CN106902822A - A kind of hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated and preparation method thereof - Google Patents
A kind of hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated and preparation method thereof Download PDFInfo
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- CN106902822A CN106902822A CN201710121153.5A CN201710121153A CN106902822A CN 106902822 A CN106902822 A CN 106902822A CN 201710121153 A CN201710121153 A CN 201710121153A CN 106902822 A CN106902822 A CN 106902822A
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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 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 41
- 229940056319 ferrosoferric oxide Drugs 0.000 title claims abstract description 35
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008187 granular material Substances 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 11
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000012153 distilled water Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 13
- 238000002955 isolation Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011943 nanocatalyst Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ion Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Silicon Compounds (AREA)
Abstract
Hollow ferroso-ferric oxide core-shell structure nano particle the invention discloses a kind of Silica-coated and preparation method thereof.The hollow ferroferric oxide nano granules prepared under certain condition as raw material with ferric chloride hexahydrate, ammonium salt, ethylene glycol are as kernel.It is raw material under certain condition by the outer layer of Silica-coated to hollow ferroferric oxide nano granules with absolute ethyl alcohol, ammoniacal liquor, tetraethyl orthosilicate, obtains the hollow ferroso-ferric oxide core-shell structure of Silica-coated.Preparation method of the present invention is simple, and the catalyst structure stabilization for obtaining, excellent adsorption can be used repeatedly.
Description
Technical field
The present invention relates to a kind of hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated and its preparation side
Method, belongs to catalyst new material technology field.
Background technology
In recent years, the application of catalyst is to developing agricultural, industry and uplifts the people's living standard and all serves great function.
The new catalyst of exploitation is undoubtedly reduces catalytic process energy consumption, the key of lifting catalytic efficiency.Catalyst in reality production should
There should be specific surface area big, good stability, the advantages of active high, and nanocatalyst can just meet these conditions.Nanometer is urged
Agent refer to use particle size for the micro- material of the nanometer of nanometer scale for main body material.Due to the unique performance of nano-particle,
The catalysis activity and selectivity of nanocatalyst are significantly larger than traditional catalyst, as an emerging research field.Magnetic Nano
Catalyst gathers high catalytic activity, magnetic recovery and the novel nano catalyst of one can be re-used in, in life as a kind of
The fields such as thing catalysis, organic synthesis catalysis, water pollution treatment show the unrivaled catalytic performance of traditional catalyst.The present invention
Disclose a kind of preparation method of the hollow ferroferric oxide magnetic nano catalyst of Silica-coated.Hollow four oxygen therein
Change three iron nano-particles merged ferriferrous oxide particles magnetic is strong and hollow material low-density, the features such as specific surface area is big,
And silica has larger specific surface area and chemical stability.Hollow four oxidation three of the Silica-coated in the present invention
Iron nanocatalyst combines the advantage of hollow material and silica well, with good catalysis activity and recycling
Property.
The content of the invention
It is an object of the invention to provide a kind of hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated
Preparation method.
The preparation method of the hollow ferroso-ferric oxide core-shell structure nano particle of described Silica-coated mainly includes：
A. by mol ratio 1:3:180~1:10:180 ferric chloride hexahydrate, ammonium salt and ethylene glycol mixing, while magnetic agitation, obtains
To mixture be put into hydrothermal synthesis reaction kettle and reacted.The hollow ferroferric oxide nano granules that reaction is obtained pass through magnetic
Property separate, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 30 ~ 60mg/L, it is 1 to be added to equipped with volume ratio:35:140~1:14:56 ammoniacal liquor：Distilled water：Absolute ethyl alcohol
In there-necked flask, then 10 ~ 20min of ultrasound will be 12 with hollow ferroferric oxide nano granules mass ratio in 10min:1~38:
1 tetraethyl orthosilicate is added dropwise in there-necked flask, at room temperature 8 ~ 12h of mechanic whirl-nett reaction.The silica bag that reaction is obtained
The hollow ferroso-ferric oxide core-shell structure nano particle wrapped up in passes through Magnetic Isolation, and with after distilled water and absolute ethyl alcohol alternately cleaning
Drying.
The mol ratio preferably 1 of ferric chloride hexahydrate used in the above method, ammonium salt and ethylene glycol:5:180~1:10:180.
The preferred ammonium acetate of ammonium salt used, urea, lauryl amine in the above method.
Preferably 190 ~ 210 DEG C of hydrothermal temperature used in the above method, reaction time preferably 10 ~ 13h.
The mass ratio preferably 15 of tetraethyl orthosilicate used and hollow ferroferric oxide nano granules in the above method:1~
30:1。
The time of mechanic whirl-nett reaction at room temperature preferably 9 ~ 11h used in the above method.
The present invention compared with prior art, has the advantages that：
1. hollow ferroferric oxide nano granules are modified using silica in the present invention, the product application for obtaining is urged
Agent is catalyzed Fenton's reaction, the shortcoming that traditional Fenton process reaction pH can be overcome low, and reacts without external energy.
2. the hollow ferroferric oxide nano granules in the present invention are by solvent structure, by the gas produced in course of reaction
Steep for template forms hollow structure, its particle diameter is determined that larger particle diameter causes the table of hollow ferroso-ferric oxide by the size of bubble
Face can reduce, it is to avoid the generation of agglomeration.Be conducive to the modified of next step silica.
3. the outer layer of the hollow ferroso-ferric oxide core-shell structure nano particle of the Silica-coated in the present invention is porous
The silica of structure, its specific surface area is big, contributes to being fully contacted for catalyst and reactant.Pollutant and peroxidating can be made
Hydrogen preenrichment is around catalyst.
4. the silica shells thickness of the nano particle in the present invention determines by the dosage of tetraethyl orthosilicate, appropriate thick
The silica shells of degree contribute to the electronics between iron ion and pollutant to conduct.The resistance to acids and bases of silica is good, can have
The ferroso-ferric oxide kernel that prevents of effect is corroded.
5. the hollow ferroso-ferric oxide core-shell structure nano particle relatively high magnetism of the Silica-coated in the present invention, is easy to
Separated by externally-applied magnetic field.
6. the hollow ferroso-ferric oxide core-shell structure nanoparticle raw materials of the Silica-coated in the present invention are cheap, reaction
Easy to operate, products therefrom cost is relatively low.
Specific embodiment
Embodiment 1：
A. by mol ratio 1:5:The mixing of 180 ferric chloride hexahydrate, ammonium acetate and ethylene glycol, while magnetic agitation, what is obtained is mixed
Compound is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained are by magnetic point
From, and dry after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 40mg/L, it is 2 to be added to equipped with volume ratio:35:140 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, surpass
Sound 15min, will be then 15 with hollow ferroferric oxide nano granules mass ratio in 10min:1 tetraethyl orthosilicate dropwise adds
Enter in there-necked flask, at room temperature mechanic whirl-nett reaction 10h.The hollow ferroso-ferric oxide shell core of the Silica-coated that reaction is obtained
Structure nano particles are by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 15 times of common ferroso-ferric oxide
Embodiment 2：
A. by mol ratio 1:10:The mixing of 180 ferric chloride hexahydrate, ammonium acetate and ethylene glycol, while magnetic agitation, what is obtained is mixed
Compound is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained are by magnetic point
From, and dry after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 50mg/L, it is 1 to be added to equipped with volume ratio:14:56 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, ultrasound
15min, will be then 20 with hollow ferroferric oxide nano granules mass ratio in 10min:1 tetraethyl orthosilicate is added dropwise over
To in there-necked flask, mechanic whirl-nett reaction 10h at room temperature.The hollow ferroso-ferric oxide shell core knot of the Silica-coated that reaction is obtained
Structure nano particle is by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 20 times of common ferroso-ferric oxide.
Embodiment 3：
A. by mol ratio 1:8:180 ferric chloride hexahydrate, urea and ethylene glycol mixing, while magnetic agitation, the mixing for obtaining
Thing is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained pass through Magnetic Isolation,
And dried after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 50mg/L, it is 1 to be added to equipped with volume ratio:14:56 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, ultrasound
15min, will be then 32 with hollow ferroferric oxide nano granules mass ratio in 5min:1 tetraethyl orthosilicate is added dropwise over
To in there-necked flask, mechanic whirl-nett reaction 10h at room temperature.The hollow ferroso-ferric oxide shell core knot of the Silica-coated that reaction is obtained
Structure nano particle is by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 16 times of common ferroso-ferric oxide.
Embodiment 4：
A. by mol ratio 1:7:180 ferric chloride hexahydrate, urea and ethylene glycol mixing, while magnetic agitation, the mixing for obtaining
Thing is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained pass through Magnetic Isolation,
And dried after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 30mg/L, it is 1 to be added to equipped with volume ratio:20:80 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, ultrasound
20min, will be then 12 with hollow ferroferric oxide nano granules mass ratio in 10min:1 tetraethyl orthosilicate dropwise adds
Enter in there-necked flask, at room temperature mechanic whirl-nett reaction 8h.The hollow ferroso-ferric oxide shell core of the Silica-coated that reaction is obtained
Structure nano particles are by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 17 times of common ferroso-ferric oxide.
Embodiment 5：
A. by mol ratio 1:3:The mixing of 180 ferric chloride hexahydrate, lauryl amine and ethylene glycol, while magnetic agitation, what is obtained is mixed
Compound is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained are by magnetic point
From, and dry after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 60mg/L, it is 1 to be added to equipped with volume ratio:35:140 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, surpass
Sound 10min, will be then 38 with hollow ferroferric oxide nano granules mass ratio in 10min:1 tetraethyl orthosilicate dropwise adds
Enter in there-necked flask, at room temperature mechanic whirl-nett reaction 12h.The hollow ferroso-ferric oxide shell core of the Silica-coated that reaction is obtained
Structure nano particles are by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 16 times of common ferroso-ferric oxide.
Embodiment 6
A. by mol ratio 1:6:The mixing of 180 ferric chloride hexahydrate, lauryl amine and ethylene glycol, while magnetic agitation, what is obtained is mixed
Compound is reacted in being put into hydrothermal synthesis reaction kettle.The hollow ferroferric oxide nano granules that reaction is obtained are by magnetic point
From, and dry after alternately being cleaned with distilled water and absolute ethyl alcohol.
B. obtained hollow ferroferric oxide nano granules in step a are made into concentration in absolute ethyl alcohol through ultrasonic disperse is
The mixed liquor of 40mg/L, it is 1 to be added to equipped with volume ratio:28:112 ammoniacal liquor：Distilled water：In the there-necked flask of absolute ethyl alcohol, surpass
Sound 18min, will be then 35 with hollow ferroferric oxide nano granules mass ratio in 10min:1 tetraethyl orthosilicate dropwise adds
Enter in there-necked flask, at room temperature mechanic whirl-nett reaction 12h.The hollow ferroso-ferric oxide shell core of the Silica-coated that reaction is obtained
Structure nano particles are by Magnetic Isolation, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, temperature be 35 DEG C under conditions of, catalysis activity is 18 times of common ferroso-ferric oxide.
Comparative example 1（Existing core shell structure fenton catalyst）
A. by mass ratio 1:5 Iron dichloride tetrahydrate is dissolved in 50ml distilled water with ferric chloride hexahydrate, and stirring is adjusted simultaneously
PH to 12.Stirring obtains ferroferric oxide nano granules after one hour.
B. obtained ferroferric oxide nano granules are dissolved in distilled water and are made the solution that concentration is 40mg/mL.Add different
Ultrasound 10min after propyl alcohol, isopropanol is 10 with distilled water volume ratio:1.It is subsequently adding ferroferric oxide nano granules：Silicic acid second
Ester is 5:1 tetraethyl orthosilicate.The mixture for obtaining reacts 5h in 35 DEG C, the shaking table of 100rpm.
C. resulting nano particle is used to be catalyzed Fenton's reaction as catalyst, is labored by target contaminant of rhodamine B
Property test, catalysis activity is 10 times of common ferroso-ferric oxide.
As heterogeneous fenton catalyst, the hollow ferroso-ferric oxide shell core knot of the Silica-coated prepared by this patent
Shortcoming and catalysis activity that structure nano particle overcomes conventional homogeneous Fenton process are higher, degradation effect is more preferable.By solvent heat
The hollow ferroferric oxide nano granules particle diameter that method is prepared is larger, and surface can be low, and agglomeration will not occur, and is conducive to connecing down
The silica modified reaction for coming.The silica shells of outer layer covers substantially increase specific surface area, improve catalyst
With the contact area of pollutant, the good absorption property of silica make hydrogen peroxide and pollutant preenrichment catalyst week
Enclose.Therefore the hydroxyl radical free radical degraded that pollutant is directly produced by catalysis.The silica shells of suitable thickness are also to iron ion
Electronics conduction between pollutant has facilitation, improves the degradation efficiency of pollutant.Silica shells have good
Corrosion resistance, effectively prevent hollow ferroso-ferric oxide kernel to be corroded, reduce active component loss.
Claims (5)
1. the hollow ferroso-ferric oxide core-shell structure nano particle of a kind of Silica-coated, it is characterised in that：It has diameter
Be the middle cavity of 150 ~ 300nm, its ferroso-ferric oxide internal layer thickness be 20 ~ 70nm, its silica outer layer thickness be 20 ~
70nm。
2. the preparation side of the hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated described in a kind of claim 1
Method, it is characterised in that comprise the steps：
A. by mol ratio 1:3:180~1:10:180 ferric chloride hexahydrate, ammonium salt and ethylene glycol mixing, while magnetic agitation, obtains
To mixture be put into hydrothermal synthesis reaction kettle and reacted, the hollow ferroferric oxide nano granules that reaction is obtained pass through magnetic
Property separate, and drying after alternately being cleaned with distilled water and absolute ethyl alcohol；
B. by obtained hollow ferroferric oxide nano granules in step a through ultrasonic disperse in absolute ethyl alcohol be made concentration for 30 ~
The mixed liquor of 60mg/L, it is 1 to be added to equipped with volume ratio:35:140~1:14:56 ammoniacal liquor：Distilled water：Three mouthfuls of absolute ethyl alcohol
In bottle, then 10 ~ 20min of ultrasound will be 12 with hollow ferroferric oxide nano granules mass ratio in 10min:1~38:1
Tetraethyl orthosilicate is added dropwise in there-necked flask, at room temperature 8 ~ 12h of mechanic whirl-nett reaction, the Silica-coated that reaction is obtained
Hollow ferroso-ferric oxide core-shell structure nano particle is by Magnetic Isolation, and baking after alternately being cleaned with distilled water and absolute ethyl alcohol
It is dry.
3. the preparation side of the hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated according to claim 2
Method, it is characterised in that the ammonium salt described in step a is the one kind in ammonium acetate, urea, lauryl amine.
4. the preparation side of the hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated according to claim 2
Method, it is characterised in that the reaction condition in hydrothermal synthesis reaction kettle is 180 ~ 220 DEG C of temperature, 10 ~ 15h of reaction time.
5. the Silica-coated described in a kind of any one of claim 1-4 hollow ferroso-ferric oxide core-shell structure nanometer
Application of the grain in Fenton's reaction.
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| CN107497434A (en) * | 2017-09-20 | 2017-12-22 | 华北电力大学 | Catalyst for heterogeneous class Fenton's reaction |
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