CN109273181A - A kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle - Google Patents
A kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle Download PDFInfo
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- CN109273181A CN109273181A CN201811230292.2A CN201811230292A CN109273181A CN 109273181 A CN109273181 A CN 109273181A CN 201811230292 A CN201811230292 A CN 201811230292A CN 109273181 A CN109273181 A CN 109273181A
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- cobalt ferrite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
The invention belongs to technical field of inorganic material, and in particular to a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle.The magnetic nano-particle is made of carboxylated carbon material cladding ferrous acid cobalt particle, and packet carbon cobalt ferrite average grain diameter is 20-40nm, and saturation magnetization 15-42emu/g, coating is rich in carboxylic group.The magnetic nano-particle preparation method is to the effect that: by cell reaction as reactor, play promotion reagentia, greatly shorten digestion time, the ferric oxalate cobalt of acquisition is presoma, magnetic particle is made by temperature-programmed calcination, using glucose as carbon source, magnetic particle surface is coated on after hydrothermal carbonization, up to carboxylated cobalt ferrite magnetic nanoparticle after being heated to reflux by aqueous slkali, surface is rich in carboxylic group.Carboxylated cobalt ferrite magnetic nanoparticle made from the method for the present invention, particle diameter distribution is uniform, hydrophily is strong, dispersion effect is good, load capacity is strong, which has a good application prospect.
Description
Technical field
The invention belongs to technical field of inorganic material, and in particular to a kind of preparation of carboxylated cobalt ferrite magnetic nanoparticle
Method.
Background technique
Magnetic nano-particle have good biocompatibility and special magnetism, Magnetic resonance imaging, targeted drug,
The fields performances such as biomedicines, water environment purification, the Industrial Catalysis such as fixation, immunoassays, tissue repair and the cell separation of enzyme
Potential application prospect out.However, magnetic nano-particle due to higher specific surface, is inclined to strong aggregation, without
It is poorly water-soluble before surface treatment, easy to reunite, field of biomedicine and water treatment field can not be up to the requirement of application.Therefore
Special modification must be carried out on magnetic nano-particle surface, improve its water solubility and improve dispersion stabilization and biocompatibility；
Furthermore the magnetic Nano modified can introduce the various biomolecules such as targeting agent, drug molecule, antibody, fluorescein as needed, with
The functionalization for realizing magnetic nano-particle, further expands its application range.
The surface modification of magnetic nano-particle is the research hotspot of current functionalized nano Material Field.Surface-functionalized
Magnetic nano-particle is easy in conjunction with target substance since partial size is small, large specific surface area, and since it is with distinctive magnetic response
Property, centrifugally operated can not be needed, the simplification and automation of separation process are conducive to by externally-applied magnetic field directional separation, therefore,
Cell separation, targeted drug delivery, tumour magnetic thermotherapy and adsorbent material solid-liquid Magnetic Isolation etc., which suffer from, to be widely applied
Prospect.For magnetic nano-particle surface modification material there are many kinds of, including polymer, non-polymer organic molecule or inorganic
Molecule, common modification group are-COO- ,-SH- ,-NH2-、-PO2, alkyl etc., different coating materials can assign it not
Same property.Magnetic nano-particle with carboxylic group can be used for combining with biological active matter qualitative response contained in virus
- NH2, the carrier of anti-tumor drug can be especially done, by external magnetic field, target administration can be carried out to diseased region.?
The fields such as environmental protection, the magnetic nano-particle with carboxylic group can cations by electrostatic interaction, in adsorbed water body
Type dye or metal cation reach water body purification purpose.
In recent years, about magnetic nano-particle carboxyl-functional.The existing a large amount of reports of research, such as following documents:
(Journal of Colloid and Interface Science, Removal of Cu2+from aqueous
solution by chitosan-coated magnetic nanoparticles modified withα-
Ketoglutaric acid, 2009,330 (1): 29-37；), (preparation of carboxylated core-shell magnetic nanometer Fe_3O_4 adsorbent and
To Cu2+ absorption property, Chemical Journal of Chinese Universities, 2012,33 (1): 107-113；),(Effects of DMSA-coated
Fe3O4magnetic nanoparticles on global gene expression of mouse macrophage
RAW264.7cells, 2011,205 (2): 130-139).In general, the carboxylated of magnetic nano-particle mainly includes coprecipitated
Investment and monomer polymerization method is blended in shallow lake method.Report or disclosed method, exist water body dispersion effect difference or step it is numerous
Trivial, the deficiencies of functionalization is at high cost, time-consuming.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of carboxylated cobalt ferrite magnetic nanoparticle.The carboxylated iron
Sour cobalt magnetic nano-particle particle diameter distribution is uniform, hydrophily is strong, dispersion effect is good, load capacity is strong.Magnetic nano-particle surface
Carboxylic group can be by electrostatic interaction Liquidity limit type dye, metal cation and weakly basic drugs, in pH regulating and controlling effect
Lower autonomous " receipts ", " putting ", have applications well prospect, while shortening digestion time, and optimize the condition of ageing, on realizing
Purpose is stated, The technical solution adopted by the invention is as follows:
A kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle, specific step is as follows for the preparation method:
(a) by certain density soluble cobalt aqueous solution, trivalent iron salt aqueous solution and certain density oxalic acid or oxalic acid
Saline solution mixes in electrolysis unit, in electrolysis unit iron be anode, ferric iron be catholyte reaction generate ferrous iron from
Son is powered and cell reaction occurs, while promoting soluble cobalt aqueous solution and reacting with ferrous iron salt water, improves ageing item
Part, Aging Temperature are room temperature, shorten digestion time, and filter cake is obtained by filtration after being aged 1-3h, the filter cake is dehydrated, is dried
Ferric oxalate cobalt precursor object, by the ferric oxalate cobalt precursor object at 300~600 DEG C of air atmosphere, heating rate 1~5 are made afterwards
DEG C/min, cobalt ferrite is made after calcining 2~4h；The mass ratio of the soluble cobalt and divalent iron salt is 1:2, the solubility
The mass ratio of cobalt salt and divalent iron salt and oxalic acid or oxalates is 1:(1~2)；The soluble cobalt is cobalt chloride or sulfuric acid
Cobalt or cobalt nitrate, the soluble divalent iron salt are iron ammonium sulfate or frerrous chloride or ferrous sulfate, the oxalates
For sodium oxalate or potassium oxalate；
(b) by cobalt ferrite hydrothermal carbonization in the aqueous solution containing glucose obtained by step (a), after being cooled to room temperature, magnetic
Property separation, washing obtain filter cake, by the filter cake 100 DEG C of progresss forced air dryings be made packet carbon cobalt ferrite, the cobalt ferrite and
The mass ratio of glucose is 1:(3~10), hydro-thermal activation time 10~for 24 hours, activation temperature is 160 DEG C~200 DEG C；
(c) packet carbon cobalt ferrite made from step (b) is heated to reflux in aqueous slkali, after being cooled to room temperature, magnetism point
Filter cake is obtained from, washing, by the filter cake in the obtained target product of 100 DEG C of progresss forced air dryings: carboxylated cobalt ferrite magnetic is received
Rice corpuscles；The alkaline concentration is 0.05-0.5mol/L, 1~6h of return time, the matter of the packet carbon cobalt ferrite and solid base
Amount is than being 1:(1~5), the solid base is sodium hydroxide or potassium hydroxide.
The average grain diameter of carboxylated cobalt ferrite magnetic nanoparticle prepared by the present invention is 20~40nm, and saturated magnetization is strong
Spend 15~42emu/g.The carboxylated cobalt ferrite magnetic nanoparticle be it is a kind of rich in carboxylic acid group, with good magnetic induction
The cobalt ferrite of carbon-based material cladding；Reaction, which is located in electrolysis unit, to be carried out, and it is anti-that ferrous iron generation is mainly constantly generated by electrolysis
It answers, while reaction can be effectively facilitated by electrolysis, shorten digestion time.
Preferably, the preparation method of carboxylated cobalt ferrite magnetic nanoparticle carries out in electrolysis unit, the electrolysis unit
Including reactive tank, it is provided with horizontal rotating shaft above the reactive tank, the both ends of the horizontal rotating shaft are mounted on described by bearing block
On reactive tank, one end of the horizontal rotating shaft is connected with driving device, at least one anode block is equipped on the horizontal rotating shaft,
The scraping device is fixedly mounted on reaction tank bottom；The anode block two sides are correspondingly provided with scraping device, scraping device and sun
The contact of pole block.When work, by certain density soluble cobalt aqueous solution, trivalent iron salt aqueous solution and certain density oxalic acid or
Oxalic acid saline solution mixes in electrolysis unit, and iron is anode in electrolysis unit, and ferric iron is cathode, carries out cell reaction generation
Ferrous ion reacts, and driving device drives horizontal rotating shaft rotation, drives anode block rotation, and anode block rotation is filled with scraping
It sets and is scraped, generate iron powder and ferrous iron is accelerated to generate, reaction is promoted to carry out.
Preferably, the inner wall of the reactive tank is semicircle cambered surface, and the edge of the reactive tank extends to form anti-straight up
Overflow weir.
Preferably, the anode block is three, and three anode blocks equidistantly distributed on the horizontal rotating shaft is described
Anode block includes suction tray and iron ring；The suction tray passes through horizontal rotating shaft, is fixedly connected with horizontal rotating shaft；Two iron rings
Positioned at suction tray two sides, it is close together with suction tray.
Preferably, the driving device includes rotating electric machine and speed changer, the output shaft of the rotating electric machine and speed changer
Axis connection is inputted, the output shaft of the speed changer is connect with the horizontal rotating shaft, and the rotating electric machine and speed changer are fixedly installed
In the outer wall of the reactive tank.
Preferably, it is respectively equipped with water inlet pipe and outlet pipe on the waste water reaction slot, on the water inlet pipe and outlet pipe
It is respectively arranged with water check valve.
Preferably, the scraping device includes main body, push plate, scrapes nail and spring；The push plate is located at body interior sliding slot
It is interior, it can move left and right；It is fixedly connected on the left of the spring side and push plate, the other end is fixedly connected with main body, push plate and master
At least three spring is set between body；The nail of scraping is evenly arranged on the right side of push plate, obtains iron powder for scraping iron ring surface.It is logical
Cross spring and connect push plate with main body, when scraping iron ring surface, iron ring surface is constantly thinning, by spring make to scrape nail always with
The contact of iron ring surface.
Preferably, the suction tray is electromagnet, for adsorbing iron ring；The suction tray is recessed with iron ring outer surface
The rough surface of convex injustice prevents suction tray sliding opposite with iron ring.When scraping device scrapes iron ring surface, suction tray can prevent iron
Opposite sliding occurs for circle, and generates iron powder, and suction tray has magnetic force by iron powder adsorption on surface, and as anode reaction, iron powder is more sharp
In accelerating reaction speed, promote the progress entirely reacted.
Preferably, the nail of scraping is cemented carbide material, for scraping iron ring surface.Cemented Carbide Hardness is greater than iron, can
Iron is scraped.
Preferably, air bag is equipped between the scraping device, air bag is located between two adjacent and opposite scraping devices,
And it is constantly in squeezed state, scraping device support is given, while scraping device being promoted to be close to iron ring.Air bag is in compression always
State, compressed gas act between main body and push plate, and push plate is made to be in the state pushed out always, and guarantee, which is scraped, clenches patch iron
Enclose surface.
The beneficial effects of the present invention are:
1. by the present invention in that using electrolysis unit as reactor, by certain density soluble cobalt aqueous solution, trivalent
Molysite aqueous solution mixes in electrolysis unit with certain density oxalic acid or oxalic acid saline solution, and iron is anode in electrolysis unit,
Ferric iron is cathode, carries out cell reaction generation ferrous ion and reacts, ferrous iron is continuously replenished by way of electrolysis
Ion, while under the action of electricity, promotes soluble cobalt aqueous solution and divalent iron salt reactant aqueous solution, under energized state, changes
Condition needed for being aged has been apt to it, ageing can carry out at normal temperature, the digestion time greatly shortened, and then shorten whole preparation process
The required time.
2. scraping device scrapes iron ring by the present invention in that scraping device is arranged in electrolysis unit with electrolysis unit, produce
Pig iron powder is adsorbed on iron ring surface as anode, promotes cell reaction progress, accelerates the formation speed of ferrous ion, from
And the efficiency of whole preparation process is further increased, shorten preparation time.
3. carboxylated cobalt ferrite magnetic nanoparticle prepared by the present invention, particle diameter distribution is uniform, and magnetic correspondence is good, passes through
Regulation to pH is, it can be achieved that " receipts " " the putting " for being loaded into body.The magnetic particle of carboxylated in shell carboxyl group, particle it
Between it is ionized in aqueous environments, there are electrostatic repulsion, dispersion stabilization is good.Directly use carboxylated cobalt ferrite magnetic particle
Convey drug or processing waste water from dyestuff as carrier, no matter from raw material sources, preparation cost or in applying to magnetic particle
Manipulation aspect have a clear superiority, is easy in the realization application of the fields such as biomedicine, environmental protection.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the carboxylated cobalt ferrite magnetic nanoparticle of preparation；
Fig. 2 is the main view of electrolysis unit；
Fig. 3 is the side view of electrolysis unit；
Fig. 4 is the cross-sectional view of scraping device；
Reactive tank 1 in figure, horizontal rotating shaft 2, driving device 3, rotating electric machine 31, speed changer 32, anode block 4, suction tray 41,
Iron ring 42, bearing block 5, water inlet pipe 6, outlet pipe 7, water check valve 8, scraping device 9, main body 94, push plate 91, scrape nail 93, spring 92,
Air bag 10 and anti-overflow weir 11.
Specific embodiment
Below in conjunction with attached drawing, the present invention is further illustrated.
As shown in Figures 1 to 4, the preparation method of a kind of carboxylated cobalt ferrite magnetic nanoparticle, the preparation side
Specific step is as follows for method:
(a) by certain density soluble cobalt aqueous solution, trivalent iron salt aqueous solution and certain density oxalic acid or oxalic acid
Saline solution mixes in electrolysis unit, in electrolysis unit iron be anode, ferric iron be catholyte reaction generate ferrous iron from
Son, Aging Temperature are room temperature, and filter cake is obtained by filtration after being aged 1-3h, and ferric oxalate cobalt is made after the filter cake is dehydrated, is dried
Predecessor, by the ferric oxalate cobalt precursor object at 300~600 DEG C of air atmosphere, 1~5 DEG C/min of heating rate, calcining 2~
Cobalt ferrite is made after 4h；The mass ratio of the soluble cobalt and divalent iron salt is 1:2, the soluble cobalt and divalent iron salt
It is 1:(1~2 with the mass ratio of oxalic acid or oxalates)；The soluble cobalt is cobalt chloride or cobaltous sulfate or cobalt nitrate, institute
The soluble divalent iron salt stated is iron ammonium sulfate or frerrous chloride or ferrous sulfate, and the oxalates is sodium oxalate or oxalic acid
Potassium；
(b) by cobalt ferrite hydrothermal carbonization in the aqueous solution containing glucose obtained by step (a), after being cooled to room temperature, magnetic
Property separation, washing obtain filter cake, by the filter cake 100 DEG C of progresss forced air dryings be made packet carbon cobalt ferrite, the cobalt ferrite and
The mass ratio of glucose is 1:(3~10), hydro-thermal activation time 10~for 24 hours, activation temperature is 160 DEG C~200 DEG C；
(c) packet carbon cobalt ferrite made from step (b) is heated to reflux in aqueous slkali, after being cooled to room temperature, magnetism point
Filter cake is obtained from, washing, by the filter cake in the obtained target product of 100 DEG C of progresss forced air dryings: carboxylated cobalt ferrite magnetic is received
Rice corpuscles；The alkaline concentration is 0.05-0.5mol/L, 1~6h of return time, the matter of the packet carbon cobalt ferrite and solid base
Amount is than being 1:(1~5), the solid base is sodium hydroxide or potassium hydroxide.
The average grain diameter of carboxylated cobalt ferrite magnetic nanoparticle prepared by the present invention is 20~40nm, and saturated magnetization is strong
Spend 15~42emu/g.The carboxylated cobalt ferrite magnetic nanoparticle be it is a kind of rich in carboxylic acid group, with good magnetic induction
The cobalt ferrite of carbon-based material cladding；Reaction, which is located in electrolysis unit, to be carried out, and it is anti-that ferrous iron generation is mainly constantly generated by electrolysis
It answers, while reaction can be effectively facilitated by electrolysis, shorten digestion time.
As one embodiment of the present invention, the preparation method of carboxylated cobalt ferrite magnetic nanoparticle is in electrolysis unit
Middle progress, the electrolysis unit include reactive tank 1, are provided with horizontal rotating shaft 2 above the reactive tank 1, the both ends of the horizontal rotating shaft 2
It is mounted on the reactive tank 1 by bearing block 5, one end of the horizontal rotating shaft 2 is connected with driving device 3, at described horizontal turn
At least one anode block 4 is installed, the scraping device 9 is fixedly mounted on reaction tank bottom on axis 2；4 two sides of anode block
It is correspondingly provided with scraping device 9, scraping device 9 is contacted with anode block 4.When work, by certain density soluble cobalt aqueous solution,
Trivalent iron salt aqueous solution mixes in electrolysis unit with certain density oxalic acid or oxalic acid saline solution, and iron is sun in electrolysis unit
Pole, ferric iron are cathode, carry out cell reaction generation ferrous ion and react, driving device 3 drives 2 turns of horizontal rotating shaft
It is dynamic, drive anode block 4 to rotate, the rotation of anode block 4 is scraped with scraping device 9, generates iron powder and ferrous iron is accelerated to generate, promote
Reaction carries out.
As one embodiment of the present invention, the inner wall of the reactive tank 1 is semicircle cambered surface, the side of the reactive tank 1
Edge extends to form anti-overflow weir 11 straight up.
As one embodiment of the present invention, the anode block 4 is three, and three anode blocks 4 are in the level
Equidistantly distributed in shaft 2, the anode block 4 include suction tray 41 and iron ring 42；The suction tray 41 passes through horizontal rotating shaft 2,
It is fixedly connected with horizontal rotating shaft 2；Two iron rings 42 are located at 41 two sides of suction tray, are close together with suction tray 41.
As one embodiment of the present invention, the driving device 3 includes rotating electric machine 31 and speed changer 32, the rotation
The output shaft of motor 31 and the input axis connection of speed changer 32, the output shaft of the speed changer 32 are connect with the horizontal rotating shaft 2, institute
It states rotating electric machine 31 and speed changer 32 is fixed at the outer wall of the reactive tank 1.
As one embodiment of the present invention, it is respectively equipped with water inlet pipe 6 and outlet pipe 7 on the waste water reaction slot,
Water check valve 8 is respectively arranged on the water inlet pipe 6 and outlet pipe 7.
As one embodiment of the present invention, the scraping device 9 includes main body 94, push plate 91, scrapes nail 93 and spring
92；The push plate 91 is located in 94 inside sliding slot of main body, can move left and right；It is fixed on the left of 92 side of spring and push plate 91
Connection, the other end are fixedly connected with main body 94, and at least three spring 92 is arranged between push plate 91 and main body 94；It is described to scrape nail 93
It is even to be arranged in 91 right side of push plate, iron powder is obtained for scraping 42 surface of iron ring.Push plate 91 is connect with main body 94 by spring 92,
When scraping 42 surface of iron ring, 42 surface of iron ring is constantly thinning, makes to scrape nail 93 by spring 92 and contacts always with 42 surface of iron ring.
As one embodiment of the present invention, the suction tray 41 is electromagnet, for adsorbing iron ring 42；The suction
Attached disk 41 and 42 outer surface of iron ring are rough rough surface, prevent suction tray 41 and the opposite sliding of iron ring 42.Work as scraping
Device 9 scrapes 42 surface of iron ring, and suction tray 9 can prevent iron ring 42 from occurring to slide relatively, and generate iron powder, and suction tray 9 has magnetic force
By iron powder adsorption on surface, as anode reaction, iron powder is more conducive to accelerate reaction speed, promotes the progress entirely reacted.
As one embodiment of the present invention, the nail 93 of scraping is cemented carbide material, for scraping 42 surface of iron ring.
Cemented Carbide Hardness is greater than iron, can scrape to iron.
As one embodiment of the present invention, air bag 10 is equipped between the scraping device 9, air bag 10 is located at two phases
Between adjacent and opposite scraping device 9, and it is constantly in squeezed state, gives the support of scraping device 9, while promoting scraping device
9 are close to iron ring 42.Air bag 10 is in compressive state always, and compressed gas acts between main body 94 and push plate 91, makes push plate 91
Always in the state pushed out, guarantee scrapes nail 93 and is close to 42 surface of iron ring.
When electrolysis unit works, by certain density soluble cobalt aqueous solution, trivalent iron salt aqueous solution and a certain concentration
Oxalic acid or oxalic acid saline solution mixed in electrolysis unit, in electrolysis unit iron be anode, ferric iron is cathode, is electrolysed
Reaction generates ferrous ion and reacts, and driving device 3 drives horizontal rotating shaft 2 to rotate, and drives anode block 4 to rotate, anode block 4
Rotation is scraped with scraping device 9, and when scraping device 9 scrapes 42 surface of iron ring, suction tray 9 can prevent iron ring 42 from occurring relatively
Sliding, and iron powder is generated, suction tray 9 has magnetic force by iron powder adsorption on surface, and as anode reaction, iron powder is more conducive to accelerate reaction
Speed promotes the progress entirely reacted, and generates iron powder and ferrous iron is accelerated to generate, reaction is promoted to carry out, be equipped between scraping device 9
Air bag 10, air bag 10 is located between two adjacent and opposite scraping devices 9, and is constantly in squeezed state, gives scraping dress
9 supports are set, while scraping device 9 being promoted to be close to iron ring 42.Air bag 10 is in compressive state always, and compressed gas acts on main body
Between 94 and push plate 91, make push plate 91 always in the state pushed out, guarantee scrapes nail 93 and is close to 42 surface of iron ring.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (10)
1. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle, it is characterised in that: the preparation method specific steps are such as
Under:
(a) by certain density soluble cobalt aqueous solution, trivalent iron salt aqueous solution and certain density oxalic acid or oxalic acid salt water
Solution mixes in electrolysis unit, and iron is anode in electrolysis unit, and ferric iron is that catholyte reaction generates ferrous ion, old
Change temperature is room temperature, and filter cake is obtained by filtration after being aged 1-3h, and ferric oxalate cobalt precursor is made after the filter cake is dehydrated, is dried
Object, by the ferric oxalate cobalt precursor object at 300~600 DEG C of air atmosphere, 1~5 DEG C/min of heating rate, after calcining 2~4h
Cobalt ferrite is made；The mass ratio of the soluble cobalt and divalent iron salt is 1:2, the soluble cobalt and divalent iron salt and grass
The mass ratio of acid or oxalates is 1:(1~2)；The soluble cobalt is cobalt chloride or cobaltous sulfate or cobalt nitrate, described
Soluble divalent iron salt is iron ammonium sulfate or frerrous chloride or ferrous sulfate, and the oxalates is sodium oxalate or potassium oxalate；
(b) by cobalt ferrite hydrothermal carbonization in the aqueous solution containing glucose obtained by step (a), after being cooled to room temperature, magnetism point
Filter cake is obtained from, washing, by the filter cake in the obtained packet carbon cobalt ferrite of 100 DEG C of progresss forced air dryings, the cobalt ferrite and grape
The mass ratio of sugar is 1:(3~10), hydro-thermal activation time 10~for 24 hours, activation temperature is 160 DEG C~200 DEG C；
(c) packet carbon cobalt ferrite made from step (b) is heated to reflux in aqueous slkali, after being cooled to room temperature, Magnetic Isolation is washed
It washs to obtain filter cake, target product: carboxylated cobalt ferrite magnetic nanoparticle is made in 100 DEG C of progress forced air dryings in the filter cake
Son；The alkaline concentration is 0.05-0.5mol/L, 1~6h of return time, the mass ratio of the packet carbon cobalt ferrite and solid base
For 1:(1~5), the solid base is sodium hydroxide or potassium hydroxide.
2. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 1, it is characterised in that:
The preparation method of carboxylated cobalt ferrite magnetic nanoparticle carries out in electrolysis unit, which includes reactive tank (1),
Horizontal rotating shaft (2) are provided with above the reactive tank (1), the both ends of the horizontal rotating shaft (2) are mounted on described anti-by bearing block (5)
It answers on slot (1), one end of the horizontal rotating shaft (2) is connected with driving device (3), is equipped at least on the horizontal rotating shaft (2)
One anode block (4), the scraping device (9) are fixedly mounted on reaction tank bottom；Anode block (4) two sides, which are correspondingly provided with, scrapes
It takes device (9), scraping device (9) is contacted with anode block (4).
3. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, it is characterised in that:
The inner wall of the reactive tank (1) is semicircle cambered surface, and the edge of the reactive tank (1) extends to form anti-overflow weir straight up
(11)。
4. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, it is characterised in that:
The anode block (4) is three, three anode blocks (4) equidistantly distributed, anode blocks on the horizontal rotating shaft (2)
It (4) include suction tray (41) and iron ring (42)；The suction tray (41) passes through horizontal rotating shaft (2), with horizontal rotating shaft (2) fixed company
It connects；Two iron rings (42) are located at suction tray (41) two sides, are close together with suction tray (41).
5. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, it is characterised in that:
The driving device (3) includes rotating electric machine (31) and speed changer (32), the output shaft and speed changer of the rotating electric machine (31)
(32) output shaft of input axis connection, the speed changer (32) is connect with the horizontal rotating shaft (2), the rotating electric machine (31) and
Speed changer (32) is fixed at the outer wall of the reactive tank (1).
6. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, it is characterised in that:
It is respectively equipped with water inlet pipe (6) and outlet pipe (7) on the waste water reaction slot, distinguishes on the water inlet pipe (6) and outlet pipe (7)
It is provided with water check valve (8).
7. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, it is characterised in that:
The scraping device (9) includes main body (94), push plate (91), scrapes nail (93) and spring (92)；The push plate (91) is located at main body
(94) it in internal sliding slot, can move left and right；It is fixedly connected on the left of spring (92) side and push plate (91), the other end and master
Body (94) is fixedly connected, and at least three spring (92) are arranged between push plate (91) and main body (94)；The nail (93) of scraping is evenly arranged
On the right side of push plate (91), iron powder is obtained for scraping iron ring (42) surface.
8. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 4, it is characterised in that:
The suction tray (41) is electromagnet, for adsorbing iron ring (42)；The suction tray (41) is with iron ring (42) outer surface
Rough rough surface prevents suction tray (41) and iron ring (42) are opposite from sliding.
9. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 7, it is characterised in that:
Described scrape nail (93) are cemented carbide material, for scraping iron ring (42) surface.
10. a kind of preparation method of carboxylated cobalt ferrite magnetic nanoparticle according to claim 2, feature exist
In: be equipped with air bag (10) between the scraping device (9), air bag (10) be located at two adjacent and opposite scraping devices (9) it
Between, and it is constantly in squeezed state, scraping device (9) support is given, while scraping device (9) being promoted to be close to iron ring (42).
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| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
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| CN102976418A (en) * | 2012-12-02 | 2013-03-20 | 安徽工业大学 | Preparation method of caboxylated cobalt ferrite magnetic nanoparticles |
| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
| CN107012473A (en) * | 2017-04-24 | 2017-08-04 | 北京化工大学 | A kind of double metallic composite material and its preparation method and application |
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| CN111137988A (en) * | 2020-01-18 | 2020-05-12 | 安徽工程大学 | Method for decoloring dye wastewater |
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