CN105772097A - Preparation method of silver silicate coated spherical ferroferric oxide core-shell material - Google Patents
Preparation method of silver silicate coated spherical ferroferric oxide core-shell material Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 57
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 230000005291 magnetic effect Effects 0.000 claims description 30
- 230000001476 alcoholic effect Effects 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 230000009514 concussion Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 230000005294 ferromagnetic effect Effects 0.000 abstract 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 abstract 2
- 238000007885 magnetic separation Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000006249 magnetic particle Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- -1 after stirring 30min Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229950000845 politef Drugs 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- 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
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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
- B01J35/30—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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a preparation method of a silver silicate coated spherical ferroferric oxide core-shell material.The preparation method comprises the following steps that a ferromagnetic ferroferric oxide core sample is prepared; the ferromagnetic ferroferric oxide core sample is taken and soaked in an ethanol solution of thioglycolic acid for oscillating reaction, product washing is performed through magnetic separation to obtain a product A after the reaction is completed; the product A is completely soaked in a silver nitrate aqueous solution to obtain a mixed solution C, the mixed solution C undergoes stirring reaction under the dark condition; after the reaction is completed, magnet separation and washing are conducted on the product to obtain a product B; the product B is completely soaked in a sodium silicate aqueous solution to obtain a mixed solution D, mixed solution D undergoes stirring reaction, and after the reaction is completed, magnet separation and washing are conducted on the product to obtain a product C; the steps are repeated for 2 times, product washing is performed, and finally the product is dried to obtain the product silver silicate coated spherical ferroferric oxide core-shell material.The finally prepared product is remarkable in photocatalytic effect and easy to separate.
Description
Technical field
The invention belongs to material preparation and photocatalysis technical field of environment pollution control, be specifically related to the preparation method that a kind of silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Background technology
Along with the constantly discharge of the industrial wastewaters such as printing and dyeing and continuing on of various dyestuffs, problem of environmental pollution is day by day serious, and the dye quantity of entered environment and kind are continuously increased, the Faced In Sustainable Development of human society huge challenge, photocatalysis technology has important application prospect in field of environment pollution control, and traditional photocatalyst also exists preparative separation complexity, reclaim the shortcomings such as difficulty, thus the photocatalyst of development of new has attracted the extensive concern of researcher.
Core-shell material generally by the core at center and be coated on outside shell form.Core-shell material can be macromolecule, inorganic matter and metal etc..Core-shell material has merged the material advantage of each component own, shows the performance being better than each component；It is coated on the shell outside particle and can change the surface nature of nuclear material, and give the characteristics such as particle is optical, electrical, magnetic, catalysis, as changed particle surface electric charge, give that particle is functional, strengthen surface reaction activity, improve particle stability and prevent core and external agency from physically or chemically effect etc. occurring.And the nucleocapsid structure intrinsic due to it and make the controllability of its performance strong, thus have broad application prospects in various fields, have become as the important component part of nanometer material science research.
Ferroso-ferric oxide is a kind of common magnetic material, has important application in various fields.Nano ferriferrous oxide compound other materials also early has relevant report, including metal or nonmetal, semiconductor light-catalyst compound etc..The Fe of a kind of hollow ball structure disclosed in Chinese patent application CN201110127573.73O4/ C nano granule.The mean diameter of the product of hollow ball structure 750 nanometers, wall thickness 250 nanometers.This composite is after repeatedly circulation, it is shown that excellent chemical property.Chinese Patent Application No. CN201210261156.6 discloses a kind of carbon coated ferriferrous oxide and buries ion battery cathode material and preparation method thereof, and this lithium ion battery negative material has higher reversible capacity and good cyclical stability.Chinese Patent Application No. CN201410051760.5 discloses synthetic method and the purposes of a kind of silver/ferroso-ferric oxide/earth silicon/titanic oxide/tetra-layer nucleocapsid structure, greatly improves the regulation effect of organic pollution and heavy metal contaminants in sewage disposal.Nano metal material has bigger specific surface area, and surface activity is high, but very easily reunites, bad dispersibility, has a strong impact on its application.Magnetic ferroferric oxide microspherulite diameter is little, specific surface is bigger, coupling capacity is big, utilize and either physically or chemically its surface is modified or is coated with, by changing its surface group, structure or state, can better improve its dispersibility, and modify the physics that different group generation is new, chemistry, mechanical performance and new function by it.Silver silicate is a kind of photocatalyst preferably, owing to the particular electrical minor structure of silver silicate makes it all have higher reactivity in whole visible-range.Silver silicate is modified ferroso-ferric oxide surface not only to retain its good photocatalytic activity but also make photocatalyst have magnetic, it is simple to separation and recovery.
Summary of the invention
It is an object of the invention to provide the preparation method that a kind of silver silicate is coated with spherical ferroso-ferric oxide core-shell material, by magnetic Nano material with photocatalyst connected applications in technical field of environment pollution control.
The present invention is achieved through the following technical solutions:
The preparation method that a kind of silver silicate is coated with spherical ferroso-ferric oxide core-shell material, comprises the steps:
Step 1, iron chloride is joined in ethylene glycol, stirring and dissolving, obtains mixed liquor A, adds sodium acetate in mixed liquor A, stirring and dissolving, obtain mixed liquid B, mixed liquid B is poured in autoclave, carry out constant temp. heating reaction, after reaction terminates, by Magnet reaction product isolated, washed product, dry and obtain ferroso-ferric oxide magnetic core sample；
Step 2, the ferroso-ferric oxide magnetic core sample taking step 1 preparation are immersed in the alcoholic solution of TGA to carry out concussion reaction, separate with Magnet after completion of the reaction, washed product, obtain product A；
Step 3, product A is all immersed in silver nitrate aqueous solution, obtains mixed liquor C, by stirring reaction under mixed liquor C lucifuge；After completion of the reaction, Magnet separation product, washed product, obtain product B；
Step 4, product B is all immersed in sodium silicate aqueous solution, obtains mixed liquor D, by mixed liquor D stirring reaction, after completion of the reaction, Magnet separation product, washed product, obtain product C；
Step 5, product C is repeated in operating procedure 3 and step 4, circulates 2 times, washed product, finally product is dried acquisition product silver silicate and is coated with spherical ferroso-ferric oxide core-shell material.
In step 1, in mixed liquor A, iron chloride concentration in ethylene glycol is 0.04～0.06g/mL；In mixed liquid B, sodium acetate concentration in ethylene glycol is 0.1～0.125g/mL.
In step 1, the temperature of constant temp. heating reaction is 160～200 DEG C, and the response time is 6～8h.
In step 2, ferroso-ferric oxide magnetic core sample concentration in the alcoholic solution of TGA is 12.5mg/mL, and the concentration of the alcoholic solution of TGA used is 0.2～0.4mmol/L, and the time of concussion reaction is 24h.
In step 3, in mixed liquor C, the concentration of the ferroso-ferric oxide magnetic core sample in product A is 12.5mg/mL, and the time of stirring reaction is 30min, and silver nitrate aqueous solution concentration used is 0.02～0.04mol/L.
In step 4, in mixed liquor D, the concentration of the ferroso-ferric oxide magnetic core sample in product B is 12.5mg/mL, and the time of stirring reaction is 30min, and sodium silicate aqueous solution concentration used is 0.001～0.003g/mL.
In step 1～5, being with distilled water wash once to the mode of washing of product, the baking temperature in step 1 and step 5 is 60 DEG C.
Beneficial effect:
(1) the ferroso-ferric oxide globulate synthesized is good, and particle diameter is less, and dispersibility is better.
(2) by after sulfhydryl modified, it is possible to by finishing silver silicate, formed and have magnetic photocatalyst, recyclable repetition
(3) photocatalysis effect is notable, it is easy to separate.
(4) easy and simple to handle, equipment is simple, and operating cost is low.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the material of preparation in present example 2；
Fig. 2 is the scanning electron microscope (SEM) photograph of the material of preparation in present example 3；
Fig. 3 is the XRD spectra of the material of preparation in present example 1；
Fig. 4 is the magnetic effect figure of the material of preparation in present example 2；
Fig. 5 is the material of the preparation degradation effect figure to methylene blue in present example 1.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described:
Embodiment 1
Take 2g iron chloride, it is added in 40mL ethylene glycol solution, after stirring and dissolving, add 4.3g sodium acetate, after stirring 30min, solution is poured in politef autoclave, react 8h at 200 DEG C, after cooling, separated by Magnet, with distillation washing once, 60 DEG C of drying baker inner dryings obtain ferroso-ferric oxide magnetic core.Taking 0.1g ferroso-ferric oxide magnetic core sample and be immersed in the TGA alcoholic solution interior vibration 24h that 8ml concentration is 0.2mmol/L, obtain sulfhydrylation magnetic particle, Magnet is washed once with distillation after separating.It is in 0.03mol/L silver nitrate aqueous solution that the product being obtained by reacting in the TGA alcoholic solution of 0.2mmol/L is all immersed in 8ml concentration, stirring reaction 30min under lucifuge, and product is washed once with distillation after separating with Magnet.The product that obtains after reaction in 0.03mol/L silver nitrate aqueous solution is all immersed in the sodium silicate aqueous solution that 8ml concentration is 0.0014g/mL, stirring reaction 30min, after by product with distillation washing once；Product after being soaked by sodium silicate aqueous solution at 0.0014g/mL repeats to soak with 0.03mol/L silver nitrate solution and 0.0014g/mL sodium silicate solution respectively, circulate altogether twice, by dry for final product 60 DEG C that silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Embodiment 2
Take 2g iron chloride, it is added in 40mL ethylene glycol solution, after stirring and dissolving, add 4.3g sodium acetate, after stirring 30min, solution is poured in politef autoclave, react 8h at 200 DEG C, after cooling, separated by Magnet, with distillation washing once, 60 DEG C of drying baker inner dryings obtain ferroso-ferric oxide magnetic core.Taking 0.1g ferroso-ferric oxide magnetic core sample and be immersed in the TGA alcoholic solution interior vibration 24h that 8ml concentration is 0.3mmol/L, obtain sulfhydrylation magnetic particle, Magnet is washed once with distillation after separating.It is in 0.03mol/L silver nitrate aqueous solution that the product being obtained by reacting in the TGA alcoholic solution of 0.3mmol/L is all immersed in 8ml concentration, stirring reaction 30min under lucifuge, and product is washed once with distillation after separating with Magnet.The product obtained after reaction in 0.03mol/L silver nitrate aqueous solution is all immersed in the sodium silicate aqueous solution that 8ml concentration is 0.003g/mL, stirring reaction 30min, rear with distilling washing once；Product after being soaked by sodium silicate aqueous solution at 0.003g/mL repeats to soak with 0.03mol/L silver nitrate solution and 0.003g/mL sodium silicate solution respectively, circulates altogether twice, by dry for final product 60 DEG C that silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Embodiment 3
Take 2g iron chloride, it is added in 40mL ethylene glycol solution, after stirring and dissolving, add 4.3g sodium acetate, after stirring 30min, solution is poured in politef autoclave, react 8h at 200 DEG C, after cooling, separated by Magnet, with distillation washing once, 60 DEG C of drying baker inner dryings obtain ferroso-ferric oxide magnetic core.Taking 0.1g ferroso-ferric oxide magnetic core sample and be immersed in the TGA alcoholic solution interior vibration 24h that 8ml concentration is 0.4mmol/L, obtain sulfhydrylation magnetic particle, Magnet is washed once with distillation after separating.It is in 0.03mol/L silver nitrate aqueous solution that the product being obtained by reacting in the TGA alcoholic solution of 0.4mmol/L is all immersed in 8ml concentration, stirring reaction 30min under lucifuge, and product is washed once with distillation after separating with Magnet.The product obtained after reaction in 0.03mol/L silver nitrate aqueous solution is all immersed in the sodium silicate aqueous solution that 8ml concentration is 0.002g/mL, stirring reaction 30min, rear with distilling washing once；Product after being soaked by sodium silicate aqueous solution at 0.002g/mL repeats to soak with 0.03mol/L silver nitrate solution and 0.002g/mL sodium silicate solution respectively, circulates altogether twice, by dry for final product 60 DEG C that silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Embodiment 4
Take 2.4g iron chloride, it is added in 40mL ethylene glycol solution, after stirring and dissolving, add 4g sodium acetate, after stirring 30min, solution is poured in politef autoclave, react 7h at 160 DEG C, after cooling, separated by Magnet, with distillation washing once, 60 DEG C of drying baker inner dryings obtain ferroso-ferric oxide magnetic core.Taking 0.1g ferroso-ferric oxide magnetic core sample and be immersed in the TGA alcoholic solution interior vibration 24h that 8ml concentration is 0.3mmol/L, obtain sulfhydrylation magnetic particle, Magnet is washed once with distillation after separating.It is in 0.02mol/L silver nitrate aqueous solution that the product being obtained by reacting in the TGA alcoholic solution of 0.3mmol/L is all immersed in 8ml concentration, stirring reaction 30min under lucifuge, and product is washed once with distillation after separating with Magnet.The product obtained after reaction in 0.02mol/L silver nitrate aqueous solution is all immersed in the sodium silicate aqueous solution that 8ml concentration is 0.0014g/mL, stirring reaction 30min, rear with distilling washing once；Product after being soaked by sodium silicate aqueous solution at 0.0014g/mL repeats to soak with 0.02mol/L silver nitrate solution and 0.0014g/mL sodium silicate solution respectively, circulate altogether twice, by dry for final product 60 DEG C that silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Embodiment 5
Take 1.6g iron chloride, it is added in 40mL ethylene glycol solution, after stirring and dissolving, add 5g sodium acetate, after stirring 30min, solution is poured in politef autoclave, react 6h at 180 DEG C, after cooling, separated by Magnet, with distillation washing once, 60 DEG C of drying baker inner dryings obtain ferroso-ferric oxide magnetic core.Taking 0.1g ferroso-ferric oxide magnetic core sample and be immersed in the TGA alcoholic solution interior vibration 24h that 8ml concentration is 0.3mmol/L, obtain sulfhydrylation magnetic particle, Magnet is washed once with distillation after separating.It is in 0.04mol/L silver nitrate aqueous solution that the product being obtained by reacting in the TGA alcoholic solution of 0.3mmol/L is all immersed in 8ml concentration, stirring reaction 30min under lucifuge, and product is washed once with distillation after separating with Magnet.The product obtained after reaction in 0.04mol/L silver nitrate aqueous solution is all immersed in the sodium silicate aqueous solution that 8ml concentration is 0.001g/mL, stirring reaction 30min, rear with distilling washing once；Product after being soaked by sodium silicate aqueous solution at 0.001g/mL repeats to soak with 0.04mol/L silver nitrate solution and 0.001g/mL sodium silicate solution respectively, circulates altogether twice, by dry for final product 60 DEG C that silver silicate is coated with spherical ferroso-ferric oxide core-shell material.
Fig. 1 is the transmission electron microscope picture of the material of preparation in present example 2.As seen from Figure 1, after sulfhydrylation is modified, having less granule around magnetic particle, this is the silver silicate granule of cladding, is closely coated on around magnetic core, can react with dye contacts fully.
Fig. 2 is the scanning electron microscope (SEM) photograph of the material of preparation in present example 3.From Figure 2 it can be seen that after sulfhydrylation modification, silver silicate particle is combined closely by sulfydryl and magnetic core, form nucleocapsid structure, make both have good stability.
Fig. 3 is the XRD spectra of the material of preparation in present example 1.As seen from Figure 3, at 36 °, near 57 ° and 62 °, there are obvious ferroso-ferric oxide diffraction maximum, corresponding (311) (511) (440) crystal face.
Fig. 4 is the magnetic effect figure of the material of preparation in present example 2.From fig. 4, it can be seen that photocatalyst has good magnetic, it is easy to separate.
Fig. 5 is the material of the preparation degradation effect figure to methylene blue in present example 1.As seen from Figure 5, photocatalysis effect is better, can reach 90%.
Claims (7)
1. the preparation method that a silver silicate is coated with spherical ferroso-ferric oxide core-shell material, it is characterised in that comprise the steps:
Step 1, iron chloride is joined in ethylene glycol, stirring and dissolving, obtains mixed liquor A, adds sodium acetate in mixed liquor A, stirring and dissolving, obtain mixed liquid B, mixed liquid B is poured in autoclave, carry out constant temp. heating reaction, after reaction terminates, by Magnet reaction product isolated, washed product, dry and obtain ferroso-ferric oxide magnetic core sample；
Step 2, the ferroso-ferric oxide magnetic core sample taking step 1 preparation are immersed in the alcoholic solution of TGA to carry out concussion reaction, separate with Magnet after completion of the reaction, washed product, obtain product A；
Step 3, product A is all immersed in silver nitrate aqueous solution, obtains mixed liquor C, by stirring reaction under mixed liquor C lucifuge；After completion of the reaction, Magnet separation product, washed product, obtain product B；
Step 4, product B is all immersed in sodium silicate aqueous solution, obtains mixed liquor D, by mixed liquor D stirring reaction, after completion of the reaction, Magnet separation product, washed product, obtain product C；
Step 5, product C is repeated in operating procedure 3 and step 4, circulates 2 times, washed product, finally product is dried acquisition product silver silicate and is coated with spherical ferroso-ferric oxide core-shell material.
2. the preparation method that a kind of silver silicate according to claim 1 is coated with spherical ferroso-ferric oxide core-shell material, it is characterised in that in step 1, in mixed liquor A, iron chloride concentration in ethylene glycol is 0.04～0.06g/mL；In mixed liquid B, sodium acetate concentration in ethylene glycol is 0.1～0.125g/mL.
3. the preparation method that a kind of silver silicate according to claim 1 and 2 is coated with spherical ferroso-ferric oxide core-shell material, it is characterised in that in step 1, the temperature of constant temp. heating reaction is 160～200 DEG C, and the response time is 6～8h.
4. the preparation method that a kind of silver silicate according to claim 1 is coated with spherical ferroso-ferric oxide core-shell material, it is characterized in that, in step 2, ferroso-ferric oxide magnetic core sample concentration in the alcoholic solution of TGA is 12.5mg/mL, the concentration of the alcoholic solution of TGA used is 0.2～0.4mmol/L, and the time of concussion reaction is 24h.
5. the preparation method that a kind of silver silicate according to claim 1 is coated with spherical ferroso-ferric oxide core-shell material, it is characterized in that, in step 3, in mixed liquor C, the concentration of the ferroso-ferric oxide magnetic core sample in product A is 12.5mg/mL, the time of stirring reaction is 30min, and silver nitrate aqueous solution concentration used is 0.02～0.04mol/L.
6. the preparation method that a kind of silver silicate according to claim 1 is coated with spherical ferroso-ferric oxide core-shell material, it is characterized in that, in step 4, in mixed liquor D, the concentration of the ferroso-ferric oxide magnetic core sample in product B is 12.5mg/mL, the time of stirring reaction is 30min, and sodium silicate aqueous solution concentration used is 0.001～0.003g/mL.
7. the preparation method that a kind of silver silicate according to claim 1 is coated with spherical ferroso-ferric oxide core-shell material, it is characterised in that in step 1～5, being with distilled water wash once to the mode of washing of product, the baking temperature in step 1 and step 5 is 60 DEG C.
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