CN105536877A - Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure - Google Patents

Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure Download PDF

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CN105536877A
CN105536877A CN201510948963.9A CN201510948963A CN105536877A CN 105536877 A CN105536877 A CN 105536877A CN 201510948963 A CN201510948963 A CN 201510948963A CN 105536877 A CN105536877 A CN 105536877A
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solution
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tio
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丛日敏
于怀清
张红松
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Shandong University of Technology
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Abstract

The present invention relates to a method for preparing superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with a core-shell composite structure by using a polyamide-amine (PAMAM) dendrimer as a template and a spacer layer in a low temperature aqueous solution. The method is characterized by comprising the following steps: first preparing a superparamagnetic Fe3O4-PAMAM nanoparticle colloidal solution by using a PAMAM dendrimer as a template, then adding a right amount of PAMAM dendrimer to wrap the Fe3O4-PAMAM nanoparticles, under alkaline condition adding a solution of soluble zinc salt and a titanium tetrachloride solution at the same time; conducting atmospheric reaction and a hydrothermal reaction to obtain the superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure and with a complete ZnO/TiO2 composite shell layer. The particles can be dispersed in the form of individual particle in solution, and has high photocatalytic activity and magnetic recovery rate.

Description

Superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles
Technical field
The present invention relates to a kind of superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation method of core-Composite Shell structure nano particles, belongs to technical field of material.
Background technology
The development of modern industry improves the living standard of the mankind, but trade waste and residual chemical substance cause serious threat to environment and ecological safety, and human residential environment is constantly worsened.Nowadays, Green Development rises to national strategy, and wherein, water treatment, air improvement and soil restoring technology become the emphasis of environmental protection industry development.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.ZnO, TiO 2deng semiconductor nanoparticle, there is excellent photocatalytic activity, cheap and easy to get and nontoxic, band gap is about 3.2eV, under UV-irradiation, show good photocatalytic activity, effectively can decompose the organic pollution in water and air, become the study hotspot of photocatalysis field.
After catalytic reaction terminates, these semiconductor nanoparticles are difficult to be separated and reclaim, and the efficiency of the semiconductor light-catalyst of one pack system is lower, thus limit its extensive use.Through extensively research, it is found that, semiconductor nanoparticle is made loaded photocatalyst, greatly can improve it and be separated and recovery utilization rate, and, by ZnO and TiO 2make composite particles, the photocatalysis efficiency of semiconductor nanoparticle can be made to be promoted.Scientific research personnel is by semiconductor deposition on paramagnetic nanoparticle surface, and obtained nucleocapsid structure composite particles, under the effect of outside magnetic field, easily realizes separation and the recovery of catalyst.But, by TiO 2be deposited directly to Fe 3o 4on magnetic core, TiO 2catalytic activity can decline.At magnetic core and TiO 2between grow one deck SiO 2, Al 2o 3, the inorganic or polymeric isolation layer of PPY or PS, magnetic can be reduced and check TiO 2the impact of photocatalytic activity.The heat treatment process of preparation inorganic barrier can make magnetic core be oxidized, and 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; Prepare linear polymeric separation layer without the need to high heat treatment, but high molecular bridging effect can cause magnetic core to be assembled in coated process, particle size increases, and particulate surface hydrophobic increases, 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 of high algebraically is that diameter is from several nanometer to tens nanometers, monodispersed global molecular, surface has intensive hydrophilic functional groups, I with it for Template preparation has gone out size CdS, CdS-ZnS, Fe at below 10nm 3o 4nano particle, has excellent dispersiveness in water, can exist by colloidal state; Be also that separation layer has prepared Fe with PAMAM 3o 4-PAMAM-TiO 2nuclear shell structured nano-particle photochemical catalyst, has good dispersiveness, magnetic recyclability and higher photocatalysis efficiency.The present invention adopt can in water stable dispersion, the Fe with superparamagnetism 3o 4-PAMAM nano particle is magnetic core, utilizes the dendrimer of different end group fully coated to magnetic core surface, under alkali condition, synchronously on magnetic core, deposits ZnO, TiO 2nano particle, after synthesis under normal pressure and hydro-thermal reaction, forms ZnO/TiO on magnetic core surface 2composite shell, thus obtained superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles, this nano particle can disperse with single particle form, has photocatalytic activity high, the feature that the magnetic 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-ZnO/TiO 2the method of core-Composite Shell structure nano particles, makes gained Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles has highlight catalytic active and high-recovery.Its technology contents is:
Described superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, is characterized in that: comprise the following steps:
(1) Fe of the abundant coated pamam dendrimer molecule in the surface described in 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: be 1 × 10 to concentration -5~ 1 × 10 -4mol/L end group be ester group, hydroxyl or carboxyl, algebraically is pass into nitrogen in the pamam dendrimer molecular water solution in 4 ~ 6 generations and stir more than 30min, add molysite mixed liquor, nitrogen is passed into and more than mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 70 ~ 90 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.01 ~ 0.1mol/L is 10 ~ 12 to pH, more than Keep agitation 1h, obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -4~ 1 × 10 -3the end group of mol/L be amido or ester group, algebraically is the pamam dendrimer molecular water solution in 5 ~ 7 generations, slowly drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, and reaction solution stirs more than 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
(2) superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles
Described superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation process of core-Composite Shell structure nano particles is: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature is adjusted to 80 ~ 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the soluble Zn saline solution of 0.01 ~ 0.1mol/L, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.01 ~ 0.1mol/L simultaneously, after titanium tetrachloride and zinc salt dropwise, Keep agitation 2 ~ 4 hours at the reaction temperatures, then reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 130 ~ 190 DEG C, after insulation 8 ~ 12h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
Described superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, 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 ~ 0.1mol/L, ferric trichloride is 1.5 ~ 2 with the amount of substance ratio of ferrous chloride or ferrous sulfate, and the amount of substance that the addition of molysite mixed liquor is ester group with ferric iron with the end group initially added, hydroxyl or carboxyl, algebraically are the pamam dendrimer molecule in 4 ~ 6 generations is than for 120:1 ~ 10:1 is for standard; The end group of rear dropping be amido or ester group, 10 ~ 40 times of algebraically to be the pamam dendrimer molecule addition in 5 ~ 7 generations the be amount of the pamam dendrimer molecular substance that initial end group is ester group, hydroxyl or carboxyl, algebraically was 4 ~ 6 generations.
Described superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, it is characterized in that: the soluble zinc salt in described step (2) is zinc acetate, zinc propionate, zinc nitrate, zinc chloride or zinc sulfate, the addition of titanium tetrachloride is 1 ~ 5 times of the amount of substance of ferric trichloride in described step (1), and the addition of zinc salt is 0.1 ~ 2 times of the amount of substance of titanium tetrachloride.
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-ZnO/TiO 2core-Composite Shell structure nano particles (see accompanying drawing 1), dendrimer is between Fe 3o 4magnetic core and ZnO/TiO 2between Composite Shell, form the dendrimer mechanical isolation layer that thickness is about 3 ~ 5nm, the direct contact surface decreasing core-shell structure copolymer amasss, and has intercepted Fe 3+to ZnO/TiO 2the direct penetration route of Composite Shell; The highest preparation temperature, not higher than 190 DEG C, avoids high-temperature roasting, slow down Fe 3+to ZnO/TiO 2the diffusion of Composite Shell and the oxidation of magnetic core, remain a large amount of activity hydroxies of particle surface, and the specific area avoided caused by the gathering of nano particle high temperature declines.In addition, these have the functional group of powerful coordination function to have a large amount of tertiary amine groups, amide groups and ester group in dendrimer structure, the micro Fe making this nano particle photochemical catalyst in use to produce because magnetic core generation light dissolves 2+and Fe 3+by dendrimer complexing, be difficult to enter solution, thus reduce Fe 2+be oxidized to Fe 3+reaction on the impact of catalytic activity.Based on above principle, stuctures and properties feature, the superparamagnetism Fe that the present invention obtains 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles has high catalytic activity.
2, the present invention adopts low temperature liquid phase preparation method, simple for process, obtained superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles size is at about 30 ~ 110nm, and good dispersion in the solution, product has superparamagnetism, and saturation magnetization reaches 60 ~ 110emu/g, and single uses the rate of recovery to reach 97%, uses for 3 times the rate of recovery to reach 90%.
3, the Fe that obtains of the present invention 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure magnetic nano particle can individual particle form be distributed in solution, 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 95%.
4, the superparamagnetism Fe that obtains of the present invention 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles stable performance, fill nitrogen lucifuge sealing preservation after 6 months in room temperature, the magnetic rate of recovery reaches 90%, and the percent of decolourization of the above-mentioned dyestuff of photocatalytic degradation can reach more than 90%, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the Superparamagnetic Fe_3O_4-PAMAM-ZnO/TiO that the present invention obtains 2high resolution transmission electron microscopy (HRTEM) photo of core-Composite Shell structure nano particles, particle diameter is about 90nm, and granular center color comparatively dark-part is Fe 3o 4core, outer color comparatively shallow portion is ZnO/TiO 2composite Shell.
Detailed description of the invention
embodiment 1:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -5mol/L end group is pass into nitrogen in 6 generation pamam dendrimer molecular water solution of ester group and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.1mol/L, ferric trichloride is 2 with the ratio of the amount of substance of ferrous chloride, the addition of molysite mixed liquor compares for 120:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 90 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.1mol/L is 12 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -4the end group of mol/L be amido 7 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be ester group 6 generation dendrimer 10 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature remains on 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the aqueous zinc acetate solution of 0.1mol/L, the addition of titanium tetrachloride is 5 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc acetate is 0.1 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.1mol/L simultaneously, after titanium tetrachloride and zinc acetate dropwise, Keep agitation 4h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 190 DEG C, after insulation 8h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
embodiment 2:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -5mol/L end group is pass into nitrogen in 6 generation pamam dendrimer molecular water solution of hydroxyl and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.1mol/L, ferric trichloride is 2 with the ratio of the amount of substance of ferrous sulfate, the addition of molysite mixed liquor compares for 100:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 90 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.1mol/L is 11 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -4the end group of mol/L be ester group 7 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be hydroxyl 6 generation dendrimer 10 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature remains on 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the zinc propionate aqueous solution of 0.1mol/L, the addition of titanium tetrachloride is 4 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc propionate is 0.5 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.1mol/L simultaneously, after titanium tetrachloride and zinc propionate dropwise, Keep agitation 4h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 180 DEG C, after insulation 10h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
embodiment 3:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -5mol/L end group is pass into nitrogen in 5 generation pamam dendrimer molecular water solution of carboxyl and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.1mol/L, ferric trichloride is 2 with the ratio of the amount of substance of ferrous sulfate, the addition of molysite mixed liquor compares for 60:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 80 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.1mol/L is 10 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -4the end group of mol/L be amido 6 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be carboxyl 5 generation dendrimer 20 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature remains on 80 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the zinc nitrate aqueous solution of 0.1mol/L, the addition of titanium tetrachloride is 3 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc nitrate is 1 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.1mol/L simultaneously, after titanium tetrachloride and zinc nitrate dropwise, Keep agitation 3h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 170 DEG C, after insulation 10h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
embodiment 4:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4mol/L end group is pass into nitrogen in 4 generation pamam dendrimer molecular water solution of ester group and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.01mol/L, ferric trichloride is 1.5 with the ratio of the amount of substance of ferrous sulfate, the addition of molysite mixed liquor compares for 20:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 70 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.01mol/L is 11 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -3the end group of mol/L be amido 5 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be ester group 4 generation dendrimer 40 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature rises to 80 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the zinc sulfate solution of 0.01mol/L, the addition of titanium tetrachloride is 2 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc sulfate is 2 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.01mol/L simultaneously, after titanium tetrachloride and zinc sulfate dropwise, Keep agitation 3h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 150 DEG C, after insulation 12h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
embodiment 5:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4mol/L end group is pass into nitrogen in 4 generation pamam dendrimer molecular water solution of hydroxyl and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.01mol/L, ferric trichloride is 1.5 with the ratio of the amount of substance of ferrous sulfate, the addition of molysite mixed liquor compares for 20:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 80 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.01mol/L is 10 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -3the end group of mol/L be ester group 5 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be hydroxyl 4 generation dendrimer 40 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature rises to 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the solder(ing)acid of 0.01mol/L, the addition of titanium tetrachloride is 1 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc chloride is 0.5 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.01mol/L simultaneously, after titanium tetrachloride and zinc chloride dropwise, Keep agitation 2h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 130 DEG C, after insulation 12h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
embodiment 6:
Step (1): the Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution: be 1 × 10 to concentration -4mol/L end group is pass into nitrogen in 4 generation pamam dendrimer molecular water solution of carboxyl and after stirring 30min, add molysite mixed liquor, in molysite mixed liquor, ferric trichloride concentration is 0.01mol/L, ferric trichloride is 1.5 with the ratio of the amount of substance of ferrous sulfate, the addition of molysite mixed liquor compares for 10:1 is for standard with the amount of substance of ferric iron with pamam dendrimer molecule, nitrogen is passed into and after mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 90 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.01mol/L is 12 to pH, after Keep agitation 1h, obtain superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -3the end group of mol/L be amido 5 generation pamam dendrimer molecular water solution, its addition to be the end group initially added be carboxyl 4 generation dendrimer 40 times of amount of substance, drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, after reaction solution stirs 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution.
Step (2): superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature remains on 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the aqueous zinc acetate solution of 0.01mol/L, the addition of titanium tetrachloride is 1 times of the amount of substance of ferric trichloride in described step (1), the addition of zinc acetate is 0.5 times of the amount of substance of titanium tetrachloride, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.01mol/L simultaneously, after titanium tetrachloride and zinc acetate dropwise, Keep agitation 2h at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 190 DEG C, after insulation 8h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.

Claims (3)

1. superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, is characterized in that: comprise the following steps:
(1) Fe of the abundant coated pamam dendrimer molecule in surface 3o 4the preparation of-PAMAM nanoparticle colloid solution
The Fe of the abundant coated pamam dendrimer molecule in described surface 3o 4the preparation process of-PAMAM nanoparticle colloid solution is: be 1 × 10 to concentration -5~ 1 × 10 -4mol/L end group be ester group, hydroxyl or carboxyl, algebraically is pass into nitrogen in the pamam dendrimer molecular water solution in 4 ~ 6 generations and stir more than 30min, add molysite mixed liquor, nitrogen is passed into and more than mechanical agitation 4h under room temperature, make iron ion and the abundant coordination of dendrimer, then bath temperature is adjusted to 70 ~ 90 DEG C, mixing speed rises to more than 800r/min, dropping concentration is the sodium hydrate aqueous solution of 0.01 ~ 0.1mol/L is 10 ~ 12 to pH, more than Keep agitation 1h, obtains superparamagnetism Fe 3o 4-PAMAM nanoparticle colloid solution, then dripping concentration is 1 × 10 -4~ 1 × 10 -3the end group of mol/L be amido or ester group, algebraically is the pamam dendrimer molecular water solution in 5 ~ 7 generations, slowly drip concentration is 1 × 10 simultaneously -3the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of mol/L, and reaction solution stirs more than 2h under nitrogen protection, has obtained the fully coated Fe of pamam dendrimer molecule in surface 3o 4-PAMAM nanoparticle colloid solution;
(2) superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles
Described superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2the preparation process of core-Composite Shell structure nano particles is: the fully coated Fe of pamam dendrimer molecule to the surface that above-mentioned steps (1) is obtained 3o 4nitrogen is passed in-PAMAM nanoparticle colloid solution, mixing speed is more than 800r/min, temperature is adjusted to 80 ~ 90 DEG C, synchronous slowly dropping concentration is titanium tetrachloride ethanol solution and the soluble Zn saline solution of 0.01 ~ 0.1mol/L, drip concentration is that the pH of reaction solution is remained on 10 ~ 11 scopes by the sodium hydrate aqueous solution of 0.01 ~ 0.1mol/L simultaneously, after titanium tetrachloride and zinc salt dropwise, Keep agitation 2 ~ 4 hours at the reaction temperatures, reactant liquor is moved in hydrothermal reaction kettle, after passing into high pure nitrogen 30min, hydrothermal reaction kettle is sealed, be placed in resistance furnace and be heated to 130 ~ 190 DEG C, after insulation 8 ~ 12h, take out hydrothermal reaction kettle cool to room temperature, precipitated product is separated in magnetic field, gained magnetic-particle and superparamagnetism Fe 3o 4-PAMAM-ZnO/TiO 2core-Composite Shell structure nano particles.
2. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, 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 ~ 0.1mol/L, ferric trichloride is 1.5 ~ 2 with the amount of substance ratio of ferrous chloride or ferrous sulfate, and the amount of substance that the addition of molysite mixed liquor is ester group with ferric iron with the end group initially added, hydroxyl or carboxyl, algebraically are the pamam dendrimer molecule in 4 ~ 6 generations is than for 120:1 ~ 10:1 is for standard; The pamam dendrimer molecule addition that the end group of rear dropping is amido or ester group, algebraically was 5 ~ 7 generations is 10 ~ 40 times of the amount of the pamam dendrimer molecular substance initially added.
3. superparamagnetism Fe as claimed in claim 1 3o 4-PAMAM-ZnO/TiO 2the preparation of core-Composite Shell structure nano particles, it is characterized in that: the soluble zinc salt in described step (2) is zinc acetate, zinc propionate, zinc nitrate, zinc chloride or zinc sulfate, the addition of titanium tetrachloride is 1 ~ 5 times of the amount of substance of ferric trichloride in described step (1), and the addition of zinc salt is 0.1 ~ 2 times of the amount of substance of titanium tetrachloride.
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