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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- pamam
- solution
- zno
- core
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 32
- 239000011258 core-shell material Substances 0.000 title abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 8
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 95
- 239000000243 solution Substances 0.000 claims abstract description 91
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 25
- 230000005291 magnetic effect Effects 0.000 claims abstract description 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 41
- 239000000084 colloidal system Substances 0.000 claims description 33
- 238000013019 agitation Methods 0.000 claims description 24
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000412 dendrimer Substances 0.000 claims description 19
- 229920000736 dendritic polymer Polymers 0.000 claims description 19
- 125000004185 ester group Chemical group 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- -1 iron ion Chemical class 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 239000006249 magnetic particle Substances 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- UKDYPJBSLOCNRU-UHFFFAOYSA-J ethanol tetrachlorotitanium Chemical compound CCO.Cl[Ti](Cl)(Cl)Cl UKDYPJBSLOCNRU-UHFFFAOYSA-J 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 230000001360 synchronised effect Effects 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 125000006850 spacer group Chemical group 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4084—Regeneration or reactivation of catalysts containing metals involving electromagnetic wave energy, e.g. UV or visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compounds Of Iron (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510948963.9A CN105536877A (en) | 2015-12-18 | 2015-12-18 | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510948963.9A CN105536877A (en) | 2015-12-18 | 2015-12-18 | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105536877A true CN105536877A (en) | 2016-05-04 |
Family
ID=55816713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510948963.9A Pending CN105536877A (en) | 2015-12-18 | 2015-12-18 | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105536877A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970881A (en) * | 2017-10-31 | 2018-05-01 | 广东石油化工学院 | A kind for the treatment of of Organic Wastewater functionalization filler and preparation method thereof |
| CN108281244A (en) * | 2017-12-07 | 2018-07-13 | 广东南芯医疗科技有限公司 | A kind of ferroferric oxide magnetic nano-material and its preparation method and application of dendrimer modification |
| CN108485313A (en) * | 2018-03-09 | 2018-09-04 | 浙江华源颜料股份有限公司 | A kind of cladded type heatproof iron oxide yellow |
| CN110228815A (en) * | 2019-05-10 | 2019-09-13 | 山西大学 | A method of phenolic waste water containing zinc salt produces compound zinc carbonate sodium salt |
| CN110665486A (en) * | 2019-10-17 | 2020-01-10 | 福州大学 | Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof |
| CN112557384A (en) * | 2020-12-10 | 2021-03-26 | 贵州大学 | Hydrogen sulfide detection method based on colorimetric analysis and application |
| CN114590834A (en) * | 2022-03-30 | 2022-06-07 | 广州天赐高新材料股份有限公司 | Nano titanium dioxide-zinc oxide hybrid material and synthetic method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344170A (en) * | 2011-08-28 | 2012-02-08 | 山东理工大学 | Method for preparing water-based Fe3O4 magnetic fluid by using polyamide-amine dendrimer as template |
| CN102658112A (en) * | 2012-04-14 | 2012-09-12 | 黑龙江省金昇新能源与环境材料研究院 | Preparation method of ZnO-TiO2 composite photocatalyst |
| US20140183141A1 (en) * | 2012-12-31 | 2014-07-03 | Ms. Deepika Saraswathy Kurup | Photocatalytic Composition for Water Purification |
| CN104923309A (en) * | 2015-04-14 | 2015-09-23 | 山东理工大学 | Preparation method for superparamagnetic nanoparticle photocatalyst with Fe3O4-PAMAM-TiO2 core-shell structure |
-
2015
- 2015-12-18 CN CN201510948963.9A patent/CN105536877A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344170A (en) * | 2011-08-28 | 2012-02-08 | 山东理工大学 | Method for preparing water-based Fe3O4 magnetic fluid by using polyamide-amine dendrimer as template |
| CN102658112A (en) * | 2012-04-14 | 2012-09-12 | 黑龙江省金昇新能源与环境材料研究院 | Preparation method of ZnO-TiO2 composite photocatalyst |
| US20140183141A1 (en) * | 2012-12-31 | 2014-07-03 | Ms. Deepika Saraswathy Kurup | Photocatalytic Composition for Water Purification |
| CN104923309A (en) * | 2015-04-14 | 2015-09-23 | 山东理工大学 | Preparation method for superparamagnetic nanoparticle photocatalyst with Fe3O4-PAMAM-TiO2 core-shell structure |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970881A (en) * | 2017-10-31 | 2018-05-01 | 广东石油化工学院 | A kind for the treatment of of Organic Wastewater functionalization filler and preparation method thereof |
| CN108281244A (en) * | 2017-12-07 | 2018-07-13 | 广东南芯医疗科技有限公司 | A kind of ferroferric oxide magnetic nano-material and its preparation method and application of dendrimer modification |
| CN108485313A (en) * | 2018-03-09 | 2018-09-04 | 浙江华源颜料股份有限公司 | A kind of cladded type heatproof iron oxide yellow |
| CN110228815A (en) * | 2019-05-10 | 2019-09-13 | 山西大学 | A method of phenolic waste water containing zinc salt produces compound zinc carbonate sodium salt |
| CN110228815B (en) * | 2019-05-10 | 2021-05-14 | 山西大学 | Method for producing compound zinc carbonate sodium salt from phenol wastewater containing zinc salt |
| CN110665486A (en) * | 2019-10-17 | 2020-01-10 | 福州大学 | Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof |
| CN110665486B (en) * | 2019-10-17 | 2021-05-18 | 福州大学 | Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof |
| CN112557384A (en) * | 2020-12-10 | 2021-03-26 | 贵州大学 | Hydrogen sulfide detection method based on colorimetric analysis and application |
| CN112557384B (en) * | 2020-12-10 | 2024-01-26 | 贵州大学 | Colorimetric analysis-based hydrogen sulfide detection method and application |
| CN114590834A (en) * | 2022-03-30 | 2022-06-07 | 广州天赐高新材料股份有限公司 | Nano titanium dioxide-zinc oxide hybrid material and synthetic method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105536877A (en) | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure | |
| Yu et al. | Modulation of Bi2MoO6‐based materials for photocatalytic water splitting and environmental application: a critical review | |
| Liang et al. | Surfactant-assisted synthesis of photocatalysts: Mechanism, synthesis, recent advances and environmental application | |
| Sun et al. | Mesocrystals for photocatalysis: a comprehensive review on synthesis engineering and functional modifications | |
| Kadi et al. | Decoration of g-C3N4 nanosheets by mesoporous CoFe2O4 nanoparticles for promoting visible-light photocatalytic Hg (II) reduction | |
| Ma et al. | Photocatalytic degradation of MB dye by the magnetically separable 3D flower-like Fe3O4/SiO2/MnO2/BiOBr-Bi photocatalyst | |
| CN104923309B (en) | A kind of superparamagnetism Fe3O4-PAMAM-TiO2The preparation method of nuclear shell structured nano particle photochemical catalyst | |
| Zhao et al. | From solid-state metal alkoxides to nanostructured oxides: a precursor-directed synthetic route to functional inorganic nanomaterials | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN101599335B (en) | Oxidation resistant dimethyl silicon oil based magnetic fluid and preparation method thereof | |
| CN104078229B (en) | A kind of method of coated with silica magnetic ferric oxide nano particles | |
| Xu et al. | BiOCl-based photocatalysts: Synthesis methods, structure, property, application, and perspective | |
| Rasheed et al. | Highly efficient photocatalytic degradation of the Tetracycline hydrochloride on the α-Fe2O3@ CN composite under the visible light | |
| Ahmad et al. | Novel prism shaped C 3 N 4-doped Fe@ Co 3 O 4 nanocomposites and their dye degradation and bactericidal potential with molecular docking study | |
| CN105032418B (en) | The preparation method of diverse microcosmic appearance Ag/ZnO carbon ball ternary shell dyskaryosis knot photochemical catalysts | |
| CN105271405A (en) | Material based on bismuth oxycarbonate or bismuth oxide nano tube and preparation method thereof | |
| Mao et al. | Effective loading of well-doped ZnO/Ag3PO4 nanohybrids on magnetic core via one step for promoting its photocatalytic antibacterial activity | |
| Xiong et al. | Yolk-Shell catalyst: From past to future | |
| CN103447549A (en) | Preparation method of cobalt nanosphere | |
| CN101786601B (en) | Preparation method of compound nano particle with Fe3O4/CoO core shell structure | |
| CN110227515A (en) | Bi2MoO6/BiPO4P-n heterojunction photochemical catalyst, preparation method and applications | |
| CN105498851A (en) | Preparation method for Fe3O4-PAMAM-ZnO-TiO2 core-shell-shell-structured nanoparticles | |
| CN111517370A (en) | Preparation method of magnetic ferroferric oxide nanoparticles | |
| CN103111300B (en) | Method for preparing TiO2/ni-zn ferrite/carbon (C) magnetic photocatalyst | |
| CN113522362A (en) | Metal organic framework nano CuO composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160504 |
|
| WD01 | Invention patent application deemed withdrawn after publication |