CN1323948C - Preparation method of nanometer zinc oxide - Google Patents
Preparation method of nanometer zinc oxide Download PDFInfo
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- CN1323948C CN1323948C CNB2005100377988A CN200510037798A CN1323948C CN 1323948 C CN1323948 C CN 1323948C CN B2005100377988 A CNB2005100377988 A CN B2005100377988A CN 200510037798 A CN200510037798 A CN 200510037798A CN 1323948 C CN1323948 C CN 1323948C
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Abstract
The present invention discloses a method for preparing nanometer zinc oxide. The present invention selects soluble zinc salt as a zinc source, urea is adopted as the host of precipitant, and the soluble zinc salt and the urea are dissolved in water and react under microwave radiation by the homogeneous precipitation method; basic zinc carbonate (in a state of precipitate) synthesized after the reaction is dried in vacuum, milled with a ball and calcined to obtain crystal grains of nanometer zinc oxide; the crystal grains of nanometer zinc oxide, surface modifiers, organic solvent and dispersing agents are mixed by ball milling and dispersed uniformly, and then, the crystal grains of nanometer zinc oxide is treated under microwave radiation to carry out surface modification for the nanometer zinc oxide so as to obtain nanometer zinc oxide powder. The present invention has rapid reaction rate, and the reaction can be completed at lower temperature; meanwhile, the microwave radiation has the advantages of energy saving, few pollution and capability of preparing nanometer crystal grains which are difficult to prepare by conventional methods, etc.; the obtained crystal grains of nanometer zinc oxide have controllable operation, uniform dimension, good dispersibility and high lipophilic property.
Description
Technical field
The present invention relates to a kind of method of not having reunion, lipophilic nano zinc oxide for preparing, be specifically related to a kind of method that adopts the various zinc-oxide nano crystal grain of preparation under the microwave exposure, relate to the method for nano zine oxide surface modification and relate to corresponding apparatus.
Background technology
Nanometer be one meter part per billion, when the yardstick of material enters nano level, just have many special performances, as surface effects, volume effect, quantum effect etc.Nano zine oxide is a few the oxide type semiconductor material that can realize quantum size effect, not flammable, nontoxicity, has non-migrating, fluorescence, piezoelectricity, a series of excellent physical chemistry such as absorption and scatters ultraviolet, simultaneously cheap, thereby at the preparation ultraviolet shielding material, sunscreen, radar absorbing, gas alarm, moisture absorption ionic conduction thermometer, fluor, high efficiency photocatalyst, pottery, abrasive rubber, anti-static plastic, electro-conductive material, image recording material, piezoelectric, the lightning rod parts, aspects such as photocatalyst all are widely used.
The method for preparing nano zine oxide is a lot, generally can be divided into physics method and chemical process.Physics method (mechanical process) is to utilize special crushing technology with common powder fragmentation, but because the restriction of existing crushing technology and equipment is difficult to prepare real nano level ZnO, can only obtain the particle of submicron order at most; Chemical method mainly contains sol-gel method, microemulsion method, spray-drying process, plasma method, combustion method, the precipitator method, chemical vapor deposition (CVD) method, laser CVD method at present, or the like, though these methods all can be prepared nano level ZnO, but also exist some weakness: the reaction times is long or output is lower, control condition is strict, can not prepare the nanocrystal with special crystal formation and pattern, etc.Therefore, the scientific research personnel is seeking a kind of more effective and more economical preparation method always for many years.
The real application of nano material is the surface modification of nano material.The surface modification of nano material not only can give nano material new exceptional function, can also prepare the non-existent nano composite material of occurring in nature.The present invention has prepared the nano zine oxide of various crystal grain, and carries out modification on the surface of nanocrystal--and coat organism, the surface property, minimizing and elimination agglomeration, the surface that have changed nanocrystal are lipophilicity.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparation that is easy to realize and modified nano zinc oxide can prepare the crystal grain of different-shape, and the size of resulting nanocrystal evenly, good dispersity, surface be lipophilicity.
For achieving the above object, the technical solution used in the present invention is: a kind of nano-ZnO preparation, selecting soluble zinc salt is the zinc source, urea is the precipitation agent host, is dissolved in the water, and adopts homogeneous precipitation method to react under microwave exposure, the concentration in reactant zinc source is between 0.05mol/L～0.5mol/L, the mol ratio of zinc source and urea is between 1: 0.5～1: 5, and the irradiation reaction temperature was reacted 1～5 hour between 80 ℃～100 ℃; After will reacting zinc subcarbonate vacuum-drying of synthetic throw out and ball milling,, obtain the crystal grain of nano zine oxide 350 ℃～450 ℃ following roastings 1～5 hour; The nano zine oxide for preparing and surface-modifying agent, organic solvent, dispersion agent is even by the ball milling blending dispersion, temperature of reaction is between 80 ℃～150 ℃, irradiation is 1～3 hour under microwave, finishes the surface modification of nano zine oxide, obtains nanometer Zinc oxide powder.
In the technique scheme, soluble zinc salt can be Zinc vitriol, zinc nitrate, zinc chloride or zinc acetate etc.; Control zinc source can obtain different nanocrystals with the mol ratio of urea, can obtain torispherical, sheet and acicular nanocrystal respectively; Utilize " microwave " as type of heating, compare with the routine heating, microwave heating has its special advantage.Conventional heating is finished by conduction, convection type, is by the heating of surface to inside to reactant; And microwave radiation is a kind of dielectric heating, acts on the inside of reactant, makes the molecular motion aggravation of reactant, increased the collision frequency between reactant molecule greatly, reaching active state at short notice, be inside and outside heating together, thereby temperature is even, speed of response is fast.
When preparing the presoma of nano zine oxide under microwave exposure, following chemical reaction takes place in zinc source and urea:
Urea generation hydrolysis reaction: CO (NH
2)
2+ 3H
2O=CO
2+ 2NH
4OH
Precipitin reaction: 3Zn
2++ CO
3 2-+ 4OH
-+ H
2O=ZnCO
32Zn (OH)
2H
2O
After washing and the drying, when high-temperature roasting, following reaction takes place in the throw out zinc subcarbonate:
ZnCO
3·2Zn(OH)
2·H
2O＝3ZnO+CO
2↑+2H
2O
In the process of carrying out precipitin reaction, sedimentary size and pattern depend primarily on the growth rate of the formation speed and the nuclear of nuclear, and these two kinds of speed are relevant with factors such as the temperature of reacting, concentration, time, proportionings.Therefore, obtain that granule-morphology is controlled, the uniform nano zine oxide of yardstick, its preparation mix proportion scheme of more optimizing is: described sulfuric acid zinc concentration is between 0.15mol/L～0.2mol/L, the mol ratio of zinc sulfate and urea is between 1: 2～1: 4, the irradiation reaction temperature was reacted 1～5 hour between 88 ℃～95 ℃; After will reacting washing of synthetic throw out zinc subcarbonate and drying, 350 ℃～450 ℃ following roastings 1～3 hour.
Further technical scheme is, before roasting, described throw out zinc subcarbonate is used ammoniacal liquor, the absolute ethanol washing 3～4 times of pH=9.0 respectively, and gained solid zinc subcarbonate powder is by vacuum drier drying and ball milling, then 350 ℃～450 ℃ following roastings 1～5 hour.Can reduce the agglomeration of nanocrystal.
When the nano zine oxide surface modification, described surface-modifying agent is selected from silane coupling agent, tensio-active agent, oleic acid, stearic acid or primary alconol; Nano zine oxide that roasting is obtained and surface-modifying agent, organic solvent, dispersion agent are even by the ball milling blending dispersion, temperature of reaction is between 80 ℃～150 ℃, irradiation is 1～3 hour under microwave, finishes the surface modification of nano zine oxide, with rotatory evaporator solvent removal is also reclaimed again.Obtain having oil-wetted surface performance, finely disseminated nanometer Zinc oxide powder.
In the technique scheme, when the nano zine oxide surface modification, can select for use primary alconol as surface-modifying agent, and add organic acid as catalyzer, described organic solvent is ethanol, hexanaphthene, toluene, dimethylbenzene, trimethylbenzene, or its mixture; Described primary alconol can be n-Octanol, propyl carbinol, etc., described organic acid can adopt as toluenesulphonic acids.
In the technique scheme, described dispersion agent is selected from polyoxyethylene glycol, polyvinyl alcohol, sodium lauryl sulphate.
In the technique scheme, the microwave exposure process can be carried out at intermittence or continuum of states, and control reaction temperature.When under state intermittently, carrying out, mainly be, need stir for control reaction temperature; When continuous regime carries out, need to use the special type of cooling, with control reaction temperature.
In the technique scheme, when carrying out surface modification treatment, an oil-water separator is set in reaction unit, from organic solvent, removes the water that produces in the reaction, to impel the carrying out of surface modification reaction.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
1. the present invention adopts the microwave heating reactant.The microwave homogeneous precipitation method has rapid heating effect, focus or surface effects, pressure-cooking effect and ion overheating effect.The microwave exposure method is compared with traditional method, temperature raises faster in unit time, solution is heated more even, has that speed of response is fast, reaction conditions is gentle, the reaction efficiency advantages of higher, and product has higher purity, narrow size distribution and the form of homogeneous.Micro-wave dielectric heat-processed also is accompanied by non-thermal effect, thereby has improved the speed of response of reactant; Microwave exposure is explosive ground nucleation at short notice, and the pattern of resulting nano zine oxide is controlled, and particle diameter is comparatively even; Because the effect of electromagnetic field, some ions (or family of molecule) can be arranged by certain direction in solution, can prepare the crystal grain of some specific morphology; Microwave radiation is promoting compound also to have considerable energy saving on synthetic, reduce pollution, can realize the advantages such as reaction that some ordinary methods are difficult to realize simultaneously.
2. utilize microwave method to carry out the surface modification of nano zine oxide, the good dispersity of resulting nanometer Zinc oxide powder is lipophilicity, and contact angle is big, and performances such as its oleophylic degree are higher than the nano zine oxide that the usual way modification obtains.
Description of drawings
Accompanying drawing 1 is the reaction unit synoptic diagram of the embodiment of the invention one;
Accompanying drawing 2 and accompanying drawing 3 are the TEM picture of synthetic nanocrystal in the embodiment of the invention one.
Accompanying drawing 4 is the reaction unit synoptic diagram of the embodiment of the invention two;
Accompanying drawing 5 is the TEM picture of synthetic nanocrystal in the embodiment of the invention two.
Accompanying drawing 6 is the reaction unit synoptic diagram of the embodiment of the invention three;
Accompanying drawing 7 is the TEM picture of synthetic nanocrystal in the embodiment of the invention three.
Accompanying drawing 8 is the IR collection of illustrative plates of stearic acid modified front and back powder in the embodiment of the invention four.
Accompanying drawing 9 is the nano zine oxide of different methods modification in the embodiment of the invention four and the contact angle of water.
Accompanying drawing 10 be in the embodiment of the invention four after the modification lipophilic degree of nano zine oxide with the variation of stearic acid massfraction.
Wherein: accompanying drawing 1 is the device of intermittently reinforced batch microwave irradiation, and accompanying drawing 4 is the device of intermittently reinforced continuous microwave irradiation, and accompanying drawing 6 is the device of continuous flow continuous microwave irradiation.These devices can be used for the preparation of common nano zine oxide (former powder), can also carry out the surface modification of nano zine oxide, so that preparation does not have reunion, lipophilic nano zinc oxide.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: the preparation method of the former powder of a kind of nano zine oxide is the ZnSO of 0.15mol/L with concentration
47H
2O is a raw material, urea is the precipitation agent host, the microwave radiation temperature remains on 93 ℃, and the mol ratio of described reactant zinc sulfate and urea is 1: 2, after question response is finished, described throw out zinc subcarbonate is respectively washed 3～4 times with ammoniacal liquor and the dehydrated alcohol of pH=9.0 respectively, throw out after the washing obtains solid zinc subcarbonate powder by vacuum drier drying and ball milling, descends roasting 3 hours again about 380 ℃, ball milling obtains nanometer ZnO powder then.
Its reaction unit is provided with the reaction vessel of three inlets referring to shown in the accompanying drawing 1 in the microwave oven, have three mouths at the top of microwave oven corresponding to the reaction vessel inlet, and inlet inserts refrigerating unit, agitator and thermometer from left to right successively.Reactant places in the reaction vessel, after agitator rotates, starts microwave oven.When temperature of charge excessively rises, reduce the power (even closing microwave power) of microwave.This device reaction thing is heated fully, and reaction is fast, and the reaction times is short, the output height, but cooling performance is relatively poor, thereby when temperature of reaction is increased to 98 ℃, need close microwave oven, and treat to restart microwave oven after temperature descends, so be circulated to reaction and finish.Because microwave needs often to interrupt in the building-up process, the non-thermal effect of microwave utilizes not good enough.
Control different concentration, proportioning and reaction times in the experiment, can obtain the nanocrystal of different-shape.As, when zinc sulfate is 0.15mol/L, temperature is 93 ℃, the time is 1h, zinc sulfate: urea=1: 2 o'clock, the TEM of the nanocrystal of preparation is as shown in Figure 2.When zinc sulfate is 0.15mol/L, temperature is 93 ℃, and the time is 5h, zinc sulfate: urea=1: 2 o'clock, the TEM of the nanocrystal of preparation as shown in Figure 3, the photochemical catalysis effect of this nanoparticle sheet is better than other nanocrystal.
Embodiment two: the preparation method of the former powder of a kind of nano zine oxide is the ZnSO of 0.2mol/L with concentration
47H
2O is a raw material, urea is the precipitation agent host, the microwave radiation temperature remains on about 90 ℃, the mol ratio of described reactant zinc sulfate and urea is 1: 3, after question response is finished, described throw out zinc subcarbonate is respectively washed 3～4 times with ammoniacal liquor and the dehydrated alcohol of pH=9.0 respectively, again by vacuum drier drying and ball milling, 400 ℃ of following roastings 2 hours, last ball milling obtained nanometer ZnO powder with solid zinc subcarbonate powder.
Its reaction unit is referring to shown in the accompanying drawing 4, and different is with embodiment one, and the inlet of its refrigerant is changed to built-in prolong, and except the common feature that has embodiment one device, its good cooling results can effectively be utilized the non-thermal effect of microwave.When zinc sulfate for O.2mol/L, temperature is 90 ℃, the time is 1.5h, zinc sulfate: urea=1: 3 o'clock, the TEM of the nanocrystal of preparation as shown in Figure 5.
Embodiment three: the preparation method of the former powder of a kind of nano zine oxide, its reaction unit is referring to shown in the accompanying drawing 6, the container that fills reactant solution places microwave oven outside (seeing the bulge of microwave oven top), reactant by water pump through under meter, behind the thermometer thermometric, be transported in the spiral tube that places in the microwave oven and accept microwave exposure, the thermometer of the other end of spiral tube outside stove is communicated with cooling tube, the outlet of cooling tube is connected with bulge, cooled reactant returns in the bulge, forms circulation.Compare with two devices among the embodiment one, two, the mean power of microwave radiation when the flow that can be by under meter and the demonstration reading of thermometer get principal reaction, cooling performance is better than the device of embodiment one and embodiment two simultaneously, utilized the non-thermal effect of microwave fully, but the reaction times is elongated, and output is on the low side.If can manage to increase the volume of stove inner helix pipe, believe that output can increase, effect can be better.
With concentration is the ZnSO of 0.15mol/L
47H
2O is a raw material, urea is the precipitation agent host, the microwave radiation temperature remains on about 93 ℃, the mol ratio of described reactant zinc sulfate and urea is 1: 4, react after 1 hour, described throw out zinc subcarbonate is used the ammoniacal liquor of pH=9.0 and absolute ethanol washing respectively 3～4 times, make its complete drying and ball milling by vacuum drier again, at 450 ℃ of following roastings 2 hours and ball milling, the TEM of the nanocrystal of preparation as shown in Figure 7 at last.
Embodiment four: a kind of preparation method of scattered, lipophilic nano zinc oxide, its reaction unit can adopt a kind of in accompanying drawing 1,4 or 6.In embodiment one～three, can synthesize the former powder of the nanocrystal of various patterns, but the surface property of these crystal grain is hydrophilic, relatively poor with consistency, the affinity of organism medium or organic solvent, the agglomeration of powder is more serious.By the surface modification under the microwave exposure, can be overcome.
When the device that uses accompanying drawing 1, need increase an oil-water separator at the interface of condensing reflux pipe and reactor, so that the water of separating reaction generation in time carries out chemical reaction as early as possible.Surface-modifying agent can adopt various silane coupling agents, tensio-active agent, oleic acid, stearic acid or multiple primary alconol, etc.When using primary alconol, needs use catalyzer (certain organic acid, as toluenesulphonic acids, etc.); The organic solvent that uses is ethanol, hexanaphthene, toluene, dimethylbenzene, trimethylbenzene, etc., or its mixture.Nano zine oxide that roasting is obtained and surface-modifying agent, organic solvent, dispersion agent are even by the ball milling blending dispersion, and temperature of reaction is between 80 ℃～150 ℃, and irradiation is 1～3 hour under microwave, finishes the surface modification of nano zine oxide.The good dispersity and the surface of the nano zine oxide that obtains are lipophilicity.
The IR collection of illustrative plates of powder as shown in Figure 8 before and after the modification.Powder after the modification before making IR and analyzing, done 48 hours be that Soxhlet is extracted.From the stearic as can be seen vibration peak of the right figure of accompanying drawing 8, so show the firm chemical bond that is combined between nanocrystal and the organic surface modifying agent.
What accompanying drawing 9 showed is the nano zine oxide of usual way modification and the nano zine oxide of microwave modification, with the contact angle of water, as can be seen, the hydrophobic nature height of the nano zine oxide of microwave modification.
Accompanying drawing 10 is the variations with the stearic acid massfraction of the lipophilic degree of synthetic nano zine oxide.As can be seen, when stearic massfraction is 7%, its lipophilic degree is the highest.When using other surface-modifying agent, can draw similar conclusion.
Claims (4)
1. nano-ZnO preparation, selecting soluble zinc salt is the zinc source, urea is the precipitation agent host, be dissolved in the water, adopt homogeneous precipitation method to react under microwave exposure, the concentration in reactant zinc source is between 0.05mol/L～0.5mol/L, and the mol ratio of zinc source and urea is between 1: 0.5～1: 5, the irradiation reaction temperature was reacted 1～5 hour between 80 ℃～100 ℃; After will reacting zinc subcarbonate vacuum-drying of synthetic throw out and ball milling,, obtain the crystal grain of nano zine oxide 350 ℃～450 ℃ following roastings 1～5 hour; It is characterized in that: the nano zine oxide for preparing and surface-modifying agent, organic solvent, dispersion agent ball milling blending dispersion is even, temperature of reaction is between 80 ℃～150 ℃, irradiation is 1～3 hour under microwave, finish the surface modification of nano zine oxide, obtain nanometer Zinc oxide powder, wherein, described surface-modifying agent is a primary alconol, and adding toluenesulphonic acids as catalyzer, described organic solvent is ethanol, hexanaphthene, toluene, dimethylbenzene, trimethylbenzene or its mixture.
2. nano-ZnO preparation according to claim 1, it is characterized in that: before roasting, described throw out zinc subcarbonate is used ammoniacal liquor, the absolute ethanol washing 3～4 times of pH=9.0 respectively, gained solid zinc subcarbonate powder is dry and ball milling by vacuum drier, then 350 ℃～450 ℃ following roastings 1～5 hour.
3. nano-ZnO preparation according to claim 1 and 2 is characterized in that: described dispersion agent is selected from polyoxyethylene glycol, polyvinyl alcohol, sodium lauryl sulphate.
4. nano-ZnO preparation according to claim 1 is characterized in that: when carrying out surface modification treatment, an oil-water separator is set in reaction unit, removes the water that produces in the reaction from organic solvent.
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