CN107442085A - A kind of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material and its preparation method and application - Google Patents
A kind of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of preparation method of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material, belong to magnetic Nano material field.Present invention uses cetyl trimethylammonium bromide, makes CoFe2O4The silicon layer of surface covering becomes fluffy, specific surface area increase, is advantageous to sulfhydryl modified, and sulfydryl is introduced in inert gas, avoids sulfydryl and be oxidized, the introduction volume of sulfydryl is further improved, so as to improve CoFe2O4@SiO2SH can be realized to Hg in water to the absorption property of heavy metal ions in wastewater under relatively low dosage2+The higher synchronous removal with some organic pollutants.The as shown by data of embodiment：CoFe provided by the invention2O4@SiO2When SH sulfydryls introduction volume is 40.5wt%, to Hg2+Adsorption capacity 641.0mg/g, the adsorption capacity 192.7mg/g of Pyrogentisinic Acid, there is good absorption property.
Description
Technical field
The present invention relates to magnetic nanometer composite material technical field, more particularly to a kind of sulfhydryl modified silica ferro-cobalt oxygen
Body core-shell structure magnetic nano composite material and its preparation method and application.
Background technology
Water is one of most important resource in human survival, as economic globalization and industry are magnified, industrial wastewater
Discharge capacity it is increasing, directly or indirectly the living zone to biology is threatened, and jeopardizes human health, and particularly heavy metal is arranged
Water pollution caused by putting also turns into a Tough questions.
Removal for heavy metals in industrial wastewater and organic pollution, currently used method are mainly bioanalysis, changed
Learn the precipitation method, membrane separation process, ion-exchange and absorption method etc..Absorption method have expense it is low, it is easy to operate, do not easily cause two
Secondary pollution, the features such as removal efficiency is high.However, conventional sorbing material such as activated carbon, clay, silica, cellulose and shell gathers
Sugar etc., it is relatively weak to the affinity of some heavy metals such as mercury, cause its adsorption capacity relatively low.Magnetic Nano material is a kind of new
Clever, efficient, easily separated and reproducible heavy-metal adsorption material, quickly it can be separated from solution, and green is without dirt
Dye.In the prior art,B etc., which is disclosed, to be passed throughMethod is by tetraethyl orthosilicate and 3- mercaptopropyi trimethoxies
Base silane is combined, and sulfydryl successfully is introduced into CoFe2O4In nano material, and by this composite (CoFe2O4@SiO2- SH) it is used for
The absorption of lead and mercury is (referring to Removal ofPb (II) ions from aqueous systems using thiol-
functionalized cobalt-ferrite magnetic nanoparticles,Journal ofSol-Gel
Science and Technology,2013,68(3):365~373 and The removal ofHg (II) ions from
aqueous solutions by using thiol-functionalized cobalt ferrite magnetic
nanoparticles,Journal of Sol-Gel Science and Technology,2015,74(1):199~207),
But it is small sulfydryl introduction volume to be present, good adsorption rate can be only shown under relatively low concentration of heavy metal ion, adsorption capacity is low (right
Pb (II) adsorption capacity is 1.8mg/g, and the adsorption capacity to Hg (II) is 1.9mg/g) the problem of.
The content of the invention
In view of this, it is an object of the invention to provide a kind of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic
Nano composite material and its preparation method and application, increase sulfydryl introduction volume, improve CoFe2O4@SiO2- SH absorption property.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of preparation method of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material, the mercapto
Base improved silica Conjugate ferrite core-shell structure magnetic nano composite material has chemical composition shown in Formulas I：
CoFe2O4@SiO2- SH Formulas I,
SiO in Formulas I2- SH is sulfhydryl modified SiO2, the sulfhydryl modified SiO2For shell, the CoFe2O4For core, the system
Preparation Method comprises the following steps：
(1) Conjugate ferrite, cetyl trimethylammonium bromide, silicon source, alkali source and water are mixed and reaction is hydrolyzed, obtained
To CoFe2O4@SiO2Precursor；
(2) CoFe for obtaining the step (1)2O4@SiO2Precursor is calcined, and obtains CoFe2O4@SiO2；
(3) CoFe for obtaining the step (2)2O4@SiO2Inorganic acid activation is carried out, obtains activation products；
(4) in inert gas, activation products that the step (2) is obtained with monohydric alcohol, with the silane coupled of sulfydryl
Agent, glycerine mix with alkali source carries out Silanization reaction, obtains sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nanometer
Composite.
Preferably, the mass ratio of Conjugate ferrite, cetyl trimethylammonium bromide and silicon source is 0.3 in the step (1)
~1.2:0.15~0.6:1~4.
Preferably, the temperature of hydrolysis is 50~90 DEG C in the step (1), time of the hydrolysis for 2~
6h。
Preferably, 350~600 DEG C of the temperature calcined in the step (2), the time of the calcining is 3~6h.
Preferably, the time of inorganic acid activation is 8~12h in the step (3).
Preferably, the quality of activation products, the volume of monohydric alcohol and the silane coupler with sulfydryl in the step (4)
The ratio between volume is 0.2~0.8g:5~20mL:0.3~1.2mL.
Preferably, the silane coupler with sulfydryl includes 3-mercaptopropyi trimethoxy silane, 3- mercaptos in the step (4)
Propyl-triethoxysilicane or 2- mercaptoethyltriethoxysilanes.
Preferably, the temperature of Silanization reaction is 60~90 DEG C in the step (4), and the time of the Silanization reaction is
3~8h.
Present invention also offers sulfhydryl modified silica Conjugate ferrite made from preparation method described in above-mentioned technical proposal
Core-shell structure magnetic nano composite material, the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material
Particle diameter be 80~130nm, the CoFe2O4@SiO2Particle diameter be 70~120nm, the introduction volume of the sulfydryl is with weight percent
Content is calculated as 37.5%~42.85%.
Present invention also offers sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic described in above-mentioned technical proposal to receive
The application of nano composite material in the treatment of waste water.
The invention provides a kind of system of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material
Preparation Method, the chemical composition of the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material are
CoFe2O4@SiO2- SH, the sulfhydryl modified SiO2For shell, the CoFe2O4For core, by Conjugate ferrite, cetyl front three
Reaction is hydrolyzed in base ammonium bromide, silicon source, alkali source and water mixing, obtains CoFe2O4@SiO2Precursor, CoFe2O4@SiO2Precursor
Silane coupler, glycerine with monohydric alcohol, with sulfydryl mixes progress silane with alkali source after carrying out calcining and inorganic acid activation successively
Change reaction, obtain the sulfhydryl modified nano combined material of silica Conjugate ferrite core-shell structure magnetic.Cetyl three in the present invention
Methyl bromide ammonium is a kind of surfactant, is utilizing silicon source to CoFe2O4Surface adds cetyl three while covering silicon layer
Methyl bromide ammonium, makes CoFe2O4The silicon layer of surface covering becomes fluffy, and specific surface area substantially increases, and is advantageous to the sulfydryl of next step
It is modified, and sulfydryl is introduced in inert gas atmosphere, the problem of sulfydryl is oxidized is avoided, further increases the introducing of sulfydryl
Amount, so that CoFe2O4@SiO2- SH has good absorption property, adsorption capacity and absorption to the heavy metal ion in waste water
Efficiency is all improved, moreover it is possible under the conditions of relatively low dosage, while realizes the heavy metal Hg to being coexisted in water2+Partly have
The efficient removal of organic pollutants.The as shown by data of embodiment：CoFe provided by the invention2O4@SiO2In-SH sulfydryl introduction volume with
When weight is 40.5%, heavy metal Hg2+Adsorption capacity be 641.0mg/g, heavy metal Hg2+Absorption
For efficiency high up to 99.4%, the adsorption capacity 192.7mg/g of Pyrogentisinic Acid, the adsorption efficiency of Pyrogentisinic Acid is up to 96.4%, has good
Absorption property.
Moreover, CoFe produced by the present invention2O4@SiO2- SH has the good renewable ability of recycling, and can pass through solution
Recycling is realized in analysis-absorption, is increased operation rate, so as to reduce use cost, also can in the presence of externally-applied magnetic field, from
Magnetic Isolation comes out in water.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is CoFe made from the embodiment of the present invention 12O4@SiO2- SH nano composite material ESEM spectrograms；
Fig. 2 is CoFe made from the embodiment of the present invention 12O4@SiO2- SH nano composite material transmission electron microscope spectrograms；
Fig. 3 is CoFe made from the embodiment of the present invention 12O4@SiO2- SH nano composite materials, CoFe2O4@SiO2、CoFe2O4
Powder infrared spectrum spectrogram；
Fig. 4 is CoFe made from the embodiment of the present invention 12O4@SiO2- SH nano composite materials, CoFe2O4@SiO2、CoFe2O4
Powder hysteresis graph.
Embodiment
The invention provides a kind of system of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material
Preparation Method, the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material have chemical group shown in Formulas I
Into：
CoFe2O4@SiO2- SH Formulas I,
SiO in Formulas I2- SH is sulfhydryl modified SiO2, the sulfhydryl modified SiO2For shell, the CoFe2O4For core, the system
Preparation Method comprises the following steps：
(1) Conjugate ferrite, cetyl trimethylammonium bromide, silicon source, alkali source and water are mixed and reaction is hydrolyzed, obtained
To CoFe2O4@SiO2Precursor；
(2) CoFe for obtaining the step (1)2O4@SiO2Precursor is calcined, and obtains CoFe2O4@SiO2；
(3) CoFe for obtaining the step (2)2O4@SiO2Inorganic acid activation is carried out, obtains activation products；
(4) in inert gas, activation products that the step (2) is obtained with monohydric alcohol, with the silane coupled of sulfydryl
Agent, glycerine mix with alkali source carries out Silanization reaction, obtains sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nanometer
Composite.
The present invention mixes Conjugate ferrite, cetyl trimethylammonium bromide, silicon source, alkali source and water, is hydrolyzed anti-
Should, obtain CoFe2O4@SiO2Precursor.In the present invention, Conjugate ferrite (CoFe2O4) particle diameter be preferably 50~90nm, more preferably
For 70~80nm.
The present invention does not have any special restriction to the source of the Conjugate ferrite, and use is well known to those skilled in the art
Commercial goods are made with reference to art technology conventional technical means, such as refer to《Hydro-thermal method prepares CoFe2O4Nano particle
And characterize》(Dan Yungang, Wuhan University of Technology, 2009) is made in preparation method disclosed in [D].
In the present invention, the cetyl trimethylammonium bromide is a kind of surfactant, is utilizing silicon source pair
CoFe2O4Cetyl trimethylammonium bromide is added during surface covering silicon layer, CoFe can be made2O4The silicon of surface covering
Layer becomes fluffy, and specific surface area substantially increases, and is advantageous to the sulfhydryl modified of next step, increases the introduction volume of sulfydryl.
In the present invention, the silicon source occurs hydrolysis and produces silicon dioxide layer, is coated on CoFe2O4Surface, form nucleocapsid
Structure.In the present invention, the silicon source preferably includes positive esters of silicon acis or silicate, more preferably including methyl silicate, positive silicic acid
Ethyl ester, positive silicic acid propyl ester or sodium metasilicate.
The present invention does not have special restriction to the species of the alkali source, using alkaline matter well known to those skilled in the art
, in embodiments of the present invention, preferably ammoniacal liquor.The present invention does not have special restriction, energy to concentration, the dosage of the ammoniacal liquor
The pH value for enough ensureing hydrolysis reaction system is 10~11.
In the present invention, the mass ratio of the Conjugate ferrite, cetyl trimethylammonium bromide and silicon source be preferably 0.3~
1.2:0.15~0.6:1~4, more preferably 0.5~1:0.2~0.4:2~3.
The present invention does not have to the addition sequence of the Conjugate ferrite, cetyl trimethylammonium bromide, silicon source, alkali source and water
There is special restriction, using charging sequence well known to those skilled in the art.In the present invention, it is preferred to first by cetyl
After trimethylammonium bromide and water are mixed to get cetyl trimethylammonium bromide solution, then by Conjugate ferrite, silicon source and alkali source
Disposably add in the cetyl trimethylammonium bromide solution.In the present invention, it is preferred to including to the cetyl three
Methyl bromide ammonium is ultrasonically treated with the mixed solution of water, and the present invention is to the power of the supersound process, time without spy
Different restriction, it can ensure that cetyl trimethylammonium bromide fully dissolves.
In the present invention, the temperature of the hydrolysis is preferably 50~90 DEG C, more preferably 70~80 DEG C；The hydrolysis
The time of reaction is preferably 2~6h, more preferably 3~4h.In hydrolysis reaction, the surfactant cetyl three
Methyl bromide ammonium is modified in CoFe2O4Surface, the silicon source occur hydrolysis and produce silicon dioxide layer, be coated on by hexadecane
The CoFe of base trimethylammonium bromide modification2O4Surface, form core shell structure.The present invention is to the device of the hydrolysis without spy
Different restriction, using hydrolysis reaction device well known to those skilled in the art.
After the completion of hydrolysis, the system after hydrolysis is preferably carried out separation of solid and liquid, washing and done by the present invention successively
It is dry, obtain CoFe2O4@SiO2Precursor.System after preferred pair hydrolysis of the present invention carries out separation of solid and liquid and obtains solid product.
The present invention does not have special restriction to the concrete mode of the separation of solid and liquid, using separation of solid and liquid well known to those skilled in the art
Mode, in embodiments of the present invention, preferably filter.
After separation of solid and liquid, preferred pair solid product of the present invention is washed, and obtains washed product.In the present invention, it is described
It is preferably water to wash the detergent used.The present invention is to the washing times of the detergent, that the dosage of detergent does not have is special
Limit, solid product can be washed to neutrality.
After washing, preferred pair washed product of the present invention is dried to obtain CoFe2O4@SiO2Precursor.The present invention is to described dry
Dry concrete mode does not have special restriction, using drying mode well known to those skilled in the art, specifically, as dried
It is dry.The present invention does not have special restriction to the temperature of the drying, time, can remove the moisture in washed product completely and be
Can.
Obtain CoFe2O4@SiO2It is of the invention by the CoFe after precursor2O4@SiO2Precursor is calcined, and obtains CoFe2O4@
SiO2.In the present invention, the temperature of the calcining is preferably 350~600 DEG C, more preferably 400~500 DEG C；The calcining
Time is preferably 3~6h, more preferably 4~5h.The present invention does not have special restriction to the device of the calcining, using this area
Calciner plant known to technical staff, specifically, such as Muffle furnace.In the present invention, the calcining can remove CoFe2O4@
SiO2Cetyl trimethylammonium bromide in precursor, makes CoFe2O4@SiO2Form porous fluffy state.
Obtain CoFe2O4@SiO2Afterwards, it is of the invention by the CoFe2O4@SiO2Inorganic acid activation is carried out, obtains activation products.
In the present invention, the activation is specially by the CoFe2O4@SiO2It is dipped in inorganic acid.In the present invention, the inorganic acid
The time of activation is preferably 8~12h, more preferably 9~10h.In the present invention, the inorganic acid activation can be by CoFe2O4@
SiO2The functional groups such as the hydroxyl on surface activate, and are advantageous to the sulfhydryl modified of next step.
In the present invention, the concentration of the inorganic acid is preferably 0.5~2mol/L, more preferably 1mol/L.The present invention is right
The species of the inorganic acid does not have special restriction, using inorganic acid well known to those skilled in the art；Of the invention real
Apply in example, preferably hydrochloric acid or nitric acid.
After inorganic acid activation, preferred pair activation system of the present invention carries out separation of solid and liquid, washing and drying successively, is activated
Product.Preferred pair activation system of the present invention carries out separation of solid and liquid and obtains solid product.The present invention is to the specific of the separation of solid and liquid
Mode does not have special restriction, using solid-liquid separation method well known to those skilled in the art, in embodiments of the present invention,
Preferably filter.
After the completion of separation of solid and liquid, preferred pair solid product of the present invention is washed.In the present invention, it is described to wash what is used
Detergent is preferably water.The present invention does not have special restriction to the washing times of the detergent, the dosage of detergent, can incite somebody to action
Solid product is washed to neutrality.
After the completion of washing, preferred pair washed product of the present invention is dried to obtain activation products.The present invention is to the drying
Concrete mode there is no special restriction, using drying mode well known to those skilled in the art, specifically, as dry.
The present invention does not have special restriction to the temperature of the drying, time, can remove the moisture in washed product completely.
After obtaining activation products, the present invention is in inert gas, by the activation products, monohydric alcohol, the silane with sulfydryl
Coupling agent, glycerine mix with alkali source carries out Silanization reaction, obtains sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic
Nano composite material.
In the present invention, the silane coupler with sulfydryl preferably includes 3-mercaptopropyi trimethoxy silane, 3- mercaptos
Propyl-triethoxysilicane or 2- mercaptoethyltriethoxysilanes.The present invention does not have to the source of the silane coupler with sulfydryl
There is special restriction, using commercial goods well known to those skilled in the art.
In the present invention, the glycerine is reaction dissolvent, provides uniform reaction environment for Silanization reaction, is advantageous to silicon
Each raw material is well mixed during alkylation reaction.In the present invention, the monohydric alcohol is preferably methanol or absolute ethyl alcohol.In the present invention,
The monohydric alcohol enables activation products to be mixed well with glycerine, preferably provides ring for the Silanization reaction of next step
Border.
The present invention does not have special restriction to the species of the alkali source, using alkaline matter well known to those skilled in the art
, in embodiments of the present invention, preferably ammoniacal liquor.The present invention does not have special restriction, energy to concentration, the dosage of the ammoniacal liquor
The pH value for enough ensureing Silanization reaction system is 10~11.In the present invention, the pH value of the Silanization reaction system is
10~11 are more beneficial for the progress of Silanization reaction.
The present invention does not have special restriction to the species of the inert gas, using inertia well known to those skilled in the art
Gas, in embodiments of the present invention, preferably nitrogen.The inert gas is preferably passed into reaction system by the present invention
Obtain atmosphere of inert gases.
In the present invention, the quality of the activation products, the volume of monohydric alcohol and the volume of the silane coupler with sulfydryl
The ratio between be preferably 0.2~0.8g:5~20mL:0.3~1.2mL, more preferably 0.3~0.5g:10~15mL:0.5~1mL.
The present invention does not have to the addition sequence of the activation products, monohydric alcohol, the silane coupler with sulfydryl, glycerine and alkali source
There is special restriction, in embodiments of the present invention, preferably first will be living using charging sequence well known to those skilled in the art
Change product, monohydric alcohol and glycerine and be mixed to get mixed solution, sequentially add alkali source and the silane coupler with sulfydryl.In this hair
In bright, the mixing is preferably stirred under inert gas shielding, and the present invention is not special to time of the stirring, rotating speed
Restriction, time and rotating speed using stirring well known to those skilled in the art, can ensure well mixed.In the present invention
In, the silane coupler with sulfydryl is added in mixed solution after preferably being mixed with organic solvent；In the present invention, it is described
Organic solvent is preferably identical with above-mentioned monohydric alcohol species.The present invention does not have special restriction to the dosage of the organic solvent, protects
Silane coupler of the card with sulfydryl is sufficiently mixed uniformly with organic solvent.In the present invention, the silane with sulfydryl is even
Connection agent is slowly dropped in the mixed solution again after preferably being mixed with organic solvent.The present invention does not have to the speed of the dropwise addition
Special restriction, it can ensure that Silanization reaction fully occurs for the silane coupler with sulfydryl.
In the present invention, the temperature of the Silanization reaction is preferably 60~90 DEG C, more preferably 70~80 DEG C；The silicon
The time of alkylation reaction is preferably 3~8h, more preferably 5~6h.In the present invention, it is preferred to reached by way of heating water bath
The temperature of the Silanization reaction.In the present invention, the Silanization reaction is preferred is first being passed through reaction system by inert gas
In the case of carry out 1~3h, then again close inert gas be passed through in the case of carry out 2~5h.In the present invention, it is described
Close progress Silanization reaction in the case that inert gas is passed through and be avoided that solvent loss caused by under long-time high temperature, and will not
Reaction condition is destroyed, while cost can be saved.
The present invention does not have special restriction to the container of the Silanization reaction, using well known to those skilled in the art anti-
Container is answered, in embodiments of the present invention, preferably three-necked flask.
After the completion of Silanization reaction, the present invention preferably carries out the system after Silanization reaction separation of solid and liquid, washing successively
And drying, obtain sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material (CoFe2O4@SiO2-SH)。
System after preferred pair Silanization reaction of the present invention carries out separation of solid and liquid and obtains solid product.The present invention is to the separation of solid and liquid
Concrete mode does not have special restriction, using solid-liquid separation method well known to those skilled in the art, implements in the present invention
In example, preferably filter.
After the completion of separation of solid and liquid, preferred pair solid product of the present invention is washed.In the present invention, it is described to wash what is used
Detergent is preferably water.The present invention does not have special restriction to the washing times of the detergent, the dosage of detergent, can incite somebody to action
Solid product is washed to neutrality.
After the completion of washing, preferred pair washed product of the present invention is dried to obtain CoFe2O4@SiO2-SH.The present invention is to institute
Stating dry concrete mode does not have special restriction, using drying mode well known to those skilled in the art, specifically, such as
Vacuum drying.The present invention does not have special restriction to the vacuum drying vacuum, temperature, time, can be by washed product
In moisture completely remove.
Present invention also offers sulfhydryl modified silica Conjugate ferrite made from preparation method described in above-mentioned technical proposal
Core-shell structure magnetic nano composite material, the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material
Particle diameter be preferably 80~130nm, more preferably 90~110nm；The CoFe2O4@SiO2Particle diameter be preferably 70~120nm,
More preferably 80~100nm；The introduction volume of the sulfydryl is preferably 37.5~42.85% with weight, more preferably
For 39~42%, most preferably 40.5%.
Present invention also offers sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic described in above-mentioned technical proposal to receive
The application of nano composite material in the treatment of waste water.Sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic provided by the invention
Nano composite material can be used as sorbent treatment waste water, specific such as electroplating technology waste water, dyeing waste water, refinery effluent.
In the present invention, the pH value of the waste water is preferably 2~10, and more preferably 6~7.
In the present invention, the concentration of the heavy metal ions in wastewater is preferably 10~60mg/L, more preferably 20~
50mg/L；The concentration of the Organic Pollutants in Wastewater is preferably 5~30mg/L, more preferably 10~20mg/L；The sulfydryl changes
The property quality of silica Conjugate ferrite core-shell structure magnetic nano composite material and the volume ratio of waste water be preferably 30~
100mg:1L, more preferably 50~80mg:1L.
With reference to embodiment to sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nanometer provided by the invention
Composite and its preparation method and application is described in detail, but they can not be interpreted as to the scope of the present invention
Restriction.
Embodiment 1
Weigh 2g cobalt nitrate hexahydrates, 5g ferric acetyl acetonades, 3g anhydrous sodium acetates and 1g polyethylene glycol and be dissolved in 50mL ethylene glycol
In, it is stirred until homogeneous, moves in reactor and react 14h at 180 DEG C, washs obtained product and 12h is dried at 60 DEG C, obtain
Particle diameter is 50nm CoFe2O4Powder；
By 0.15g cetyl trimethylammonium bromides are soluble in water and ultrasonic 20min, 0.3g CoFe are added2O4Powder,
1mL tetraethyl orthosilicates and 1mL ammoniacal liquor (25-28wt%), 3h is reacted at 80 DEG C, obtained product washing is simultaneously dried at 60 DEG C,
Obtain CoFe2O4@SiO2Precursor；
Above-mentioned product is put into Muffle furnace 4h is calcined at 400 DEG C, then simultaneously dried with 1M HCl activation process 12h, washing,
Obtain CoFe2O4@SiO2。
Weigh 0.2gCoFe2O4@SiO2It is placed in three-necked flask, while adds 5mL methanol, adds 50mL glycerine, be passed through
N2It is stirred, then the heating water bath at 70 DEG C, adds 2mL ammoniacal liquor (25-28wt%), by 0.3mL 3- mercaptopropyi front threes
TMOS is slowly added dropwise into three-necked flask after being dissolved in 5mL methanol, in N2After reacting 1h under atmosphere, N is closed2Continue to react 5h,
Obtained product is washed, vacuum drying 10h obtains sulfhydryl modified CoFe at 50 DEG C2O4@SiO2- SH nano composite materials.
After testing, sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material made from the present embodiment
Particle diameter be 80nm, CoFe2O4@SiO2Particle diameter be 70nm, the introduction volume of sulfydryl is using weight as 40.5%.
To CoFe made from embodiment 12O4@SiO2- SH nano composite materials are scanned electronic microscope photos, as a result such as Fig. 1 institutes
Show, as seen from Figure 1, after adding 3-mercaptopropyi trimethoxy silane, the CoFe of preparation2O4@SiO2The nano combined materials of-SH
The favorable dispersibility of material.
To CoFe made from embodiment 12O4@SiO2- SH nano composite materials carry out transmission electron microscope analysis, as a result such as Fig. 2 institutes
Show, as seen from Figure 2, the CoFe of preparation2O4@SiO2The magnetic core of black is by translucent SiO inside-SH nano composite materials2
Layer is covered, and has obvious nucleocapsid structure.
To CoFe made from embodiment 12O4@SiO2- SH nano composite materials, CoFe2O4@SiO2、CoFe2O4Powder is carried out
Infrared spectrum analysis, as a result as shown in figure 3, as seen from Figure 3, in 2928cm-1Place observes C-H stretching vibration peaks, shows
Sulfydryl success grafting is in CoFe2O4@SiO2On.
To CoFe made from embodiment 12O4@SiO2- SH nano composite materials, CoFe2O4@SiO2、CoFe2O4Powder is carried out
Magnetic hysteresis is analyzed, as a result as shown in figure 4, as seen from Figure 4, the CoFe of preparation2O4@SiO2The saturation magnetic of-SH nano composite materials
Strong is 11.6emu/g, with CoFe2O4@SiO2、CoFe2O4Powder is compared, and has preferable Magneto separate characteristic.
Take 100mL, the heavy metal Hg containing 40mg/L2+Solion is placed in 250mL conical flask, with hydrochloric acid or hydroxide
The regulation such as sodium pH adds 6.2mg CoFe after being 82O4@SiO2- SH nano composite materials, will be above-mentioned after shaking 4h at normal temperatures
Conical flask is placed in external magnetic field, is separated after being magnetized using external magnetic field to sorbing material with solution.After separation
Supernatant is using ICP-OES to remaining heavy metal Hg in solution2+Ion concentration is detected, testing result and solution before absorption
Middle Hg2+After the initial concentration of ion is compared, by the way that CoFe is calculated2O4@SiO2- SH nano composite material heavy metals
Hg2+Adsorption capacity 641.0mg/g, now heavy metal Hg2+Removal efficiency be：99.4%.
CoFe2O4@SiO2- SH nano composite materials adsorb Hg2+Parsing recycles afterwards
(1) resolving
100mL 5%EDTA+1M HCl solutions are taken in 250mL conical flasks, add absorption Hg2+The material reclaimed afterwards, shakes
Normal temperature water-bath concussion 20min in bed, after pickling is parsed, by drying for standby after material pure water.
(2) adsorption process after parsing
Adsorption experiment is carried out after being parsed again.Take 100mL, the heavy metal Hg containing 40mg/L2+Solion is placed in
It is 8 with the regulation such as hydrochloric acid or sodium hydroxide pH in 250mL conical flask, the concussion of water-bath at normal temperatures 6h carries out adsorption experiment.5
Its adsorption capacity is the 85.6% of initial adsorption ability after secondary parsing-absorption, and the regeneration rate of material is high.
Embodiment 2
Weigh 4g acetylacetone cobalts, 10g ferric acetyl acetonades, 6g anhydrous sodium acetates and 2g polyethylene glycol and be dissolved in 100mL second two
In alcohol, it is stirred until homogeneous, moves in reactor and react 12h at 200 DEG C, washs obtained product and 12h is dried at 60 DEG C, obtain
To the CoFe that particle diameter is 90nm2O4Powder；
By 0.3g cetyl trimethylammonium bromides are soluble in water and ultrasonic 20min, 0.6g CoFe are added2O4Powder, 2mL
Methyl silicate and 0.5g sodium hydroxides, 3h is reacted at 70 DEG C, obtained product washing is simultaneously dried at 60 DEG C, is obtained
CoFe2O4@SiO2Precursor；
Above-mentioned product is put into Muffle furnace 4h is calcined at 500 DEG C, then simultaneously dried with 1M HCl activation process 12h, washing,
Obtain CoFe2O4@SiO2。
Weigh 0.4gCoFe2O4@SiO2It is placed in three-necked flask, while adds 10mL absolute ethyl alcohols, it is sweet adds 100mL
Oil, it is passed through N2It is stirred, then the heating water bath at 60 DEG C, adds 4mL ammoniacal liquor (25-28wt%), by 0.6mL 3- sulfydryls
Propyl-triethoxysilicane is slowly added dropwise into three-necked flask after being dissolved in 10mL absolute ethyl alcohols, in N2After reacting 2h under atmosphere, close
Close N2Continue to react 4h, obtained product is washed, at 60 DEG C and be dried in vacuo 12h and obtain sulfhydryl modified CoFe2O4@SiO2-
SH nano composite materials.
After testing, sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material made from the present embodiment
Particle diameter be 130nm, CoFe2O4@SiO2Particle diameter be 120nm, the introduction volume of sulfydryl is using weight as 41.3%.
100mL, the phenol solution containing 10mg/L are taken in 250mL conical flask, pH is adjusted with hydrochloric acid or sodium hydroxide etc.
For 6,5mg CoFe is added afterwards2O4@SiO2- SH nano composite materials, after 6h is shaken in water-bath at normal temperatures, by above-mentioned conical flask
It is placed in external magnetic field, is separated after being magnetized using external magnetic field to sorbing material with solution.Supernatant after separation
Remaining phenol concentration in solution is detected using ultraviolet specrophotometer, testing result and Phenol in Aqueous Solution before absorption
After initial concentration is compared, CoFe can be drawn by calculating2O4@SiO2The adsorption capacity of-SH nano composite material Pyrogentisinic Acids
192.7mg/g, now Pyrogentisinic Acid removal efficiency：96.4%.
To CoFe2O4@SiO2Parse and recycle after-SH nano composite material adsorbing phenols
(1) resolving
100mL absolute ethyl alcohols are taken in 250mL conical flasks, add the material that reclaims after adsorbing phenol, normal-temperature water in shaking table
Bath concussion 30min, after the completion of elution, by drying for standby after material pure water.
(2) adsorption process after parsing
Adsorption experiment is carried out after being parsed again.100mL, the phenol solution containing 10mg/L are taken in 250mL conical flask
In, it is 6 with the regulation such as hydrochloric acid or sodium hydroxide pH, the concussion of water-bath at normal temperatures 8h carries out adsorption experiment, after 5 parsing-absorption
Its adsorption capacity is the 81.2% of initial adsorption ability, shows that material has good regenerability.
Embodiment 3
Weigh 8g cobalt chlorides, 20g iron chloride, 12g anhydrous sodium acetates and 4g polyethylene glycol to be dissolved in 200mL ethylene glycol, stir
Mix to uniform, move in reactor and react 14h at 180 DEG C, wash obtained product and 8h is dried at 80 DEG C, obtaining particle diameter is
70nm CoFe2O4Powder；
By 0.6g cetyl trimethylammonium bromides are soluble in water and ultrasonic 20min, 1.2g CoFe are added2O4Powder, 4mL
Positive silicic acid propyl ester and 4mL ammoniacal liquor (25-28wt%), 3h is reacted at 50 DEG C, obtained product washing is simultaneously dried at 60 DEG C, is obtained
CoFe2O4@SiO2Precursor；
Above-mentioned product is put into Muffle furnace 4h is calcined at 450 DEG C, then simultaneously dried with 1M nitric acid activation process 12h, washing,
Obtain CoFe2O4@SiO2。
Weigh 0.8gCoFe2O4@SiO2It is placed in three-necked flask, while adds 20mL absolute ethyl alcohols, it is sweet adds 200mL
Oil, it is passed through N2It is stirred, then the heating water bath at 80 DEG C, adds 6mL ammoniacal liquor (25-28wt%), by 1.2mL 3- sulfydryls
Propyl-triethoxysilicane is slowly added dropwise into three-necked flask after being dissolved in 5mL absolute ethyl alcohols, in N2After reacting 2h under atmosphere, close
N2Continue to react 5h, obtained product is washed, vacuum drying 12h obtains sulfhydryl modified CoFe at 60 DEG C2O4@SiO2- SH receives
Nano composite material.
After testing, sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material made from the present embodiment
Particle diameter be 90nm, CoFe2O4@SiO2Particle diameter be 80nm；The introduction volume of sulfydryl is using weight as 39.8%.
Take 100mL, the respectively phenol containing 20mg/L and 50mg/L Hg2+Solution in 250mL conical flask, with hydrochloric acid or
The regulation such as sodium hydroxide pH is 7, adds 10mg CoFe afterwards2O4@SiO2- SH nano composite materials, the concussion of water-bath at normal temperatures
After 6h, above-mentioned conical flask is placed in external magnetic field, divided after being magnetized using external magnetic field to sorbing material with solution
From.Supernatant after separation is using ultraviolet specrophotometer to remaining phenol, Hg in solution2+Concentration is detected, detection knot
Fruit and Phenol in Aqueous Solution, Hg before absorption2+Initial concentration be compared after, by calculate can draw CCoFe2O4@SiO2-SH
Nano composite material Pyrogentisinic Acid and Hg2+Adsorption capacity be respectively：152.4mg/g and 476.1mg/g, now Pyrogentisinic Acid and Hg2+
Removal efficiency be respectively：76.2% and 95.2%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material, the sulfydryl
Improved silica Conjugate ferrite core-shell structure magnetic nano composite material has chemical composition shown in Formulas I：
CoFe2O4@SiO2- SH Formulas I,
SiO in Formulas I2- SH is sulfhydryl modified SiO2, the sulfhydryl modified SiO2For shell, the CoFe2O4For core, the preparation side
Method comprises the following steps：
(1) Conjugate ferrite, cetyl trimethylammonium bromide, silicon source, alkali source and water are mixed and reaction is hydrolyzed, obtained
CoFe2O4@SiO2Precursor；
(2) CoFe for obtaining the step (1)2O4@SiO2Precursor is calcined, and obtains CoFe2O4@SiO2；
(3) CoFe for obtaining the step (2)2O4@SiO2Inorganic acid activation is carried out, obtains activation products；
(4) it is silane coupler with monohydric alcohol, with sulfydryl of activation products that the step (2) is obtained, sweet in inert gas
Oil and alkali source mixing carry out Silanization reaction, obtain the sulfhydryl modified nano combined material of silica Conjugate ferrite core-shell structure magnetic
Material.
2. preparation method according to claim 1, it is characterised in that Conjugate ferrite, cetyl three in the step (1)
Methyl bromide ammonium and the mass ratio of silicon source are 0.3~1.2:0.15~0.6:1~4.
3. preparation method according to claim 1 or 2, it is characterised in that the temperature of hydrolysis is in the step (1)
50~90 DEG C, the time of the hydrolysis is 2~6h.
4. preparation method according to claim 1, it is characterised in that in the step (2) temperature of calcining for 350~
600 DEG C, the time of the calcining is 3~6h.
5. preparation method according to claim 1, it is characterised in that the time of inorganic acid activation is 8 in the step (3)
~12h.
6. preparation method according to claim 1, it is characterised in that the quality of activation products, unitary in the step (4)
The ratio between the volume of alcohol and the volume of silane coupler with sulfydryl are 0.2~0.8g:5~20mL:0.3~1.2mL.
7. the preparation method according to claim 1 or 6, it is characterised in that with the silane coupled of sulfydryl in the step (4)
Agent includes 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyltriethoxysilanes or 2- mercaptoethyltriethoxysilanes.
8. preparation method according to claim 1, it is characterised in that the temperature 60 of Silanization reaction in the step (4)
~90 DEG C, the time of the Silanization reaction is 3~8h.
9. sulfhydryl modified silica Conjugate ferrite core shell structure made from preparation method described in claim 1~8 any one
Magnetic nanometer composite material, it is characterised in that the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic is nano combined
The particle diameter of material is 80~130nm, the CoFe2O4@SiO2Particle diameter be 70~120nm, the introduction volume of the sulfydryl is with weight
Percentage composition is calculated as 37.5~42.85%.
10. the sulfhydryl modified silica Conjugate ferrite core-shell structure magnetic nano composite material described in claim 9 is in waste water
Application in processing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355627A (en) * | 2018-03-13 | 2018-08-03 | 苏州科技大学 | A kind of preparation method and application of polypyrrole modified magnetic nanocomposite |
| CN108822523A (en) * | 2018-05-31 | 2018-11-16 | 西安科技大学 | Modified Nano cobalt ferrite/poly (arylene ether nitrile) dielectric composite material and its preparation process |
| CN110102262A (en) * | 2019-06-21 | 2019-08-09 | 苏州科技大学 | A kind of magnetic active carbon composite material and its preparation method and application |
| CN114566589A (en) * | 2022-01-25 | 2022-05-31 | 西南交通大学 | Biological material with magnetoelectric effect and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103536935A (en) * | 2013-11-26 | 2014-01-29 | 上海师范大学 | Photosensitizer-modified core-shell structure magnetic nanocomposites and preparation method and application thereof |
| CN103599751B (en) * | 2013-10-25 | 2016-06-01 | 浙江大学 | The preparation method of thiol-functionalizedmagnetic magnetic silica nano-material |
-
2017
- 2017-08-15 CN CN201710696896.5A patent/CN107442085A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599751B (en) * | 2013-10-25 | 2016-06-01 | 浙江大学 | The preparation method of thiol-functionalizedmagnetic magnetic silica nano-material |
| CN103536935A (en) * | 2013-11-26 | 2014-01-29 | 上海师范大学 | Photosensitizer-modified core-shell structure magnetic nanocomposites and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HE ZHU，ET AL: ""Highly promoted removal of Hg(II) with magnetic CoFe2O4@SiO2 core–shell nanoparticles modified by thiol groups"", 《RSC ADVANCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355627A (en) * | 2018-03-13 | 2018-08-03 | 苏州科技大学 | A kind of preparation method and application of polypyrrole modified magnetic nanocomposite |
| CN108822523A (en) * | 2018-05-31 | 2018-11-16 | 西安科技大学 | Modified Nano cobalt ferrite/poly (arylene ether nitrile) dielectric composite material and its preparation process |
| CN110102262A (en) * | 2019-06-21 | 2019-08-09 | 苏州科技大学 | A kind of magnetic active carbon composite material and its preparation method and application |
| CN114566589A (en) * | 2022-01-25 | 2022-05-31 | 西南交通大学 | Biological material with magnetoelectric effect and preparation method thereof |
| CN114566589B (en) * | 2022-01-25 | 2024-03-12 | 西南交通大学 | Biological material with magnetoelectric effect and preparation method thereof |
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