CN104923309A - Preparation method for superparamagnetic nanoparticle photocatalyst with Fe3O4-PAMAM-TiO2 core-shell structure - Google Patents

Preparation method for superparamagnetic nanoparticle photocatalyst with Fe3O4-PAMAM-TiO2 core-shell structure Download PDF

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CN104923309A
CN104923309A CN201510172923.XA CN201510172923A CN104923309A CN 104923309 A CN104923309 A CN 104923309A CN 201510172923 A CN201510172923 A CN 201510172923A CN 104923309 A CN104923309 A CN 104923309A
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pamam
superparamagnetism
tio
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shell structured
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CN104923309B (en
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丛日敏
于怀清
杨思一
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Shandong University of Technology
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Shandong University of Technology
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Abstract

The invention relates to a method for preparing a superparamagnetic nanoparticle photocatalyst with a Fe3O4-PAMAM-TiO2 core-shell structure by using polyamide-amine (PAMAM) dendrimer as a template and an isolation layer in a low-temperature aqueous solution. The method is characterized by comprising the following steps: firstly, with the PAMAM dendrimer as the template, preparing a superparamagnetic Fe3O4-PAMAM nanoparticle colloidal solution by using a co-precipitation method; then adding the PAMAM dendrimer with different terminal groups and coating Fe3O4-PAMAM nanoparticles so as to form a dendrimer isolation layer; finally, dropwise adding a TiCl4 absolute ethanol solution, and carrying out normal pressure reaction and hydrothermal reaction so as to obtain the nanoparticles with the Fe3O4-PAMAM-TiO2 core-shell structure and a complete TiO2 shell layer; and carrying out washing and redispersion so as to obtain the nanoparticle photocatalyst with the Fe3O4-PAMAM-TiO2 core-shell structure.

Description

A kind of superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst
Technical field
The present invention relates to a kind of superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, belongs to technical field of material.
Background technology
Along with the development of modern industry, discarded, residual chemical substance causes serious threat to environment and ecological safety, and people have to seek effective mode to process these debirs.Photocatalysis is a kind of advanced technology by oxidation reaction decomposing organic waste, in oxidative degradation azo dyes and agricultural chemicals, achieve good effect, present study hotspot has focused on various organic pollutant field in water and air of how effectively degrading.Nano-TiO 2have excellent photocatalytic activity, cheap and easy to get and nontoxic, band gap is 3.2eV, under UV-irradiation, show outstanding catalytic activity, is identified as the best semiconductor light-catalyst of decomposing organic pollutant in water and air.
In order to increase the specific area of photochemical catalyst, improve catalytic efficiency, generally by TiO 2be prepared into nano particle, after light-catalyzed reaction completes, the separation of catalyst and being recycled into as a difficult problem.For this reason, scientific research personnel is by nano-TiO 2load on paramagnetic material, separation and recovery can be realized utilize under additional magnetic fields.The initial method preparing magnet carried photocatalyst makes TiO 2directly in the growth of paramagnetic particle surface deposition, obtained nucleocapsid structure composite particles.Due to the Fe in magnetic core 3+tiO can be diffused in heat treatment process 2shell, makes the oxide of the iron with narrow band gap become the center of electron-hole recombinations, reduces TiO when quantity is larger 2the quantum efficiency in light induced electron and hole, causes the catalytic activity of gained nucleocapsid structure magnetic-particle than single-phase TiO 2reduce.For overcoming the problems referred to above, scientific research personnel manages at magnetic core and TiO 2between grow one deck inert barriers, to stop photo-generated carrier to the migration of magnetic core.Research finds, coated Si O on magnetic core 2, Al 2o 3, the inorganic or Organic barriers such as PPY, PS, all can improve the stability of magnetic core to a certain extent, reduce it to TiO 2the impact of photocatalytic activity.But heat treatment process can make magnetic core be oxidized, saturated magnetization rate reduces; Make TiO 2specific area reduces, and activity hydroxy quantity reduces, and the recuperability of photochemical catalyst and catalytic activity are declined.In addition, due to the bridging effect of linear polymeric, magnetic core is easily assembled in coated process, and particle size is increased, and particulate surface hydrophobic increases simultaneously, and after sonic oscillation and milled processed, the dispersiveness of magnetic-particle still obviously declines; Further, macromolecule and inorganic mineral have diverse crystal structure, at the hydrophobic complete TiO of macromolecule top layer Epitaxial growth 2crystal shell is very difficult, therefore is difficult to obtain monodispersed, to have complete nucleocapsid structure magnet carried photocatalyst.
Polyamide-amide (PAMAM) dendrimer is the water soluble polymer with accurate molecular structure and monodispersity, the dendrimer of high algebraically is spherical, molecular diameter is from several nanometer to tens nanometers, surface has intensive functional group, excellent monodispersity soft template is can be used as when preparing nano particle, obtained nano particle has the feature of narrow size distribution, good dispersion, preparing nanocatalyst, detect on the high value added product such as reagent, biomedical product and show obvious performance advantage, have broad application prospects.The present invention adopts that end group is hydroxyl, ester group or carboxyl pamam dendrimer molecule are template, after first making iron ion and the abundant coordination of dendrimer group, add NaOH again and carry out coprecipitation reaction, prepare can in water stable dispersion, the Fe with superparamagnetism 3o 4-PAMAM nano particle.As magnetic core, utilize end group for the dendrimer of ester group or amido fully coated to its surface, under alkali condition, be conducive to TiO 2deposition thereon and growth, form complete TiO 2shell, thus obtained superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.Pamam dendrimer molecule separation layer has intercepted magnetic core and TiO 2the direct contact of shell and iron ion are to TiO 2the infiltration of shell, reduces the recombination rate of photo-generated carrier.Gained superparamagnetism Fe of the present invention 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle can be dispersed in water with single particle form, has photocatalytic activity high, the feature that the rate of recovery is high, is a kind of magnet carried photocatalyst with broad prospect of application.
Summary of the invention
The object of this invention is to provide a kind of in low-temperature aqueous solution, with pamam dendrimer molecule for template and separation layer, prepare a kind of superparamagnetism Fe 3o 4-PAMAM-TiO 2the method of nuclear shell structured nano-particle photochemical catalyst, makes gained Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle has highlight catalytic active and high-recovery.Its technology contents is:
Described a kind of superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: comprise the following steps:
(1) superparamagnetism Fe 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: be 1 × 10 to concentration -5~ 1 × 10 -4nitrogen is passed into and mechanical agitation after 30 ~ 60 minutes in the pamam dendrimer molecular water solution of mol/L, add molysite mixed liquor, pass into nitrogen under room temperature and stir 4 ~ 8 h, make iron ion and the abundant coordination of dendrimer group, then bath temperature is adjusted to 70 ~ 90 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L is 10 ~ 12 to pH, and Keep agitation 30 min ~ 60 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
(2) Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: under room temperature, to the superparamagnetism Fe that described step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -4~ 1 × 10 -3the pamam dendrimer molecular water solution of mol/L, drip concentration is 1 × 10 simultaneously -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10 ~ 11, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
(3) superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle-making step is: by fully coated for surface obtained for described step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 40 ~ 80 DEG C, and mechanical agitation speed is adjusted to 800 ~ 2000 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -3~ 1 × 10 -1mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10 ~ 11, TiCl 4after dropwising, Keep agitation 4 ~ 6 hours at the reaction temperatures, then, moves to reactant liquor in hydrothermal reaction kettle, is heated to 120 ~ 180 DEG C in resistance furnace, after insulation 8 ~ 12h, takes out hydrothermal reaction kettle cool to room temperature, namely obtains superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
(4) superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post-processing step is: described step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, then under sonic oscillation and mechanical agitation, gained sediment is distributed in absolute ethyl alcohol, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
Described superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, it is characterized in that: the molysite mixed liquor in described step (1) is the mixed solution of ferric trichloride, ferrous chloride or ferrous sulfate, wherein ferric trichloride concentration is 0.01 ~ 1 mol/L, the mol ratio of ferric trichloride and ferrous chloride or ferrous sulfate is 1.5 ~ 2, and the addition of molysite mixed liquor is with Fe 3+compare for 200:1 ~ 10:1 is standard with the amount of substance of pamam dendrimer molecule.The end group of pamam dendrimer molecule is ester group, hydroxyl or carboxyl, and algebraically was 4 ~ 6 generations.
Described superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, it is characterized in that: the end group of the pamam dendrimer molecule in described step (2) is ester group or amido, algebraically was 5 ~ 7 generations, and its addition is 10 ~ 50 times of the amount of substance of added dendrimer in described step (1).
Described superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: the TiCl in described step (3) 4addition is Fe in the middle molysite mixed liquor of described step (1) 3+1 ~ 5 times of amount of substance.
Described superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: in described step (4), mechanical agitation rotating speed is 800 ~ 2000 revs/min, stirs 5 ~ 10 minutes.Sonic oscillation adopts power to be the supersonic wave cleaning machine of 50 ~ 300W, and the time is 1 ~ 5 minute, and absolute ethyl alcohol and sedimentary volume ratio are 2:1 ~ 5:1.
Compared with prior art, tool has the following advantages in the present invention:
1, the present invention's pamam dendrimer molecule is template and separation layer, obtained superparamagnetism Fe in low-temperature aqueous solution 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst, dendrimer is between Fe 3o 4core and TiO 2between shell, form dendrimer mechanical isolation layer (see accompanying drawing 1), considerably reduce core and contact with the direct of shell, intercepted Fe 3+to TiO 2the direct penetration route of shell; These have the functional group of powerful coordination function to have a large amount of tertiary amine groups, amide groups, ester group or amido in dendrimer structure, make to be dissolved by magnetic core generation light in photochemical catalyst use procedure and the micro Fe that produces 2+and Fe 3+caught by dendrimer, reduce Fe 3+penetrate into TiO 2the quantity of shell, reduces its impact on catalytic activity; Maximum temperature higher than 180 DEG C, does not avoid high-temperature roasting, slow down oxidation and the dissolving of magnetic core, and the specific area avoided caused by the gathering of nano particle high temperature declines, and remains a large amount of activity hydroxies of particle surface; Pamam dendrimer molecule has good water-soluble, is easy to be adsorbed on Fe 3o 4around magnetic core, be conducive to growing complete TiO 2shell; Adopt spherical dendrimer to the Fe of preparation 3o 4nano particle carries out coated, can not produce bridging effect, avoid particle aggregation, make Fe 3o 4-PAMAM is dispersed in water with individual particle state, thus obtained with the Fe of individual particle state dispersion 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.Based on above principle, stuctures and properties feature, the superparamagnetism Fe that the present invention obtains 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst has high catalytic activity and magnetic recyclability.
2, the superparamagnetism Fe that obtains of the present invention 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle size, at about 30 ~ 110 nm, is dispersed in water or absolute ethyl alcohol with individual particle state, has superparamagnetism, and saturation magnetization is up to 60 ~ 100 emu/g, and single uses the rate of recovery to reach 95%, uses for 3 times the rate of recovery to reach 92%.
3, the present invention adopts low temperature liquid phase preparation method, simple for process.Obtained superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle dispersion is good, and photocatalytic activity is high, and under UV-irradiation, the percent of decolourization of the azo dyes such as photocatalytic degradation rhodamine B, methylenum careuleum, methyl orange all can reach more than 90%, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the superparamagnetism Fe that the present invention obtains 3o 4-PAMAM-TiO 2high resolution transmission electron microscopy (HRTEM) photo of nuclear shell structured nano-particle.
Detailed description of the invention
embodiment 1:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -5the end group of mol/L is pass into nitrogen in the 6th generation pamam dendrimer molecular water solution of hydroxyl and mechanical agitation after 60 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 2, and the addition of molysite mixed liquor is with Fe 3+compare for 200:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 8h, then bath temperature being adjusted to 70 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3the sodium hydrate aqueous solution of mol/L is 12 to pH, and Keep agitation 60 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -4the end group of mol/L be ester group the 7th generation pamam dendrimer molecular water solution, its addition is 50 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -1the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 11, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 60 DEG C, and mechanical agitation speed is adjusted to 2000 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -1mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -1the sodium hydrate aqueous solution of mol/L, the pH keeping system is 11, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 5:1 be standard.After dropwising, Keep agitation 4 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 180 DEG C, after insulation 8h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 5 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 1 minute of 300W, simultaneously with the rotating speed mechanical agitation 5 minutes of 2000 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
embodiment 2:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -5the end group of mol/L is pass into nitrogen in the 6th generation pamam dendrimer molecular water solution of ester group and mechanical agitation after 40 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 2, and the addition of molysite mixed liquor is with Fe 3+compare for 120:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 6h, then bath temperature being adjusted to 80 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -2the sodium hydrate aqueous solution of mol/L is 11 to pH, and Keep agitation 50 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -4the end group of mol/L be amido the 7th generation pamam dendrimer molecular water solution, its addition is 50 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -2the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 11, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 80 DEG C, and mechanical agitation speed is adjusted to 1600 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -2mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -2the sodium hydrate aqueous solution of mol/L, the pH keeping system is 11, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 3:1 be standard.After dropwising, Keep agitation 5 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 160 DEG C, after insulation 10h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 4 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 1 minute of 300W, simultaneously with the rotating speed mechanical agitation 8 minutes of 1200 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
embodiment 3:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4the end group of mol/L is pass into nitrogen in the 5th generation pamam dendrimer molecular water solution of carboxyl and mechanical agitation after 30 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 1.5, and the addition of molysite mixed liquor is with Fe 3+compare for 80:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 5h, then bath temperature being adjusted to 90 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3the sodium hydrate aqueous solution of mol/L is 11 to pH, and Keep agitation 40 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -3the end group of mol/L be amido the 6th generation pamam dendrimer molecular water solution, its addition is 30 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 80 DEG C, and mechanical agitation speed is adjusted to 1200 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -2mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -2the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 2:1 be standard.After dropwising, Keep agitation 5 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 140 DEG C, after insulation 12h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 3 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 4 minutes of 100W, simultaneously with the rotating speed mechanical agitation 8 minutes of 1200 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
embodiment 4:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4the end group of mol/L is pass into nitrogen in the 5th generation pamam dendrimer molecular water solution of ester group and mechanical agitation after 30 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 1.5, and the addition of molysite mixed liquor is with Fe 3+compare for 40:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 4h, then bath temperature being adjusted to 90 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3the sodium hydrate aqueous solution of mol/L is 10 to pH, and Keep agitation 30 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -3the end group of mol/L be amido the 6th generation pamam dendrimer molecular water solution, its addition is 30 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 60 DEG C, and mechanical agitation speed is adjusted to 800 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -3mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 1:1 be standard.After dropwising, Keep agitation 6 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 120 DEG C, after insulation 12h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 2 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 5 minutes of 50W, simultaneously with the rotating speed mechanical agitation 10 minutes of 800 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
embodiment 5:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4the end group of mol/L is pass into nitrogen in the 4th generation pamam dendrimer molecular water solution of ester group and mechanical agitation after 30 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 1.5, and the addition of molysite mixed liquor is with Fe 3+compare for 20:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 4h, then bath temperature being adjusted to 70 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3the sodium hydrate aqueous solution of mol/L is 10 to pH, and Keep agitation 60 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -3the end group of mol/L be amido the 5th generation pamam dendrimer molecular water solution, its addition is 10 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 40 DEG C, and mechanical agitation speed is adjusted to 800 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -3mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 1:1 be standard.After dropwising, Keep agitation 6 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 120 DEG C, after insulation 8h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 2 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 2 minutes of 50W, simultaneously with the rotating speed mechanical agitation 10 minutes of 2000 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
embodiment 6:
Step (1): superparamagnetism Fe 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4the end group of mol/L is pass into nitrogen in the 4th generation pamam dendrimer molecular water solution of carboxyl and mechanical agitation after 30 minutes, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 1 mol/L, and the concentration ratio of ferric trichloride and ferrous chloride is 2, and the addition of molysite mixed liquor is with Fe 3+compare for 10:1 is standard with the amount of substance of pamam dendrimer molecule, pass into nitrogen under room temperature and stir 4h, then bath temperature being adjusted to 80 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3the sodium hydrate aqueous solution of mol/L is 10 to pH, and Keep agitation 60 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution.
Step (2): the fully coated Fe of pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: under room temperature, to the superparamagnetism Fe that step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -3the end group of mol/L be amido the 5th generation pamam dendrimer molecular water solution, its addition is 10 times of the amount of substance of added dendrimer in step (1), and drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (3): superparamagnetism Fe 3o 4-PAMAM-TiO 2prepared by nuclear shell structured nano-particle: by fully coated for surface obtained for step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 50 DEG C, and mechanical agitation speed is adjusted to 1000 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -3mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -3the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10, TiCl 4addition with TiCl 4with Fe 3+amount of substance than for 1:1 be standard.After dropwising, Keep agitation 6 hours at the reaction temperatures.Then, reactant liquor is moved in hydrothermal reaction kettle, in resistance furnace, be heated to 150 DEG C, after insulation 8h, take out hydrothermal reaction kettle cool to room temperature, namely obtain superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle.
Step (4): superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post processing: step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, gained sediment is distributed in the absolute ethyl alcohol of 2 times of volumes, power is adopted to be the supersonic wave cleaning machine sonic oscillation 2 minutes of 50W, simultaneously with the rotating speed mechanical agitation 10 minutes of 1000 revs/min, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.

Claims (5)

1. a superparamagnetism Fe 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: comprise the following steps: (1) superparamagnetism Fe 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: be 1 × 10 to concentration -5~ 1 × 10 -4nitrogen is passed into and mechanical agitation after 30 ~ 60 minutes in the pamam dendrimer molecular water solution of mol/L, add molysite mixed liquor, pass into nitrogen under room temperature and stir 4 ~ 8h, make iron ion and the abundant coordination of dendrimer group, then bath temperature is adjusted to 70 ~ 90 DEG C, mixing speed rises to more than 800 revs/min, and dripping concentration is 1 × 10 -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L is 10 ~ 12 to pH, and Keep agitation 30min ~ 60 min, namely obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution; (2) Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: under room temperature, to the superparamagnetism Fe that described step (1) is obtained 3o 4dripping concentration in-PAMAM nanoparticle colloid solution is 1 × 10 -4~ 1 × 10 -3the pamam dendrimer molecular water solution of mol/L, drip concentration is 1 × 10 simultaneously -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L, keep the pH of system to be 10 ~ 11, then pass into nitrogen and stir more than 2 hours, obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution; (3) superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle-making step is: by fully coated for surface obtained for described step (2) Fe of pamam dendrimer molecule 3o 4-PAMAM nanoparticle colloid solution is warming up to 40 ~ 80 DEG C, and mechanical agitation speed is adjusted to 800 ~ 2000 revs/min, stops passing into nitrogen, and slowly dripping concentration is 1 × 10 -3~ 1 × 10 -1mol/L TiCl 4ethanol solution, drip concentration is 1 × 10 simultaneously -3~ 1 × 10 -1the sodium hydrate aqueous solution of mol/L, the pH keeping system is 10 ~ 11, TiCl 4after dropwising, Keep agitation 4 ~ 6 hours at the reaction temperatures, then, moves to reactant liquor in hydrothermal reaction kettle, is heated to 120 ~ 180 DEG C in resistance furnace, after insulation 8 ~ 12h, takes out hydrothermal reaction kettle cool to room temperature, namely obtains superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle; (4) superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-granular product post-processing step is: described step (3) products therefrom is carried out Magnetic Isolation, by the second distillation water washing more than 3 times of gained sediment, then under sonic oscillation and mechanical agitation, gained sediment is distributed in absolute ethyl alcohol, after being filled with high pure nitrogen 30 min, sealing is preserved, and namely obtains finely disseminated superparamagnetism Fe 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst.
2. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, it is characterized in that: the molysite mixed liquor in described step (1) is the mixed solution of ferric trichloride, ferrous chloride or ferrous sulfate, wherein ferric trichloride concentration is 0.01 ~ 1 mol/L, the mol ratio of ferric trichloride and ferrous chloride or ferrous sulfate is 1.5 ~ 2, and the addition of molysite mixed liquor is with Fe 3+compare for 200:1 ~ 10:1 is standard with the amount of substance of pamam dendrimer molecule, the end group of pamam dendrimer molecule is hydroxyl, ester group or carboxyl, and algebraically was 4 ~ 6 generations.
3. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, it is characterized in that: the end group of the pamam dendrimer molecule in described step (2) is ester group or amido, algebraically was 5 ~ 7 generations, and its addition is 10 ~ 50 times of the amount of substance of added dendrimer in described step (1).
4. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: the TiCl in described step (3) 4addition is 1 ~ 5 times of ferric amount of substance in the middle molysite mixed liquor of described step (1).
5. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-TiO 2the preparation method of nuclear shell structured nano-particle photochemical catalyst, is characterized in that: in described step (4), mechanical agitation rotating speed is 800 ~ 2000 revs/min, stirs 5 ~ 10 minutes; Sonic oscillation adopts power to be the supersonic wave cleaning machine of 50 ~ 300W, and the time is 1 ~ 5 minute, and absolute ethyl alcohol and sedimentary volume ratio are 2:1 ~ 5:1.
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