CN109850933A

CN109850933A - A kind of preparation method of the zinc oxide nano-particle for bio-imaging

Info

Publication number: CN109850933A
Application number: CN201910016945.5A
Authority: CN
Inventors: 郑志勤; 易发成
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology
Priority date: 2019-01-08
Filing date: 2019-01-08
Publication date: 2019-06-07

Abstract

The invention discloses a preparation method of zinc oxide nanoparticles for biological imaging. NH ₃ ·H ₂ O and NH ₄ HCO ₃ are used as precipitants to react with ZnSO ₄ to generate Zn(OH) wrapped by ZnCO ₃ ₂ precursors need to be stirred in the process of reaction, and the stirring speed is _200-500r /min; Wherein, ZnSO is alum, and the consumption ratio is that the alum of 5-10g is equipped with 25-35mlNH ₃ ·H ₂ O and NH ₄ HCO ₃ ; filter out the generated precursor, and calcine after washing, the calcination temperature is 100°C, and the calcination time is 70-80min; after calcination, the precursor is calcined; the calcination temperature is 300-400°C, and the calcination time is 300-400°C is 2‑4h. Through the parameter control of the method, the present invention does not appear too large agglomeration phenomenon, is relatively balanced, improves the yield and quality, and is suitable for biological imaging.

Description

A kind of preparation method of the zinc oxide nano-particle for bio-imaging

Technical field

The present invention relates to a kind of preparation methods of zinc oxide nano-particle for bio-imaging.

Background technique

Nano-ZnO is also known as activity ZnO, a kind of novel high function fine inorganic product geared to the 21st century.Because of its spy Different size has special function, and granular size is about in 1-100nm.Show many special properties, as non-migratory, Absorption, fluorescence, scatters ultraviolet ability and piezoelectricity etc., by apply light, electricity, in terms of performance, purple can be manufactured Outside line masking material, rheostat, effective catalyst, gas sensor, plastic film, fluorophor, piezoelectric material, varistor, Image recording material and magnetic material etc..

The preparation of nano-ZnO generally can be divided into physical method and chemical method.Physical method is called comminuting method, or mechanical Method.The zinc oxide of common grade is crushed to by special crushing technology ultra-fine.Chemical method is called comminution granulation, is certain Under conditions of, the particle with certain shapes and size is condensed by the nucleation of atom or molecule, growth or chemical combination.Chemistry side Method can be divided into vapor phase method, solid phase method and liquid phase method again, and the prior art mainly adopts the precipitation method in liquid phase method to be prepared.Precipitating Based on precipitation reaction, gained sediment all needs to obtain nano oxide powder by being filtered, washed, drying and calcine method. The common ground of all precipitation method is produced using the liquid phase reactor of production precipitating, and entire reaction equation is indicated with following formula: nA⁺+ nB⁺→[AB].During preparing nano-ZnO, easily there is agglomerated particle in the prior art, and quality is low and low yield, is unfavorable for Bio-imaging.

Therefore, how to solve above-mentioned technical problem becomes those skilled in the art's technical problem urgently to be resolved.

Summary of the invention

It is an object of the invention to provide a kind of preparation methods of zinc oxide nano-particle for bio-imaging, can be completely Solve above-mentioned the deficiencies in the prior art place.

The purpose of the present invention is realized by following technical proposals:

A kind of preparation method of the zinc oxide nano-particle for bio-imaging, with NH₃·H₂O and NH₄HCO₃For precipitating reagent With ZnSO₄It reacts, generates by ZnCO₃The Zn (OH) of package₂Precursor needs to be stirred during reaction, stirring speed Degree is 200-500r/min, reaction equation are as follows: ZnSO₄+2NH₃·H₂O=Zn (OH)₂↓+(NH₄)₂SO₄, ZnSO₄+ NH₄HCO₃=ZnCO₃↓+(NH₄)₂SO₄；Wherein, ZnSO₄For Zinc sulphate, the Zinc sulphate that consumption proportion is 5-10g matches 25-35mlNH₃· H₂O and NH₄HCO₃, NH₃·H₂O and NH₄HCO₃Arbitrarily to match；

The presoma of generation is filtered out, is roasted after being washed, maturing temperature is 100 DEG C, calcining time 70- 80min；

After roasting, presoma is calcined, reaction equation are as follows: Zn (OH)₂=ZnO+H₂O；ZnCO₃=ZnO+ CO₂；Calcination temperature is 300-400 DEG C, calcination time 2-4h.

Further, the NH₃·H₂O and NH₄HCO₃It is pure chemicals, is configured to the aqueous solution of 0.5mol/L.

Further, the Zinc sulphate that consumption proportion is 5-8g matches 28-35mlNH₃·H₂O and NH₄HCO₃。

Further, the Zinc sulphate that consumption proportion is 5-6g matches 28-32mlNH₃·H₂O and NH₄HCO₃。

Further, the Zinc sulphate that consumption proportion is 5g matches 30mlNH₃·H₂O and NH₄HCO₃。

Further, NH₃·H₂O and NH₄HCO₃Proportion be mass ratio 1:1.

Further, mixing speed 200-400r/min.

Further, calcining time 70-75min.

Further, calcination temperature is 400 DEG C, calcination time 2h.

It compared with prior art, is not in too big the beneficial effects of the present invention are: the state modulator by this method Agglomeration, more balanced, the yield and quality improved, be suitable for bio-imaging.

Detailed description of the invention

Fig. 1 is flow chart of the invention；

Fig. 2 is that ZnSO is added in the present invention₄·7H₂The amount of O (Zinc sulphate) is in the relational graph of sediment yield；

Fig. 3 is the relational graph between reaction temperature of the present invention and the sediment of generation；

Fig. 4 is the relational graph between calcining time of the present invention and sediment；

Fig. 5 is the relational graph between calcination time of the present invention and calcining surplus.

Specific embodiment

The present invention is further illustrated with attached drawing combined with specific embodiments below.

As shown in Figure 1, a kind of preparation method of the zinc oxide nano-particle for bio-imaging, with NH₃·H₂O and NH₄HCO₃For precipitating reagent and ZnSO₄It reacts, generates by ZnCO₃The Zn (OH) of package₂Precursor needs during reaction It is stirred, mixing speed 200-500r/min, preferably 200-400r/min.Its reaction equation are as follows: ZnSO₄+2NH₃· H₂O=Zn (OH)₂↓+(NH₄)₂SO₄, ZnSO₄+NH₄HCO₃=ZnCO₃↓+(NH₄)₂SO₄；Wherein, ZnSO₄For Zinc sulphate, consumption proportion Match 25-35mlNH for the Zinc sulphate of 5-10g₃·H₂O and NH₄HCO₃, the Zinc sulphate that preferable amount proportion is 5-8g is with 28-35mlNH₃· H₂O and NH₄HCO₃Or the Zinc sulphate that consumption proportion is 5-6g matches 28-32mlNH₃·H₂O and NH₄HCO₃Or consumption proportion is 5g's Zinc sulphate matches 30mlNH₃·H₂O and NH₄HCO₃。NH₃·H₂O and NH₄HCO₃Arbitrarily to match, preferred mass ratio is 1:1.By generation Presoma filters out, and roasts after being washed, and maturing temperature is 100 DEG C, calcining time 70-80min, preferably 70-75min. After roasting, presoma is calcined, reaction equation are as follows: Zn (OH)₂=ZnO+H₂O；ZnCO₃=ZnO+CO₂.Calcining temperature Degree is 300-400 DEG C, preferably 400 DEG C.Calcination time is 2-4h, preferably 3h.NH₃·H₂O and NH₄HCO₃It is pure chemicals, it will Its aqueous solution for being configured to 0.5mol/L.

As shown in Fig. 2, Zinc sulphate is divided into the several groups of 5g, 10g, 15g, 20g, zinc oxide is prepared as variable using precipitating reagent Nanoparticle.First group by 5g Zinc sulphate respectively slowly be added 10ml and 20ml the 0.5mol/L being configured to precipitating reagent water It in solution and is stirred, gained sediment is filtered, roast, is calcined, zinc oxide nano-powder is finally obtained；Second group 10g Zinc sulphate is slowly added respectively in the aqueous solution for the 0.5mol/L of 20ml, 40ml and 60ml being configured to precipitating reagent simultaneously It is stirred, gained sediment is filtered, roast, is calcined, zinc oxide nano-powder is finally obtained；Third group is white by 15g Alum is slowly added in the aqueous solution for the 0.5mol/L of 40ml, 80ml and 100ml being configured to precipitating reagent respectively and is stirred It mixes, gained sediment is filtered, roast, is calcined, zinc oxide nano-powder is finally obtained；4th group is distinguished 20g Zinc sulphate It is slowly added in the aqueous solution for the 0.5mol/L of 80ml, 100ml and 120ml being configured to precipitating reagent and is stirred, it will Gained sediment is filtered, roasts, calcines, and finally obtains zinc oxide nano-powder.

As shown in figure 3, changing reaction temperature to above-mentioned group, first group of reaction temperature is room temperature；Second group is placed in constant temperature In water-bath, temperature is 50 DEG C；Third group is placed in thermostat water bath, and temperature is 60 DEG C；4th group is placed in thermostat water bath, Temperature is 70 DEG C；Reaction time is 15min.Band is filtered after completion of the reaction, roasts, is calcined, and weighing obtains:

Reaction temperature (DEG C)	Sediment granularity
		Room temperature	It is larger
50	It is smaller
		60	It is smaller
70	It is smaller

Change mixing speed, each group acted on 0r/min, 200r/min, 400r/min respectively, is obtained:

Mixing speed (r/min)	Reaction rate	Granularity
			0	Generally	It is larger
200	It is larger	It is smaller
			400	It is larger	It is smaller

Change calcining time, each group is acted on 30min, 50min, 70min, 90min respectively, sediment is with roasting The variation of time and change, obtain shortest calcining time, as shown in Figure 4.

Change calcination time, calcination temperature remains 400 DEG C, acts on each group respectively with 1h, 2h, 3h, 4h, obtain Best calcination time, as shown in Figure 5.

The state modulator that the present invention passes through this method is not in too big agglomeration, more balanced, the production improved Rate and quality.It is easier to reunite because the probability of particle encounter increases, therefore the Zinc sulphate that consumption proportion is 5g is matched 30mlNH₃·H₂O and NH₄HCO₃It for optimal components ratio, i.e., less will appear reunion, and can ensure yield.It is anti-as the temperature increases Rate is answered to accelerate, the chance of molecular collision increases, and reunion probability increases.Since ammonium hydroxide is in aqueous solution with NH₄ ⁺And OH^-Form In the presence of simultaneously because NH₄ ⁺Hydrolysis be the endothermic reaction, as the temperature increases, NH₄ ⁺And OH^-Ion is reduced, so leading to Zn (OH)₂It reduces, ZnCO₃Increase, breaks their equilibrium, so that ZnCO₃It is easy to happen reunion, so preferably reaction temperature is Room temperature.With the increase of mixing speed, the appearance of reunion will be reduced, and mixing speed is excessive is easy for vortex occur, be easy It splashes out, it is unfavorable to reacting, so the preferable speed of stirring is 200r/min.Roasting is to evaporate the hydrone in sediment all Out, there is certain relationship with temperature to this time, be 70min with 100 DEG C of preferable calcining time.Calcining is to make presoma point For solution close to completely, calcination temperature has certain relationship with the time, is 3h with 400 DEG C of preferable calcination time.

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims

1. a preparation method of the zinc oxide nanoparticle for _bioimaging , is characterized in that: take NH ₃ H ₂ O and NH ₄ HCO ₃ as precipitating agent and ZnSO ₄ react with ZnSO , generate Zn( OH) ₂ precursor, needs to be stirred during the reaction, the stirring speed is 200-500r/min, and its reaction equation is: ZnSO ₄ +2NH ₃ ·H ₂ O=Zn(OH) ₂ ↓+(NH ₄ ) ₂ SO ₄ , ZnSO ₄ +NH ₄ HCO ₃ =ZnCO ₃ ↓+(NH ₄ ) ₂ SO ₄ ; wherein, ZnSO ₄ is alum, and the dosage ratio is 5-10g of alum with 25-35ml NH ₃ ·H ₂ O and NH ₄ HCO ₃ , NH ₃ ·H ₂ O and NH ₄ HCO ₃ are in any ratio;

The generated precursor is filtered out, washed and calcined, the calcination temperature is 100°C, and the calcination time is 70-80min;

After calcination, the precursor is calcined, and the reaction equation is: Zn(OH) ₂ =ZnO+H ₂ O; ZnCO ₃ =ZnO+CO ₂ ; the calcination temperature is 300-400°C, and the calcination time is 2-4h.

2 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 1 , wherein the NH ₃ ·H ₂ O and NH ₄ HCO ₃ are pure chemicals, which are configured to be 0.5 mol/L aqueous solution.

3. The method for preparing zinc oxide nanoparticles for bioimaging according to claim 1, characterized in that: the dosage ratio is that 5-8g of alum is mixed with 28-35ml NH ₃ H ₂ O and NH ₄ HCO ₃ .

4. The method for preparing zinc oxide nanoparticles for bioimaging according to claim 3, characterized in that: the dosage ratio is that 5-6g of alum is mixed with 28-32ml NH ₃ H ₂ O and NH ₄ HCO ₃ .

5 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 4 , wherein the dosage ratio is 5 g of alum with 30 ml of NH ₃ ·H ₂ O and NH ₄ HCO ₃ . 6 .

6 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 2 , wherein the ratio of NH ₃ ·H ₂ O to NH ₄ HCO ₃ is 1:1 by mass. 7 .

7 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 1 , wherein the stirring speed is 200-400 r/min. 8 .

8 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 1 , wherein the calcination time is 70-75 min. 9 .

9 . The method for preparing zinc oxide nanoparticles for bioimaging according to claim 1 , wherein the calcination temperature is 400° C. and the calcination time is 2 hours. 10 .