CN104445366A - Method for synthesizing spindlelike ZnO nanomaterial by adopting microwave-assisted extraction process - Google Patents

Method for synthesizing spindlelike ZnO nanomaterial by adopting microwave-assisted extraction process Download PDF

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CN104445366A
CN104445366A CN201410629058.2A CN201410629058A CN104445366A CN 104445366 A CN104445366 A CN 104445366A CN 201410629058 A CN201410629058 A CN 201410629058A CN 104445366 A CN104445366 A CN 104445366A
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solution
precursor solution
zinc
deionized water
microwave
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CN104445366B (en
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贠江妮
张志勇
尹铁恩
赵倩
吕媛媛
闫军锋
赵武
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Northwest University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions

Abstract

The invention provides a method for synthesizing a spindlelike ZnO nanomaterial by adopting the microwave-assisted extraction technology. The method is characterized in that an initial raw material is dissolved to prepare a precursor solution, and then the precursor solution is fed into a microwave-assisted reaction chamber of a microwave-assisted digestion, extraction and synthesis workstation to react to produce the spindlelike ZnO nanomaterial, wherein the initial raw material is a compound zinc salt of Zn(NO3)2.6H2O and Zn(CH3COO)2.2H2O at the molar ratio of 1:1. According to the method, because the compound zinc salt is used as the initial raw material, the microwave-assisted extraction and synthesis process can be used for preparing the spindlelike ZnO nanomaterial, and the required target product can be synthesized. According to the method provided by the invention, the microwave-assisted extraction and synthesis process is adopted, and the reaction is completed in one time in a liquid phase environment, so that the reaction time and the preparation cycle are short, the safety is high, and no complex after-treatment is required.

Description

A kind of method of microwave extracting synthesis spindle flower-like structure ZnO nano material
Technical field
The invention belongs to field of material preparation, relate to self-anchored suspension bridge, be specifically related to ZnO nano material, be specifically related to the method for a kind of microwave extracting synthesis spindle flower-like structure ZnO nano material.
Background technology
Zinc oxide (ZnO) is a kind of II-VI novel race's direct energy-gap semiconductor material, there is larger energy gap (3.37eV) and exciton bind energy (60meV), because of the wavelength of the corresponding UV-light of its energy gap, and have voltage breakdown high, maintain that electric field ability is strong, electronic noise is little, can bear power advantages of higher, therefore zinc oxide has a wide range of applications in blue laser, photodiode, display device and solar cell etc.As the very promising semiconductor material of one, zinc oxide causes mondial research interest.Because the performance of nano material, application and their appearance structure are closely related, the morphology control of nano zinc oxide material is the focus in this investigation of materials field always.Up to now, under certain reaction conditions, successfully prepare many crystal with special appearance such as ZnO nanorod, nano wire, nanometer ball, nanometer sheet, four-acicular nanometer ZnO, dendroid nano-ZnO, chrysanthemum shape nano-ZnO.
In recent years, the method preparing nano zine oxide mainly contains the methods such as molecular beam epitaxy, metal organic chemical vapor deposition, laser deposition, sputtering method, thermal evaporation, sol-gel method, the hot method of hydrothermal/solvent.These methods can key factor be gas phase synthesis method and liquid phase synthesizing method, and wherein the cost of gas phase synthesis method is higher, controllability is poor and the experiment condition that needs are accurate, is not suitable for scale operation; In liquid phase method, although hydrothermal method is with low cost, simple to operate, environmental protection, also there is the shortcoming of preparation cycle length, poor stability.In order to realize the target of industrialization scale operation, be necessary the preparation technology of the nano zine oxide that Development and Production cost is low, simple to operate, security is good, preparation cycle is short.
In recent years, obtained about the preparations and applicatio of ZnO nano material and studied widely.Microwave-assisted hydro-thermal legal system has been have employed for having gone out flower-shaped ZnO nano material in prior art.The method be by mixing solutions in model be GALANZ WD800 (B123) microwave oven in the radiation of power 8min of 800W, ultrasonic 30min again, naturally cooling afterwards, filter, dry this method of 5h. at 130 DEG C and can not adopt airtight reaction environment, therefore easily cause the pollution of sample, and cause the harm of environment, and temperature of reaction is not controlled in microwave oven, illustrate that this kind of method is not easy to control temperature of reaction.Need to carry out after microwave-assisted hydro-thermal ultrasonicly to make sample dispersion, illustrate sample prepared by this experimental technique easily reunite formed together large block.
Summary of the invention
For prior art Problems existing, the object of the invention is to, provide a kind of and do not need post-processed, the preparation method of the microwave extracting synthesis of the spindle flower-like structure ZnO nano material that simple to operate, security good, preparation cycle is short.
In order to realize above-mentioned technical assignment, the present invention adopts following technical scheme to be achieved:
A method for microwave extracting synthesis spindle flower-like structure ZnO nano material, the method using the compound zinc salt of zinc nitrate and zinc acetate as initial feed, obtained precursor solution after dissolving; The microwave reaction room microwave heating of precursor solution being put into sealing obtains the ZnO nano material of spindle flower-like structure.
Wherein, the mol ratio of the compound zinc salt in described precursor solution is: zinc nitrate: zinc acetate=(1 ~ 2): 1.
Particularly, the method is carried out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=(1 ~ 2): 1 configuration compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution;
Step 3, pH=10 ~ 12 of regulator solution, obtain uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, makes temperature control at 100 DEG C ~ 160 DEG C, is cooled to room temperature after insulation 15min ~ 30min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
In order to prepare target product, the condition that aforesaid method is suitable is as follows
Zn in described precursor solution 2+concentration is 0.01mol/L ~ 0.05mol/L.
Mol ratio in described precursor solution is C 6h 12n 4: Zn 2+=(0 ~ 1.0): 1.
The filling ratio of described precursor solution in the microwave reaction room of sealing is 50%, and the pressure under this filling ratio after heating just can prepare the target compound of the application, in micro-wave digestion extraction synthetic work station, realize the pressurization of above-mentioned heated sealed.
With pH=10 ~ 12 of ammoniacal liquor regulator solution in step 3, obtain uniform and stable precursor solution.
A preferred example, aforesaid method carries out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=4:3 configures compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution, makes the mol ratio in precursor solution be C 6h 12n 4: Zn 2+=0.5:1;
Step 3, with the pH=12 of ammoniacal liquor regulator solution, obtains uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, puts into micro-wave digestion extraction synthetic work station, makes temperature control at 100 DEG C, be cooled to room temperature after insulation 30min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
Another preferred example, aforesaid method carries out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=1:1 configures compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution, makes the mol ratio in precursor solution be C 6h 12n 4: Zn 2+=0.5:1;
Step 3, with the pH=11 of ammoniacal liquor regulator solution, obtains uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, puts into micro-wave digestion extraction synthetic work station, makes temperature control at 160 DEG C, be cooled to room temperature after insulation 15min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
In aforesaid method, the diameter of the ZnO nano material monocrystalline of the spindle flower-like structure described in target product is about 100 ~ 1200nm, and length is about 1 ~ 5 μm.
Method of the present invention compared with the existing methods, has following Advantageous Effects:
Method of the present invention adopts compound zinc salt as initial feed, and the preparation technology just making microwave extracting synthesize can be applied to the preparation of spindle flower-like structure ZnO nano material, just can synthesize required target product.Method of the present invention adopts the preparation technology of microwave extracting synthesis, and react and once complete in liquid phase environment, the reaction times is short, and the cycle is fast, and security is good, does not need complicated post-processed.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the embodiment of the present invention 1, embodiment 2, embodiment 3.
Fig. 2 is the typical front scan electron micrograph of the flower-like structure ZnO nano material of the present invention prepared by embodiment 1.
The typical front scan electron micrograph of the flower-like structure ZnO nano material of Fig. 3 the present invention prepared by embodiment 2.
The typical front scan electron micrograph of the flower-like structure ZnO nano material of Fig. 4 the present invention prepared by embodiment 3.
Fig. 5 is the typical front scan electron micrograph of the flower-like structure ZnO nano material of the present invention prepared by embodiment 4.
The typical front scan electron micrograph of the flower-like structure ZnO nano material of Fig. 6 the present invention prepared by embodiment 5.
The typical front scan electron micrograph of the flower-like structure ZnO nano material of Fig. 7 the present invention prepared by embodiment 6.
Fig. 8 is the ZnO nano material typical case front scan electron micrograph that comparative example 1 obtains.
Fig. 9 is the ZnO nano material typical case front scan electron micrograph that comparative example 2 obtains.
Figure 10 is the ZnO nano material typical case front scan electron micrograph that comparative example 3 obtains.
Figure 11 is the ZnO nano material typical case front scan electron micrograph that comparative example 4 obtains.
Figure 12 is the ZnO nano material typical case front scan electron micrograph that comparative example 5 obtains.
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Embodiment
Micro-wave digestion extraction synthetic work station in the application adopts MDS-10 type micro-wave digestion extraction synthetic work station.Microwave extracting synthetic method refers to uses microwave as the heating source to reactant, belongs to the category of liquid phase reaction method.Microwave is the hertzian wave of frequency between 300MHz ~ 300GHz, there is the advantage that wavelength is short, frequency is high and penetrance is strong, because the energy of microwave can be directly passed to molecule, all material need not be heated, and microwave reaction system is had the following advantages: rate of heating is fast, be heated evenly and without thermograde, and the reaction vessel overcoming hydrothermal method is heated uneven shortcoming; Reaction simple and sensitive, efficient energy-saving, overcome the shortcoming that hydrothermal method preparation cycle is long; Temperature-controllable is good, and simple to operate, security good, reaction system sealing and pollution-free, be applicable to scale operation.
In order to prepare the target compound spindle flower-like structure ZnO nano material of the application, present inventor has done great many of experiments, in previous work, microwave extracting synthetic method is introduced, desirable hammer flower-like structure ZnO nano material target product can not be obtained, later stage, the two kinds of zinc salts finally just determining the application as compound zinc salt, can prepare required target product under the specific proportioning of the application through a large amount of exploitative experiment.
The formation mechenism of spindle flower-like structure ZnO nano material of the present invention is: the formation of ZnO crystal comprises coring and increment two process, is added drop-wise to by ammoniacal liquor in mixing precursor solution and forms a large amount of complexing ion Zn (NH 3) 4 2+.Zn (NH 3) 4 2+it is the primitive of ZnO crystal growth.At the microwave extracting synthesis initial stage, growth unit Zn (NH 3) 4 2+first form the how twin centronucleus of multiple nucleons that can adjust nucleon geometric configuration state, when temperature maintains 90 DEG C, when degree of supersaturation exceedes threshold value, the one-nucleon in many twins ZnO core is grown up rapidly and is grown along c-axis preferred orientation.Subsequently, when temperature reaches rising, polarity and apolar surfaces are grown up sooner.In general, the face increased more fast, faster disappearance.FOR ALL WE KNOW, the maximum rate of growth in (0001) direction of ZnO crystal.Therefore, ZnO polar surface quick disappearance, in microwave extracting building-up process, causes ZnO crystal to terminate along the growth of (0001) c-axis direction.Therefore, the ZnO nano material that spindle is flower-shaped generates.
Defer to technique scheme, below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1:
The present embodiment provides the method for a kind of microwave extracting synthesis spindle flower-like structure ZnO nano material, specifically carries out according to following steps:
Step one, 2:1 takes the zinc nitrate hexahydrate of 0.3564g and the Zinc diacetate dihydrate of 0.1317g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 60ml deionized water dissolving, form Zn 2+concentration is the clear solution of 0.03mol/L;
Step 2, does not add C in the present embodiment 6h 12n 4solution;
Step 3, at room temperature continues at the uniform velocity to stir by mixed zinc salts solution in beaker A, and is the pH=10 of the ammoniacal liquor regulator solution of 25% ~ 28% with content, obtains uniform and stable precursor solution;
Step 4, take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, puts into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 120 DEG C, react 20min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering in the electric drying oven with forced convection of 60 DEG C.
Finally adopt the Morphology and structure of XRD and SEM to product to characterize, as depicted in figs. 1 and 2, as can be seen from Figure 1, sample is the ZnO of hexagonal wurtzite structure to characterization result, i.e. spindle flower dress ZnO.As can be seen from Figure 2, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, and the diameter of taper nano crystal is about 200 ~ 500nm, and length is about 1 ~ 2 μm.
Embodiment 2:
The present embodiment provides the method for a kind of microwave extracting synthesis spindle flower-like structure ZnO nano material, specifically carries out according to following steps:
Step one, 1:1 takes the zinc nitrate hexahydrate of 0.0891g and the Zinc diacetate dihydrate of 0.0659g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 20ml deionized water dissolving, form clear solution;
Step 2, the hexamethylenetetramine taking 0.084g is placed in beaker B, uses 20ml deionized water dissolving, forms clear solution;
Mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, hexamethylenetetramine solution in beaker B is slowly instilled in beaker A, use the deionized water wash beaker B of 10ml for twice respectively, and washings is slowly instilled in beaker A, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.01mol/L, C 6h 12n 4concentration be 0.01mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=1:1;
Step 3, at room temperature continues at the uniform velocity to stir by mixed zinc salts solution in beaker A, and is the pH=11 of the ammoniacal liquor regulator solution of 25% ~ 28% with content, obtains uniform and stable precursor solution;
Step 4, take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, puts into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 15min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering in the electric drying oven with forced convection of 60 DEG C.
Finally adopt the Morphology and structure of XRD and SEM to product to characterize, as shown in figures 1 and 3, as can be seen from Figure 1, sample is the ZnO of hexagonal wurtzite structure to characterization result, i.e. spindle flower dress ZnO.As can be seen from Figure 3, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, and the diameter of taper nano crystal is about 200 ~ 1000nm, and length is about 1 ~ 2 μm.
Embodiment 3:
The present embodiment provides the method for a kind of microwave extracting synthesis spindle flower-like structure ZnO nano material, specifically carries out according to following steps:
Step one, 4:3 takes the zinc nitrate hexahydrate of 0.5091g and the Zinc diacetate dihydrate of 0.2822g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 20ml deionized water dissolving, form clear solution;
Step 2, the hexamethylenetetramine taking 0.21g is placed in beaker B, uses 20ml deionized water dissolving, forms clear solution;
Mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, hexamethylenetetramine solution in beaker B is slowly instilled in beaker A, use the deionized water wash beaker B of 10ml for twice respectively, and washings is slowly instilled in beaker A, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.05mol/L, C 6h 12n 4concentration be 0.025mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=0.5:1;
Step 3, at room temperature continues at the uniform velocity to stir by mixed zinc salts solution in beaker A, and is the pH=12 of the ammoniacal liquor regulator solution of 25% ~ 28% with content (i.e. massfraction), obtains uniform and stable precursor solution;
Step 4, take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, puts into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 100 DEG C, react 30min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering in the electric drying oven with forced convection of 60 DEG C.
Finally adopt the Morphology and structure of XRD and SEM to product to characterize, as shown in Figure 1 and Figure 4, as can be seen from Figure 1, sample is the ZnO of hexagonal wurtzite structure to characterization result, i.e. spindle flower dress ZnO.As can be seen from Figure 4, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, and the diameter of taper nano crystal is about 200 ~ 1000nm, and length is about 2 ~ 4 μm.
Embodiment 4:
The preparation process of the present embodiment is similar to embodiment 1, and difference part is, 1:1 takes the zinc nitrate hexahydrate of 0.2677g and the Zinc diacetate dihydrate of 0.1976g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 60ml deionized water dissolving, form Zn 2+concentration is the clear solution of 0.03mol/L; Finally adopt the form of SEM to product to characterize, shown in characterization result Fig. 5: as can be seen from Figure 5, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, the diameter of taper nano crystal is about 200 ~ 700nm, and length is about 1 ~ 3 μm.
Embodiment 5:
The preparation process of the present embodiment is similar to embodiment 2, and difference part is, takes the hexamethylenetetramine of 0.042g, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.01mol/L, C 6h 12n 4concentration be 0.005mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=0.5:1; The form of SEM to product is finally adopted to characterize, shown in characterization result Fig. 6: as can be seen from Figure 6, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, and the diameter of taper nano crystal is about 400 ~ 1200nm, and length is about 1 ~ 4 μm.
Embodiment 6:
The present embodiment preparation process is similar to embodiment 3, and difference part is, the Zinc diacetate dihydrate of the 1:1 zinc nitrate hexahydrate and 0.3293g that take 4455g is configured to Zn in molar ratio 2+concentration is the mixed zinc salts solution of 0.05mol/L; The form of SEM to product is finally adopted to characterize, shown in characterization result Fig. 7: as can be seen from Figure 7, prepared flower-like structure ZnO nano material form is homogeneous, be evenly distributed, and the diameter of taper nano crystal is about 100 ~ 1000nm, and length is about 1 ~ 5 μm.
In the test determining technological process of the present invention, the product morphology that the Selection experiment of zinc salt obtains does not meet the pattern requirement of the present invention to product, now extracts following several comparative example and is described.
Comparative example 1:
1) zinc nitrate hexahydrate taking 0.1782g is placed in beaker A, and uses 60ml deionized water dissolving, forms Zn 2+concentration is the clear solution of 0.01mol/L;
2) zinc solution in beaker A is at room temperature continued at the uniform velocity to stir, and be the pH=11 of the ammoniacal liquor regulator solution of 25% ~ 28% with content, obtain uniform and stable precursor solution;
3) take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, put into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 20min;
4) reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing are filtered, until filtrate pH=7, the product after filtering is dried in the electric drying oven with forced convection of 60 DEG C, the form of SEM to product is finally adopted to characterize, as shown in Figure 8, prepared ZnO nano material is the ZnO nanorod of the dispersion having certain length-to-diameter ratio.
Comparative example 2:
1) 2:3 takes the zinc nitrate hexahydrate of 0.0713g and the Zinc diacetate dihydrate of 0.0790g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 20ml deionized water dissolving, form clear solution;
2) hexamethylenetetramine taking 0.0840g is placed in beaker B, uses 20ml deionized water dissolving respectively, forms clear solution;
3) mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, hexamethylenetetramine solution in beaker B is slowly instilled in beaker A, use the deionized water wash beaker B of 10ml for twice respectively, and washings is slowly instilled in beaker A, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.01mol/L, C 6h 12n 4concentration be 0.01mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=1:1;
4) mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, and be the pH=10 of the ammoniacal liquor regulator solution of 25% ~ 28% with content, obtain uniform and stable precursor solution;
5) take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, put into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 20min;
6) reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing are filtered, until filtrate pH=7, the product after filtering is dried in the electric drying oven with forced convection of 60 DEG C, the form of SEM to product is finally adopted to characterize, as shown in Figure 9, prepared ZnO nano material, some is the ZnO nanorod packed structures of dispersion, and some becomes corynebacterium flower-like structure.
In addition, in the test determining processing parameter process of the present invention, the product morphology that the Selection experiment of some parameters obtains does not meet the pattern requirement of the present invention to product, now extracts following several comparative example and is described:
Comparative example 3:
1) 1:1 takes the zinc nitrate hexahydrate of 0.0891g and the Zinc diacetate dihydrate of 0.0659g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 60ml deionized water dissolving, form Zn 2+concentration is the clear solution of 0.01mol/L;
2) mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, and be the pH=9 of the ammoniacal liquor regulator solution of 25% ~ 28% with content, obtain uniform and stable precursor solution;
3) take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, put into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 20min;
4) reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing are filtered, until filtrate pH=7, the product after filtering is dried in the electric drying oven with forced convection of 60 DEG C, the form of SEM to product is finally adopted to characterize, as shown in Figure 10, prepared ZnO nano material is the ZnO nanorod that pattern is even, have the dispersion of certain length-to-diameter ratio.
Comparative example 4:
1) 1:1 takes the zinc nitrate hexahydrate of 0.5346g and the Zinc diacetate dihydrate of 0.3951g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 20ml deionized water dissolving, form clear solution;
2) hexamethylenetetramine taking 0.1680g is placed in beaker B; And use 20ml deionized water dissolving respectively, form clear solution;
3) mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, hexamethylenetetramine solution in beaker B is slowly instilled in beaker A, use the deionized water wash beaker B of 10ml for twice respectively, and washings is slowly instilled in beaker A, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.06mol/L, C 6h 12n 4concentration be 0.02mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=1:3;
4) with content be 25% ~ 28% ammoniacal liquor regulating step 2) pH=9 of gained solution, obtain uniform and stable precursor solution;
5) take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, put into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 15min;
6) reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing are filtered, until filtrate pH=7, the product after filtering is dried in the electric drying oven with forced convection of 60 DEG C, the form of SEM to product is finally adopted to characterize, as shown in figure 11, prepared ZnO nano material is the ZnO nanorod that pattern is even, have the dispersion of certain length-to-diameter ratio.
Comparative example 5:
1) 1:1 takes the zinc nitrate hexahydrate of 0.4455g and the Zinc diacetate dihydrate of 0.3293g in molar ratio, two kinds of zinc source mixing is placed in beaker A, and uses 20ml deionized water dissolving, form clear solution;
2) hexamethylenetetramine taking 0.5040g is placed in beaker B; And use 20ml deionized water dissolving respectively, form clear solution;
3) mixed zinc salts solution in beaker A is at room temperature continued at the uniform velocity to stir, hexamethylenetetramine solution in beaker B is slowly instilled in beaker A, use the deionized water wash beaker B of 10ml for twice respectively, and washings is slowly instilled in beaker A, the one-tenth Zn of the solution of the uniform and stable mixing be configured to 2+concentration is 0.05mol/L, C 6h 12n 4concentration be 0.06mol/L, wherein mol ratio is C 6h 12n 4: Zn 2+=1.2:1;
4) with content be 25% ~ 28% ammoniacal liquor regulating step 2) pH=8 of gained solution, obtain uniform and stable precursor solution;
5) take 50ml precursor solution with graduated cylinder to be transferred in microwave reaction room and to seal, its uniform and stable mixing precursor solution is 50% in the compactedness of reactor, put into MDS-10 type micro-wave digestion extraction synthetic work station, select temperature control mode, at 160 DEG C, react 25min;
6) reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing are filtered, until filtrate pH=7, the product after filtering is dried in the electric drying oven with forced convection of 60 DEG C, the form of SEM to product is finally adopted to characterize, as shown in figure 12, prepared ZnO nano material is two is cone-shaped, middle become the ZnO nanorod of the uneven dispersion of bar-shaped diameter.

Claims (10)

1. a method for microwave extracting synthesis spindle flower-like structure ZnO nano material, is characterized in that:
The method using the compound zinc salt of zinc nitrate and zinc acetate as initial feed, obtained precursor solution after dissolving;
The microwave reaction room microwave heating of precursor solution being put into sealing obtains the ZnO nano material of spindle flower-like structure.
2. the method for claim 1, is characterized in that: the mol ratio of the compound zinc salt in described precursor solution is: zinc nitrate: zinc acetate=(1 ~ 2): 1.
3. method as claimed in claim 2, is characterized in that: the method is carried out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=(1 ~ 2): 1 configuration compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution;
Step 3, pH=10 ~ 12 of regulator solution, obtain uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, makes temperature control at 100 DEG C ~ 160 DEG C, is cooled to room temperature after insulation 15min ~ 30min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
4. method as claimed in claim 3, is characterized in that: Zn in described precursor solution 2+concentration is 0.01mol/L ~ 0.05mol/L.
5. method as claimed in claim 3, is characterized in that: the mol ratio in described precursor solution is C 6h 12n 4: Zn 2+=(0 ~ 1.0): 1.
6. the method for claim 1, is characterized in that: the filling ratio of described precursor solution in the microwave reaction room of sealing is 50%.
7. method as claimed in claim 3, is characterized in that: with pH=10 ~ 12 of ammoniacal liquor regulator solution in step 3, obtain uniform and stable precursor solution.
8. method as claimed in claim 3, is characterized in that: the method is carried out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=4:3 configures compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution, makes the mol ratio in precursor solution be C 6h 12n 4: Zn 2+=0.5:1;
Step 3, with the pH=12 of ammoniacal liquor regulator solution, obtains uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, puts into micro-wave digestion extraction synthetic work station, makes temperature control at 100 DEG C, be cooled to room temperature after insulation 30min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
9. method as claimed in claim 3, is characterized in that: the method is carried out according to following steps:
Step one is zinc nitrate according to mol ratio: zinc acetate=1:1 configures compound zinc salt, and be dissolved in deionized water, at room temperature Keep agitation is evenly mixed with composite zinc salts solution;
Step 2, by C 6h 12n 4be dissolved in deionized water and support solution, by C in the process stirred 6h 12n 4solution slowly instills in composite zinc salts solution, makes the mol ratio in precursor solution be C 6h 12n 4: Zn 2+=0.5:1;
Step 3, with the pH=11 of ammoniacal liquor regulator solution, obtains uniform and stable precursor solution;
Step 4, the precursor solution of preparation is transferred in microwave reaction room, is then sealed microwave reaction room, puts into micro-wave digestion extraction synthetic work station, makes temperature control at 160 DEG C, be cooled to room temperature after insulation 15min;
Step 5, filters reaction products therefrom deionized water and dehydrated alcohol repetitive scrubbing, until filtrate pH=7, dries the product after filtering, obtains the ZnO nano material of spindle flower-like structure.
10. the method as described in claim as arbitrary in claim 1 to 9, is characterized in that: the diameter of the ZnO nano material monocrystalline of described spindle flower-like structure is about 100 ~ 1200nm, and length is about 1 ~ 5 μm.
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