CN114471473A - Preparation method of functionalized magnetic nano composite material ferroferric oxide/silicon dioxide-APTMS - Google Patents
Preparation method of functionalized magnetic nano composite material ferroferric oxide/silicon dioxide-APTMS Download PDFInfo
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- CN114471473A CN114471473A CN202210121732.0A CN202210121732A CN114471473A CN 114471473 A CN114471473 A CN 114471473A CN 202210121732 A CN202210121732 A CN 202210121732A CN 114471473 A CN114471473 A CN 114471473A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 title abstract description 3
- 239000010703 silicon Substances 0.000 title abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 61
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 61
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 61
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 31
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 claims abstract 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000007885 magnetic separation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000004277 Ferrous carbonate Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- 229960004652 ferrous carbonate Drugs 0.000 claims description 2
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 16
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 65
- 238000012360 testing method Methods 0.000 description 52
- 238000001179 sorption measurement Methods 0.000 description 22
- 229910001868 water Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 230000004580 weight loss Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 229910008051 Si-OH Inorganic materials 0.000 description 7
- 229910006358 Si—OH Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000006557 surface reaction Methods 0.000 description 7
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- 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
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Abstract
The invention discloses a preparation method of functionalized magnetic nano composite material ferroferric oxide/silicon dioxide-APTMS, which is characterized in that magnetic nano Fe is prepared under the condition of ultrasonic wave3O4The particles are synthesized in one step by a coprecipitation method under the irradiation of ultrasonic waves, and the particles have good dispersibility, uniform particle, larger specific surface area and convenient recoveryThe obtained functional magnetic nano composite material Fe3O4@SiO2-APTMS; the method of the invention is adopted to synthesize the functional magnetic nano composite material Fe3O4@SiO2The APTMS equipment is simple, the operation is convenient, the particle size distribution of the product is uniform, the particle size range is about 10-100 nm, and the functionalized magnetic nano composite material Fe3O4@SiO2The APTMS specific surface area is 100-150 m2And/g, no obvious oxidation phenomenon of the nano particles occurs.
Description
Technical Field
The invention relates to a functionalized magnetic nanocomposite Fe3O4@SiO2A method for preparing APTMS.
Background
At present, the methods for removing the heavy metal ions in the water body at home and abroad mainly comprise a chemical precipitation method, a membrane separation method, an electrolysis method, an ion exchange method, a biological method, an adsorption method and the like. The adsorption method is widely used because of its advantages of high efficiency, economy, simplicity and the like. Traditional adsorbents such as activated carbon, zeolite, molecular sieve and the like are based on the fact that heavy metals (Sunxiefei, Zhang Ning, Liushuyan, and the like) in water are removed by physical adsorption on the basis of larger specific surface area and higher surface energy of the adsorbent (J) recent research progress of hexavalent chromium Cr (VI) (applied chemical industry, 2020,49(04): 1035-1038). However, most of these materials have the disadvantages of poor selectivity, difficult regeneration, easy generation of secondary pollution, etc., and particularly after adsorption treatment, the adsorbent and the wastewater cannot be separated quickly and effectively, which is one of the problems to be solved urgently in sewage treatment.
With the rapid development of nanotechnology, various magnetic nanomaterials are successfully synthesized and applied to the remediation of environmental pollution. Nano Fe3O4The particles are widely used due to the advantages of relatively simple and convenient preparation process, low price, no toxicity and the like. The nano-scale adsorption material has the nano-scale effects such as surface effect, quantum size effect, volume effect, macroscopic quantum tunneling effect and the like, and has good adsorption performance due to extremely high specific surface area and surface activity. When the particle size is less than 20nm, the particle shows superparamagnetism at normal temperature, is easy to modify functional groups, generates specific affinity adsorption with a target object, and can rapidly separate the target object from a multicomponent environment through cleaning and desorption operations under the directional control of an external magnetic field (Cendrowski K, Sikorab P, Zielinska B.chemical and thermal stability of core-shelled magnetic nanoparticles and solid silica [ J ] J].Applied Surface Science,2017,407:391–397；Liu J,Zhang J,Xing L,et al.Magnetic Fe3O4/attapulgite hybrids for Cd(II)adsorption:Performance,mechanism and recovery[J]Journal of Hazardous Materials,2021,412(14): 125-. Furthermore, nano-Fe3O4The excellent thermal stability and mechanical strength of the granules make them suitable for many applicationsAnd (4) planting the environment.
At present, for nano Fe3O4Research on the preparation method and properties thereof has become a hot spot in the field of nano materials and functional materials. The chemical method is the present nano Fe3O4The main preparation methods of the particles comprise a coprecipitation method, a microemulsion method, a water (solvent) thermal method, a thermal decomposition method, a sol-gel method and the like. The coprecipitation method has the advantages of simple operation, low equipment requirement, large-scale production, mild reaction conditions and high product purity, and is one of the most commonly used classical methods at present. However, magnetic nano-Fe3O4There are also problems with the use of particles: the bare particles are very susceptible to oxidation in air; is susceptible to corrosion in acidic environments; the magnetic dipole interaction makes the magnetic dipole easy to agglomerate and lose the single domain magnetic pole, which results in the deterioration of the adsorption effect and the adsorption selectivity. To make magnetic nano Fe3O4The material can adsorb heavy metal ions more effectively and selectively, and must be protected, modified and modified, and active functional group (amino (-NH) with strong chemical stability is introduced on the surface of the material2) Carboxyl (-COOH), sulfonic acid (-SO)3H) Hydroxyl (-OH), etc.) to reduce the occurrence of agglomeration phenomenon, so that it has good dispersibility, oxidation resistance and acid and alkali resistance. Research finds that the amino functionalized nano Fe3O4Material, carboxyl functionalized nano Fe3O4Material and sulfonic group functionalized nano Fe3O4The material and the like have good dispersibility and oxidation resistance, and have better removal effect on heavy metal ions in water than the non-functionalized nano Fe3O4The adsorption effect of the material is obviously improved (Tan L S, Xu J, Xue X Q, et al3O4@SiO2–mPD/SP for selective removal of Pb(Ⅱ)and Cr(Ⅵ)from aqueous solutions[J].RSC Advances,2014,4(86):45920-45929；Feng Z G,Zhu S,Godoi D.Adsorption of Cd2+on carboxyl-terminated superparamagnetic iron oxide nanoparticles[J].Analytical Chemistry,2012,84(8):3764-3770)。
For preparing nano iron and nano iron by utilizing the physical characteristics of ultrasonic acoustic cavitationThe research reports of series of substances, thereby increasing the dispersibility of the nano-sized zero-valent iron and nano-sized bimetallic Cu/Fe have proved the feasibility of the technology (Zhang Ming, Zhang. A method for preparing nano-sized zero-valent iron and nano-sized bimetallic Cu/Fe, ZL 201410554866.7,2017-01-11), and at the same time, the existence of ultrasonic wave can improve the dispersibility of the nano-sized bimetallic iron and the nano-sized bimetallic Cu/Fe, strengthen the chemical reaction and transfer process between interfaces, promote the renewal of the reaction surfaces (Zhang Z, Lv X S, Baig S A. catalytic reduction of 2,4-dichloro by Ni/Fe nanoparticles in the presence of the present of the human acid: intermediate products and the magnetic experimental parameters [ J. B]Journal of Experimental Nanoscience,2014,9(6):603- > 615). The invention applies ultrasonic waves to the functional magnetic nano composite material Fe3O4@SiO2In the preparation process of APTMS, the energy characteristic and the frequency characteristic are expressed by pyrolysis, dispersion, shearing and crushing, and the like, and the effects exerted on the solid-liquid surface are expressed by the influence on the shape, the composition, the structure and the chemical reaction activity of the solid surface, so that the functional magnetic nanocomposite Fe is effectively improved3O4@SiO2The mineralogical characteristics of APTMS promote the full dispersion and the reduction of agglomeration of the APTMS, and the prepared functional magnetic nano composite material Fe with smaller particle size, larger specific surface area, higher reaction activity and convenient recovery3O4@SiO2-APTMS。
Disclosure of Invention
For magnetic nano Fe3O4The particles have stronger polymerization property, are easy to agglomerate and have nano Fe3O4The invention provides a functional magnetic nano composite material Fe which is easy to oxidize and has serious agglomeration phenomenon to cause the problems of reduced reaction activity and the like3O4@SiO2A method for preparing APTMS.
The method is to nano Fe3O4Particle size SiO2The mesoporous material and the amino functional group are cooperatively modified, the cavitation effect of ultrasonic waves is utilized to promote the full dispersion and the reduction of agglomeration of the mesoporous material and the amino functional group, and the functional magnetic nanocomposite Fe with smaller particle size, larger specific surface area, higher reaction activity and convenient recovery is prepared3O4@SiO2-APTMS。
The technical scheme of the invention is as follows:
functional magnetic nanocomposite Fe3O4@SiO2-a process for the preparation of APTMS, which process comprises:
under the conditions of ultrasonic irradiation and nitrogen protection, uniformly mixing soluble ferric salt, soluble ferrous salt and oxygen-free deionized water, dropwise adding an ammonia water solution until the pH value is 9-11, stirring and reacting at normal temperature (20-30 ℃) for 20-30 min to generate nanoscale Fe in the system3O4Particles; then adding 3-Aminopropyltrimethoxysilane (APTMS), Tetraethoxysilane (TEOS) and polyethylene glycol into the system, stirring and reacting for 3-5 h at 40-50 ℃ to prepare the functional magnetic nanocomposite Fe3O4@SiO2-APTMS, separating from the reaction system by using a magnetic separation method, washing and then drying in vacuum (50-60 ℃ for 10-15 hours) to obtain the APTMS;
the mass ratio of the soluble ferrous salt to the soluble ferric salt is 1: 1-4, preferably 1: 1-2;
such as: ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous carbonate, and the like;
such soluble iron salts are for example: ferric chloride, ferric sulfate, ferric nitrate, etc.;
the weight ratio of the soluble ferrite to the 3-aminopropyltrimethoxysilane, the ethyl orthosilicate and the polyethylene glycol is 1: 1-1.04: 0.8-0.9: 1.6 to 1.8;
the ammonia water solution is prepared fresh, and the concentration is 0.5-1.5 mol/L;
the frequency of the ultrasonic wave is 40-80 KHz, and the power is 80-160W;
separating the functional magnetic nano composite material Fe by a magnetic separation method3O4@SiO2After APTMS, the method of washing is recommended as: washing with oxygen-free deionized water, and washing with anhydrous alcohol or acetone. The magnetic separation method is described in the liquid phase preparation, surface modification and structural characterization of metallic iron nanoparticles (journal of physico-chemistry, vol.12, No. 6 of 1999),namely, the functional magnetic nano composite material Fe is prepared by utilizing a magnet to adsorb and separate from a reaction system3O4@SiO2-APTMS。
The invention uses TEM (transmission electron microscope), XRD (X-ray diffractometer), IR (Fourier infrared spectroscopy), VSM (magnetic property analysis), TGA (thermogravimetric analysis) and BET (nitrogen adsorption specific surface determinator) to carry out Fe on the obtained functionalized magnetic nanocomposite material3O4@SiO2APTMS, the results are as follows:
(1) TEM test results
The TEM test result shows that: the particles are uniformly distributed, and the particle size range is about 5-80 nm.
(2) XRD test results
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Of (3) corresponding to the characteristic 7 characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74.8 °) corresponding to Fe, respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
(3) IR test results
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
(4) VSM test results
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 9.0-21.0 emu g-1. Under the external magnetic field, only 25-35 s of Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
(5) TGA test results
The TGA test results show that: weight loss before less than 200 deg.C, mainly due to evaporation of free moisture adsorbed on the surfaceAfter the temperature is 900 ℃, the weight is basically stable and does not change any more, and the weight loss between 200 and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2the-APTMS copolymer accounts for about 15-29%, and has good thermal stability.
(6) BET test results
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2The APTMS specific surface area is 95-160 m2/g-1。
The principle of the preparation method of the invention is as follows: under the conditions of ultrasonic irradiation and continuous stirring and nitrogen introduction, FeSO4·7H2O and FeCl3·6H2Slowly dripping the freshly prepared ammonia water solution into the mixed solution of O to obtain the magnetic nano Fe3O4And (3) particles. Under the irradiation of ultrasonic wave, the newly prepared magnetic nano Fe3O4Mixing and dissolving the particles with 3-Aminopropyltrimethoxysilane (APTMS), Tetraethoxysilane (TEOS) and polyethylene glycol, stirring uniformly, and synthesizing the amino-modified functionalized magnetic nanocomposite Fe with smaller particle size, larger specific surface area and higher reaction activity by a coprecipitation method in one step3O4@SiO2-APTMS。
The reaction formula involved in the preparation method of the invention is as follows:
nanoscale Fe3O4：Fe3++3OH-→Fe(OH)3
Fe(OH)3→FeO(OH)+H2O
Fe2++2OH-→Fe(OH)2
2FeO(OH)+Fe(OH)2→Fe3O4+2H2O
Nanoscale Fe3O4@SiO2-APTMS：
The invention has the beneficial effects that:
the invention firstly prepares magnetic nano Fe under the condition of ultrasonic wave3O4Particles are synthesized into the functional magnetic nano composite material Fe with good dispersity, uniform particles, larger specific surface area and convenient recovery in one step by a coprecipitation method under the irradiation of ultrasonic waves3O4@SiO2-APTMS. The method of the invention is adopted to synthesize the functional magnetic nano composite material Fe3O4@SiO2The APTMS equipment is simple, the operation is convenient, the particle size distribution of the product is uniform, the particle size range is about 10-100 nm, and the functionalized magnetic nano composite material Fe3O4@SiO2The APTMS specific surface area is 100-150 m2And/g, no obvious oxidation phenomenon of the nano particles occurs.
Drawings
FIG. 1 is a functionalized magnetic nanocomposite Fe prepared in example 13O4@SiO2TEM spectrum of APTMS.
FIG. 2 is the functionalized magnetic nanocomposite Fe prepared in example 13O4@SiO2-XRD spectrum of APTMS.
FIG. 3 is the functionalized magnetic nanocomposite Fe prepared in example 13O4@SiO2IR spectrum of APTMS.
FIG. 4 is the functionalized magnetic nanocomposite Fe prepared in example 13O4@SiO2VSM profile of APTMS.
FIG. 5 is the functionalized magnetic nanocomposite Fe prepared in example 13O4@SiO2-TGA profile of APTMS.
FIG. 6 is a functionalized magnetic nanocomposite Fe prepared according to example 13O4@SiO2APTMS adsorption of heavy metal Cr (VI) test data.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Example 1
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, adding ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) into a three-neck flask, adding 50mL of deionized oxygen-free water, uniformly mixing, and ultrasonically stirring for 20 min; a constant-pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and 100mL of deionized oxygen-free water into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) as a surfactant was added to the flask, and 2mL of TEOS and 1.75mL of APTMS were added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, carrying out magnetic separation, washing with oxygen-free deionized water (50mL multiplied by 3) to prepare nano particles, and drying in a vacuum drying oven at 50 ℃ for 12h to prepare the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
All the solutions added dropwise in the above operations need to be deoxidized.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 10-50 nm, and the average particle size is 30 nm.
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Of (3) corresponding to the characteristic 7 characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74.8 °) corresponding to Fe, respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 12.00emu g-1. Under the external magnetic field, only 30s of Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The TGA test results show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-APTMS envelope about 22.5%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area 138m2/g-1。
Example 2
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, adding ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) into a three-neck flask, adding 50mL of deionized oxygen-free water, uniformly mixing, and ultrasonically stirring for 20 min; a constant pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and deionized oxygen-free water (100mL) into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) is added into the flask as a surfactant, and then 2mL of TEOS and 2mL of APTMS are added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, magnetic separation is carried out, oxygen-free deionized water (50mL multiplied by 3) is used for washing to prepare the nano particles, and the solutions dripped in the operations are required to be deoxidized. Drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 20-60 nm, and the average particle size is 40 nm.
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O47 typical characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74 °) of the peaks8 ℃ each corresponding to Fe3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which indicates that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 11.20emu g-1. Under the external magnetic field, only 30s of Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The TGA test results show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-an APTMS coating of about 24.5%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area of 142m2/g-1。
Example 3
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, adding ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) into a three-neck flask, adding 50mL of deionized oxygen-free water, uniformly mixing, and ultrasonically stirring for 20 min; a constant pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and deionized oxygen-free water (100mL) into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) is added into the flask as a surfactant, and then2mL TEOS and 2.25mL APTMS were added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, magnetic separation is carried out, oxygen-free deionized water (50mL multiplied by 3) is used for washing to prepare the nano particles, and the solutions dripped in the operations are required to be deoxidized. Drying in a vacuum drying oven at 50 ℃ for 12 hours to obtain the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 25-80 nm, and the average particle size is 52.5 nm.
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Of (3) corresponding to the characteristic 7 characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74.8 °) corresponding to Fe, respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 9.40emu g-1. Under the external magnetic field, only 35s, Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The results of the TGA test show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-an APTMS coating of about 28.5%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area 158.5m2/g-1。
Example 4
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, adding ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) into a three-neck flask, adding 50mL of deionized oxygen-free water, uniformly mixing, and ultrasonically stirring for 20 min; a constant pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and deionized oxygen-free water (100mL) into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) is added into the flask as a surfactant, and then 2mL of TEOS and 1.5mL of APTMS are added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, magnetic separation is carried out, oxygen-free deionized water (50mL multiplied by 3) is used for washing to prepare the nano particles, and the solutions dripped in the operations are required to be deoxidized. Drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 10-45 nm, and the average particle size is 27.5 nm.
The XRD test result shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Of (3) corresponding to the characteristic 7 characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74.8 °) corresponding to Fe, respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 15.40emu g-1. Under the external magnetic field, only 30s of Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The TGA test results show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-an APTMS coating of about 20.5%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area 122m2/g-1。
Example 5
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, adding ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) into a three-neck flask, adding 50mL of deionized oxygen-free water, uniformly mixing, and ultrasonically stirring for 20 min; a constant pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and deionized oxygen-free water (100mL) into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) is added into the flask as a surfactant, and then 2mL of TEOS and 1.25mL of APTMS are added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, magnetic separation is carried out, oxygen-free deionized water (50mL multiplied by 3) is used for washing to prepare the nano particles, and the solutions dripped in the operations are required to be deoxidized. Drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 8-40 nm, and the average particle size is 24 nm.
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Corresponding to Fe (30.1 deg., 35.5 deg., 43.3 deg., 53.4 deg., 57.2 deg., 62.6 deg., and 74.8 deg.), respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 18.20emu g-1. Under the external magnetic field, only 30s of Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The TGA test results show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2SiO on the surface of APTMS2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-an APTMS coating of about 18.2%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area of 104m2/g-1。
Example 6
Under the irradiation of ultrasonic waves (40KHz, 150W) and the protection of nitrogen, ferrous sulfate heptahydrate (2.78g, 0.01mol) and ferric chloride hexahydrate (4.05g, 0.015mol) are added into a three-neck flask, 50mL of deionized oxygen-free water is added and mixed evenly, and the mixture is stirred ultrasonically20 min; a constant pressure dropping funnel is used for dropping a mixed solution of 14mL of ammonia water and deionized oxygen-free water (100mL) into the flask at the dropping speed of 2 s/drop; after the dropwise addition, 1mL of polyethylene glycol 400(PEG-400) is added into the flask as a surfactant, and then 2mL of TEOS and 1mL of APTMS are added to introduce SiO2and-NH2Stirring and reacting for 4 hours at 40 ℃ under ultrasonic irradiation; after the reaction is finished, magnetic separation is carried out, oxygen-free deionized water (50mL multiplied by 3) is used for washing to prepare the nano particles, and the solutions dripped in the operations are required to be deoxidized. Drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the functional Fe3O4@SiO2-APTMS magnetic nanocomposite.
The TEM test result shows that: the particles are uniformly distributed, the particle size range is about 5-35 nm, and the average particle size is 20 nm.
The test result of XRD shows that: when the scanning diffraction angle (2 theta) is 20-80 degrees, Fe appears3O4Of (3) corresponding to the characteristic 7 characteristic peaks (30.1 °, 35.5 °, 43.3 °, 53.4 °, 57.2 °, 62.6 ° and 74.8 °) corresponding to Fe, respectively3O4The different crystal planes (220), (311), (400), (422), (511), (440) and (533), with no other impurity peaks, are indicated in Fe3O4The crystal form of the particles is not changed during surface functionalization modification, and Fe is not caused3O4Change of crystalline phase
The IR test results show that: 1097.3cm-1Is the Si-OH vibration peak at 750.21cm-1The larger and wider absorption peak is the bending vibration outside the N-H bond surface, which shows that SiO2And amino groups have been successfully modified.
The VSM test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2-APTMS saturation magnetic strength of 20.40emu g-1. Under the applied magnetic field, only 27s, Fe is needed3O4@SiO2APTMS can be isolated from the aqueous solution.
The TGA test results show that: the weight loss before the temperature is less than 200 ℃ is mainly caused by the evaporation of surface adsorbed free moisture, the weight is basically stable after the temperature is 900 ℃, the weight is not changed any more, and the weight loss between 200 ℃ and 900 ℃ is mainly caused by Fe3O4@SiO2-APTMSSiO of the surface2-decomposition of APTMS coating. As can be seen from the figure, the magnetic nanocomposite Fe is functionalized by ultrasonic wave enhancement3O4@SiO2SiO on the surface of APTMS2-an APTMS coating of about 15.5%. And has good thermal stability.
The BET test results show that: functionalized magnetic nanocomposite Fe3O4@SiO2APTMS specific surface area of 98.1m2/g-1。
Adsorption test data
Functionalized magnetic nanocomposite Fe prepared according to example 13O4@SiO2The test data of adsorption of heavy metal Cr (VI) by APTMS is shown in figure 6 (wherein the abscissa is adsorption time t, min, and the ordinate is adsorption capacity q, mg. g)-1)。
The conditions of the adsorption test were as follows: the initial concentration of heavy metal Cr (VI) is 100mg/L, the volume of the solution is 50mL, the pH value is 1, and the adsorbent is Fe3O4@SiO2The dosage of APTMS is 0.03g, the adsorption temperature is 40 ℃, and the frequency of a constant temperature oscillator is 180 r/min.
The performance of the material of the invention on adsorbing heavy metal Cr (VI) is compared with that of the adsorbing materials described in other documents shown in the following Table 1. As can be seen from Table 1, the material of the invention respectively has advantages in adsorption capacity and adsorption removal rate, the comprehensive performance is best, and the removal rate is as high as 92.96%.
TABLE 1
Claims (7)
1. Functional magnetic nanocomposite Fe3O4@SiO2-a process for the preparation of APTMS, characterized in that the process comprises:
under the conditions of ultrasonic irradiation and nitrogen protection, uniformly mixing soluble ferric salt, soluble ferrous salt and oxygen-free deionized water, dropwise adding an ammonia water solution until the pH value is 9-11, stirring at normal temperature for reaction for 20-30 min, and generating nanoscale Fe in the system3O4Particles; then adding 3-aminopropyltrimethoxysilane, ethyl tetrasilicate and polyethylene glycol into the system, stirring and reacting for 3-5 h at 40-50 ℃ to prepare the functional magnetic nano composite material Fe3O4@SiO2And (3) APTMS, separating from the reaction system by using a magnetic separation method, washing and then drying in vacuum to obtain the APTMS.
2. The functionalized magnetic nanocomposite material Fe of claim 13O4@SiO2-APTMS preparation method, characterized in that the soluble ferrous salt is selected from ferrous chloride, ferrous sulfate, ferrous nitrate or ferrous carbonate.
3. The functionalized magnetic nanocomposite material Fe of claim 13O4@SiO2-a process for the preparation of APTMS, characterized in that the soluble ferric salt is selected from ferric chloride, ferric sulphate or ferric nitrate.
4. The functionalized magnetic nanocomposite material Fe of claim 13O4@SiO2-APTMS, characterized in that the mass ratio of the soluble ferrous and ferric salts is 1: 1 to 4.
5. The functionalized magnetic nanocomposite material Fe of claim 13O4@SiO2The preparation method of APTMS is characterized in that the weight ratio of the soluble ferrous salt to the substances of 3-aminopropyl trimethoxy silane, ethyl tetrasilicate and polyethylene glycol is 1: 1-1.04: 0.8-0.9: 1.6 to 1.8.
6. The functionalized magnetic nanocomposite material Fe of claim 13O4@SiO2The preparation method of the APTMS is characterized in that the ammonia water solution is prepared freshly and has the concentration of 0.5-1.5 mol/L.
7. Functionalized magnetic nanocomposite material Fe according to claim 13O4@SiO2The preparation method of APTMS is characterized in that the frequency of the ultrasonic wave is 40-80 KHz, and the power is 80-160W.
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