 10cm apart from sample.Every 30min sampling, centrifugation 10min under rotating speed is 3000r/min, gets supernatant liquor and surveys its absorbance, and wavelength is set to methyl orange maximum absorbance 463nm.Calculate degradation rate and analyze photo-catalysis capability, formula is as follows:
In formula, η is photodegradation rate; A
0for processing the absorbance of front methyl orange; A is the absorbance of methyl orange after process.
Degradation rate and the relation of time of the photo-catalytic degradation of methyl-orange of experiment gained are as shown in the table:
Catalysis time (min) | 30 | 60 | 90 | 120 | 150 | 180 |
Degradation rate (%) under uviol lamp | 49.07 | 78.34 | 89.31 | 93.74 | 95.13 | 95.50 |
Degradation rate (%) under sunshine | 20.09 | 43.21 | 55.79 | 70.31 | 85.93 | 86.13 |
Known PPy-TiO is shown by experimental result
2/ M-Mn
0.4zn
0.6fe
2o
4under uviol lamp and sunshine, 95.50% and 86.13% are reached respectively to the photocatalytic activity of methyl orange in sample 180min, demonstrate good photo-catalysis capability.
Research separating for several times recovery experiment:
Take appropriate PPy-TiO
2/ M-Mn
0.4zn
0.6fe
2o
4sample dispersion, in methyl orange solution, utilizes magnetic to carry TiO
2magnetic property by its separation and recovery from methyl orange solution, be positioned over by reactant liquor on disk, catalyst sample can very fast sedimentation, is removed by supernatant liquid, repeatedly with distillation washing, dry after the sample that must reclaim.Sample after reclaiming is weighed, calculates the rate of recovery.
Rate of recovery computing formula is as follows:
In formula, R is catalyst recovery yield; m
0for catalyst initial mass; m
nfor using the loss quality of n rear catalyst.
Experiment gained PPy-TiO
2/ M-Mn
0.4zn
0.6fe
2o
4sample rate of recovery after recovery five times can reach 98.83%, and separation and recovery ability is stronger.
Claims (2)
1. a polypyrrole-TiO
2magnetic photocatalyst composite, comprises magnetic matrix and photochemical catalyst, it is characterized in that, described magnetic matrix is the ferrite being carried out surface organic modification by silane coupler, and described photochemical catalyst is the TiO being carried out surface sensitization process by polypyrrole
2, be respectively ferrite, silane coupler, TiO from inside to outside
2, polypyrrole multi-layer core-shell structure;
Described ferrite is Fe
3o
4, or Mn
0.4zn
0.6fe
2o
4;
Described silane coupler is 3-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β
-aminoethyl)-gamma-aminopropyl-triethoxy-silane or γ-r-chloropropyl trimethoxyl silane;
During preparation, use silane coupler to carry out organically-modified to ferrite, make silane coupler cover ferrite surfaces, the ferrite of obtained surface modification, by the ferrite of surface modification by the coated amorphous TiO of sol-gel process
2, after high-temperature calcination, obtain TiO
2magnetic photocatalyst composite, then by in-situ oxidizing-polymerizing method, at TiO
2magnetic photocatalyst composite material surface coated with conductive polymer poly pyrroles, obtains polypyrrole-TiO
2magnetic photocatalyst composite.
2. polypyrrole-TiO according to claim 1
2the preparation method of magnetic photocatalyst composite, it is characterized in that, comprise the following steps: use silane coupler to carry out organically-modified to ferrite, silane coupler is made to cover ferrite surfaces, the ferrite of obtained surface modification, by the ferrite of surface modification by the coated amorphous TiO of sol-gel process
2, after high-temperature calcination, obtain TiO
2magnetic photocatalyst composite, then by in-situ oxidizing-polymerizing method, at TiO
2magnetic photocatalyst composite material surface coated with conductive polymer poly pyrroles, obtains polypyrrole-TiO
2magnetic photocatalyst composite;
Wherein, when using silane coupler to carry out organically-modified to ferrite, volume ratio silane coupler being joined distilled water and absolute ethyl alcohol is in the ethanol water of 100:30, volume ratio shared by silane coupler is 1.51%, then add ferrite, react and obtain the ferrite of surface modification;
Described at TiO
2during magnetic photocatalyst composite material surface coated with conductive polymer poly pyrroles, the addition of pyrrole and TiO
2the ratio of amount of substance be 0.069.
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