CN107628635A - A kind of method and nano zine oxide of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide - Google Patents
A kind of method and nano zine oxide of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide Download PDFInfo
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Abstract
The invention discloses a kind of method and nano zine oxide of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide, step 1：At 20 DEG C, 1.0mmol Zn (NO are weighed3)2·6H2O and 20.0mmol NaOH adds 40.0mL deionized waters in beaker, is placed in the SDS of addition 1.0mmol after magnetic stirrer, continues 23 hour to solution of stirring and is well mixed；Step 2：Above-mentioned solution is moved in reactor, is placed in 200 DEG C of thermostatic drying chamber and is incubated 24h；Step 3：After reaction terminates, reactor is with after being originally water-cooled to room temperature, opening reactor；Step 4：By solution left standstill, precipitation, separation, washed 3 times with absolute ethyl alcohol, obtain white four-blade propeller shape zinc oxide nano powder.Li Shui of the present invention is solvent, using soluble zinc nitrate as zinc source, using SDS as pattern to directed agents, and one-step synthesis four-blade propeller shape nano zine oxide.
Description
Technical field
The invention belongs to semiconductor nano material preparation field, and it is nano oxidized to be related to a kind of Hydrothermal Synthesiss four-blade propeller shape
The method and nano zine oxide of zinc.
Background technology
Zinc oxide is the second B metal oxide, is a kind of N-type wide-band-gap semiconductor material, and energy gap reaches
3.37eV, there is chemically and thermally stability, photoelectricity and piezoelectric property not available for general material, be a kind of multifunctional usage
Material, is quite suitable for the application in terms of high-and-new science and technology, and relatively common has light emitting diode, photodetector and photoelectricity
Optical modulator of diode etc..Nano zinc oxide material is again due to its unique surface and interfacial effect, small-size effect, quantum
Dimensional effect and macro quanta tunnel effect, thus, shown in electricity, magnetics, optics, mechanics and chemistry etc. very excellent
Different performance, while it is many also by increasing scholar to be widely applied to sewage disposal, sensor and solar cell etc.
Field.
Due to its unique optical property, except in the side such as light emitting diode, ultraviolet light detector and ultraviolet laser device
There are many applications in face；Also occupy irreplaceable effect in terms of uvioresistant and photocatalytic degradation.In addition militarily
Absorbing radar wave and for shielding ultraviolet rays and absorb infrared light building inside and outside wall emulsion in coating can aspect have
It is widely applied.Based on the distinctive chemical property of zinc oxide and semiconducting behavior, in terms of photosensitizer is catalyzed solar cell
Surface goes out good prospect.Additionally due to its under ultraviolet irradiation, make it in water and air in can allow substance decomposition output
The electronics moved freely and hole, this hole can activate the oxygen in air, so that it becomes active oxygen, has extremely strong chemistry
Activity, sterilization, sterilization, deodorization in terms of biologic pharmacological science are directly applied to, while are also applied to examine as semi-conducting material
In terms of the biology sensor for surveying glucolase, the specific target molecule of identification and detection nerve cell activity voltage etc..Though
Right nano zine oxide has various excellent performances, but also has with the pattern result of its own and closely contact.In recent years, state
It is inside and outside to have had been developed for a variety of zinc oxide appearance structures such as nanometer wire, bar-shaped, flower-shaped, tubulose and sea urchin shape, such as：Lee's magnitude
People's (application number：CN201410377082.1 after) being mixed a certain amount of zinc solution and alkali source and it is already prepared to big
Porous materials cuttlebone is put into reactor clock and obtains degree homogeneous nanometer wire oxidation in footpath after held for some time at a certain temperature
Zinc；The long brightness of leaf et al. (application number：CN200510094806.2 a kind of single crystal zinc oxide nanometer yarn array/poly crystal aluminium lining) is disclosed
Bottom complex and preparation method thereof；Smelting silver equality people's (application number：CN201010606346.8 a kind of nano flower-like oxygen) is disclosed
Change the preparation method of zinc；Zhu Ziqiang et al. (application numbers：CN200610117564.9) disclose one kind and utilize hydrothermally synthesizing series
The method of flower shape zinc oxide micrometer/nanometer structure；Xu Jun green grass or young crops et al. (application number：CN201410012786.9) disclosing one kind has
Zinc oxide catalytic of sequence layer structure and preparation method thereof, SDS are template, and zinc nitrate hexahydrate is zinc source, and sodium hydroxide is
It is prepared by alkali source, the hydro-thermal method for carrying out Zinc oxide powder；A Yue Hong men of virtue and ability et al. (application number：CN201611174173.0 one kind) is disclosed
The method of hydro-thermal method synthesizing zinc oxide nanometer rods, by certain density zinc nitrate solution, sodium hydroxide solution and pregnancy level tetramine
Solution be blended in obtains zinc oxide nano rod at 100 DEG C after insulation a period of time；Dong Hongxing et al. (application numbers：
CN201310208236.X) certain density zinc nitrate solution is coated in certain material substrate, after calcining 30min at 500 DEG C
It is incubated 8 hours acquisition presomas at a certain temperature in zinc acetate solution, the presoma is calcined into 24h at 150 DEG C and obtained
Obtain three-dimensional flower-shaped zinc oxide；(the application numbers such as Tang Pinggui：CN201410764240.9 club shaped structure oxygen) is obtained by precipitation reaction
Change zinc, then nanometer rods is gradually transformed into the tubulose multilevel hierarchy presoma being made up of nanometer sheet by dissolving regrowth, finally
Presoma is set to decompose to obtain the tubulose multilevel-structure zinc oxide obtained by nano-particles self assemble by high-temperature roasting；Li great Zhi
(application number：CN201410536535.0) find, at room temperature by a certain amount of Zn (NO3)2·6H2O is dissolved in 0.01mol/L
Sodium dodecyl sulfate solution in, nitric acid zinc concentration is reached 0.5mol/L, under magnetic stirring by zinc nitrate and bicarbonate
Sodium 1:1 mol ratio is slowly added to anhydrous sodium bicarbonate, and fully reaction obtains white precipitate, filters, white precipitate is used respectively
High purity water and absolute ethyl alcohol washing are placed in 24h in 50 DEG C of insulating boxs and obtain white presoma afterwards for several times；Presoma is placed on small magnetic boat
It is interior, it is placed in electric furnace the thermal decomposition 2h at 280 DEG C and obtains finished product.
The zinc oxide of above method synthesis, is the patterns such as common nanometer wire, bar-shaped, flower-shaped, tubulose and sea urchin shape,
This case synthesizes four-blade propeller shape nano zinc oxide material first.In addition, the nano zinc oxide material synthesized in the above method, its
Operation is very cumbersome, need to use the substrate as synthesis specific morphology zinc oxide such as cuttlebone or silicon chip, most of synthesis
Method is not all avoided that the higher high-temperature calcination of energy consumption, and also useful glycerine is as reaction dissolvent, cost height.Therefore, one is developed
It is environment-friendly, cost is cheap, the nano zinc oxide material of the simple unprecedented new pattern of synthesis route, have very high
Challenge.
Hydro-thermal method is also known as solvent-thermal method, refers in special closed reactor, using the aqueous solution as reaction system,
By being heated to reaction system, the environment of a HTHP is produced, accelerates ionic reaction and promotes hydrolysis, in the aqueous solution
Or the standby oxide of steam flow recasting, then by separation and oxide nano-particles are thermally treated resulting in, some can be made in normal temperature
The very slow thermodynamical reaction of reaction rate realizes fast reaction under hydrothermal conditions under normal pressure.Therefore, the present inventor this is done into
One step research, a kind of method and nano zine oxide of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide are developed, this case is thus
Produce.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide
Method and nano zine oxide, by the use of generally the least expensive water as solvent, using soluble zinc nitrate as zinc source, with SDS (dodecyl sodium sulfonates
Sodium) as pattern to directed agents, a period of time, one-step synthesis high-purity, monodispersed four leaves spiral shell are incubated within specified temperatures
Revolve oar shape nano zine oxide.
In order to solve the above technical problems, the technical solution of the present invention is：
A kind of method of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide, is comprised the following steps that：
Step 1：Under conditions of temperature is 20 DEG C, 1.0mmol Zn (NO are weighed respectively3)2·6H2O and 20.0mmol
NaOH in beaker, measure 40.0mL deionized waters in the beaker with graduated cylinder, be placed on magnetic stirring apparatus and be stirred until homogeneous
1.0mmol dodecyl sodium sulfate is added after solution, the mixed liquor is continued on magnetic stirring apparatus to stir 2-3 hour extremely
Solution is well mixed, and obtains homogeneous solution；
Step 2：Above-mentioned solution is transferred in the reactor of cleaning, the reactor is placed in 200 DEG C of thermostatic drying chamber
Middle insulation 24h；
Step 3：After reaction terminates, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, is opened
Reactor；
Step 4：Solution in reactor is poured into crystallising dish, stands, precipitate, separation, absolute ethyl alcohol is used after separation
Washing 3 times is carried out, white four-blade propeller shape zinc oxide nano powder is obtained, powder is placed in 60 DEG C of thermostatic drying chambers and carried out
Dry.
Further, it is further comprising the steps of in step 1：By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with originally
After washing is clean, with deionized water rinsing 2-3 times, dried for standby.
Further, in step 2, the volume of reactor is 50.0mL.
Further, the vane propeller shape zinc oxide nano powder, the angle between blade and axle are 109 °.
A kind of nano zine oxide, it is prepared by above-described preparation method.
After such scheme, the present invention has advantages below：
1st, the present invention is under specific reaction temperature (200 DEG C), specific reaction time (24h) and specific material proportion
Brand-new four-blade propeller shape zinc oxide appearance structure is synthesized；
2nd, the present invention is all carried out in aqueous, and technique is simple, cost is cheap, environment protecting and power-saving, avoids existing
High energy consumption in technology, is advantageous to environmental protection；
3rd, the material purity height of the invention synthesized, crystallinity height, good dispersion, its morphology controllable degree height etc..
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the nano zine oxide of the gained of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph one of the nano zine oxide of the gained of the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of the nano zine oxide of the gained of the embodiment of the present invention 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of the nano zine oxide of the gained of the embodiment of the present invention 3；
Fig. 5 is the scanning electron microscope (SEM) photograph of the nano zine oxide of the gained of the embodiment of the present invention 4；
Fig. 6 is the scanning electron microscope (SEM) photograph of the nano zine oxide of the gained of the embodiment of the present invention 5；
Fig. 7 is the scanning electron microscope (SEM) photograph of the nano zine oxide of the gained of the embodiment of the present invention 6；
Fig. 8 is the scanning electron microscope (SEM) photograph two of the nano zine oxide of the gained of the embodiment of the present invention 1.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.Disclosed is a kind of hydro-thermal
The method for synthesizing four-blade propeller shape nano zine oxide, in an embodiment of the present invention reagent used be on the market can be public
Open what is bought.
Embodiment 1
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 200 DEG C of thermostatic drying chamber and is incubated 24h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.
In embodiment 1 gained powder X ray diffracting spectrum as shown in figure 1, scanning electron microscope (SEM) photograph as shown in Figure 2 and Figure 8.Figure
1 X ray diffracting spectrum shows that the Zinc oxide powder purity obtained by this method is high, crystallinity is high；Its SEM knot
Fruit shows, as shown in Figure 2 and Figure 8, it is four-blade propeller shape to define the pattern to the microscopic appearance, and as shown in Fig. 2 blade and axle
Between angle be 109 °.
Embodiment 2
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 160 DEG C of thermostatic drying chamber and is incubated 24h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.The scanning electron microscopy of the sample of embodiment 2
Mirror result is as shown in Figure 3.
Embodiment 3
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 180 DEG C of thermostatic drying chamber and is incubated 24h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.The scanning electron microscopy of the sample of embodiment 3
Mirror result is as shown in Figure 4.
Embodiment 4
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 220 DEG C of thermostatic drying chamber and is incubated 24h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.The scanning electron microscopy of the sample of embodiment 4
Mirror result is as shown in Figure 5.
Embodiment 5
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 180 DEG C of thermostatic drying chamber and is incubated 36h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.The scanning electron microscopy of the sample of embodiment 5
Mirror result is as shown in Figure 6.
Embodiment 6
By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, with deionized water rinsing 2-3 times, do
It is dry stand-by.Under conditions of temperature is 20 DEG C, 1.0mmol (0.2975g) Zn (NO are weighed with assay balance respectively3)2·6H2O、
20.0mmol (0.8g) NaOH measures 40.0mL deionized waters in the beaker in beaker, with graduated cylinder, is placed in magnetic stirring apparatus
1.0mmol (0.2724g) SDS (dodecyl sodium sulfate) is added after being stirred until homogeneous solution with suitable rotational speed, by the mixed liquor
Continue stirring 2-3 hour to solution on magnetic stirring apparatus to be well mixed, obtain homogeneous solution；Above-mentioned solution is transferred to
Clean volume is in 50.0mL reactor；The reactor is placed in 180 DEG C of thermostatic drying chamber and is incubated 48h；Reaction knot
Shu Hou, reactor is removed from thermostatic drying chamber, after originally room temperature is water-cooled to, opens reactor, be taken out inner bag；Will
Solution in its inner bag is poured into crystallising dish, standing, precipitation, separation, and 3 acquisitions of washing are carried out in vain with absolute ethyl alcohol after separation
Color zinc oxide nano powder, powder is placed in 60 DEG C of thermostatic drying chambers and is dried.The scanning electron microscopy of the sample of embodiment 6
Mirror result is as shown in Figure 7.
6 embodiments contrast to more than, are different with the reaction time in identical proportioning in embodiment 1,2,3 and 4
Reaction temperature under the different zinc oxide patterns that synthesize.ESEM result shows that reaction temperature generates difference to pattern
The influence of degree, when reaction temperature that and if only if is 200 DEG C, the pattern of synthesis is four-blade propeller shape, under other temperature conditionss
Certain needle-like, the bar-shaped and nanometer wire of synthesis, and it is scattered and uneven.Embodiment 3,5 and 6 be in identical reaction temperature and
Match the different zinc oxide patterns synthesized under the different reaction time.ESEM result shows different reaction time synthesis
Zinc oxide microstructure difference it is larger, be presented nanowire shape and lath-shaped, and pattern disperse it is uneven.Therefore embodiment 2-6
Sharp contrast is formed with embodiment 1, demonstrating the four-blade propeller shape zinc oxide structures synthesized in embodiment 1 can only be specific
Synthesized under reaction temperature, specific reaction time and specific material proportion.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore the change or modification that claim under this invention and specification are done in every case, it should all belong to the scope that patent of the present invention covers
Within.
Claims (5)
- A kind of 1. method of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide, it is characterised in that：Comprise the following steps that：Step One：Under conditions of temperature is 20 DEG C, 1.0mmol Zn (NO are weighed respectively3)2·6H2O and 20.0mmol NaOH is in beaker In, 40.0mL deionized waters are measured in the beaker with graduated cylinder, are placed on magnetic stirring apparatus after being stirred until homogeneous solution and are added 1.0mmol dodecyl sodium sulfate, the mixed liquor is continued to stir 2-3 hour to solution mixing on magnetic stirring apparatus It is even, obtain homogeneous solution；Step 2：Above-mentioned solution is transferred in the reactor of cleaning, the reactor is placed in 200 DEG C 24h is incubated in thermostatic drying chamber；Step 3：After reaction terminates, reactor is removed from thermostatic drying chamber, with being originally water-cooled to After room temperature, reactor is opened；Step 4：Solution in reactor is poured into crystallising dish, stands, precipitate, separation, after separation Washing 3 times is carried out with absolute ethyl alcohol, obtains white four-blade propeller shape zinc oxide nano powder, powder is placed in into 60 DEG C of constant temperature does It is dried in dry case.
- A kind of 2. method of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide according to claim 1, it is characterised in that： It is further comprising the steps of in step 1：By beaker, medicine spoon, graduated cylinder and magnetic agitation rotor with after running water wash clean, spend Ionized water rinses 2-3 times, dried for standby.
- A kind of 3. method of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide according to claim 1, it is characterised in that： In step 2, the volume of reactor is 50.0mL.
- A kind of 4. method of Hydrothermal Synthesiss four-blade propeller shape nano zine oxide according to claim 1, it is characterised in that： The vane propeller shape zinc oxide nano powder, the angle between blade and axle are 109 °.
- A kind of 5. nano zine oxide, it is characterised in that：The nano zine oxide is as the preparation side described in claim any one of 1-4 Method is prepared.
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| CN113616787A (en) * | 2021-08-12 | 2021-11-09 | 国药集团动物保健股份有限公司 | Litchi branch-shaped nano zinc oxide cluster adjuvant, preparation method thereof and application of litchi branch-shaped nano zinc oxide cluster adjuvant as vaccine adjuvant |
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| CN103721698A (en) * | 2014-01-10 | 2014-04-16 | 中国天辰工程有限公司 | Zinc oxide catalyst of ordered layered structure and preparation method thereof |
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| CN103721698A (en) * | 2014-01-10 | 2014-04-16 | 中国天辰工程有限公司 | Zinc oxide catalyst of ordered layered structure and preparation method thereof |
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| DONYA RAMIMOGHADAM等: "The Effect of Sodium Dodecyl Sulfate (SDS) and Cetyltrimethylammonium Bromide (CTAB) on the Properties of ZnO Synthesized by Hydrothermal Method", 《INT. J. MOL. SCI.》 * |
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| CN113616787A (en) * | 2021-08-12 | 2021-11-09 | 国药集团动物保健股份有限公司 | Litchi branch-shaped nano zinc oxide cluster adjuvant, preparation method thereof and application of litchi branch-shaped nano zinc oxide cluster adjuvant as vaccine adjuvant |
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