CN106745302A - A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof - Google Patents
A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses coralloid zinc ferrite powder of a kind of three-dimensional network and preparation method thereof, including：With Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is raw material, nanometer zinc ferrite presoma is prepared with hydro-thermal method, again by the treatment of presoma molten-salt growth method, obtain the zinc ferrite of shape of octahedron, finally with N, N dimethylformamides are solvent, and hydrazine hydrate is reducing agent, methyl thioglycolate is complexing agent, and the coralloid zinc ferrite of three-dimensional network is obtained through a step etch.Preparation technology of the present invention is simple to operate, cycle is short, and the coralliform zinc ferrite diameter prepared is about 75~90nm, and uniform in size, its specific surface area improves.
Description
【Technical field】
The invention belongs to material science, and in particular to a kind of coralloid zinc ferrite powder of three-dimensional network and its preparation
Method.
【Background technology】
Zinc ferrite (ZnFe2O4) belong to the spinel structure of cubic system, it is a kind of important low-gap semiconductor material,
Its energy gap is 1.9eV.Due to its unique magnetics, electrical and optical properties, ZnFe2O4Be widely used in making magnetic material,
Gas sensitive, catalysis material, sorbing material and lithium ion battery material etc..
Zinc ferrite is a kind of important soft magnetic ferrite, and nanometer zinc ferrite particle is in magnetic fluid, storage, drug targeting
The fields such as transmission have broad application prospects.The ferrous acid Zinc material of block is presented ferromagnetism, but when the size of zinc ferrite reaches
During nanoscale, its crystal structure changes, and this causes the magnetic of nanometer zinc ferrite to be undergone mutation, and superparamagnetism is presented.It is sharp brilliant
Stone class material has good chemical stability and heat endurance, and its high temperature coefficient of thermal expansion is small, and the corrosion to various melts has
Preferable resistivity.The resistance order of magnitude of zinc ferrite gas sensor in 103k Ω, by the relation for measuring electrical conductivity and temperature
Surface Oxygen activation energy of adsorption very little can be calculated.Surface Oxygen activation energy of adsorption is for reaction between surface adsorbed oxygen and adsorbed gas
Complexity, activation energy is smaller, illustrates that Surface Oxygen is more active, easier to be reacted with reducibility gas, sensitive to reducibility gas
Degree is higher.Zinc ferrite is the semiconductor of 1.9eV as a kind of energy gap, under radiation of visible light of the wavelength more than 420nm i.e.
Photo-generate electron-hole pair can be produced, is a kind of semiconductor light-catalyst very high to visible light utilization efficiency.Zinc ferrite as lithium from
Sub- cell negative electrode material, ZnFe2O4Conversion reaction can occur, and compared with general transition metal oxide, its conversion reaction life
Into Zn can also with Li occur alloying reaction, thus its more general transition metal oxide have theoretical capacity higher
(1000.5mAh/g), and because its more general transition metal oxide of removal lithium embedded platform is low, in following cell negative electrode material
Application aspect has good prospect.
Hydro-thermal method, sol-gal process and solid phase method are generally used at present prepares zinc ferrite, but zinc ferrite prepared by hydro-thermal method
The general less rule of pattern；And zinc ferrite prepared by sol-gal process and solid phase method all compares reunion, specific surface area is relatively low.
【The content of the invention】
It is an object of the invention to provide coralloid zinc ferrite powder of a kind of three-dimensional network and preparation method thereof, by one
Step corrosion reaction, can prepare the zinc ferrite powder that pattern is good and is evenly distributed, and specific surface area is higher.
To realize goal of the invention of the invention, the present invention is adopted the following technical scheme that,
Comprise the following steps：
(1) zinc ferrite precursor powder is prepared by hydro-thermal method, reuses molten-salt growth method and ZnFe is obtained2O4Powder；
(2) by obtained ZnFe in step (1)2O4Powder and corrosion solvent press mass volume ratio for 0.2g：(90~180)
ML mixes, and carries out ultrasonic disperse, obtains mixed liquor A；
(3) under protective atmosphere, mixed liquor A is carried out into heating water bath and is stirred, while to reducing agent is added dropwise in mixed liquor A
And complexing agent, rapid cooling terminates after 60~120min of reaction；Wherein, the volume ratio of corrosion solvent, reducing agent and complexing agent is
(30~60)：(2~4)：1；
(4) dried after the sediment obtained after reaction is washed, obtain the coralloid zinc ferrite powder of three-dimensional network.
Further, zinc ferrite precursor powder is prepared by hydro-thermal method in step (1) to specifically include：
(101) according to ZnFe2O4Stoichiometric proportion, take Zn (NO3)3·6H2O and Fe (NO3)3·9H2O is added to ultrapure
Solution is prepared in water, orange solution is obtained after abundant magnetic agitation；Wherein Zn (NO3)3·6H2The ratio of O and ultra-pure water is
5mmol：(50~70) mL；
(102) to being slowly added to NaOH in orange solution and stir, Zn (NO3)3·6H2The mol ratio of O and NaOH
It is 5：(80~120), obtain bronzing suspension；
(103) bronzing suspension is transferred in reactor, hydro-thermal reaction is carried out 12~24 hours at 180~200 DEG C；
(104) after question response kettle is cooled to room temperature, dried after the product washing that will be obtained after reaction, obtain ferrous acid zinc precursor
Body powder.
Further, stirred 30~60 minutes in step (101) and step (102)；At 40~70 DEG C in step (104)
4~6h of lower drying.
Further, ZnFe is obtained by molten-salt growth method in step (1)2O4Powder is specifically included：
(111) the zinc ferrite precursor powder and fused salt for preparing hydro-thermal method are 1 in mass ratio：(3~6) mix, ball milling is simultaneously
It is dried to obtain kermesinus powder；
(112) 4~8h is calcined at 800~1000 DEG C after kermesinus powder is ground, ZnFe is obtained2O4Powder and salt it is mixed
Compound；
(113) to ZnFe2O4Ultra-pure water desalination is added in the mixture of powder and salt, ZnFe is dried to obtain2O4Powder.
Further, it is 1 that fused salt uses mass ratio in step (111):The mixture of 1 NaCl and KCl, ball milling is to turn
4~7h of ball milling in the ball mill of fast 500r/min；After adding ultra-pure water in step (113), 4~6h is heated at 65~85 DEG C, then
1~2h of ultrasound, then suction filtration, ZnFe is obtained by gained solid in 40~70 DEG C of 4~6h of drying2O4Powder.
Further, 20~30min of ultrasonic disperse in step (2)；Water bath heating temperature is 70~90 DEG C in step (3).
Further, corrosion solvent is DMF in step (2)；Reducing agent is hydrazine hydrate in step (3),
Complexing agent is methyl thioglycolate.
Further, in step (3), protective atmosphere is nitrogen or inert gas；Carried out using -2 DEG C of supercooling ethanol fast
Quickly cooling but terminates.
Further, 4~7h is dried in step (4) at 40~70 DEG C.
The pattern of zinc ferrite powder of the present invention is three-dimensional of the diameter in the mutually arranged formation of bar-shaped zinc ferrite of 75~90nm
Network coralliform.
Compared with prior art, the device have the advantages that：The present invention is prepared for zinc ferrite by hydro-thermal method first
Precursor powder, is further obtaining the zinc ferrite powder of the uniform shape of octahedron of complete crystal form, crystal grain, then using molten-salt growth method
Corrosion process is carried out by a step etch, the coralloid zinc ferrite powder of three-dimensional network is obtained.Hydro-thermal method is used in the present invention
With the method that molten-salt growth method is combined, the octahedral shape ZnFe of favorable dispersibility is obtained2O4Presoma, overcomes conventional hydrothermal legal system
Standby ZnFe2O4Group's crystal formation is imperfect and traditional molten salt growth prepares ZnFe2O4The serious situation of reunion.The present invention uses etching process,
ZnFe after corrosion2O4Specific surface area increases, and preparation condition used can be controlled preferably.What the present invention was obtained
ZnFe2O4Novel in shape, particle is uniform and equipment operation requires low, process is simple, energy consumption is low, can operate continuously and be easier to control
System.Therefore the present invention overcomes crystal formation bad and the shortcoming reunited using hydro-thermal method with the method that molten-salt growth method is combined, and in this base
Its surface is modified on plinth, finally gives the coralloid zinc ferrite of three-dimensional network.
Obtained ZnFe of the invention2O4Powder purity is high, crystallinity is good, pattern is uniform, obtain be a kind of nanometer rods from
The three-dimensional network coralliform structure for being formed is assembled, compared with before corrosion, specific surface area is from 0.381m2g-1Bring up to 76.216m2 g-1, over two hundred times is improved, the effect and raising of specific surface area has greatly improved to the correlated performance of material such as, works as material
Apply when on lithium ion battery, specific surface area increase means the lifting of Lithium-ion embeding and deintercalation efficiency, can be very big
Improve battery performance in ground.
【Brief description of the drawings】
Fig. 1 is ZnFe prepared by hydro-thermal method of the present invention2O4The XRD of precursor powder.
Fig. 2 is ZnFe prepared by molten-salt growth method of the present invention2O4The XRD of powder.
Fig. 3 is the three-dimensional network coralliform ZnFe that the present invention is prepared2O4XRD.
Fig. 4 is ZnFe prepared by hydro-thermal method of the present invention2O4The SEM figures of precursor powder.
Fig. 5 is ZnFe prepared by molten-salt growth method of the present invention2O4The SEM figures of powder.
Fig. 6 is the three-dimensional network coralliform ZnFe that the present invention is prepared2O4SEM figure.
【Specific embodiment】
By specific embodiment, the present invention is described in detail below in conjunction with the accompanying drawings.
Preparation method of the present invention, comprises the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to mol ratio 5mmol:10mmol is weighed, it is added to 50~
Solution is prepared in 70mL ultra-pure waters, abundant magnetic agitation obtains orange solution A after 30~60 minutes；
(2) to the granular NaOH that 80~120mmol is slowly added in solution A and stir, to precipitate Zn2+And Fe3+,
The time of stirring is 30~60 minutes, obtains uniform bronzing suspension B；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 180~200 DEG C, and the time of reaction is 12~24 hours；
(4) after question response kettle is cooled to room temperature, the hydrothermal product obtained after reaction is brownish red powder, by deionized water
Washing three times, absolute ethanol washing dries 4~6h after twice at 40~70 DEG C, obtains nanometer zinc ferrite presoma powder；
(5) the presoma powder and NaCl, KCl example in mass ratio for preparing hydro-thermal are 1:1 weighing, presoma powder and salt
Mass ratio be 1:3~6,500r/min 4~7h of ball milling in ball mill are put into, obtain kermesinus powder after drying；
(6) corundum crucible is put into after kermesinus powder is ground, 800~1000 DEG C of 4~8h of calcining, obtain in Muffle furnace
ZnFe2O4The mixture of powder and salt；
(7) to ultra-pure water is added in crucible, 4~6h and then at normal temperatures 1~2h of ultrasound are heated at 65~85 DEG C, will be mixed
Salt dissolving, ZnFe is obtained after suction filtration, 40~70 DEG C of 4~6h of drying in thing2O4Powder；
(8) the zinc ferrite powder and DMF that will be obtained in step 7 are mixed in silk mouthful bottle, ultrasound point
Dissipate 20~30min；The mass volume ratio of zinc ferrite powder and N,N-dimethylformamide is 0.2g：(90~180) mL；
(9) gained mixed liquor in step 8 heating water bath and is stirred at 65~85 DEG C, while be passed through nitrogen persistently protecting
Shield, to completely cut off air, it would however also be possible to employ other such as helium inert gases are used as protective atmosphere；
(10) to dropwise addition hydrazine hydrate and methyl thioglycolate in mixed liquor, nitrogen sustainable protection, after 60~120min of reaction,
The supercooling ethanol of -2 DEG C of rapid use is needed to cool down rapidly and terminate；N,N-dimethylformamide in corrosion process：Hydrazine hydrate：Sulfydryl
The volume ratio of methyl acetate mixed liquor is (30~60)：(2~4)：1.
(11) sediment that will be obtained after reaction is dried after absolute ethyl alcohol and deionized water are washed at 40~70 DEG C
4~7h, obtains the coralloid zinc ferrite powder of three-dimensional network.
The present invention is with Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is raw material, and nanometer zinc ferrite forerunner is prepared with hydro-thermal method
Body, then by the treatment of presoma molten-salt growth method, the zinc ferrite of shape of octahedron is obtained, finally with DMF as solvent,
Hydrazine hydrate is reducing agent, and methyl thioglycolate is complexing agent, and hydrazine hydrate is reacted Fe with zinc ferrite3+It is reduced into Fe2+Generation Fe
(OH)2,Fe(OH)2With methyl thioglycolate react generation complex compound be dissolved in DMF, corroded through above-mentioned
Ferric ion corrosion in zinc ferrite is fallen into and obtains the coralloid zinc ferrite of three-dimensional network by journey.Preparation technology operation letter of the present invention
Single, cycle is short, the coralliform zinc ferrite diameter prepared is about 75~90nm, and uniform in size, its specific surface area improves.
Embodiment 1
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, comprise the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to mol ratio 1:2 weigh, and are added in 60mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 30min；
(2) to 80mmol NaOH are slowly added in solution A and the 30min that stirs, suspension B russet is obtained；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 180 DEG C, and the reaction time is 18h；
(4) after question response kettle is cooled to room temperature, the product that will be obtained after reaction passes through deionized water and absolute ethanol washing
After be put into 70 DEG C of baking oven and dry 4h, obtain the nanometer zinc ferrite presoma powder of hydro-thermal method preparation；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio for preparing hydro-thermal：1.5：1.5 weigh, and are put into ball mill
Middle ball milling 4h, kermesinus powder is obtained after drying；
(6) corundum crucible is put into after kermesinus powder is ground, 800 DEG C of calcining 4h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt
(7) to ultra-pure water is added in crucible, heat 4h at 65 DEG C and then ultrasound 1h dissolves salt in mixture, suction filtration, 40
ZnFe is obtained after DEG C drying 4h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 90mL N,N-dimethylformamide that will be obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 30min；
(9) will be obtained 65 DEG C of heating water baths of solution in step 8 and stirred, while being passed through nitrogen；
(10) it is 6mL to volume ratio is added dropwise in mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Shield 30min, is cooled down and terminating reaction rapidly after reaction 1h by supercooling ethanol；
(11) sediment that will be obtained after reaction is put into 50 DEG C of dryings of baking oven after absolute ethyl alcohol and deionized water are washed
7h, obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 2
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, comprise the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to mol ratio 1:2 weigh, and are added in 50mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 40min；
(2) to 90mmol NaOH are slowly added in solution A and the 40min that stirs, suspension B russet is obtained；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 180 DEG C, and the reaction time is 12h；
(4) after question response kettle is cooled to room temperature, the product that will be obtained after reaction passes through deionized water and absolute ethanol washing
After be put into 60 DEG C of baking oven and dry 6h, obtain the nanometer zinc ferrite presoma powder of hydro-thermal method preparation；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio for preparing hydro-thermal：2.5：2.5 weigh, and are put into ball mill
Middle ball milling 5h, kermesinus powder is obtained after drying；
(6) corundum crucible is put into after kermesinus powder is ground, 900 DEG C of calcining 5h in Muffle furnace, molten-salt growth method is obtained
ZnFe2O4The mixture of powder and salt；
(7) to ultra-pure water is added in crucible, heat 5h at 80 DEG C and then ultrasound 2h dissolves salt in mixture, suction filtration, 60
ZnFe is obtained after DEG C drying 6h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 150mL N,N-dimethylformamide that will be obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 30min；
(9) will be obtained 80 DEG C of heating water baths of solution in step 8 and stirred, while being passed through nitrogen；
(10) it is 9mL to volume ratio is added dropwise in mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Shield 30min, is cooled down and terminating reaction rapidly after reaction 2h by supercooling ethanol；
(11) sediment that will be obtained after reaction is put into 60 DEG C of dryings of baking oven after absolute ethyl alcohol and deionized water are washed
6h, obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 3
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, comprise the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to mol ratio 1:2 weigh, and are added in 70mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 50min；
(2) to 110mmol NaOH are slowly added in solution A and the 50min that stirs, suspension B russet is obtained；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 190 DEG C, and the reaction time is 24h；
(4) after question response kettle is cooled to room temperature, the product that will be obtained after reaction passes through deionized water and absolute ethanol washing
After be put into 50 DEG C of baking oven and dry 6h, obtain the nanometer zinc ferrite presoma powder of hydro-thermal method preparation；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio for preparing hydro-thermal：2：2 weigh, and are put into ball in ball mill
Mill 6h, kermesinus powder is obtained after drying；
(6) corundum crucible is put into after kermesinus powder is ground, 1000 DEG C of calcining 7h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt；
(7) to ultra-pure water is added in crucible, heat 5h at 75 DEG C and then ultrasound 1h dissolves salt in mixture, suction filtration, 50
ZnFe is obtained after DEG C drying 5h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 180mL N,N-dimethylformamide that will be obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 20min；
(9) will be obtained 85 DEG C of heating water baths of solution in step 8 and stirred, while being passed through nitrogen；
(10) it is 12mL to volume ratio is added dropwise in mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Shield 30min, is cooled down rapidly by supercooling ethanol and is terminated after reaction 1.5h；
(11) sediment that will be obtained after reaction is put into 60 DEG C of dryings of baking oven after absolute ethyl alcohol and deionized water are washed
4h, obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 4
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, comprise the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to mol ratio 1:2 weigh, and are added in 60mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 60min；
(2) to 120mmol NaOH are slowly added in solution A and the 60min that stirs, suspension B russet is obtained；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 200 DEG C, and the reaction time is 12h；
(4) after question response kettle is cooled to room temperature, the product that will be obtained after reaction passes through deionized water and absolute ethanol washing
After be put into 40 DEG C of baking oven and dry 5h, obtain the nanometer zinc ferrite presoma powder of hydro-thermal method preparation；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio for preparing hydro-thermal：3：3 weigh, and are put into ball in ball mill
Mill 7h, kermesinus powder is obtained after drying；
(6) corundum crucible is put into after kermesinus powder is ground, 1000 DEG C of calcining 8h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt；
(7) to ultra-pure water is added in crucible, heat 6h at 85 DEG C and then ultrasound 2h dissolves salt in mixture, suction filtration, 70
ZnFe is obtained after DEG C drying 6h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 150mL N,N-dimethylformamide that will be obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 20min；
(9) silk mouthful bottle is carried out 70 DEG C of heating water baths and is stirred, while being passed through nitrogen；
(10) it is 9mL to volume ratio is added dropwise in mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Shield 30min, is cooled down rapidly by supercooling ethanol and is terminated after reaction 2h；
(11) sediment that will be obtained after reaction is put into 40 DEG C of dryings of baking oven after absolute ethyl alcohol and deionized water are washed
5h, obtains the coralloid zinc ferrite powder of three-dimensional network.
Product to embodiment 2 is tested, as a result as shown in Figures 1 to 6.
It will be seen from figure 1 that presoma prepared by hydro-thermal method has been the ZnFe of pure phase2O4, there is no other dephasigns.
Figure it is seen that processing the ZnFe that the powder for obtaining is still pure phase by further molten-salt growth method2O4.And molten-salt growth method
ZnFe after treatment2O4Diffraction peak intensity is remarkably reinforced, and its crystallinity is preferable.
From figure 3, it can be seen that by the ZnFe after step corrosion process treatment2O4Still generated without dephasign, and after corroding
ZnFe2O4Substantially reduced before diffraction peak intensity is relatively corrosive.
From fig. 4, it can be seen that the ZnFe that hydro-thermal method is prepared2O4It is that particle diameter is the nanometer ball of 20nm or so.
From fig. 5, it can be seen that processing the ZnFe for obtaining by further molten-salt growth method2O4Powder for the length of side be about 300nm~
The octahedron of 600nm, surface is smooth and smooth, and shape is uniform, favorable dispersibility.
From fig. 6, it can be seen that by the ZnFe obtained after step corrosion process treatment2O4For diameter is about 75~90nm's
The three-dimensional network coralliform pattern of the bar-shaped mutually arranged formation of zinc ferrite, compared with before corrosion, specific surface area is from 0.381m2g-1Carry
Height arrives 76.216m2 g-1, improve over two hundred times.
The factor for influenceing maximum in the present invention is hydrazine hydrate in corrosion process：The volume ratio of methyl thioglycolate and corrosion
Influence of the time to pattern, optimal solution proportion and reaction time, experiment knot are determined by constantly changing experimental factors
Really show, hydrazine hydrate：The volume ratio of methyl thioglycolate is 2~4：1, etching time can be obtained between 30min~120min
Three-dimensional network coralliform zinc ferrite, wherein 3 are can be seen that from SEM figures:1 and 120min is optimum reaction condition.With etching time
Growth, template ferrous acid zine corrosion must be more thorough, but zinc ferrite structure can cave in when etching time is more than 120min.
Claims (10)
1. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network, it is characterised in that comprise the following steps：
(1) zinc ferrite precursor powder is prepared by hydro-thermal method, reuses molten-salt growth method and ZnFe is obtained2O4Powder；
(2) by obtained ZnFe in step (1)2O4Powder and corrosion solvent press mass volume ratio for 0.2g：(90~180) mL is mixed
Close, carry out ultrasonic disperse, obtain mixed liquor A；
(3) under protective atmosphere, mixed liquor A is carried out into heating water bath and is stirred, while to dropwise addition reducing agent and network in mixed liquor A
Mixture, rapid cooling terminates after 60~120min of reaction；Wherein, corrosion solvent, reducing agent and complexing agent volume ratio for (30~
60)：(2~4)：1；
(4) dried after the sediment obtained after reaction is washed, obtain the coralloid zinc ferrite powder of three-dimensional network.
2. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
Zinc ferrite precursor powder is prepared in step (1) by hydro-thermal method to specifically include：
(101) according to ZnFe2O4Stoichiometric proportion, take Zn (NO3)3·6H2O and Fe (NO3)3·9H2O is added in ultra-pure water
Solution is prepared, orange solution is obtained after abundant magnetic agitation；Wherein Zn (NO3)3·6H2The ratio of O and ultra-pure water is 5mmol：
(50~70) mL；
(102) to being slowly added to NaOH in orange solution and stir, Zn (NO3)3·6H2The mol ratio of O and NaOH is 5：
(80~120), obtain bronzing suspension；
(103) bronzing suspension is transferred in reactor, hydro-thermal reaction is carried out 12~24 hours at 180~200 DEG C；
(104) after question response kettle is cooled to room temperature, dried after the product washing that will be obtained after reaction, obtain zinc ferrite precursor
Body.
3. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 2, it is characterised in that
Stirred 30~60 minutes in step (101) and step (102)；4~6h is dried in step (104) at 40~70 DEG C.
4. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
ZnFe is obtained by molten-salt growth method in step (1)2O4Powder is specifically included：
(111) the zinc ferrite precursor powder and fused salt for preparing hydro-thermal method are 1 in mass ratio：(3~6) mix, ball milling is simultaneously dried
Obtain kermesinus powder；
(112) 4~8h is calcined at 800~1000 DEG C after kermesinus powder is ground, ZnFe is obtained2O4The mixture of powder and salt；
(113) to ZnFe2O4Ultra-pure water desalination is added in the mixture of powder and salt, ZnFe is dried to obtain2O4Powder.
5. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 4, it is characterised in that
It is 1 that fused salt uses mass ratio in step (111):The mixture of 1 NaCl and KCl, ball milling is the ball milling in rotating speed 500r/min
4~7h of ball milling in machine；After adding ultra-pure water in step (113), 4~6h, then 1~2h of ultrasound are heated at 65~85 DEG C, then taken out
Filter, ZnFe is obtained by gained solid in 40~70 DEG C of 4~6h of drying2O4Powder.
6. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
20~30min of ultrasonic disperse in step (2)；Water bath heating temperature is 70~90 DEG C in step (3).
7. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
Corrosion solvent is N,N-dimethylformamide in step (2)；Reducing agent is hydrazine hydrate in step (3), and complexing agent is TGA
Methyl esters.
8. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
In step (3), protective atmosphere is nitrogen or inert gas；Rapid cooling is carried out using -2 DEG C of supercooling ethanol to terminate.
9. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, it is characterised in that
4~7h is dried in step (4) at 40~70 DEG C.
10. the coralloid zinc ferrite powder of a kind of three-dimensional network, it is characterised in that the pattern of the zinc ferrite powder is diameter 75
The three-dimensional network coralliform of the mutually arranged formation of bar-shaped zinc ferrite of~90nm.
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| CN107960050A (en) * | 2017-12-12 | 2018-04-24 | 陕西科技大学 | A kind of preparation method of graphene/three-dimensional flower-shaped bismuth ferrite composite wave-suction material |
| CN108358604A (en) * | 2018-03-29 | 2018-08-03 | 广西钦州市品艺堂坭兴陶有限公司 | The production method of colored Nixing pottery |
| CN108766780A (en) * | 2018-05-16 | 2018-11-06 | 陕西科技大学 | A kind of ferrous acid lithium@PPy electrode material for super capacitor of nucleocapsid and preparation method thereof |
| CN108793261A (en) * | 2018-08-22 | 2018-11-13 | 浙江理工大学 | It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material |
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| CN101289228A (en) * | 2008-06-03 | 2008-10-22 | 浙江理工大学 | Method for preparing porous zinc ferrite nano-rods |
| CN102531067A (en) * | 2012-03-20 | 2012-07-04 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
| CN103803658A (en) * | 2014-01-20 | 2014-05-21 | 复旦大学 | Method for preparing porous magnetic nanoclusters through etching |
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| CN101289228A (en) * | 2008-06-03 | 2008-10-22 | 浙江理工大学 | Method for preparing porous zinc ferrite nano-rods |
| CN102531067A (en) * | 2012-03-20 | 2012-07-04 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
| CN103803658A (en) * | 2014-01-20 | 2014-05-21 | 复旦大学 | Method for preparing porous magnetic nanoclusters through etching |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107960050A (en) * | 2017-12-12 | 2018-04-24 | 陕西科技大学 | A kind of preparation method of graphene/three-dimensional flower-shaped bismuth ferrite composite wave-suction material |
| CN108358604A (en) * | 2018-03-29 | 2018-08-03 | 广西钦州市品艺堂坭兴陶有限公司 | The production method of colored Nixing pottery |
| CN108358604B (en) * | 2018-03-29 | 2021-04-20 | 广西钦州市品艺堂坭兴陶有限公司 | Manufacturing method of colored nixing pottery |
| CN108766780A (en) * | 2018-05-16 | 2018-11-06 | 陕西科技大学 | A kind of ferrous acid lithium@PPy electrode material for super capacitor of nucleocapsid and preparation method thereof |
| CN108793261A (en) * | 2018-08-22 | 2018-11-13 | 浙江理工大学 | It is a kind of using monheimite as the preparation method of the nanometer zinc ferrite of raw material |
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