CN110075846A - A kind of titanium MODIFIED Fe3O4Magnetic nanoparticle and its preparation method and application - Google Patents
A kind of titanium MODIFIED Fe3O4Magnetic nanoparticle and its preparation method and application Download PDFInfo
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- CN110075846A CN110075846A CN201910380119.9A CN201910380119A CN110075846A CN 110075846 A CN110075846 A CN 110075846A CN 201910380119 A CN201910380119 A CN 201910380119A CN 110075846 A CN110075846 A CN 110075846A
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- 239000010936 titanium Substances 0.000 title claims abstract description 62
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 62
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 44
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 230000005496 eutectics Effects 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 11
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229960003178 choline chloride Drugs 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VYWQTJWGWLKBQA-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;chloride Chemical compound Cl.NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-N 0.000 claims description 6
- 229960001231 choline Drugs 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 14
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 238000002955 isolation Methods 0.000 abstract description 6
- 238000004042 decolorization Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- -1 titanium MODIFIED Fe3O4 Chemical class 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 229910052603 melanterite Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003248 quinolines Chemical group 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of titanium MODIFIED Fes3O4Magnetic nanoparticle and its preparation method and application.The preparation method specifically: in choline chloride and urea eutectic solvent, using ferrous salt as source of iron, tetrabutyl titanate is titanium source, and air is oxidant, using oxidation-precipitation method one-step synthesis titanium MODIFIED Fe3O4Magnetic nanoparticle.The preparation method resulting materials provided according to the present invention show excellent catalytic degradation ability (such as under room temperature and condition of neutral pH to organic wastewater, to the percent of decolourization of 0.01mmol/L methylene blue solution up to 93.8% in 2h, to the removal efficiency of 20mg/L ciprofloxacin solution up to 96.5%), it is easy to Magnetic Isolation recycling, repeat performance is stablized, and is that one kind is at low cost, operates the novel magnetic environment-friendly materials that quick and convenient, effect is obvious, has a extensive future.
Description
Technical field
The invention belongs to the synthesis of magnetic functional material and sewage treatment application fields, and in particular to a kind of titanium MODIFIED Fe3O4
Magnetic nanoparticle and its preparation method and application.
Background technique
Organic wastewater seriously threatens human health and the ecosystem.Organic pollutant category is various, and (such as organic dyestuff resists
Raw element etc.), it is difficult to adopt conventional water treatment technology (such as filtering, absorption, coagulation, biodegrade) and completely removes, and with
Fenton oxidation method is that the high-level oxidation technology of representative has many advantages, such as that applicability is wide, degradation is thorough, is currently processed organic waste
The relatively inexpensive effective method of water.But homogeneous Fenton oxidation technical requirements pH~3, and iron cement secondary pollution is generated after reacting,
Its popularization and application is limited, therefore with Fe3O4Magnetic nanoparticle is that the multiphase Fenton oxidation technology of representative becomes current research
Hot spot.But Fe3O4Magnetic nanoparticle is catalyzed H2O2The efficiency of decomposition is not high enough, and it is big that there are catalyst amounts, H2O2Waste is serious,
The deficiencies of reaction temperature is high, the time is long.
Fe can be improved using transition metal (such as Ti, Co, Mn, Cr) doping3O4Catalyzing and decomposing H at neutral ph2O2's
Ability.The magnetic iron ore of the doping such as Co, Mn, Cr is distributed seldom in nature, and titanomagnetite is widely distributed, reinforces closing to artificial
At titanium doped Fe3O4Research be beneficial to practical application of the titanomagnetite in environmental improvement, reduce operating cost.Titanium is modified
It will increase Fe3O4The specific surface area and surface hydroxyl number of catalyst, improve its thermal stability, so as to effectively improve it to pollution
Absorption, catalytic degradation and the recycling performance of object.
Artificial synthesized titanium doped Fe3O4Magnetic nanoparticle all takes water as a solvent at present, and synthesis in water is asked there are following
Topic: titanium source and source of iron are both needed to be dissolved in HCl solution (pH < 1) before the reaction, then by the way that a large amount of alkali are added, improve system pH
Value both promotes to react, entire reaction process need in glove box N2Protection is lower to be carried out, therefore complicated for operation, to equipment requirement
Height, wastage of material is serious, and it is more to generate waste liquid.
Summary of the invention
In order to overcome the disadvantages of the prior art mentioned above and insufficient, the object of the present invention is to provide a kind of titanium MODIFIED Fes3O4Magnetic
Property nano particle and its preparation method and application.The preparation method uses eutectic solvent as reaction medium, preparation method
It is environmentally protective, it is not high to equipment requirement, and raw material can be saved.The titanium MODIFIED Fe being prepared by this method3O4Magnetic nanoparticle
Organic wastewater suitable for catalytic degradation containing pollutants such as dyestuffs and antibiotic, with reaction rate is fast, low energy consumption, without secondary dirt
Dye, can Magnetic Isolation and reuse the advantages that.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, which is characterized in that include the following steps:
Using eutectic solvent as reaction medium, source of iron, alkali source and titanium source is added, at a certain temperature reaction a period of time,
After reaction product is cooled and separated, washs and dries, the titanium MODIFIED Fe is obtained3O4Magnetic nanoparticle.
According to the above scheme, it is preferable that the eutectic solvent is choline chloride-urea eutectic solvent, by choline chloride
1:2 is prepared in molar ratio with urea.
According to the above scheme, it is preferable that the source of iron is ferrous sulfate or frerrous chloride；The titanium source is tetrabutyl titanate；
The alkali source is one or more of KOH, NaOH, NaOAc.
According to the above scheme, it is preferable that the molar ratio of the source of iron and the titanium source is (300~0.5): 1.It is highly preferred that
The molar ratio of the source of iron and the titanium source is (20~1): 1.
According to the above scheme, it is preferable that the molar ratio of the alkali source and the source of iron is (2.5~3.5): 1.
According to the above scheme, it is preferable that the alkali source is added in two portions, specifically: first be added alkali source total addition level 1/3~
2/3, to react with source of iron, titanium source is then added, finally adds remaining alkali source.
According to the above scheme, it is preferable that molar concentration of the source of iron in the eutectic solvent is (0.18~1.44)
mol/L。
According to the above scheme, it is preferable that the certain temperature is 80~170 DEG C, and described a period of time is 2~12h；More preferably
Ground, the certain temperature are 110~130 DEG C, and described a period of time is 4~8h.
The present invention also provides a kind of titanium MODIFIED Fes3O4Magnetic nanoparticle, which is characterized in that it is prepared by the above method
It arrives.
The present invention also provides above-mentioned titanium MODIFIED Fes3O4The application of magnetic nanoparticle, which is characterized in that the titanium is modified
Fe3O4Magnetic nanoparticle can be used as catalyst, be used for catalytic degradation antibiotic.
According to the above scheme, it is preferable that the catalyst is multiphase-fenton fenton catalyst；The antibiotic is Ciprofloxacin.
The present invention is for the first time in eutectic solvent, and using ferrous sulfate or frerrous chloride as source of iron, tetrabutyl titanate is titanium source,
Air is oxidant, and the principles of chemistry based on oxidation-precipitation method are successfully prepared titanium MODIFIED Fe3O4Magnetic nanoparticle.
Compared with prior art, main advantages of the present invention are as follows:
1) preparation method of the invention uses environmentally protective eutectic solvent as reaction medium, avoids titanium source in water
Fast hydrolyzing in phase overcomes many operating procedure problems present in aqueous phase reactions system, such as: the initial pH of reaction system
< 1, the later period needs a large amount of alkali neutralizations, not only the high requirements on the equipment, but also wastage of material is serious, generates waste liquid mostly etc..In addition, this
It is environmentally protective to invent the preparation method provided, it is not high to equipment requirement, and raw material can be saved.
2) titanium MODIFIED Fe provided by the invention3O4Magnetic nanoparticle shows excellent catalysis to common organic wastewater and drops
Solution ability is (such as under room temperature and condition of neutral pH, to 0.01mmol/L methylene blue percent of decolourization up to 93.8% in 2h, to 20mg/L
Ciprofloxacin removal efficiency is up to 96.5%), much larger than the titanium MODIFIED Fe prepared in water phase3O4Magnetic nanoparticle is (such as degradation methylene
Blue reaction rate is respectively 0.116min-1With 2.15 × 10-3min-1), and catalyst amount is few, stability is good, without secondary dirt
It contaminates, be easy to Magnetic Isolation recycling and recycle (to methylene blue percent of decolourization still up to 94% after reusing 5 times).
3) the titanium MODIFIED Fe for preparation method provided by the present invention3O4Magnetic nanoparticle is catalyzed as multiphase-fenton Fenton
Agent, be used for catalytic degradation organic pollutant (such as methylene blue, Ciprofloxacin), it is high-efficient, be easy to Magnetic Isolation recycling and again
Multiple service performance is stablized.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram (XRD) of 1 products therefrom of the embodiment of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of 1 products therefrom of the embodiment of the present invention.
Fig. 3 is the transmission electron microscope picture (TEM) of 1 products therefrom of the embodiment of the present invention.
Fig. 4 is the N of 1 products therefrom of the embodiment of the present invention2Adsorption-desorption isothermal.
Fig. 5 is the room temperature magnetization curve figure of 1 products therefrom of the embodiment of the present invention.
Fig. 6 is the circulation experiment figure of 1 products therefrom catalytic degradation methylene blue of the embodiment of the present invention.
Specific embodiment
For a better understanding of the present invention, the contents of the present invention are further illustrated below with reference to embodiment, but the present invention is not
It is limited only to the following examples, any modification done within the spirit and principles of the present invention, replacement and improves,
It should be included within protection scope of the present invention.
Unless specific instructions, the reagent used is commercially available chemical reagent to following embodiment.
Embodiment 1
A kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, comprising the following steps:
1) it weighs 5.586g (0.04mol) choline chloride and 4.804g urea (0.08mol) is added in 60mL reaction kettle,
Stirring is changed into liquid to solid mixture at 50 DEG C, obtains choline chloride-urea eutectic solvent.
2) it is first added into choline chloride made from step 1)-urea eutectic solvent 1.668g (0.0060mol)
FeSO4·7H2O and 0.584g (0.0104mol) KOH simultaneously stirs 30min, adds 0.408g (0.0012mol) tetrabutyl titanate
5min is stirred, 0.420g (0.0075mol) KOH is eventually adding, after 80 DEG C of stirring 30min, reaction kettle is put into 110 DEG C of baking ovens
Reaction 4h obtains solid particle, is centrifuged, distilled water (3 × 20mL) and ethyl alcohol (1 × 20mL) wash, obtain after air drying
Product titanium MODIFIED Fe3O4Magnetic nanoparticle.
The present embodiment products therefrom titanium MODIFIED Fe3O4The X ray diffracting spectrum of magnetic nanoparticle is as shown in Figure 1, it is seen that its
With Fe3O4Standard diagram it is consistent (JCPDS No.65-3107), show that product has cube inverse spinel phase structure.
The present embodiment products therefrom titanium MODIFIED Fe3O4The SEM figure of magnetic nanoparticle is as shown in Figure 2, it is seen that products therefrom with
Based on spheric granules, average grain diameter about 35.9 ± 10.5nm.
The present embodiment products therefrom titanium MODIFIED Fe3O4The TEM figure of magnetic nanoparticle is as shown in Figure 3, it is seen that its nano particle
Uniform in size, partial size is between 20~40nm.
The present embodiment products therefrom titanium MODIFIED Fe3O4The N of magnetic nanoparticle2Adsorption-desorption isothermal as shown in figure 4, by
The specific surface area that figure can calculate products therefrom is 117m2/g。
The present embodiment products therefrom titanium MODIFIED Fe3O4The magnetization curve figure of magnetic nanoparticle is as shown in Figure 5, it is seen that it is full
It is 31.6emu/g, remanent magnetization 4.3emu/g, coercivity 36.7Oe with the intensity of magnetization, shows that product has and be suitable for
The magnetic property of Magnetic Isolation.
Embodiment 2
A kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, comprising the following steps:
1) it weighs 5.586g (0.04mol) choline chloride and 4.804g (0.08mol) urea is added in 60mL reaction kettle,
Stirring is changed into liquid to solid mixture at 50 DEG C, obtains choline chloride-urea eutectic solvent.
2) it is first added into choline chloride made from step 1)-urea eutectic solvent 1.668g (0.0060mol)
FeSO4·7H2O and 0.584g (0.0104mol) KOH simultaneously stirs 30min, adds the positive fourth of 0.050g (0.00015mol) metatitanic acid
Ester stirs 5min, is eventually adding 0.420g (0.0075mol) KOH, after 80 DEG C of stirring 30min, reaction kettle is put into 110 DEG C of bakings
Case reaction 4h obtains solid particle, is centrifuged, distilled water (3 × 20mL) and ethyl alcohol (1 × 20mL) wash, after air drying
Obtain product.
Embodiment 3
A kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, comprising the following steps:
1) 5.586g (0.04mol) choline chloride and 4.804g (0.08mol) urea are weighed in 60mL reaction kettle, 50
Stirring is changed into liquid to solid mixture at DEG C, obtains choline chloride-urea eutectic solvent.
2) it is sequentially added into choline chloride made from step 1)-urea eutectic solvent 1.668g (0.0060mol)
FeSO4·7H2O and 0.584g (0.0104mol) KOH simultaneously stirs 30min, adds 4.080g (0.012mol) tetrabutyl titanate
5min is stirred, 0.420g (0.0075mol) KOH is eventually adding, after 80 DEG C of stirring 30min, reaction kettle is put into 110 DEG C of baking ovens
Reaction 4h obtains solid particle, is centrifuged, distilled water (3 × 20mL) and ethyl alcohol (1 × 20mL) wash, obtain after air drying
Product.
Embodiment 4
A kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, comprising the following steps:
1) it weighs 5.586g (0.04mol) choline chloride and 4.804g (0.08mol) urea is added in 60mL reaction kettle,
Stirring is transformed into liquid to solid mixture at 50 DEG C, obtains choline chloride-urea eutectic solvent.
2) it is first added into choline chloride made from step 1)-urea eutectic solvent 1.668g (0.0060mol)
FeSO4·7H2O and 0.584g (0.0104mol) KOH simultaneously stirs 30min, adds 0.408g (0.0012mol) tetrabutyl titanate
5min is stirred, 0.420g (0.0075mol) KOH is eventually adding, after 80 DEG C of stirring 30min, reaction kettle is put into 130 DEG C of baking ovens
Reaction 2h obtains solid particle, is centrifuged, distilled water (3 × 20mL) and ethyl alcohol (1 × 20mL) wash, obtain after air drying
Product titanium MODIFIED Fe3O4Magnetic nanoparticle.
Application Example 1
Titanium MODIFIED Fe prepared by embodiment 13O4Magnetic nanoparticle is applied to 25 DEG C of catalytic degradation methylene blues, specifically
Steps are as follows:
By the resulting titanium MODIFIED Fe of 0.025g embodiment 13O4Magnetic nanoparticle and 50mL methylene blue (0.01mmol/L)
Solution mixing adsorbs 15min when being 6.5 for 25 DEG C and pH in advance, 0.230g H is then added2O2(30wt%) degradation of methylene blue,
The percent of decolourization of methylene blue solution is 93.8% (calculation formula is as follows), reaction rate 0.0209min after reaction 2h-1。
C in formula0For the initial concentration (mg/L) of methylene blue solution, C is the residue of methylene blue solution after catalytic degradation
Concentration (mg/L)；The concentration of methylene blue solution is determined by detecting it in the absorbance of 664nm.
Application Example 2 (circulation experiment)
Titanium MODIFIED Fe in the reaction solution as obtained by Magnetic Isolation recycle embodiment 13O4Magnetic nanoparticle, again
The methylene blue solution that 50mL concentration is 0.01mmol/L is added, continues Asia according to the operating procedure in Application Example 1
Methyl blue degradation experiment.So circulation, gained circulation degradation results are shown in Fig. 6.Experimental result is shown, by titanium MODIFIED Fe3O4Magnetism is received
Rice grain is used continuously as catalyst still keeps high catalytic activity (methylene blue solution 2h percent of decolourization up to 94.3%) for 5 times.
Application Example 3
Titanium MODIFIED Fe prepared by embodiment 13O4Magnetic nanoparticle is applied to 25 DEG C of degradation Ciprofloxacins, specific steps
It is as follows:
By the resulting titanium MODIFIED Fe of 0.025g embodiment 13O4Magnetic nanoparticle and 50mL Ciprofloxacin (20mg/L) solution
Mixing adsorbs 15min when being 6.5 for 25 DEG C and pH in advance, 0.230g H is then added2O2(30wt%) oxidative degradation Ciprofloxacin,
For the removal efficiency of Ciprofloxacin up to 96.5%, reaction rate reaches 0.079min after reaction 2h-1。
Above embodiments are merely used to help understand method and its core concept of the invention.It should be pointed out that for this skill
For the those of ordinary skill in art field, without departing from the principle of the present invention, several change can also be carried out to the present invention
Into and modification, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of titanium MODIFIED Fe3O4The preparation method of magnetic nanoparticle, which is characterized in that include the following steps:
Using eutectic solvent as reaction medium, source of iron, alkali source and titanium source is added, at a certain temperature reaction a period of time, reaction
After product is cooled and separated, washs and dries, the titanium MODIFIED Fe is obtained3O4Magnetic nanoparticle.
2. titanium MODIFIED Fe according to claim 13O4The preparation method of magnetic nanoparticle, which is characterized in that described low total
Molten solvent are as follows: by choline chloride and urea choline chloride-urea eutectic solvent that 1:2 is prepared in molar ratio.
3. titanium MODIFIED Fe according to claim 13O4The preparation method of magnetic nanoparticle, which is characterized in that the source of iron
For ferrous sulfate or frerrous chloride；The titanium source is tetrabutyl titanate；The alkali source be one of KOH, NaOH, NaOAc or
It is several.
4. titanium MODIFIED Fe according to claim 13O4The preparation method of magnetic nanoparticle, which is characterized in that
The molar ratio of the source of iron and the titanium source is (300~0.5): 1；
The molar ratio of the alkali source and the source of iron is (2.5~3.5): 1；
The alkali source is added in two portions, specifically: it is first added the 1/3~2/3 of alkali source total addition level, to react with source of iron, then
Titanium source is added, finally adds remaining alkali source.
5. titanium MODIFIED Fe according to claim 13O4The preparation method of magnetic nanoparticle, which is characterized in that the source of iron
Molar concentration in the eutectic solvent is (0.18~1.44) mol/L.
6. titanium MODIFIED Fe according to claim 13O4The preparation method of magnetic nanoparticle, which is characterized in that described certain
Temperature is 80~170 DEG C, and described a period of time is 2~12h.
7. titanium MODIFIED Fe according to claim 63O4The preparation method of magnetic nanoparticle, which is characterized in that described certain
Temperature is 110~130 DEG C, and described a period of time is 4~8h.
8. a kind of titanium MODIFIED Fe3O4Magnetic nanoparticle, which is characterized in that its titanium as described in any one of claim 1~7 changes
Property Fe3O4The preparation method of magnetic nanoparticle is prepared.
9. titanium MODIFIED Fe described in claim 83O4The application of magnetic nanoparticle, which is characterized in that it can be used as catalyst,
For catalytic degradation antibiotic.
10. titanium MODIFIED Fe according to claim 93O4The application of magnetic nanoparticle, which is characterized in that the catalyst
For multiphase-fenton fenton catalyst；The antibiotic is Ciprofloxacin.
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