CN107930544B - Magnetic responsiveness load type Janus hierarchical pore SiO2Composite microsphere and preparation method thereof - Google Patents
Magnetic responsiveness load type Janus hierarchical pore SiO2Composite microsphere and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 87
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000004043 responsiveness Effects 0.000 title claims abstract description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 26
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000001841 cholesterols Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- QIJRTFXNRTXDIP-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride;hydrate Chemical compound O.Cl.SCC(N)C(O)=O QIJRTFXNRTXDIP-UHFFFAOYSA-N 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 6
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 6
- -1 amino Chemical group 0.000 claims description 6
- 229960002130 benzoin Drugs 0.000 claims description 6
- 229960001305 cysteine hydrochloride Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000019382 gum benzoic Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 6
- 229960003080 taurine Drugs 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 8
- 238000004945 emulsification Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 12
- 239000000696 magnetic material Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007777 multifunctional material Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a magnetic responsiveness load type Janus hierarchical pore SiO2Composite microsphere and preparation method thereof, Fe is prepared by emulsion method3O4The nano particles are uniformly dispersed in the hierarchical pore SiO2then loading active components such as Au, Ag nano particles and the like in the multilevel pore canal to obtain the magnetic response load type Janus hierarchical pore SiO2And (3) compounding the microspheres. In the process of preparing the magnetic porous material by the emulsion method, Fe3O4The nano particles do not need to be modified, can be fully dispersed in an emulsion system under low pH value and effectively enter hierarchical pore SiO2The high dispersion and loading of the magnetic nano particles are realized in the pore channels. The invention relates to a magnetic responsiveness load type Janus hierarchical pore SiO2The composite microsphere can be used as a solid surfactant and a solid catalyst, a water phase containing pollutants and a Pickering emulsion formed by using a common organic solvent as an oil phase are stabilized, the interface catalytic degradation of the pollutants is realized, and the composite microsphere can be recycled.
Description
Technical Field
The invention belongs to the technical field of multifunctional materials, and particularly relates to a magnetic-responsiveness load type Janus hierarchical pore SiO2Composite microspheres and a preparation method thereof.
Background
For many years, the preparation research of intelligent materials has attracted great interest in the scientific and technical field, and the reason for the great interest is that the materials have stimulus responsiveness to changes of external conditions such as light, heat, electric field, magnetic field, chemical environment and the like. As an important component of the magnetic responsive material, magnetic nanoparticles are very easy to separate from a multi-phase or complex system without additional chemical components (without changing the properties of the system) with the help of an external magnetic field, and thus are receiving attention. Therefore, the industrial applications of magnetic nanoparticles are extremely wide, such as: novel magneto-optical-electric materials, recyclable catalysts, adsorbents of heavy metal ions and organic pollutants in wastewater, and the like. Meanwhile, in order to realize the properties of catalysis, photoelectricity and the like of the magnetic responsiveness material, some functional nanoparticles (such as Au nanoparticles and Ag nanoparticles) are required to be compounded with the magnetic nanoparticles, so that the magnetic responsiveness is compounded with other functions to obtain the multifunctional nano material. The magnetic-responsive metal nano composite material becomes a very important research direction in the field of intelligent multifunctional materials due to the simple separation and the efficient coupling of the functions of catalysis, photoelectricity and the like.
In the aspect of material preparation, the preparation method has the advantages of simple operation, easy removal of templates, mild reaction conditions, easy amplification of preparation and the like, and arouses the interest of numerous researchers. In the preparation of magnetic materials, there are two main methods for preparing magnetic materials by emulsion method in the current report: (1) FeCl is added3·6H2O and FeCl2·4H2O is preset in the system, and the magnetic material is obtained after the initiation reaction. (2) Direct reaction of Fe3O4Or gamma-Fe2O3And placing the mixture in a reaction system to obtain the magnetic material. In the case of the (1) case, other chemical components are required to be added to the system to initiate the reaction, and the added components can destroy the structure and stability of the emulsion, so that the application is greatly limited, and even the effective preparation of the magnetic material cannot be realized. For the preparation method of the magnetic material (2), although no external chemical component influences the emulsion, Fe3O4And gamma-Fe2O3Self-polymerization easily occurs in the preparation process of the material, so that the magnetic response of the material is influenced, and the emulsion stability is also influenced, so that good dispersibility is very important for the magnetic response and the material structure of the final material. Generally, if the magnetic particles are dispersed in the oil phase, treatments such as modification of lipophilic components, coating of silanization reagents and the like are often required, so that stable suspension of the magnetic nanoparticles in the oil phase is realized; if the magnetic component is dispersed in the water phase, the magnetic component needs to be subjected to hydrophilic treatment; hydrophilic and hydrophobic modification can be simultaneously carried out on the surface of the magnetic component, and the magnetic component can be further used as an emulsion stabilizer to realize the preparation of the magnetic material. However, in these magnetic propertiesIn the preparation process of the material, hydrophilic and hydrophobic treatment needs to be carried out on the magnetic component, and the emulsion polymerization can be realized only by introducing one or more additional organic solvents, the process is complex and difficult to control, the reaction system is selected rigorously, and a large amount of organic solvents are needed in the modification process.
In the reports at present, the successfully modified magnetic components achieve effective dispersion in the aqueous phase under neutral or alkaline conditions. However, under acidic conditions due to Fe3O4A certain degree of reaction occurs, so that no report about successful preparation of magnetic materials by an emulsion method under an acidic condition exists, which results in that efficient preparation and application of some materials are hindered. Meanwhile, in order to realize the greening, simplification and high efficiency of the preparation process, the non-modified Fe is used3O4Emulsion systems of particles to prepare magnetic materials remain a challenge. .
Disclosure of Invention
The invention aims to provide a magnetically responsive load type Janus hierarchical pore SiO2Composite microspheres and a preparation method of the composite microspheres.
The magnetic responsiveness load type Janus hierarchical pore SiO adopted for solving the technical problems2The composite microsphere is prepared by the following method:
1. Mixing Fe3O4Ultrasonically dispersing nano particles in distilled water with the pH value of 0.8-1 uniformly, adding the nano particles into a vinyl triethoxysilane solution of a small molecular stabilizer, uniformly stirring, reacting the obtained mixed solution at normal temperature for 12-48 hours in an ammonia atmosphere, centrifugally separating, washing and drying to obtain the magnetic hierarchical pore SiO with the C-C double bond on the surface2microspheres, denoted hierarchical porous SiO2@Fe3O4And (3) microspheres.
2. mixing the aqueous solution of cysteine hydrochloride with the ethanol solution of benzoin dimethyl ether, and then adding the hierarchical pore SiO obtained in step 12@Fe3O4Uniformly mixing the microspheres, and irradiating for 12-48 hours under ultraviolet light to obtain the hierarchical pore SiO with the surface modified with amino2@Fe3O4And (3) microspheres.
3. Hierarchical porous SiO with surface modified with amino2@Fe3O4Fully dispersing the microspheres in methanol or ethanol, then adding soluble salt of metal and polyvinylpyrrolidone, stirring at room temperature for reaction for 1-8 hours to obtain the magnetic hierarchical pore SiO loaded with metal nanoparticles2Microspheres, denoted hierarchical porous SiO2@Fe3O4@ M microsphere, where M represents a metal.
4. SiO the hierarchical pore obtained in the step 32@Fe3O4Dispersing the @ M microspheres in molten paraffin, adding distilled water, stirring for 3-5 minutes, cooling to room temperature, filtering, adding the obtained solid particles into a phosphate buffer solution with the pH value of 7.4, adding a glutaraldehyde aqueous solution and sodium cyanoborohydride with the mass fraction of 50%, reacting at room temperature for 3-6 hours, adding taurine, continuing reacting at room temperature for 6-12 hours, filtering, washing with water, washing with n-hexane to remove paraffin, and obtaining the hierarchical pore SiO with part of surface modified sulfonic groups2@Fe3O4@ M microspheres.
5. Part of the surface of the hierarchical porous SiO with modified sulfonic groups2@Fe3O4Adding the @ M microspheres, cholesterol derivative and potassium carbonate into tetrahydrofuran, and carrying out reflux reaction for 12-24 hours to obtain the magnetically-responsive load type Janus hierarchical pore SiO2And (3) compounding the microspheres.
The structural formula of the small molecule stabilizer is shown as follows:
The structural formula of the cholesterol derivative is shown as follows:
In the step 1, the mass-volume ratio of the small-molecule stabilizer to the mixed solution is preferably 15mg to 20mg:1mL, and the volume ratio of the vinyltriethoxysilane to distilled water having a pH of 0.8 to 1 is preferably 1:7 to 9, wherein the pH of the distilled water having a pH of 0.8 to 1 is adjusted by hydrochloric acid.
In the step 2, benzoin dimethyl ether and hierarchical porous SiO are preferably selected2@Fe3O4The mass ratio of the microspheres to the cysteine hydrochloride is 1:2: 100.
In the step 3, hierarchical porous SiO with surface modified amino group is preferable2@Fe3O4The mass ratio of the microspheres to the soluble salt of the metal to the polyvinylpyrrolidone is 10-50: 1: 1-2, wherein the soluble salt of the metal is any one of chloroauric acid, silver nitrate, palladium nitrate, chloroplatinic acid and the like.
In the step 4, hierarchical porous SiO is preferable2@Fe3O4The mass ratio of the @ M microspheres to the molten paraffin, the distilled water, the 50% glutaraldehyde water solution, the sodium cyanoborohydride and the taurine is 1: 50-75: 300-500: 15-20: 0.2-0.4: 15-50.
In the step 5, hierarchical porous SiO with part of the surface modified with sulfonic acid group is preferable2@Fe3O4The mass ratio of the @ M microspheres to the cholesterol derivative to the potassium carbonate is 1: 5-15.
The invention prepares magnetic hierarchical pore SiO by emulsion method at room temperature in one step2Microspheres, amino-functionalizing the magnetic particles, and in-situ reduction of metal salt precursors to prepare magnetic particles on SiO2The Janus composite microspheres successfully load metal nanoparticles such as Au, Ag and the like in the pore channels of the microspheres. Compared with the prior art, the invention has the following beneficial effects:
1. The process for preparing the magnetic porous material by the emulsion method does not introduce any additional organic solvent, greatly realizes the green process of emulsion polymerization, and has the advantages of economy, convenience and mild conditions.
2. In the process of preparing the magnetic porous material by the emulsion method, Fe3O4The nano particles do not need to be modified, can be fully dispersed in an emulsion system under low pH value and effectively enter hierarchical pore SiO2The high dispersion and load of the magnetic nano particles are realized in the pore channels, and the application of the magnetic material is expanded.
3. hair brushBright magnetic response load type Janus hierarchical pore SiO2The composite microsphere can be used as a solid surfactant, can be used for stabilizing water phases polluted by p-nitroanisole, p-nitrophenol, eosin, methyl blue, methyl orange, rhodamine B and the like and Pickering emulsion formed by taking benzene, toluene, ethylbenzene, dichloromethane, trichloromethane and the like as oil phases, can be used as a solid catalyst, can be used for realizing interface catalytic degradation of pollutants in the Pickering emulsion, and can be recycled.
Drawings
FIG. 1 is a hierarchical porous SiO as in example 12@Fe3O4Scanning electron microscope image of microsphere field emission.
FIG. 2 is a hierarchical porous SiO in example 12@Fe3O4Photo of the response of the microspheres to an external magnetic field.
FIG. 3 is a Janus hierarchical pore SiO of Au-loaded in magnetic responsiveness in example 12Environmental scanning electron microscope images of the composite microspheres.
Fig. 4 is a corresponding energy spectrum of fig. 3.
FIG. 5 is a Janus hierarchical pore SiO of Au-loaded in magnetic responsiveness in example 12XRD pattern of composite microspheres.
FIG. 6 is a Janus hierarchical pore SiO of Au-loaded in magnetic responsiveness in example 12Photograph of Pickering emulsion formed by composite microspheres, toluene and distilled water.
FIG. 7 is a Janus hierarchical pore SiO of Au-loaded with magnetic responsiveness in example 12And (3) a picture of Pickering emulsion formed by the composite microspheres, toluene and distilled water containing rhodamine B.
FIG. 8 is a Janus hierarchical pore SiO of Au-loaded in magnetic responsiveness in example 12And (3) a picture of Pickering emulsion formed by the composite microspheres, toluene and distilled water containing p-nitrophenol.
FIG. 9 is a Janus hierarchical pore SiO of Au-loaded magnetically responsive in example 12Photograph of Pickering emulsion of composite microspheres with toluene and distilled water containing methyl blue.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
example 1
1. Mixing 75mg of Fe3O4Ultrasonically dispersing nano particles (the particle size is 2-50 nm) in 15mL of distilled water with the pH value of 1 uniformly, adding 9mL of dispersion liquid into 1mL of vinyl triethoxysilane solution containing 0.15g of micromolecule stabilizer, stirring uniformly, placing the obtained mixed solution above 25% ammonia water at normal temperature in a sealed manner for reaction for 24 hours to form brown floccule, centrifugally separating, washing with tetrahydrofuran, and drying at 80 ℃ to obtain the magnetic hierarchical pore SiO with C-C double bonds on the surface2Microspheres, denoted hierarchical porous SiO2@Fe3O4And (3) microspheres. As can be seen from fig. 1, the resulting sample was spherical and had a distinct porous structure. As can be seen from FIG. 2, the microspheres respond to an external magnetic field.
2. Mixing 50mL of an aqueous solution containing 2g of cysteine hydrochloride with 20mL of an ethanol solution containing 0.4g of benzoin dimethyl ether, and then adding 0.2g of the hierarchical pore SiO obtained in step 12@Fe3O4Mixing the microspheres uniformly, and irradiating for 24 hours under ultraviolet light to obtain the hierarchical pore SiO with the surface modified with amino2@Fe3O4And (3) microspheres.
3. 0.2g of hierarchical porous SiO with surface modified with amino groups2@Fe3O4Fully dispersing the microspheres in 20mL of methanol, then adding 0.01g of tetrachloroauric acid trihydrate and 0.01g of polyvinylpyrrolidone, stirring at room temperature for reaction for 2 hours, centrifugally separating, washing with ethanol, and drying at 80 ℃ to obtain the Au nanoparticle-loaded magnetic hierarchical pore SiO2Microspheres, denoted hierarchical porous SiO2@Fe3O4@ Au microspheres.
4. 0.2g of the hierarchical pore SiO obtained in step 32@Fe3O4@ Au microspheres are dispersed in 10g of molten paraffin, 60g of distilled water is added, the mixture is stirred for 3 minutes, cooled to room temperature and filtered, the obtained solid particles are added into 100mL of phosphate buffer solution with pH 7.4, 3g of glutaraldehyde aqueous solution with the mass fraction of 50% and 0.04g of sodium cyanoborohydride are added, the mixture is reacted for 5 hours at normal temperature, 4g of taurine is added, and the reaction is continued at normal temperatureFiltering and washing for 10 hours, and then washing paraffin by using normal hexane to obtain hierarchical pore SiO with part of surface modified sulfonic groups2@Fe3O4@ Au microspheres.
5. 0.2g of hierarchical pore SiO with sulfonic acid group partially modified on the surface2@Fe3O4Adding @ Au microspheres, 2g cholesterol derivative and 2g potassium carbonate into 30mL tetrahydrofuran, and carrying out reflux reaction at 80 ℃ for 24 hours to obtain the Janus hierarchical pore SiO supported with Au in magnetic responsiveness2And (3) compounding the microspheres. As can be seen from FIGS. 3 to 5, Au nanoparticles are successfully loaded in the pore channels of the composite microspheres.
Example 2
1. Mixing 75mg of Fe3O4Ultrasonically dispersing nano particles (the particle size is 2-50 nm) in 15mL of distilled water with the pH value of 1 uniformly, adding 9mL of dispersion liquid into 1mL of vinyl triethoxysilane solution containing 0.20g of micromolecule stabilizer, stirring uniformly, placing the obtained mixed solution above 25% ammonia water at normal temperature in a sealed manner for reaction for 24 hours to form brown floccule, centrifugally separating, washing with tetrahydrofuran, and drying at 80 ℃ to obtain the magnetic hierarchical pore SiO with C-C double bonds on the surface2Microspheres, denoted hierarchical porous SiO2@Fe3O4And (3) microspheres.
2. mixing 50mL of an aqueous solution containing 2g of cysteine hydrochloride with 20mL of an ethanol solution containing 0.4g of benzoin dimethyl ether, and then adding 0.2g of the hierarchical pore SiO obtained in step 12@Fe3O4Mixing the microspheres uniformly, and irradiating for 24 hours under ultraviolet light to obtain the hierarchical pore SiO with the surface modified with amino2@Fe3O4And (3) microspheres.
3. 0.1g of hierarchical porous SiO with surface modified with amino groups2@Fe3O4Fully dispersing the microspheres in 20mL of methanol, then adding 0.01g of silver nitrate and 0.02g of polyvinylpyrrolidone, stirring at room temperature for reaction for 2 hours, centrifugally separating, washing with ethanol, and drying at 80 ℃ to obtain the Ag nanoparticle-loaded magnetic hierarchical pore SiO2Microspheres, denoted hierarchical porous SiO2@Fe3O4@ Ag microspheres.
4. 0.2g of the hierarchical pore SiO obtained in step 32@Fe3O4@ Ag microspheres are dispersed in 15g of molten paraffin, 100g of distilled water is added, stirring is carried out for 3 minutes, cooling is carried out to room temperature, filtering is carried out, obtained solid particles are added into 100mL of phosphate buffer solution with pH 7.4, 4g of glutaraldehyde aqueous solution with mass fraction of 50% and 0.06g of sodium cyanoborohydride are added, reaction is carried out for 5 hours at normal temperature, 8g of taurine is added, reaction is carried out for 10 hours at normal temperature, after filtering and washing, paraffin is washed away by normal hexane, and hierarchical pore SiO with part of surface modified sulfonic groups is obtained2@Fe3O4@ Ag microspheres.
5. 0.2g of hierarchical pore SiO with sulfonic acid group partially modified on the surface2@Fe3O4Adding the @ Ag microsphere, 1g of cholesterol derivative and 1g of potassium carbonate into 20mL of tetrahydrofuran, and carrying out reflux reaction at 80 ℃ for 24 hours to obtain the Ag-loaded Janus hierarchical pore SiO with magnetic responsiveness2And (3) compounding the microspheres.
To demonstrate the beneficial effects of the present invention, the inventors took the magnetically responsive Au-loaded Janus hierarchical pore SiO in example 1210mg of composite microspheres are respectively added with 1mL of distilled water, 1mL of distilled water containing 0.02g of rhodamine B, 1mL of distilled water containing 0.02g of p-nitrophenol, 1mL of distilled water containing 0.02g of methyl blue and 1mL of methylbenzene, and as shown in figures 6-9, Pickering emulsion can be formed, so that the magnetic-response Au-loaded Janus hierarchical pore SiO disclosed by the invention can be illustrated2The composite microspheres can stabilize a water phase containing p-nitrophenol, methyl blue and rhodamine B and a Pickering emulsion formed by taking toluene as an oil phase.
Claims (9)
1. Magnetic responsiveness load type Janus hierarchical hole SiO2The preparation method of the composite microsphere is characterized by comprising the following steps:
(1) Mixing Fe3O4Ultrasonically dispersing nano particles in distilled water with the pH value of 0.8-1 uniformly, adding the nano particles into a vinyl triethoxysilane solution of a small molecular stabilizer, uniformly stirring, reacting the obtained mixed solution at normal temperature for 12-48 hours in an ammonia atmosphere, centrifugally separating, washing and drying to obtain the magnetic hierarchical pore SiO with the C-C double bond on the surface2Microspheres, denoted hierarchical porous SiO2@Fe3O4Microspheres;
The structural formula of the small molecule stabilizer is shown as follows:
(2) Mixing the aqueous solution of cysteine hydrochloride with the ethanol solution of benzoin dimethyl ether, and then adding the hierarchical pore SiO obtained in the step (1)2@Fe3O4Uniformly mixing the microspheres, and irradiating for 12-48 hours under ultraviolet light to obtain the hierarchical pore SiO with the surface modified with amino2@Fe3O4microspheres;
(3) Hierarchical porous SiO with surface modified with amino2@Fe3O4Fully dispersing the microspheres in methanol or ethanol, then adding soluble salt of metal and polyvinylpyrrolidone, stirring at room temperature for reaction for 1-8 hours to obtain the magnetic hierarchical pore SiO loaded with metal nanoparticles2Microspheres, denoted hierarchical porous SiO2@Fe3O4@ M microsphere, wherein M represents a metal;
(4) The hierarchical pore SiO obtained in the step (3)2@Fe3O4Dispersing the @ M microspheres in molten paraffin, adding distilled water, stirring for 3-5 minutes, cooling to room temperature, filtering, adding the obtained solid particles into a phosphate buffer solution with the pH value of 7.4, adding a glutaraldehyde aqueous solution and sodium cyanoborohydride with the mass fraction of 50%, reacting at room temperature for 3-6 hours, adding taurine, continuing reacting at room temperature for 6-12 hours, filtering, washing with water, washing with n-hexane to remove paraffin, and obtaining the hierarchical pore SiO with part of surface modified sulfonic groups2@Fe3O4@ M microspheres;
(5) Part of the surface of the hierarchical porous SiO with modified sulfonic groups2@Fe3O4Adding the @ M microspheres, cholesterol derivative and potassium carbonate into tetrahydrofuran, and carrying out reflux reaction for 12-24 hours to obtain the magnetically-responsive load type Janus hierarchical pore SiO2Compounding the microspheres;
The structural formula of the cholesterol derivative is shown as follows:
2. The magnetically responsive supported Janus hierarchical pore SiO according to claim 12the preparation method of the composite microsphere is characterized by comprising the following steps: in the step (1), the mass-volume ratio of the small-molecule stabilizer to the mixed solution is 15mg to 20mg:1mL, and the volume ratio of the vinyltriethoxysilane to distilled water having a pH of 0.8 to 1 is 1:7 to 9.
3. The magnetically responsive supported Janus hierarchical pore SiO according to claim 22The preparation method of the composite microsphere is characterized by comprising the following steps: the pH value of the distilled water with the pH value of 0.8-1 is adjusted by hydrochloric acid.
4. The magnetically responsive supported Janus hierarchical pore SiO according to claim 12The preparation method of the composite microsphere is characterized by comprising the following steps: in the step (2), the benzoin dimethyl ether and the hierarchical porous SiO2@Fe3O4the mass ratio of the microspheres to the cysteine hydrochloride is 1:2: 100.
5. The magnetically responsive supported Janus hierarchical pore SiO according to claim 12The preparation method of the composite microsphere is characterized by comprising the following steps: in the step (3), the surface-modified amino hierarchical porous SiO2@Fe3O4The mass ratio of the microspheres to the soluble salt of the metal and the polyvinylpyrrolidone is 10-50: 1: 1-2.
6. The magnetically-responsive supported Janus hierarchical pore SiO of claim 52The preparation method of the composite microsphere is characterized by comprising the following steps: the soluble salt of the metal is any one of chloroauric acid, silver nitrate, palladium nitrate and chloroplatinic acid.
7. The magnetically responsive supported Janus hierarchical pore SiO according to claim 12The preparation method of the composite microsphere is characterized by comprising the following steps: in the step of(4) In (2), the hierarchical pore SiO2@Fe3O4The mass ratio of the @ M microspheres to the molten paraffin, the distilled water, the 50% glutaraldehyde water solution, the sodium cyanoborohydride and the taurine is 1: 50-75: 300-500: 15-20: 0.2-0.4: 15-50.
8. The magnetically responsive supported Janus hierarchical pore SiO according to claim 12The preparation method of the composite microsphere is characterized by comprising the following steps: in the step (5), the hierarchical pore SiO with sulfonic acid group partially modified on the surface2@Fe3O4The mass ratio of the @ M microspheres to the cholesterol derivative to the potassium carbonate is 1: 5-15.
9. Magnetically responsive supported Janus hierarchical pore SiO prepared according to any one of claims 1-82And (3) compounding the microspheres.
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