CN106955672A - A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application - Google Patents
A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application Download PDFInfo
- Publication number
- CN106955672A CN106955672A CN201710261398.8A CN201710261398A CN106955672A CN 106955672 A CN106955672 A CN 106955672A CN 201710261398 A CN201710261398 A CN 201710261398A CN 106955672 A CN106955672 A CN 106955672A
- Authority
- CN
- China
- Prior art keywords
- sio
- treatment agent
- group
- magnetic
- water treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses enhanced magnetic nano water treatment agent of a kind of group and its preparation method and application, it is characterized in that, the accurate six directions water iron chloride and anhydrous sodium acetate of weighing is reaction raw materials, first raw material is dissolved in ethylene glycol, polyethylene glycol is added to be disperseed, solution is added in autoclave container again and reacted, magnetic obtains Fe3O4Magnetic nanoparticle, then make Fe using tetraethyl orthosilicate as silicon source3O4Magnetic nanoparticle Surface coating silica；And make its surface graft NH by amino source of silane coupler2Group, obtains Fe3O4@SiO2‑NH2Magnetic nanoparticle；Finally stirring makes the amino and mercapto groups of cysteine modify in Fe at normal temperatures3O4@SiO2‑NH2The surface of magnetic nanoparticle, obtains the enhanced magnetic nano water treatment agent Fe of group3O4‑SiO2‑NH2‑L‑Cys；The present invention preparation process is simple to operate, reaction condition is easily realized, and the particle diameter distribution of the enhanced magnetic nanoparticle of group prepared by the present invention is narrow, good stability, have good adsorption function, adsorption efficiency high the contents of many kinds of heavy metal ion.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of enhanced magnetic nano water treatment agent of group and its system
Preparation Method and application.
Background technology
With the fast development of modern industry, increasingly serious the problem of environmental pollution, wherein heavy metal pollution is to animals and plants
Growth, the healthy and living environment of breeding and the mankind bring serious threat, therefore, present heavy metal waste water
Carry out the vital task that effective, environmentally friendly and low-cost processes are field of Environment Protection.At present, the processing method master of heavy metal wastewater thereby
Will be by bioanalysis, chemical method and Physical；Bioanalysis is also in developing stage because adsorption efficiency is low；Chemical method efficiency high, but
Energy consumption is big, is also easy to produce secondary pollution；And Physical be by ion exchange etc. effect will be heavy metal ion adsorbed in Shui Chu in water
Agent surface is managed, so as to go heavy metal ion in water removal, the method is simple and easy to apply, and secondary pollution is small, low cost, useless in heavy metal
It is used widely in water process.
It is widely studied in recent years to regard ferroso-ferric oxide as the magnetic water treatment agent on processing heavy metal wastewater thereby basis, but mesh
The preceding ferroferric oxide magnetic nano-material product applied to water treatment field also has some shortcomings：Fe 3 O 4 magnetic
The particle diameter of nano material is distributed that wide, in irregular shape, dispersion stabilization is poor, preparation technology is complicated, Adsorption of Heavy Metals ion
Species is single, adsorption efficiency is low and sediment weight is big etc., cause the processing of current heavy metal wastewater thereby to there is processing procedure not ring
Guarantor, high and treatment time length and heavy metal ion the low shortcoming of clearance of processing cost.
At present, Heavy Metals in Waters pollution problem caused society extensive concern, can heavy metal waste water enter
Row is efficient, environmental protection treatment has become mankind's problem urgently to be resolved hurrily, therefore, a kind of heavy metal containing wastewater treatment time is researched and developed now
The magnetic Nano water treatment agent that short, sediment weight is small, convenient for production and removal of heavy metal ions rate is high is used at heavy metal wastewater thereby
Reason is extremely necessary.
The content of the invention
For above-mentioned the deficiencies in the prior art, the technical problems to be solved by the invention are：How a kind of particle is provided
Footpath distribution with, dispersion stabilization is good, preparation technology is simple, adsorption efficiency is high and contents of many kinds of heavy metal ion can be inhaled
Enhanced magnetic nano water treatment agent of attached group and its preparation method and application.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of enhanced magnetic nano water treatment agent of group, it is characterised in that the molecular formula of the water treatment agent is Fe3O4-
SiO2-NH2-L-Cys。
A kind of preparation method of the enhanced magnetic nano water treatment agent of group, six directions water iron chloride and anhydrous sodium acetate is molten
Solution adds polyethylene glycol until being uniformly dispersed, reaction obtains Fe in ethylene glycol3O4Magnetic nanoparticle；With tetraethyl orthosilicate
Make Fe as silicon source3O4Magnetic nanoparticle Surface coating silica, obtains Fe3O4@SiO2Magnetic nanoparticle；Again with silane
Silane coupler makes its surface graft-NH for amino source2Group, obtains Fe3O4@SiO2-NH2Magnetic nanoparticle；In phosphate
By Fe in cushioning liquid3O4@SiO2-NH2With cysteine acid amides reaction occurs for magnetic nanoparticle, obtains group enhancement magnetism
Property nano water treatment agent Fe3O4-SiO2-NH2-L-Cys。
Preferably, a kind of preparation method of the enhanced magnetic nano water treatment agent of group, is comprised the following specific steps that：
(1) accurately six directions water iron chloride and anhydrous sodium acetate powder are weighed, and add ethylene glycol solution, under normal temperature condition
It is stirred vigorously to being completely dissolved；Add appropriate polyethylene glycol and stir to system and be uniformly dispersed；
(2) solution that stirring is obtained in step (1) is poured into titanium-zirconium alloy autoclave container and reacted 7~9 hours
Reaction product is obtained, reaction temperature is 180~200 DEG C；
(3) reaction product obtained in step (2) is subjected to magnetic, and reaction product carried out with deionized water with ethanol
It is dried in vacuo after cleaning, obtains Fe3O4Magnetic nanoparticle；
(4) Fe obtained in step (3)3O4The ethanol that volumetric concentration is 70%~80% is added in magnetic nanoparticle
The aqueous solution, is added after ammoniacal liquor, after progress ultrasonic wave is uniformly dispersed, and tetraethyl orthosilicate is instilled dropwise, and side is stirred 5~7 hours, and
Cleaned and dried to obtaining reaction product；Obtain Fe3O4@SiO2Magnetic nanoparticle；
(5) Fe obtained in step (4)3O4@SiO2It is 92%~98% that volumetric concentration is added in magnetic nanoparticle
Ethanol water；Ultrasonic wave adds silane coupler after being uniformly dispersed, and is reacted 10~12 hours at a temperature of 55~65 DEG C
To Fe3O4@SiO2-NH2Magnetic nanoparticle；
(6) Fe that will be obtained in step (5)3O4@SiO2-NH2Magnetic nanoparticle ultrasonic wave is dispersed in volumetric concentration
In 0.1~0.2mol/L phosphate buffer solution (PBS), appropriate cysteine, 1- (3- dimethylamino-propyls) -3- are added
Stirred under ethyl-carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS), normal temperature 10~12 hours, finally will be anti-
Product vacuum is answered to be dried to obtain the enhanced magnetic nano water treatment agent Fe of group3O4-SiO2-NH2-L-Cys。
Technical grade six directions water iron chloride and anhydrous sodium acetate are used in the technical program for primary raw material, in normal temperature condition
Under, add ethylene glycol and be stirred dissolving reaction, then add polyethylene glycol stirring, solution system is dispersed to uniformly, then
Solution is added to the reaction of titanium-zirconium alloy autoclave container and obtains Fe within 7~9 hours3O4Nano particle；Due to generation
Fe3O4The particle diameter of nano particle is smaller, and Fe3O4There is strong magnetic dipole-dipole attraction, acetic anhydride between nano particle
Sodium as activating agent, prevents the Fe of generation during the course of the reaction3O4There is the phenomenon reunited in nano particle, and causes Fe3O4Receive
The particle diameter of rice grain is small and particle diameter distribution is narrow, Fe3O4The regular shape of nano particle；Polyethylene glycol divides whole solution system
Cloth is more uniform, adds the contact area between reactant；So that the reaction rate of reaction is accelerated, reactant reaction get Geng Che
Bottom；Simultaneously to the Fe of generation3O4Nano particle also has certain dispersibility so that be not in Fe in whole reaction3O4Receive
The phenomenon that rice grain is reunited.Then again to Fe3O4Nano particle carries out magnetic, then carries out being cleaned and dried to obtain Fe3O4Magnetic Nano
Particle.
In the technical program, Fe after the drying3O4Ethanol water is added in magnetic nanoparticle, ammoniacal liquor is added；Ammonia
Water is used to promote teos hydrolysis；So that the reaction rate of tetraethyl orthosilicate is improved；Then after progress ultrasonic wave is scattered, by
Tetraethyl orthosilicate is added dropwise in drop, stirs 5~7 hours；This is to make Fe using tetraethyl orthosilicate as silicon source3O4The table of magnetic nanoparticle
Face coated silica, obtains Fe3O4@SiO2Magnetic nanoparticle；Tetraethyl orthosilicate is added dropwise dropwise so that Fe in step (4)3O4
The silica that is coated on magnetic nanoparticle surface is uniform, all Fe3O4The surface of magnetic nanoparticle can be by dioxy
SiClx is coated；So it is coated on Fe3O4Silica shells on magnetic nanoparticle surface are served not only as by Fe3O4Magnetic is received
The protective layer of the magnetic core of rice grain composition, also causes Fe3O4Magnetic nanoparticle dispersion stabilization is good.
In the technical program, with silane coupler as amino source in Fe3O4@SiO2Transferred on the surface of magnetic nanoparticle
Meet-NH2Group, obtains Fe3O4@SiO2-NH2Magnetic nanoparticle；Again by Fe3O4@SiO2-NH2Magnetic nanoparticle ultrasound wavelength-division
It is dispersed in phosphate buffer, by Fe3O4@SiO2-NH2Magnetic nanoparticle disperses in phosphate buffer that Fe can be promoted3O4@
SiO2-NH2Magnetic nanoparticle reacts with cysteine；Cysteine is added, then by adding 1- (3- dimethylaminos
Propyl group) -3- ethyl-carbodiimide hydrochlorides (EDC), N-hydroxy-succinamide (NHS) by cysteine carboxylic group live
Change, under normal temperature condition, stirring causes cysteine and Fe3O4@SiO2-NH2Acid amides reaction occurs for magnetic nanoparticle so that half
Amino on cystine is with sulfydryl modification in Fe3O4@SiO2-NH2On the surface of magnetic nanoparticle, group enhancement magnetism is obtained
Property nano water treatment agent Fe3O4-SiO2-NH2-L-Cys。
Preferably, the mass ratio of six directions water iron chloride and anhydrous sodium acetate powder is 1 in the step (1):2~3；
So that the Fe of generation3O4Nano particle will not reunite, and the particle diameter of particle is small, the particle of particle diameter narrowly distributing and generation
Shape matching it is regular while, the consumption of anhydrous sodium acetate is few, cost-effective.
Preferably, the vacuum drying temperature in the step (3) is 60~80 DEG C so that Fe3O4Magnetic nanoparticle
Drying effect it is good, and avoid to Fe3O4The structure of magnetic nanoparticle changes in drying process.
Preferably, Fe in the step (6)3O4@SiO2-NH2The mass ratio of magnetic nanoparticle and cysteine is
1：2~3；Due to Fe3O4@SiO2-NH2There are multiple-NH on the surface of magnetic nanoparticle2；Such quality proportioning can cause
Cysteine can be with Fe3O4@SiO2-NH2All-NH on the surface of magnetic nanoparticle2While carrying out acid amides reaction, make
Half Guang acid amides consumption it is few, reduce raw material waste.
The application of the enhanced magnetic nano water treatment agent of group as claimed in claim 1, by the enhanced magnetic water of group
Inorganic agent is used for the removal of Heavy Metals in Waters ion.The enhanced magnetic nano water treatment agent of group prepared in the present invention can be wide
The general processing for Heavy Metals in Waters, is due to have substantial amounts of amino on the surface of the enhanced magnetic nano water treatment agent of group
And sulfydryl；It is fabulous to the adsorption effect of the contents of many kinds of heavy metal ion such as Zn, Pb, Cu, Cr, Ni in water body；And in magnetic attachment
Under the conditions of, the water treatment agent can 30s or so just complete adsorb, and precipitate, conveniently from the water body after processing separate,
Secondary pollution will not be caused to the water body of processing, the effect of water body processing is more stablized.
Compared with prior art, the present invention has the advantage that：
(1) Fe prepared by the present invention3O4@SiO2-NH2There is substantial amounts of-NH on the surface of magnetic nanoparticle2, substantial amounts of-
NH2It can be used for the absorption of part heavy metal ion；Then it is of the invention by Fe3O4@SiO2-NH2It is big on magnetic nanoparticle surface
- the NH of amount2Acid amides reaction is carried out with cysteine so that by cysteine and Fe3O4@SiO2-NH2On magnetic nanoparticle surface
- NH2Connection；Due to there is adsorption group amino and sulfydryl on cysteine, the group enhancement magnetism prepared is so allowed for
Adsorption group on property nano water treatment agent is added twice, and substantial amounts of in the enhanced magnetic nano water treatment agent of group
Adsorption group sulfydryl, and the magnetic suck of sulfydryl is good；So not only cause the suction of the enhanced magnetic nano water treatment agent of group
Attached ability is greatly improved, and adsorption time is greatly shortened, and saturation is reached in 50~60 minutes adsorbances；In the bar of magnetic attachment
Under part, 30s or so water treatment agent agent is precipitable, is conveniently quickly efficiently separated water treatment agent with the water body separated, and
The adsorption time of present adsorbent for heavy metal was at 90~100 minutes；And cause at the enhanced magnetic nanometer water of group
Reason agent can have good adsorption effect to the contents of many kinds of heavy metal ion in water body, further such that heavy metal of the present invention is useless
The comprehensive treatment effect of water is more preferable；So it is achieved that the efficient process of Heavy Metals in Waters.
(2) the particle diameter narrowly distributing of the enhanced magnetic nano water treatment agent of group prepared in the present invention, the shape of particle
Shape is regular, and the particle diameter of particle is in Nano grade, and the magnetic responsiveness of ion can be good, and the dispersion stabilization of particle is good, in water body
Heavy metal ion there is preferable removal to act on, substantially reduce the number consumption of the water treatment agent in water body processing；And group
Enhanced magnetic nano water treatment agent can be rapidly completed absorption in water body processing procedure and be precipitated in water body, use base
The sediment weight of the enhanced magnetic nano water treatment agent of group is substantial amounts of to be reduced, so convenient to be divided water treatment agent from water body
From secondary pollution will not be caused to the water body of processing so that water body treatment effect is more stablized so that the processing of heavy metal wastewater thereby
It is more environmentally-friendly and efficient, while also considerably reducing the processing cost of heavy metal wastewater thereby.
(3) in the preparation method of the enhanced magnetic nano water treatment agent of group of the invention, defined reaction thing in step (2)
The reaction time is 7~9 hours in a kettle., is proved by substantial amounts of experimental study, the reaction time is limited to 7~9 hours, both
Avoid that the reaction time is long, cause the Fe of generation3O4Magnetic nanoparticle particle diameter is excessive and causes heterogeneity and causes what is produced
Fe3O4The magnetic response of magnetic nanoparticle poor situation excessively occurs, and it is too short to turn avoid the reaction time, causes reactant unreacted
Completely so that cause wastage of material, the increased situation of production cost is caused to occur.
(4) in the step of preparation method of the enhanced magnetic nano water treatment agent of group of the present invention (6), in Fe3O4@SiO2-
NH2When being crosslinked on magnetic nanoparticle, with 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC), N- hydroxyls
Succinimide (NHS) synthesized as acid amides in carboxyl activator, made by acid amides reaction between bioactive molecule or biological
When being crosslinked fixed between bioactive molecule and carrier, N-hydroxy-succinamide (NHS) exists as nucleophile, can be effective
Increase the speed and the extent of reaction of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) coupling reaction；So that
Half Guang acid amides can be with magnetic Fe3O4@SiO2-NH2Acid amides reaction occurs for all amino on nano grain surface.
(5) preparation technology of the enhanced magnetic nano water treatment agent of group of the present invention is simple, it is not necessary to pressurize, and reduces pair
The corrosivity of reactor, it is ensured that the security of production process；The heat time is short in course of reaction, energy consumption is small, reduce production
Cost；Operation condition requires low, it is easy to operation and control.
Brief description of the drawings
Fig. 1 is the Fe for preparing in the embodiment of the present invention 13O4The X-ray diffraction analysis spectrogram of magnetic nanoparticle.
Fig. 2 is the Fe for preparing in the embodiment of the present invention 13O4The SEM scanning electron microscope (SEM) photographs of magnetic nanoparticle.
Fig. 3 is the Fe for preparing in the embodiment of the present invention 13O4The VSM figures of magnetic nanoparticle.
Fig. 4 is the enhanced magnetic nano water treatment agent Fe of group for preparing in the embodiment of the present invention 13O4-SiO2-NH2-L-
Cys infrared spectrogram.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
(1) accurately six directions water iron chloride 3g and anhydrous sodium acetate powder 7.5g are weighed, and add 75ml ethylene glycol solutions,
It is stirred vigorously under normal temperature condition to being completely dissolved；Add 0.5g polyethylene glycol (Mw=10000) stir 2 hours it is scattered to system
Uniformly；
(2) solution that stirring is obtained in step (1) is poured into reaction in titanium-zirconium alloy autoclave container to obtain for 8 hours
Reaction product, reaction temperature is 200 DEG C；
(3) reaction product obtained in step (2) is subjected to magnetic, and reaction product cleaned with deionized water with ethanol
After 5 times, it is placed in freeze drier and dries 10 hours, drying temperature is 60 DEG C, and vacuum is less than 1000Pa；Obtain Fe3O4
Magnetic nanoparticle；
(4) magnetic Fe obtained in step (3)3O4The ethanol water that 500ml volumetric concentrations are 75% is added in nano particle
Solution, is added after 6ml ammoniacal liquor, and after progress ultrasound 30min is uniformly dispersed, 10ml tetraethyl orthosilicates are instilled into reactant dropwise
System, side is stirred 6 hours, and clean for 3 times to obtaining reaction product respectively with absolute ethyl alcohol and deionized water and be placed in 60 DEG C
Vacuum drying；Obtain Fe3O4@SiO2Magnetic nanoparticle；
(5) Fe that 1g is obtained in step (4) is weighed3O4@SiO2The three neck round bottoms that magnetic nanoparticle pours into 250ml burn
In bottle, add 208ml volumetric concentrations and be 95% ethanol water, then condenser pipe is installed in three neck round bottom；Ultrasound
30min is with addition (10) ml amino silanes NH after being uniformly dispersed2(CH2)3Si(OCH3)3(99%, APTS) ultrasound 10min again,
Reaction obtains Fe in 12 hours at a temperature of 60 DEG C3O4@SiO2-NH2Magnetic nanoparticle；
(6) Fe obtained in 0.5g steps (5) is weighed3O4@SiO2-NH2Magnetic nanoparticle ultrasonic wave is dispersed in 100ml
Volumetric concentration is in 0.1mol/L phosphate buffer solution (PBS), adds 1g cysteines, 0.28g 1- (3- dimethylaminos
Propyl group) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.175gN- HOSu NHSs (NHS), stirring 12 is small under normal temperature
When, reaction product vacuum drying is finally obtained into the enhanced magnetic nano water treatment agent Fe of group3O4-SiO2-NH2-L-Cys。
Embodiment 2
(1) accurately six directions water iron chloride 3g and anhydrous sodium acetate powder 9g are weighed, and add 75ml ethylene glycol solutions, normal
It is stirred vigorously under the conditions of temperature to being completely dissolved；Add 0.5g polyethylene glycol (Mw=10000) and stir 2 hours and disperse equal to system
It is even；
(2) solution that stirring is obtained in step (1) is poured into reaction in titanium-zirconium alloy autoclave container to obtain for 7 hours
Reaction product, reaction temperature is 200 DEG C；
(3) reaction product obtained in step (2) is subjected to magnetic, and reaction product cleaned with deionized water with ethanol
After 5 times, it is placed in freeze drier and dries 10 hours, drying temperature is 70 DEG C, and vacuum is less than 1000Pa；Obtain magnetic
Fe3O4Nano particle；
(4) Fe obtained in step (3)3O4The ethanol water that 500ml volumetric concentrations are 70% is added in magnetic nanoparticle
Solution, is added after 6ml ammoniacal liquor, and after progress ultrasound 30min is uniformly dispersed, 10ml tetraethyl orthosilicates are instilled into reactant dropwise
System, side is stirred 5 hours, and clean for 3 times to obtaining reaction product respectively with absolute ethyl alcohol and deionized water and be placed in 60 DEG C
Vacuum drying；Obtain Fe3O4@SiO2Magnetic nanoparticle；
(5) Fe that 1g is obtained in step (4) is weighed3O4@SiO2The three neck round bottoms that magnetic nanoparticle pours into 250ml burn
In bottle, add 208ml volumetric concentrations and be 92% ethanol water, then condenser pipe is installed in three neck round bottom；Ultrasound
30min is with addition (10) ml amino silanes NH after being uniformly dispersed2(CH2)3Si(OCH3)3(99%, APTS) ultrasound 10min again,
Reaction obtains Fe in 10 hours at a temperature of 55 DEG C3O4@SiO2-NH2Magnetic nanoparticle；
(6) Fe obtained in 0.5g steps (5) is weighed3O4@SiO2-NH2Magnetic nanoparticle ultrasonic wave is dispersed in 100ml
Volumetric concentration is in 0.1mol/L phosphate buffer solution (PBS), adds 1.25g cysteines, 0.28g 1- (3- diformazan ammonia
Base propyl group) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.175gN- HOSu NHSs (NHS), stirring 10 is small under normal temperature
When, reaction product vacuum drying is finally obtained into the enhanced magnetic nano water treatment agent Fe of group3O4-SiO2-NH2-L-Cys。
Embodiment 3
(1) accurately six directions water iron chloride 3g and anhydrous sodium acetate powder 6g are weighed, and add 75ml ethylene glycol solutions, normal
It is stirred vigorously under the conditions of temperature to being completely dissolved；Add 0.5g polyethylene glycol (Mw=10000) and stir 2 hours and disperse equal to system
It is even；
(2) solution that stirring is obtained in step (1) is poured into reaction in titanium-zirconium alloy autoclave container to obtain for 9 hours
Reaction product, reaction temperature is 200 DEG C；
(3) reaction product obtained in step (2) is subjected to magnetic, and reaction product cleaned with deionized water with ethanol
After 5 times, it is placed in freeze drier and dries 10 hours, drying temperature is 80 DEG C, and vacuum is less than 1000Pa；Obtain magnetic
Fe3O4Nano particle；
(4) Fe obtained in step (3)3O4The ethanol water that 500ml volumetric concentrations are 80% is added in magnetic nanoparticle
Solution, is added after 6ml ammoniacal liquor, and after progress ultrasound 30min is uniformly dispersed, 10ml tetraethyl orthosilicates are instilled into reactant dropwise
System, stir 7 hours, and with absolute ethyl alcohol and deionized water respectively to obtain reaction product carries out 3 times cleaning and be placed in 60 DEG C very
Sky is dried；Obtain Fe3O4@SiO2Magnetic nanoparticle；
(5) Fe that 1g is obtained in step (4) is weighed3O4@SiO2The three neck round bottoms that magnetic nanoparticle pours into 250ml burn
In bottle, add 208ml volumetric concentrations and be 98% ethanol water, then condenser pipe is installed in three neck round bottom；Ultrasound
30min is with addition (10) ml amino silanes NH after being uniformly dispersed2(CH2)3Si(OCH3)3(99%, APTS) ultrasound 10min again,
Reaction obtains Fe in 12 hours at a temperature of 65 DEG C3O4@SiO2-NH2Magnetic nanoparticle；
(6) Fe obtained in 0.5g steps (5) is weighed3O4@SiO2-NH2Magnetic rice grain ultrasonic wave of receiving is dispersed in 100ml
Volumetric concentration is in 0.1mol/L phosphate buffer solution (PBS), adds 1.5g cysteines, 0.28g 1- (3- diformazan ammonia
Base propyl group) -3- ethyl-carbodiimide hydrochlorides (EDC) and 0.175gN- HOSu NHSs (NHS), stirring 12 is small under normal temperature
When, reaction product vacuum drying is finally obtained into the enhanced magnetic nano water treatment agent Fe of group3O4-SiO2-NH2-L-Cys。
To the Fe prepared in embodiment 1,2,33O4Magnetic nanoparticle carries out material phase analysis and respectively obtains X-ray diffraction point
Analyse collection of illustrative plates, from obtained X-ray diffraction analysis figure analysis of spectrum, 2 θ=30.11 °, 35.41 °, 43.11 °, 53.41 °, 57.01 °
At 62.61 °, the Fe prepared in embodiment 1,2,33O4There is obvious diffraction maximum in magnetic nanoparticle, it and spinelle
Emission in Cubic Fe3O4(220) of magnetic nanoparticle, (311), (400), (422), the feature of (511) and (440) crystal plane is spread out
Penetrate peak closely, illustrate to prepare gained Fe3O4Magnetic nanoparticle particle diameter is small and homogeneous, and magnetic responsiveness can be good.In solvent-thermal method
The Fe of middle preparation3O4The diffraction maximum of magnetic nanoparticle is more sharp, and with tetraethyl orthosilicate (TEOs), silane coupler and half
Fe after cystine modification3O4-SiO2-NH2- L-Cys diffraction peak-to-peak value is relatively low.This illustrates that final product does not have
Change Fe3O4The crystalline form of magnetic nanoparticle, diffraction maximum peak intensity has died down a bit compared to mother crystal after simply wrapping up.Therefore, explanation
Under experimental conditions, the preferable Fe of crystallinity has been obtained3O4Magnetic nanoparticle, and successfully wrapped up objective function on its surface
Group；Fig. 1 is the Fe for preparing in embodiment 13O4The X-ray diffraction analysis figure spectrum of magnetic nanoparticle.
To the Fe prepared in embodiment 1,2,33O4The configuration of surface of magnetic nanoparticle is with SEM (SEM)
Observed respectively.The Fe prepared in embodiment 13O4Magnetic nanoparticle is in spherical, and shape is more regular, and particle diameter distribution is uniform,
Single bulb diameter is in Nano grade, and well, magnetic responsiveness can be good for configuration of surface, and surface can be high and dispersiveness is preferable；Made in embodiment 2
Standby Fe3O4Magnetic nanoparticle has part Fe in spherical compared with embodiment3O4Not advising occurs in the shape of magnetic nanoparticle
Whole situation, particle diameter distribution has a small number of Fe than more uniform3O4Magnetic nanoparticle particle diameter is smaller；Prepared in embodiment 3
Fe3O4Magnetic nanoparticle is in spherical compared with embodiment, Fe3O4The shape of magnetic nanoparticle is more regular, particle diameter distribution compared with
To be uniform, but there are the Fe of minority3O4The particle diameter of magnetic nanoparticle is excessive；Fig. 2 is the Fe for preparing in embodiment 13O4Magnetic is received
The SEM scanning electron microscope (SEM) photographs of rice grain.
To the Fe prepared in embodiment 1,2,33O4The magnetic performance of magnetic nanoparticle carries out VSM signs and analyzed.It is logical
The Fe prepared in embodiment 1,2,3 can be analyzed by crossing specific saturation magnetization numerical value and hysteresis curve3O4The magnetic of magnetic nanoparticle
It is functional；Fig. 3 is the Fe for preparing in embodiment 13O4The VSM figures of magnetic nanoparticle.
Infrared spectrum (FT- is carried out respectively to the enhanced magnetic nano water treatment agent of group prepared in embodiment 1,2,3
IR) characterize.The results of FT-IR shows, 3464cm-1And 1639cm-1The characteristic peak correspondence Fe at place3O4- OH the keys on surface,
1116cm-1Correspondence Si-O keys, 585cm-1Correspondence Fe-O keys, thus prove amino silane success in Fe3O4Surface.According to embodiment
1st, 2,3 preparation method by cysteine to Fe3O4@SiO2-NH2Surface be modified obtained Fe3O4@SiO2-NH2- L-Cys points
Carry out not infrared spectrum (FT-IR) sign 4.By Fe3O4@SiO2-NH2- L-Cys and L-Cys infrared spectrum (FT-IR) combination
Knowable to figure, Fe3O4@SiO2-NH23463cm in-L-Cys infrared spectrums-1And 1623cm-1Characteristic peak correspondence Fe3O4Surface
- OH keys；2585cm-1Place correspondence L-Cys-SH groups；2916 and 2849cm-1For-CH2The asymmetric and symmetrical-CH of group
Stretching vibration；1623 and 1408cm-1The characteristic peak at place is COO- asymmetric and symmetrical stretching vibration；1025cm-1And 1489cm-1Place's characteristic peak is respectively C-N stretching vibrations and N-H flexural vibrations in L-Cys.L-Cys infrared spectrum is contrasted, L-Cys's
Characteristic peak there occurs certain migration.Fe3O4-SiO2-NH2- L-Cys infrared spectrogram (FT-IR) existing Fe3O4The spy of group
Levying peak also has the characteristic peak of L-Cys groups, thus proves that the successful scion graftings of cysteine L-Cys exist in embodiment 1,2,3
Fe3O4Surface；Prove that the product finally obtained in embodiment 1,2,3 is Fe3O4-SiO2-NH2-L-Cys；Fig. 4 makes to apply in example 1
The enhanced magnetic nano water treatment agent Fe of standby group3O4-SiO2-NH2- L-Cys infrared spectrogram.
By the enhanced magnetic nano water treatment agent Fe of obtained group in embodiment 1,2,33O4-SiO2-NH2- L-Cys and
Existing Fe3O4-SiO2-NH2Magnetic Nano water treatment agent is carried out at absorption to the heavy metal ion in the water body of preparation respectively
Reason, analyzes result, four kinds of water treatment agents is put into 50mg/L respectively in staying water respectively respectively, inhales within 1 hour
To the detection of heavy metal ion in water body after the attached precipitation through 30s magnetic sucks, table 1 is obtained.
The enhanced magnetic nano water treatment agent of the group of table 1 is used for the actual processing effect that Heavy Metals in Waters is handled
The obtained enhanced magnetic nano water treatment agent of group is in water body in embodiment it can be seen from upper table 11,2,3
The contents of many kinds of heavy metal ion such as Zn, Pb, Cu, Cr, Ni have good removal effect；And the consumption of water treatment agent is few；The present invention's
The energy of adsorption ability of water treatment agent compares Fe3O4-SiO2-NH2Adsorption capacity it is good, and Fe3O4-SiO2-NH2To part heavy metal from
The adsorption effect of son is poor；The adsorption effect of heavy metal ion in embodiment 1 is best；Main cause is because the group prepared
Sulfydryl and amino heavy metal in enhanced magnetic nano water treatment agent have preferable adsorption capacity, so that integrated treatment is imitated
Fruit is preferably.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (7)
1. a kind of enhanced magnetic nano water treatment agent of group, it is characterised in that the molecular formula of the water treatment agent is Fe3O4-
SiO2-NH2-L-Cys。
2. a kind of preparation method of the enhanced magnetic nano water treatment agent of group, it is characterised in that by six directions water iron chloride and nothing
Water acetic acid sodium is dissolved in ethylene glycol, adds polyethylene glycol until being uniformly dispersed, reaction obtains Fe3O4Magnetic nanoparticle；With
Tetraethyl orthosilicate makes Fe as silicon source3O4Magnetic nanoparticle Surface coating silica, obtains Fe3O4@SiO2Magnetic Nano
Grain；Make its surface graft-NH by amino source of silane silane coupler again2Group, obtains Fe3O4@SiO2-NH2Magnetic Nano
Grain；By Fe in phosphate buffer solution3O4@SiO2-NH2With cysteine acid amides reaction occurs for magnetic nanoparticle, obtains base
The enhanced magnetic nano water treatment agent Fe of group3O4-SiO2-NH2-L-Cys。
3. the preparation method of the enhanced magnetic nano water treatment agent of group according to claim 2, it is characterised in that including
Following specific steps：
（1）Take six directions water iron chloride and anhydrous sodium acetate powder, and add ethylene glycol solution, be stirred vigorously under normal temperature condition to
It is completely dissolved；Add appropriate polyethylene glycol and stir to system and be uniformly dispersed；
（2）By step（1）The solution that middle stirring is obtained pours into reaction in titanium-zirconium alloy autoclave container and obtains within 7 ~ 9 hours anti-
Product is answered, reaction temperature is 180 ~ 200 DEG C；
（3）By step（2）In obtained reaction product carry out magnetic, and laggard is cleaned to reaction product with deionized water with ethanol
Row vacuum drying, obtains Fe3O4Magnetic nanoparticle；
（4）In step（3）In obtained Fe3O4The ethanol water that volumetric concentration is 70% ~ 80% is added in magnetic nanoparticle,
Add after ammoniacal liquor, carry out after ultrasonic wave is uniformly dispersed, tetraethyl orthosilicate being instilled dropwise, side is stirred 5 ~ 7 hours, and to obtaining
Reaction product is cleaned and dried；Obtain Fe3O4@SiO2Magnetic nanoparticle；
（5）In step（4）In obtained Fe3O4@SiO2The ethanol water that volumetric concentration is 92% ~ 98% is added in magnetic nanoparticle
Solution；Ultrasonic wave adds silane coupler after being uniformly dispersed, and reaction obtains Fe in 10 ~ 12 hours at a temperature of 55 ~ 65 DEG C3O4@
SiO2-NH2Magnetic nanoparticle；
（6）By step（5）In obtained Fe3O4@SiO2-NH2Magnetic nanoparticle ultrasonic wave be dispersed in volumetric concentration for 0.1 ~
In 0.2mol/L phosphate buffer solution, appropriate cysteine, 1- (3- dimethylamino-propyls) -3- ethyls carbon two are added sub-
Stirred under amine hydrochlorate and N-hydroxy-succinamide, normal temperature 10 ~ 12 hours, reaction product vacuum drying is finally obtained into group
Enhanced magnetic nano water treatment agent Fe3O4-SiO2-NH2-L-Cys。
4. the preparation method of the enhanced magnetic nano water treatment agent of group according to claim 3, it is characterised in that institute
State step（1）The mass ratio of middle six directions water iron chloride and anhydrous sodium acetate powder is 1:2~3.
5. the preparation method of the enhanced magnetic nano water treatment agent of group according to claim 3, it is characterised in that institute
State step（3）In vacuum drying temperature be 60 ~ 80 DEG C.
6. the preparation method of the enhanced magnetic nano water treatment agent of group according to claim 3, it is characterised in that described
Step（6）Middle Fe3O4@SiO2-NH2The mass ratio of magnetic nanoparticle and cysteine is 1：2~3.
7. the application of the enhanced magnetic nano water treatment agent of group as claimed in claim 1, it is characterised in that strengthen group
Type magnetic water treatment agent is used for the removal of Heavy Metals in Waters ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710261398.8A CN106955672A (en) | 2017-04-20 | 2017-04-20 | A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710261398.8A CN106955672A (en) | 2017-04-20 | 2017-04-20 | A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106955672A true CN106955672A (en) | 2017-07-18 |
Family
ID=59484856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710261398.8A Pending CN106955672A (en) | 2017-04-20 | 2017-04-20 | A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106955672A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376871A (en) * | 2017-07-31 | 2017-11-24 | 淮海工学院 | A kind of high-efficiency adsorbent of heavy metal lead ion and preparation method and application |
| CN107381749A (en) * | 2017-08-29 | 2017-11-24 | 南京华淳环保股份有限公司 | A kind of magnetic flocculant and its preparation method and application |
| CN108147518A (en) * | 2017-12-29 | 2018-06-12 | 湖南省塑料研究所有限公司 | Modified starch water treatment agent and its preparation method and application |
| CN108928880A (en) * | 2018-08-10 | 2018-12-04 | 南华大学 | A kind of processing method of the waste water containing radioactive element |
| CN109806868A (en) * | 2018-07-02 | 2019-05-28 | 陈天仪 | A kind of organic wastewater degraded agent of recyclable recycling |
| CN111068057A (en) * | 2019-12-31 | 2020-04-28 | 广东药科大学 | PH/redox dual-response magnetic nano drug-loaded system and construction method thereof |
| CN111468066A (en) * | 2020-04-24 | 2020-07-31 | 吉林化工学院 | Amino modified Fe3O4Preparation method and application of microspheres |
| CN112044460A (en) * | 2020-08-05 | 2020-12-08 | 太原理工大学 | Method for enhancing mineralization of tetracycline antibiotics by graphite-phase carbon nitride |
| CN113058576A (en) * | 2021-03-08 | 2021-07-02 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN113233563A (en) * | 2021-03-17 | 2021-08-10 | 重庆大学 | Preparation method and application of cationic chitosan-based magnetic flocculant initiated by low-pressure ultraviolet light |
| CN113893834A (en) * | 2021-11-15 | 2022-01-07 | 北京新风航天装备有限公司 | Preparation method of nano magnetic particles for adsorbing chromium ions |
| CN114887584A (en) * | 2022-05-20 | 2022-08-12 | 陕西正元粉煤灰综合利用有限公司 | Modified fly ash and preparation method and application thereof |
| CN117550650A (en) * | 2023-11-21 | 2024-02-13 | 无锡国盛生物工程股份有限公司 | SiO (silicon dioxide) 2 Wrapping magnetic Fe 3 O 4 Method for preparing nano particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013439A (en) * | 2015-06-26 | 2015-11-04 | 同济大学 | Preparation method of nitrogen and sulfur functionalized carbon foam magnetic microspheres |
-
2017
- 2017-04-20 CN CN201710261398.8A patent/CN106955672A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013439A (en) * | 2015-06-26 | 2015-11-04 | 同济大学 | Preparation method of nitrogen and sulfur functionalized carbon foam magnetic microspheres |
Non-Patent Citations (3)
| Title |
|---|
| 成国良: "Pb2+磁纳米固相萃取剂的制备与性能", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 蔡少伟: "新型纳米磁性材料的制备及其在痕量元素与形态分析中的应用", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
| 闫军锋等: "《电子材料与器件实验教程》", 31 May 2016 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376871B (en) * | 2017-07-31 | 2019-07-23 | 淮海工学院 | A kind of high-efficiency adsorbent and the preparation method and application thereof of heavy metal lead ion |
| CN107376871A (en) * | 2017-07-31 | 2017-11-24 | 淮海工学院 | A kind of high-efficiency adsorbent of heavy metal lead ion and preparation method and application |
| CN107381749A (en) * | 2017-08-29 | 2017-11-24 | 南京华淳环保股份有限公司 | A kind of magnetic flocculant and its preparation method and application |
| CN107381749B (en) * | 2017-08-29 | 2020-11-27 | 南京华淳环保股份有限公司 | Magnetic flocculant and preparation method and application thereof |
| CN108147518A (en) * | 2017-12-29 | 2018-06-12 | 湖南省塑料研究所有限公司 | Modified starch water treatment agent and its preparation method and application |
| CN108147518B (en) * | 2017-12-29 | 2020-10-30 | 湖南省塑料研究所有限公司 | Modified starch water treatment agent and preparation method and application thereof |
| CN109806868A (en) * | 2018-07-02 | 2019-05-28 | 陈天仪 | A kind of organic wastewater degraded agent of recyclable recycling |
| CN109806868B (en) * | 2018-07-02 | 2021-10-26 | 陈天仪 | Recyclable and reusable organic wastewater degrading agent |
| CN108928880B (en) * | 2018-08-10 | 2021-07-09 | 南华大学 | Method for treating wastewater containing radioactive elements |
| CN108928880A (en) * | 2018-08-10 | 2018-12-04 | 南华大学 | A kind of processing method of the waste water containing radioactive element |
| CN111068057A (en) * | 2019-12-31 | 2020-04-28 | 广东药科大学 | PH/redox dual-response magnetic nano drug-loaded system and construction method thereof |
| CN111468066A (en) * | 2020-04-24 | 2020-07-31 | 吉林化工学院 | Amino modified Fe3O4Preparation method and application of microspheres |
| CN112044460A (en) * | 2020-08-05 | 2020-12-08 | 太原理工大学 | Method for enhancing mineralization of tetracycline antibiotics by graphite-phase carbon nitride |
| CN112044460B (en) * | 2020-08-05 | 2022-11-08 | 太原理工大学 | Method for enhancing graphite-phase carbon nitride mineralization tetracycline antibiotics |
| CN113058576A (en) * | 2021-03-08 | 2021-07-02 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN113058576B (en) * | 2021-03-08 | 2024-01-26 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN113233563A (en) * | 2021-03-17 | 2021-08-10 | 重庆大学 | Preparation method and application of cationic chitosan-based magnetic flocculant initiated by low-pressure ultraviolet light |
| CN113893834A (en) * | 2021-11-15 | 2022-01-07 | 北京新风航天装备有限公司 | Preparation method of nano magnetic particles for adsorbing chromium ions |
| CN114887584A (en) * | 2022-05-20 | 2022-08-12 | 陕西正元粉煤灰综合利用有限公司 | Modified fly ash and preparation method and application thereof |
| CN114887584B (en) * | 2022-05-20 | 2024-03-29 | 陕西正元粉煤灰综合利用有限公司 | Modified fly ash and preparation method and application thereof |
| CN117550650A (en) * | 2023-11-21 | 2024-02-13 | 无锡国盛生物工程股份有限公司 | SiO (silicon dioxide) 2 Wrapping magnetic Fe 3 O 4 Method for preparing nano particles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955672A (en) | A kind of enhanced magnetic nano water treatment agent of group and its preparation method and application | |
| Wang et al. | Magnetic nanoparticles grafted with amino-riched dendrimer as magnetic flocculant for efficient harvesting of oleaginous microalgae | |
| Fang et al. | Immobilization of pectinase onto Fe3O4@ SiO2–NH2 and its activity and stability | |
| CN105565506B (en) | It is a kind of to load Biocomposite material of magnetic nanoparticle with core shell structure and its production and use | |
| CN106057394B (en) | A kind of preparation method of immune magnetic Nano particulate | |
| CN106582560A (en) | Preparation of magnetic chitosan composite adsorption material and application in dye wastewater treatment | |
| CN107583617B (en) | Magnetic microsphere for adsorbing diclofenac sodium | |
| CN106237947A (en) | Magnetic microsphere of high density carboxyl modified and preparation method thereof | |
| CN105969331A (en) | Preparation method of nano-material suitable for targeting drug carriers | |
| CN107486157B (en) | Multi-walled carbon nanotube/metal organic framework composite material and preparation method | |
| Zhang et al. | Tris (hydroxymethyl) aminomethane-modified magnetic microspheres for rapid affinity purification of lysozyme | |
| CN103962110B (en) | Multifunction Fe 3o 4the preparation method of magnetic Nano material | |
| CN109289772B (en) | Carbon nano tube/hydrotalcite material for removing nitrate nitrogen in water and preparation method thereof | |
| CN105140018A (en) | Preparation method for magnetic macromolecule nanoball | |
| CN105854839B (en) | Enzyme crosslinking shell glycan/grafting polyethylene imine magnetic gelatine material and preparation method and application | |
| CN109207143A (en) | A kind of fluorescent carbon quantum dot of functional modification and its preparation method and application | |
| CN113070036A (en) | Biomass-based functional carbon, preparation method thereof and application of biomass-based functional carbon in removal of micro-plastics in water body | |
| CN104475040B (en) | Modified magnetic nano adsorption material as well as preparation method and application thereof | |
| CN107486156B (en) | A kind of method of magnetic nanoparticle adsorbing separation bovine serum albumin(BSA) | |
| CN109627765A (en) | A kind of biodegradation type composite hydrogel and its preparation method and application | |
| Zhao et al. | Application of Fe3O4 coated with modified plant polyphenol to harvest oleaginous microalgae | |
| CN108854938A (en) | Amino modified magnetism CoFe2O4The preparation method and application of composite material | |
| CN112573642A (en) | Water treatment denitrification filler and preparation method thereof | |
| CN107522239A (en) | A kind of method based on gallic acid metallic ion coordination chemical regulation nano ferriferrous oxide decentralization and particle diameter | |
| CN107051392A (en) | The functionalization aeroge and preparation method acted on heavy metal ion adsorption desorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170718 |