CN104128207A - Preparation method of core-shell pseudo template imprinted magnetic nano-catalyst for use in degradation of Congo red - Google Patents
Preparation method of core-shell pseudo template imprinted magnetic nano-catalyst for use in degradation of Congo red Download PDFInfo
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- CN104128207A CN104128207A CN201410335610.7A CN201410335610A CN104128207A CN 104128207 A CN104128207 A CN 104128207A CN 201410335610 A CN201410335610 A CN 201410335610A CN 104128207 A CN104128207 A CN 104128207A
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Abstract
The invention discloses a preparation method of a core-shell pseudo template imprinted magnetic nano-catalyst for use in degradation of Congo red. The method comprises the following steps: preparing Fe3O4 nanoparticles; preparing Fe3O4@SiO2 magnetic nanoparticles; preparing Fe3O4@SiO2@TiO2 core-shell nanoparticles; and preparing Fe3O4@SiO2@TiO2@MIP core-shell imprinted nanoparticles. The imprinted catalyst plays a remarkable role in catalyzing degradation of the Congo red, and can be easily and rapidly separated from a solution through an external magnetic field to realize environment-friendly and low-cost degradation of polluting dyes. As proved by an experimental result, the catalyst has a high degradation catalyzing rate without illumination, and the first-order reaction rate coefficient of a catalytic reaction is 0.09615min<-1>. After the catalyst is recycled repeatedly, the catalytic capability does not change remarkably. The catalyst has a good application prospect in degradation catalyzing of the Congo red in dyeing wastewater.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate in particular to a kind of preparation method of the Congo red hud typed pseudo-template imprinting magnetic nanocatalyst of degrading.
Background technology
Conductor photocatalysis is because making full use of sunshine or artificial light source becomes one of the most promising contaminant degradation technology.The advantages such as it is stable, harmless, cheap and efficient that titanium dioxide has are most widely used semiconductor light-catalyst at present.But due to TiO
2mainly just have catalytic activity at ultraviolet region, and ultraviolet light proportion in sunshine only has 3-4%, therefore TiO
2photochemical catalyst is extremely low to the utilization rate of sunshine.In order to improve TiO
2at visible region response efficiency, people have attempted the multiple technologies such as noble metal loading, metal and nonmetal doping, surface dye sensitization, have to a certain degree improved TiO
2to the sensitiveness of visible ray.But these TiO
2catalyst selectivity is all not good, is unfavorable for the degraded of trace contaminant in complex system, and what therefore how effectively to improve catalyst is also selectively the task of top priority.Someone passes through regulator solution pH value, at TiO
2finishing specific molecular or preparation dual area catalyst, attempt to improve TiO
2catalytic selectivity, but its selective or stability all can not be satisfactory.
Utilize in recent years molecular imprinting to improve TiO
2catalytic selectivity cause people's extensive concern.Molecular imprinting can be prepared the molecularly imprinted polymer (MIP) template molecule to high specific recognition capability.The TiO modifying through MIP
2object is had to high selection adsorption capacity, thereby can greatly improve the selective of catalyst.Tang and Zhu seminar are at TiO
2nanoparticle surface has been prepared the MIP film of 2-nitrophenol (or 4-nitrophenol) trace, has greatly improved catalyst selective to the light degradation of template molecule.They are also at TiO
2nanoparticle surface has been prepared doped with Al
3+diethyl phthalate imprinted silica gel film, the ability of its light degradation template molecule is far better than other catalyst, and good stability.In addition, they also utilize improvement liquid phase deposition to prepare trace TiO at glass surface
2film, for salicylic efficient light degraded.But these catalyst all only have response to ultraviolet region.
The people such as Deng are at TiO
2nanoparticle surface has been prepared conductivity type polypyrrole MIP film.Because polypyrrole has good electric conductivity, can be by TiO
2light sensitive area move to visible region, therefore can be used for the Visible Light Induced Photocatalytic of methyl orange.The people such as Liu utilize sol-gel technique at TiO
2nanotube surface is coated with last layer trace TiO
2film, for the visible light efficient degraded of 9-anthroic acid.But these catalyst are difficult for separating with reaction solution in use, this is also that current nano-photocatalyst is applied the problem that middle urgent need solves.
The present invention has prepared Fe taking methyl orange as pseudo-template
3o
4tiO
2conductivity type MIP nucleocapsid magnetic nanometer, has realized unglazed photograph lower to Congo red high selectivity catalytic degradation, and can make by external magnetic field easily that catalyst and solution are quick to be separated, can recycled for multiple times.
Summary of the invention
The present invention has prepared Fe3O4TiO2 conductivity type MIP nucleocapsid magnetic nanometer taking methyl orange as pseudo-template, realize unglazed photograph lower to Congo red high selectivity catalytic degradation, and can make by external magnetic field easily that catalyst and solution are quick to be separated, can recycled for multiple times.
The present invention adopts following technical scheme:
The preparation method's of the Congo red hud typed pseudo-template imprinting magnetic nanocatalyst of degraded of the present invention concrete steps are as follows:
1Fe
3o
4the preparation of nano particle
Ultra-pure water is placed in three-neck flask by 1.1, continues logical nitrogen 30min deoxygenation;
1.2 add anhydrous FeCl in ultra-pure water
3, anhydrous FeCl
3with the w/v of ultra-pure water be 4-7:160g/ml, under mechanical agitation, add again FeCl
24H
2o, anhydrous FeCl
3with FeCl
24H
2the weight ratio of O is 4-7:2-4;
1.3 water-baths are warming up to 80 DEG C, keep temperature, dropwise drip concentrated ammonia liquor, and the volume ratio of concentrated ammonia liquor addition and ultra-pure water is 1:8, after dropwising, at 80 DEG C, reacts 30min;
1.4 reactant liquors are standing separation under externally-applied magnetic field, and nano particle successively washs after 4 times through absolute ethyl alcohol and ultra-pure water, dry for standby in drying box;
2Fe
3o
4siO
2the preparation of magnetic nano-particle
2.1 Fe prepared by step 1
3o
4nano particle is placed in absolute ethyl alcohol and ultra-pure water mixed liquor, ultrasonic processing 15min, Fe
3o
4nano particle is 0.2-1:195g/ml with the molal volume ratio of absolute ethyl alcohol and ultra-pure water mixed liquor;
2.2 add tetraethoxysilane and concentrated ammonia liquor after ultrasonic in solution, the volume ratio of tetraethoxysilane and absolute ethyl alcohol and ultra-pure water mixed liquor is 0.5-1:195, the volume ratio of concentrated ammonia liquor and absolute ethyl alcohol and ultra-pure water mixed liquor is 3-8:195, mechanical agitation reaction 24h at 40 DEG C of water-baths;
2.3 reactant liquors are standing separation under externally-applied magnetic field, and nano particle successively washs 4 times through absolute ethyl alcohol and ultra-pure water, the vacuum drying of spending the night under 60 DEG C of conditions;
3Fe
3o
4siO
2tiO
2the preparation of nuclear shell type nano meter particle
3.1 Fe prepared by step 2
3o
4siO
2be scattered in isopropyl alcohol Fe
3o
4siO
2with the w/v of isopropyl alcohol be 0.3-0.5:50g/ml, then ultrasonic dispersion 15min;
3.2 add after ultra-pure water and isopropyl alcohol mixing in dispersion liquid again, and the volume ratio of ultra-pure water and dispersion liquid is 40-60:50, and the volume ratio of isopropyl alcohol and dispersion liquid is 100-200:50, and ultrasonic processing 30min, obtains mixed liquor;
3.3 add titanium isopropoxide again in mixed liquor, and the volume ratio of titanium isopropoxide and mixed liquor is 3-4:250, and then at 25 DEG C, continuous ultrasound is processed 3h;
3.4 reactant liquors standing separation in externally-applied magnetic field, nano particle is after ethanol washing 3 times, and at 60 DEG C, vacuum drying is spent the night;
3.5 will be dried gained nano particle grinds completely, transfers in monkey, puts into Muffle furnace, under 500 DEG C of conditions, calcines 3h, obtains the Fe of catalytic activity
3o
4siO
2tiO
2nuclear shell type nano meter particle.
4Fe
3o
4siO
2tiO
2the preparation of the hud typed trace nano particle of MIP
4.1 get methyl orange and pyrroles is dissolved in the mixed solution of methyl alcohol and pure water, the w/v of the mixed solution of methyl orange and methyl alcohol and pure water is 0.03-0.05:10g/ml, the volume ratio of the mixed solution of pyrroles and methyl alcohol and pure water is 0.03-0.04:10, under dark condition, logical nitrogen deoxygenation 30min, sealing, as pre-assembled solution;
4.2 Fe prepared by step 3
3o
4siO
2tiO
2nano particle is dispersed in HCl solution, Fe
3o
4siO
2tiO
2the w/v of nano particle and HCl solution is 0.5-0.7:100g/ml, ultrasonic processing 30min, logical nitrogen deoxygenation 20min, then adds above-mentioned pre-assembled solution, pre-assembled solution with contain Fe
3o
4siO
2tiO
2the volume ratio of the HCl solution of nano particle is 8-12:100, then at 0 DEG C, continues electric stirring, after 20 minutes, dropwise adds containing FeCl
3hCl solution, FeCl
3with Fe
3o
4siO
2tiO
2the weight ratio of nano particle is 0.2-0.3:0.5-0.7, and the volume ratio of HCl solution and pre-assembled solution is 1-3:10, then under dark condition, reacts 4h in 0 DEG C, during this time with the protection of nitrogen balloon;
4.3 under externally-applied magnetic field standing separation, the nano particle obtaining is through twice of the HCL of pH=1 solution washing, each 3h that continues, the ammonia spirit that is 1%, pH=8 by concentration again washing 3 times continues 1h at every turn, remove residual ammonia spirit with distilled water washing again, wash 3 times, last products therefrom, in 70 DEG C of dried overnight, is obtained to Fe
3o
4siO
2tiO
2mIP trace nano-particle catalyst, sealing is placed in drier preserves.
In step 1.2, preferred anhydrous FeCl
3with the w/v of ultra-pure water be 5.6785:160g/ml, anhydrous FeCl
3with FeCl
24H
2the weight ratio of O is 5.6785:3.4449.
In step 2.1, in absolute ethyl alcohol and ultra-pure water mixed liquor, the volume ratio of absolute ethyl alcohol and ultra-pure water is 155:40.
In step 2.1, preferably Fe
3o
4nano particle is 0.5:195g/ml with the molal volume ratio of absolute ethyl alcohol and ultra-pure water mixed liquor.
In step 2.2, preferably the volume ratio of tetraethoxysilane and absolute ethyl alcohol and ultra-pure water mixed liquor is 0.7:195, and the volume ratio of concentrated ammonia liquor and absolute ethyl alcohol and ultra-pure water mixed liquor is 5:195.
In step 3.1, preferably Fe
3o
4siO
2with the w/v of isopropyl alcohol be 0.4016:50g/ml.
In step 3.2, preferably the volume ratio of ultra-pure water and dispersion liquid is 50:50, and the volume ratio of isopropyl alcohol and dispersion liquid is 150:50.
In step 3.3, preferably the volume ratio of titanium isopropoxide and mixed liquor is 3.698:250.
In step 4.1, the w/v of the mixed solution of methyl orange and methyl alcohol and pure water is preferably 0.0404:10g/ml, the volume ratio of the mixed solution of pyrroles and methyl alcohol and pure water is preferably 0.0346:10, and in the mixed solution of methyl alcohol and pure water, the volume ratio of methyl alcohol and pure water is 1:1.
In step 4.2, Fe
3o
4siO
2tiO
2the w/v of nano particle and HCl solution is preferably 0.6012:100g/ml, the pH=2 of HCl solution, pre-assembled solution with contain Fe
3o
4siO
2tiO
2the volume ratio of the HCl solution of nano particle is preferably 10:100, FeCl
3with Fe
3o
4siO
2tiO
2the weight ratio of nano particle is preferably 0.27:0.6012, and the volume ratio of HCl solution and pre-assembled solution is preferably 2:10.
Good effect of the present invention is as follows:
The present invention successfully prepares the trace magnetic catalyst taking methyl orange as pseudo-template, thus solved taking Congo red in template Kaolinite Preparation of Catalyst process template molecule very easily degrade, cannot obtain the problem of target catalyst.
Trace type catalyst of the present invention has obvious degradation effect to Congo red, and can separate with solution is quick easily by external magnetic field, realizes the environmental protection low cost degraded to polluting dyestuff.Experimental result shows that its catalytic degradation speed is fast under unglazed photograph, and the first order reaction speed constant of catalytic reaction is 0.09615min
-1.After recycled for multiple times, catalytic capability, without significant change, has a good application prospect to Congo red catalytic degradation in dyeing and printing sewage.
Brief description of the drawings
Fig. 1 is Fe prepared by the embodiment of the present invention 1
3o
4siO
2tiO
2the thermogravimetic analysis (TGA) figure of the hud typed trace nano particle of MIP.
Fig. 2 is Fe prepared by the embodiment of the present invention 1
3o
4siO
2tiO
2the degrade graph of relation of Congo red absorbance ratio-Congo red degradation time of the hud typed trace nano particle of MIP.
Fig. 3 is Fe prepared by the embodiment of the present invention 1
3o
4siO
2tiO
2the hud typed trace nano particle of MIP is to Congo red catalytic degradation kinetic curve and first order reaction matched curve figure.
Fig. 4 is Fe prepared by the embodiment of the present invention 1
3o
4siO
2tiO
2the absorption figure of the hud typed trace nano particle of MIP to methyl orange.
Detailed description of the invention
The following examples are to describe in further detail of the present invention.
Embodiment 1
Fe
3o
4the preparation of nano particle
(1) measure 160mL ultra-pure water in 250mL three-neck flask, continue logical nitrogen 30min deoxygenation;
(2) add the anhydrous FeCl of 5.6785g
3, under mechanical agitation, add again 3.4449g FeCl
24H
2o;
(3) water-bath is warming up to 80 DEG C, keeps temperature, dropwise drips 20ml concentrated ammonia liquor, after dropwising, at 80 DEG C, reacts 30min;
(4) reactant liquor standing separation under externally-applied magnetic field, nano particle successively washs after 4 times through absolute ethyl alcohol and ultra-pure water, dry for standby in drying box.
Fe
3o
4siO
2the preparation of magnetic nano-particle
(1) above-mentioned Fe
3o
4nano particle (0.5g) is placed in 155mL absolute ethyl alcohol and 40mL ultra-pure water mixed liquor, ultrasonic processing 15min;
(2) after ultrasonic, in solution, add 0.7mL tetraethoxysilane and 5mL concentrated ammonia liquor, mechanical agitation reaction 24h at 40 DEG C of water-baths;
(3) reactant liquor standing separation under externally-applied magnetic field, nano particle successively washs 4 times through absolute ethyl alcohol and ultra-pure water, the vacuum drying of spending the night under 60 DEG C of conditions.
Fe
3o
4siO
2tiO
2the preparation of nuclear shell type nano meter particle
(1) take 0.4016g Fe
3o
4siO
2be scattered in 50mL isopropyl alcohol ultrasonic processing 15min.Pre-dispersed;
(2) dispersion liquid is transferred in conical flask, then after adding 50mL ultra-pure water and 150mL isopropyl alcohol to mix, ultrasonic processing 30min;
(3) add titanium isopropoxide 3.698mL, at 25 DEG C, continuous ultrasound is processed 3h again;
(4) reactant liquor standing separation in externally-applied magnetic field, nano particle is after ethanol washing 3 times, and at 60 DEG C, vacuum drying is spent the night
(5) will be dried gained nano particle and grind completely, transfer in monkey, put into Muffle furnace, under 500 DEG C of conditions, calcine 3h (amorphous titania is converted into has photocatalytic activity titanium dioxide), obtain the Fe of catalytic activity
3o
4siO
2tiO
2nuclear shell type nano meter particle.
Fe
3o
4siO
2tiO
2the preparation of the hud typed trace nano particle of MIP
(1) get in the mixed solution that 0.0404g methyl orange and 34.6 μ L pyrroles are dissolved in 10mL methyl alcohol and pure water (1:1, v/v), under dark condition, logical nitrogen deoxygenation 30min, sealing, as pre-assembled solution;
(2) take 0.6012g Fe
3o
4siO
2tiO
2nano particle is dispersed in 100mL HCl solution (pH=2), ultrasonic processing 30min, and logical nitrogen deoxygenation 20min, then adds above-mentioned pre-assembled solution, continues electric stirring at 0 DEG C, after about 20 minutes, dropwise adds the FeCl containing 0.2700g
32ml HCl solution (pH=1, deoxygenation), under dark condition, react 4h in 0 DEG C, during this time with the protection of nitrogen balloon;
(3) standing separation under externally-applied magnetic field, the nano particle obtaining, through 100mL HCL solution (pH=1) washed twice, continues 3h at every turn, then uses 100mL ammonia spirit (1%, pH=8) washing 3 times, continues 1h at every turn.Remove residual ammonia spirit with distilled water washing again, wash 3 times, last products therefrom, in 70 DEG C of dried overnight, is obtained to Fe
3o
4siO
2tiO
2mIP trace nano particle, sealing is placed in drier and saves backup.
Fe
3o
4siO
2tiO
2the preparation (as a comparison) of the hud typed non-trace nano particle of NIP
(1) get in the mixed solution that 34.6 μ L pyrroles are dissolved in 10mL methyl alcohol and pure water (1:1, v/v), under dark condition, logical nitrogen deoxygenation 30min, sealing, as pre-assembled solution;
(2) take 0.8928g Fe
3o
4siO
2tiO
2nano particle is dispersed in 100mL HCl solution (pH=2), ultrasonic processing 30min, and logical nitrogen deoxygenation 20min, then adds above-mentioned pre-assembled solution, continues electric stirring at 0 DEG C, after about 20 minutes, dropwise adds the FeCl containing 0.2695g
32ml HCl solution (pH=1, deoxygenation), under dark condition, react 4h in 0 DEG C, during this time with the protection of nitrogen balloon;
(3) standing separation under externally-applied magnetic field, the nano particle obtaining, through 100mL HCL solution (pH=1) washed twice, continues 3h at every turn, then uses 100mL ammonia spirit (1%, pH=8) washing 3 times, continues 1h at every turn.Remove residual ammonia spirit with distilled water washing again, wash 3 times, last products therefrom, in 70 DEG C of dried overnight, is obtained to Fe
3o
4siO
2tiO
2nIP trace nano particle, sealing is placed in drier and saves backup.
Fig. 1 is Fe prepared by the present invention
3o
4siO
2tiO
2the thermogravimetic analysis (TGA) figure of the hud typed trace nano particle of MIP, as can be seen from Figure 1 500 DEG C of left and right, imprinted material has obvious weightlessness (approximately 4%), illustrates that magnetic particle surface has imprinted polymer to generate.
Imprinted material is to Congo red catalytic degradation experiment
Accurately take the Congo red particle of 0.0250g, add 250mL water to be configured to the Congo red mother liquor of 100mg/L, dark place saves backup; With the Congo red solution 30ml of Congo red mother liquor preparation 30mg/L.Taking 30mg MIP-PPY/TiO2 nano-complex particle is scattered in above-mentioned Congo red solution, constant temperature oscillation certain hour (5 in dark at 25 DEG C, 10,15,20,25min) after, through external magnetic field and 0.22um filter isolated by filtration, parting liquid is through spectrophotometric determination absorbance, thereby draws out trace and non-imprinted material to Congo red degradation curve (relation curve of absorbance ratio-Congo red degradation time)
Taking initial concentration as the Congo red solution of 30mg/L is as simulating pollution thing, to its photocatalytic degradation to investigate its catalytic activity; The relation curve of absorbance ratio-Congo red degradation time as shown in Figure 2, kinetic curve and first order reaction matched curve are as shown in Figure 3, result shows without under illumination condition, and imprinted material has a fine catalytic degradation effect to Congo red, is obviously better than non-imprinted material.The Congo red First-order kinetics equation that meets of prepared catalyst photocatalytic degradation, and the first order reaction speed constant of imprinted material is 0.09615min
-1, much larger than general literature value (0.0154min
-1).
The Staticadsorption experiment of imprinted material to methyl orange
(1) configure respectively 2mg/L with methyl orange stock solution, 4mg/L, 6mg/L, 8mg/L, 10mg/L, 15mg/L, the methyl orange solution 50ml of 20mg/L, dark place saves backup.
(2) get 20mg MIP-PPY/TiO
2/ NIP-PPY/TIO
2composite nanoparticle is respectively with above-mentioned 4mL storage liquid at room temperature after lucifuge constant temperature oscillation 5h; separate through external magnetic field; clarified solution after separation records the concentration of methyl orange in equilibrium liquid by AAS; thereby calculate the adsorbance of magnetic particle to methyl orange, draw trace or the adsorption curve of non-imprinted material to methyl orange.
Adsorption curve as shown in Figure 4.Result shows, along with the increase of concentration, trace and non-trace particle increase gradually to the adsorbance of methyl orange.Comparatively speaking, the adsorption capacity of trace particle is larger than the adsorption capacity of non-trace particle.Result is basically identical with expection, and the trace effect that nano material is described is obvious.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, amendment, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (10)
1. the preparation method of the Congo red hud typed pseudo-template imprinting magnetic nanocatalyst of degraded, is characterized in that: the concrete steps of described method are as follows:
1Fe
3o
4the preparation of nano particle
Ultra-pure water is placed in three-neck flask by 1.1, continues logical nitrogen 30min deoxygenation;
1.2 add anhydrous FeCl in ultra-pure water
3, anhydrous FeCl
3with the w/v of ultra-pure water be 4-7:160g/ml, under mechanical agitation, add again FeCl
24H
2o, anhydrous FeCl
3with FeCl
24H
2the weight ratio of O is 4-7:2-4;
1.3 water-baths are warming up to 80 DEG C, keep temperature, dropwise drip concentrated ammonia liquor, and the volume ratio of concentrated ammonia liquor addition and ultra-pure water is 1:8, after dropwising, at 80 DEG C, reacts 30min;
1.4 reactant liquors are standing separation under externally-applied magnetic field, and nano particle successively washs after 4 times through absolute ethyl alcohol and ultra-pure water, dry for standby in drying box;
2Fe
3o
4siO
2the preparation of magnetic nano-particle
2.1 Fe prepared by step 1
3o
4nano particle is placed in absolute ethyl alcohol and ultra-pure water mixed liquor, ultrasonic processing 15min, Fe
3o
4nano particle is 0.2-1:195g/ml with the molal volume ratio of absolute ethyl alcohol and ultra-pure water mixed liquor;
2.2 add tetraethoxysilane and concentrated ammonia liquor after ultrasonic in solution, the volume ratio of tetraethoxysilane and absolute ethyl alcohol and ultra-pure water mixed liquor is 0.5-1:195, the volume ratio of concentrated ammonia liquor and absolute ethyl alcohol and ultra-pure water mixed liquor is 3-8:195, mechanical agitation reaction 24h at 40 DEG C of water-baths;
2.3 reactant liquors are standing separation under externally-applied magnetic field, and nano particle successively washs 4 times through absolute ethyl alcohol and ultra-pure water, the vacuum drying of spending the night under 60 DEG C of conditions;
3Fe
3o
4siO
2tiO
2the preparation of nuclear shell type nano meter particle
3.1 Fe prepared by step 2
3o
4siO
2be scattered in isopropyl alcohol Fe
3o
4siO
2with the w/v of isopropyl alcohol be 0.3-0.5:50g/ml, then ultrasonic dispersion 15min;
3.2 add after ultra-pure water and isopropyl alcohol mixing in dispersion liquid again, and the volume ratio of ultra-pure water and dispersion liquid is 40-60:50, and the volume ratio of isopropyl alcohol and dispersion liquid is 100-200:50, and ultrasonic processing 30min, obtains mixed liquor;
3.3 add titanium isopropoxide again in mixed liquor, and the volume ratio of titanium isopropoxide and mixed liquor is 3-4:250, and then at 25 DEG C, continuous ultrasound is processed 3h;
3.4 reactant liquors standing separation in externally-applied magnetic field, nano particle is after ethanol washing 3 times, and at 60 DEG C, vacuum drying is spent the night;
3.5 will be dried gained nano particle grinds completely, transfers in monkey, puts into Muffle furnace, under 500 DEG C of conditions, calcines 3h, obtains the Fe of catalytic activity
3o
4siO
2tiO
2nuclear shell type nano meter particle;
4Fe
3o
4siO
2tiO
2the preparation of the hud typed trace nano particle of MIP
4.1 get methyl orange and pyrroles is dissolved in the mixed solution of methyl alcohol and pure water, the w/v of the mixed solution of methyl orange and methyl alcohol and pure water is 0.03-0.05:10g/ml, the volume ratio of the mixed solution of pyrroles and methyl alcohol and pure water is 0.03-0.04:10, under dark condition, logical nitrogen deoxygenation 30min, sealing, as pre-assembled solution;
4.2 Fe prepared by step 3
3o
4siO
2tiO
2nano particle is dispersed in HCl solution, Fe
3o
4siO
2tiO
2the w/v of nano particle and HCl solution is 0.5-0.7:100g/ml, ultrasonic processing 30min, logical nitrogen deoxygenation 20min, then adds above-mentioned pre-assembled solution, pre-assembled solution with contain Fe
3o
4siO
2tiO
2the volume ratio of the HCl solution of nano particle is 8-12:100, then at 0 DEG C, continues electric stirring, after 20 minutes, dropwise adds containing FeCl
3hCl solution, FeCl
3with Fe
3o
4siO
2tiO
2the weight ratio of nano particle is 0.2-0.3:0.5-0.7, and the volume ratio of HCl solution and pre-assembled solution is 1-3:10, then under dark condition, reacts 4h in 0 DEG C, uses during this time nitrogen protection;
4.3 under externally-applied magnetic field standing separation, the nano particle obtaining is through twice of the HCL of pH=1 solution washing, each 3h that continues, the ammonia spirit that is 1%, pH=8 by concentration again washing 3 times continues 1h at every turn, remove residual ammonia spirit with distilled water washing again, wash 3 times, last products therefrom, in 70 DEG C of dried overnight, is obtained to Fe
3o
4siO
2tiO
2mIP trace nano-particle catalyst, sealing is placed in drier preserves.
2. preparation method as claimed in claim 1, is characterized in that: in step 1.2, and anhydrous FeCl
3with the w/v of ultra-pure water be 5.6785:160g/ml, anhydrous FeCl
3with FeCl
24H
2the weight ratio of O is 5.6785:3.4449.
3. preparation method as claimed in claim 1, is characterized in that: in step 2.1, in absolute ethyl alcohol and ultra-pure water mixed liquor, the volume ratio of absolute ethyl alcohol and ultra-pure water is 155:40.
4. preparation method as claimed in claim 1, is characterized in that: in step 2.1, and Fe
3o
4nano particle is 0.5:195g/ml with the molal volume ratio of absolute ethyl alcohol and ultra-pure water mixed liquor.
5. preparation method as claimed in claim 1, is characterized in that: in step 2.2, the volume ratio of tetraethoxysilane and absolute ethyl alcohol and ultra-pure water mixed liquor is 0.7:195, and the volume ratio of concentrated ammonia liquor and absolute ethyl alcohol and ultra-pure water mixed liquor is 5:195.
6. preparation method as claimed in claim 1, is characterized in that: in step 3.1, and Fe
3o
4siO
2with the w/v of isopropyl alcohol be 0.4016:50g/ml.
7. preparation method as claimed in claim 1, is characterized in that: in step 3.2, the volume ratio of ultra-pure water and dispersion liquid is 50:50, and the volume ratio of isopropyl alcohol and dispersion liquid is 150:50.
8. preparation method as claimed in claim 1, is characterized in that: in step 3.3, the volume ratio of titanium isopropoxide and mixed liquor is 3.698:250.
9. preparation method as claimed in claim 1, it is characterized in that: in step 4.1, the w/v of the mixed solution of methyl orange and methyl alcohol and pure water is 0.0404:10g/ml, the volume ratio of the mixed solution of pyrroles and methyl alcohol and pure water is 0.0346:10, in the mixed solution of methyl alcohol and pure water, the volume ratio of methyl alcohol and pure water is 1:1.
10. preparation method as claimed in claim 1, is characterized in that: in step 4.2, and Fe
3o
4siO
2tiO
2the w/v of nano particle and HCl solution is 0.6012:100g/ml, the pH=2 of HCl solution, pre-assembled solution with contain Fe
3o
4siO
2tiO
2the volume ratio of the HCl solution of nano particle is 10:100, FeCl
3with Fe
3o
4siO
2tiO
2the weight ratio of nano particle is 0.27:0.6012, and the volume ratio of HCl solution and pre-assembled solution is 2:10.
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