CN102807249B - Method for controlling shapes of zinc oxide nanoparticles - Google Patents
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- CN102807249B CN102807249B CN201110146022.5A CN201110146022A CN102807249B CN 102807249 B CN102807249 B CN 102807249B CN 201110146022 A CN201110146022 A CN 201110146022A CN 102807249 B CN102807249 B CN 102807249B
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Abstract
The invention provides a method for controlling shapes of zinc oxide nanoparticles. The method includes enabling N,N-dimethylformamide, water and zinc nitrate hexahydrate to contact with one another at the temperature ranging from 110 DEG C to 140 DEG C. The method is characterized in that the zinc oxide nanoparticles with different shapes can be obtained by controlling the proportion of the N,N-dimethylformamide to the water and contacting time of the N,N-dimethylformamide, the water and the zinc nitrate hexahydrate. By the method, the zinc oxide nanoparticles with controllable shapes and controllable defect concentrations can be prepared, and surface stabilizers are omitted in the preparation method.
Description
Technical field
The present invention relates to a kind of method of controlling Zinc oxide nanoparticle pattern.
Background technology
Nano zine oxide is compared with common zinc oxide, has more good physics-chem characteristic.Especially at piezoelectricity, fluorescence, photocatalysis characteristic aspect is comparatively outstanding.These good character make nano zine oxide have potential value in Application Areass such as the energy, environment and Industrial Catalysis, thereby are subject to the common concern of researcher.Owing to there are a large amount of defects in surface of nanometer zinc oxide structure, make its effect aspect photocatalysis degradation organic contaminant remarkable.The band-gap energy Eg of zinc oxide is 3.2eV, and wavelength all can be used as its excitation light source lower than the ultraviolet source of 387.5nm (λ g=1240/Eg).When nano zinc oxide material is subject to being greater than after the photon irradiation of energy gap energy, electronics transits to conduction band from valence band, produces electron-hole pair, and electronics has reductibility, and hole has oxidisability.Photoproduction e
-and h
+except can be directly and reactant effect, also can be adsorbed on other electron acceptor(EA) on catalyzer or react to body.The OH on hole and nano zinc oxide material surface
-reaction generates the very high OH free radical of oxidisability, and active OH can be CO by the organic-fuel pollutant oxidation in water
2and H
2o.Because the surface tissue difference of the different crystal faces of zinc oxide makes its stability and surface imperfection quantity have larger difference, therefore the photocatalysis effect of zinc oxide that causes having different crystal faces is different, for example: Hajime Haneda (Morphologies of zinc oxide particles and their effects on photocatalysis, Chemosphere, 2003,5,129-137) group adopts different methods to synthesize the zinc oxide nanocrystalline of different-shape, finds that its photocatalytic activity and surface topography have substantial connection.Based on such reason, the pattern of nano zinc oxide material and surface tissue are controlled becomes a large study hotspot.People have been developed many preparation methods with the nano granular of zinc oxide of different surfaces structure and pattern.Most typical is vapour deposition and wet chemical method.CVD (Chemical Vapor Deposition) method is rarely used in photocatalyst research because of shortcomings such as circulation ratio are bad, cannot produce in a large number.Wet chemical method is a good selection preparing in a large number pattern and the controlled nano zinc oxide material of structure.Yet, adopt at present wet chemical method mostly to utilize the adsorption of surface stabilizer to control the pattern of nano zinc oxide material.The nano zinc oxide material of preparation surface makes its photocatalytic activity be affected and reduce because there being stablizer parcel like this.So how by selecting suitable synthesis condition, avoiding surface stabilizer becomes on the impact of zinc oxide surface structure the key challenge that can following nano zinc oxide material be applied in photocatalysis field.
Summary of the invention
Object of the present invention is for providing a kind of method that can control Zinc oxide nanoparticle pattern, by the method, can prepare and there is the controlled and controlled zinc oxide nano-crystal particle of defect density of pattern, and in this preparation method, not need to use surface stabilizer.
The present inventor is through deep research, found that by controlling N, the duration of contact of the ratio of dinethylformamide and water and DMF, water and zinc nitrate hexahydrate, can prepare and there is the controlled and controlled zinc oxide nano-crystal particle of defect density of pattern.
; the invention provides a kind of method of controlling Zinc oxide nanoparticle pattern; it is at 110-140 ℃ that the method is included in temperature; by N; dinethylformamide, water and zinc nitrate hexahydrate contact, wherein, and by controlling N; obtain the Zinc oxide nanoparticle of different-shape the duration of contact of the ratio of dinethylformamide and water and DMF, water and zinc nitrate hexahydrate.
Compared with prior art, the present invention has following advantage:
1, the simple and easy handling of the inventive method, only adopts solvent thermal chemosynthesis zinc oxide nano-crystal particle, and required step is less.
2, the present invention makes zinc nitrate hexahydrate spontaneous hydrolysis in DMF, and not needing to add other can provide material hydroxy, and required reactive material is less.
3, the zinc oxide nano-crystal particle that prepared by the present invention, does not add any surface stabilizer, and avtive spot is uncovered, and contributes to strengthen it as the catalytic efficiency of catalyzer.
4, three kinds of zinc oxide nano-crystal particles that prepared by the present invention, its surface imperfection concentration is controlled by reacting the water yield, and the growth of its crystal face is also relevant to the water yield, can regulate the different photocatalytic activities of preparation, the nano zinc oxide material of luminosity by the simple water yield.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of the prepared Zinc oxide nanoparticle of the present invention, and wherein, a in Fig. 1 and b are the scanning electron microscope diagram sheet of the prepared bar-shaped Zinc oxide nanoparticle of embodiment 1; C in Fig. 1 and d are the scanning electron microscope diagram sheet of the prepared rescinded angle hecaprismo shape Zinc oxide nanoparticle of embodiment 2; E in Fig. 1 and f are the scanning electron microscope diagram sheet of the prepared multilayer plate-like Zinc oxide nanoparticle of embodiment 3.
Fig. 2 is the x-ray photoelectron power spectrum O1s peak figure of the prepared bar-shaped Zinc oxide nanoparticle of embodiment 1.
Fig. 3 is the x-ray photoelectron power spectrum O1s peak figure of the prepared rescinded angle hecaprismo shape Zinc oxide nanoparticle of embodiment 2.
Fig. 4 is the x-ray photoelectron power spectrum O1s peak figure of the prepared multilayer plate-like Zinc oxide nanoparticle of embodiment 3.
Embodiment
The invention provides a kind of method of controlling Zinc oxide nanoparticle pattern, it is at 110-140 ℃ that the method is included in temperature, by N, dinethylformamide, water and zinc nitrate hexahydrate contact, wherein, by controlling DMF and the ratio of water and the Zinc oxide nanoparticle that obtains different-shape duration of contact of DMF, water and zinc nitrate hexahydrate.
The method according to this invention, the zinc oxide nano-crystal particle of a kind of bar-shaped, rescinded angle hecaprismo shape or multilayer plate-like pattern can be provided, described zinc oxide nano-crystal particle size is nano level, and the defect density that in three kinds of patterns, its surface is contained exists significant difference.Above-mentioned zinc oxide nanocrystalline particle is in DMF solvent, by adding different water (H
2o) amount spontaneous hydrolysis is synthetic, without adding other reagent.
Above-mentioned preparating mechanism is inferred: DMF is a kind of material of high-k, because this high-k makes electric charge be easy to separation, thereby makes it become a kind of good solvent.When DMF and water mix, obtain mixed solvent a kind of polarity, non-proton property, for the spontaneous hydrolysis of metal ion, be a kind of suitable medium.Adopt in the present invention DMF and H
2the mixture of O, as solvent, makes Zn (NO
3)
26H
2also there is condensation reaction formation zinc oxide nanocrystalline particle in O spontaneous hydrolysis, in solution, without adding other, can provide reagent hydroxy (as: sodium hydroxide, ammoniacal liquor etc.) and any surface stabilizer, and the avtive spot on ZnO surface is uncovered.The process of this hydrolysis can use equation (1), (2), (3) to represent:
Zn
2++4OH
-＝Zn(OH)
4 2-(2)
The method according to this invention, described temperature is preferably 115-125 ℃.
The method according to this invention, the consumption of the quality of described zinc nitrate hexahydrate and DMF and water can in very large range change.Generally, the total volume ratio of the quality of described zinc nitrate hexahydrate and DMF and water is 5-10: 1g/L; From cost, consider, the total volume ratio of the quality of preferred described zinc nitrate hexahydrate and DMF and water is 7-8: 1g/L.
In the present invention, the control of the ratio of described DMF and water is necessary.Its reason may be:
(1) the zinc oxide nano-crystal particle of Rod-like shape: contain sufficient water in its synthesis condition, hydrolysis reaction can fully be carried out.On the other hand, because end face is polar surface, belong to high-energy surface and there is higher activity, based on surface energy, minimize, this high-energy surface be easy to growth, so ZnO in the axial speed of growth faster than the horizontal speed of growth.The abundant reaction of hydrolysis has guaranteed there is sufficient zinc oxide nucleating growth, is so axially tending towards a definite value with horizontal relative velocity ratio, makes finally to have formed Rod-like shape.
(2) the zinc oxide nano-crystal particle of rescinded angle hecaprismo shape pattern: contain appropriate water in its synthesis condition, in the process of growth, along with the water yield of carrying out of reacting reduces gradually, the speed of growth starts to slow down so, axial and horizontal relative growth rate is changed gradually, finally caused the formation of hecaprismo pattern zinc oxide nano-crystal.
(3) the zinc oxide nanocrystalline particle of multilayer plate-like pattern: due to water anhydrous in its synthesis condition or that contain minute quantity, therefore, the water of hydrolysis reaction comes from the crystal water in zinc nitrate hexahydrate, in this extreme, lack under the condition of water, nucleation and the speed of growth are subject to great restriction, axial and horizontal Absolute growthiness and the relative growth rate between them are affected, in axial direction, belong to layer growth, in the situation that there is no sufficient zinc oxide nucleus, its each layer growth may not exclusively, finally form multilayer disc structure.
The method according to this invention, the diameter of described bar-shaped zinc oxide nano-crystal particle is that 100-150nm, length are 800-1000nm.In order to obtain above-mentioned bar-shaped zinc oxide nano-crystal particle, the volume ratio of described DMF and water can be 6-25: 1, can be 1-4 hour duration of contact; In order further to improve the homogeneity of the bar-shaped zinc oxide nano-crystal particle obtaining, the volume ratio of preferred described DMF and water is 9-19: 1, and be 2-3 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
The method according to this invention, the zinc oxide nano-crystal particle height of described rescinded angle hecaprismo shape is that 50-150nm, end face diameter are that 160-240nm, bottom surface diameter are 280-320nm.In order to obtain the zinc oxide nano-crystal particle of above-mentioned rescinded angle hecaprismo shape, the volume ratio of described DMF and water is 45-110: 1, and be 5-8 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate; In order further to improve the homogeneity of the bar-shaped zinc oxide nano-crystal particle obtaining, preferred described N, the volume ratio of dinethylformamide and water is 49-100: 1, and be 5-7 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
The method according to this invention, the diameter of the zinc oxide nano-crystal particle of described multilayer plate-like is that 300-400nm, the number of plies are that 8-20 layer, the thickness of every layer are 20-40nm.In order to obtain the zinc oxide nano-crystal particle of above-mentioned multilayer plate-like, the volume ratio of described DMF and water is greater than 500: 1, and be 8-20 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate; In order further to improve the homogeneity of the bar-shaped zinc oxide nano-crystal particle obtaining, preferred described N, the volume ratio of dinethylformamide and water is 600-100000: 1, and be 9-15 hour the duration of contact of preferred described DMF, water and zinc nitrate hexahydrate.
The method according to this invention, because the control of the ratio of described DMF and water is necessary, the ratio regular meeting of DMF and water affects the pattern of resulting zinc oxide nano-crystal particle.Therefore the water containing in the DMF, using is to be also calculated in aforementioned proportion.For the accessibility operating, preferably use anhydrous DMF, more preferably use water content for the anhydrous DMF below 50ppm, further preferably use the anhydrous DMF below 10ppm.This anhydrous DMF can be by commercially available.
The method according to this invention, the method comprises carries out solid-liquid separation by reacted product, and after the solid obtaining is washed, is dried, obtains zinc oxide nano-crystal particle.
The method of above-mentioned solid-liquid separation is the whole bag of tricks known in the field.For example can be by the centrifugal solid that obtains.
The method of above-mentioned washing is method known in the field.For example will in the solid obtaining, add after ethanol, carry out ultrasonic cleaning, the number of times of ultrasonic cleaning can be selected according to actual situation.The preferred ultrasonic cleaning of the present invention 2 times.Described ethanol is preferably dehydrated alcohol.
Above-mentioned dry method is method known in the field.For example can be by the dry 10-24 hour at 40-95 ℃ of isolated solid after washing.
In the present invention, obtain the Zinc oxide nanoparticle of different-shape by the ratio of DMF and water, the Zinc oxide nanoparticle of described different-shape can have different defect densities.This is owing to adopting in the present invention solvent-thermal method, and in synthetic process, DMF is easily deprived the lattice oxygen of zinc oxide surface, makes surface form oxygen vacancy defect, and its reaction process can use reaction formula (4) to represent:
V wherein
orepresent zinc oxide surface oxygen vacancy defect.Water, as the source of lattice oxygen in zinc oxide, when extremely lacking, can not be supplemented lattice oxygen timely simultaneously, has also indirectly accelerated the formation of defect, and from the present invention, water can be used as a kind of conditioning agent of oxygen defect concentration.
The Zinc oxide nanoparticle of above-mentioned different-shape can be according to its characteristic, as various materials'uses, for example, owing to not using in the methods of the invention without in surface stabilizer situation, can obtain the bar-shaped Zinc oxide nanoparticle of high stability, and this bar-shaped Zinc oxide nanoparticle is not wrapped up by surface stabilizer, can be used as stable photocatalyst material; Rescinded angle hecaprismo shape Zinc oxide nanoparticle is because the reason of polarity side can be prepared as film, as the material of condenser type nano generator; Multilayer plate-like Zinc oxide nanoparticle has more oxygen defect, and the narrow energy level of this defect state can be modified its surface by excited by visible light, suppresses its photoetch, can be used as a kind of more wide band optically active material that has.
By the following examples the present invention is further detailed, but the present invention is not limited in following embodiment.
DMF in following examples is purchased from lark prestige (anhydrous DMF, purity is 99.8%, water content is that 50ppm is following); Zinc nitrate hexahydrate and ethanol are purchased from Beijing chemical reagent factory; The ultrapure water that the resistivity that water is all used the electrodeionization machine purchased from U.S. Electropure company to purify is 18.2M Ω cm standard.
In following examples, adopt the cold field emission scanning electron microscope of hitach S-4800 to carry out SEM sign to the Zinc oxide nanoparticle obtaining.SEM characterizes the preparation method of the sample that uses in the Zinc oxide nanoparticle (200mg) obtaining in following examples, add 3ml ultrapure water, fully mix, getting the mixed solution of 10 μ l drops on the silicon chip of a 5mm * 5mm, in the thermostat container of 60 ℃, after placement 1h, take out for SEM and characterize.
In following examples, adopt Bruker D8 Focus x-ray powder diffraction instrument to carry out XRD sign to the Zinc oxide nanoparticle obtaining.The preparation method that XRD characterize to be used sample is for dropping in above-mentioned liquid 2mL after fully mixing on a glass slide data characterization for XRD.
Embodiment 1
The DMF that adds 95ml in the glass containers of 150ml, then adds the H of 5ml
2zn (the NO of O and 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 2.5 hours at 120 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain bar-shaped Zinc oxide nanoparticle precipitation, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the dehydrated alcohol of 4mL will be added in the precipitation obtaining again, ultrasonic cleaning is after 20 minutes again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried bar-shaped Zinc oxide nanoparticle.By scanning electron photomicrograph, as shown in a and the b in Fig. 1 in Fig. 1, the diameter of known this bar-shaped Zinc oxide nanoparticle is 100-150nm, and length is 800-1000nm; To obtaining bar-shaped Zinc oxide nanoparticle, carry out XPS sign, as shown in Figure 2, Fig. 2 is its xps energy spectrum O1s peak to its result.
Embodiment 2
The DMF that adds 98.5ml in the glass containers of 150ml, then adds the H of 1.5ml
2zn (the NO of O and 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 6 hours at 120 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain rescinded angle hecaprismo shape Zinc oxide nanoparticle precipitation, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, 4mL dehydrated alcohol will be added in the precipitation obtaining again, ultrasonic cleaning is after 20 minutes again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried rescinded angle hecaprismo shape Zinc oxide nanoparticle.By scanning electron photomicrograph, as shown in c and d in Fig. 1, the height of known this rescinded angle hecaprismo shape Zinc oxide nanoparticle is 50-150nm, and end face diameter is 160-240nm, and bottom surface diameter is 280-320nm; To obtaining rescinded angle hecaprismo shape Zinc oxide nanoparticle, carry out XPS sign, as shown in Figure 3, Fig. 3 is its xps energy spectrum O1s peak to its result.
Embodiment 3
The DMF that adds 100ml in the glass containers of 150ml, then adds the Zn (NO of 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 15 hours at 120 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain multilayer plate-like Zinc oxide nanoparticle precipitation, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, 4mL dehydrated alcohol will be added in the precipitation obtaining again, ultrasonic cleaning again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried multilayer plate-like Zinc oxide nanoparticle, pass through scanning electron photomicrograph, as shown in e and f in Fig. 1, the diameter of known this multilayer plate-like Zinc oxide nanoparticle is 300-400nm, the number of plies is 8-20 layer, every layer thickness is 20nm-40nm, to obtaining multilayer plate-like Zinc oxide nanoparticle, carry out XPS sign, as shown in Figure 4, Fig. 4 is its xps energy spectrum O1s peak to its result.
Embodiment 4
The DMF that adds 90ml in the glass containers of 150ml, then adds the H of 10ml
2o and 0.75g Zn (NO
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 3 hours at 120 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain bar-shaped Zinc oxide nanoparticle precipitation, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the dehydrated alcohol of 4mL will be added in the precipitation obtaining again, ultrasonic cleaning is after 20 minutes again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried bar-shaped Zinc oxide nanoparticle.By scanning electron photomicrograph, the diameter of known this bar-shaped Zinc oxide nanoparticle is 100-150nm, and length is 800-1000nm; And measured its xps energy spectrum.
Embodiment 5
The DMF that adds 98ml in the glass containers of 150ml, then adds the H of 2ml
2zn (the NO of O and 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 5 hours at 125 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain rescinded angle hecaprismo shape zinc oxide precipitation nano particle, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, 4mL dehydrated alcohol will be added in the precipitation obtaining again, ultrasonic cleaning is after 20 minutes again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dry rear rescinded angle hecaprismo shape Zinc oxide nanoparticle.By scanning electron photomicrograph, the height of known this rescinded angle hecaprismo shape Zinc oxide nanoparticle is 50-150nm, and end face diameter is 160-240nm, and bottom surface diameter is 280-320nm; And measured its xps energy spectrum.
Embodiment 6
The DMF that adds 100ml in the glass containers of 150ml, then adds the H of 1ml
2zn (the NO of O and 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 7 hours at 115 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain rescinded angle hecaprismo shape zinc oxide precipitation nano particle, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, 4mL dehydrated alcohol will be added in the precipitation obtaining again, ultrasonic cleaning is after 20 minutes again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried bar-shaped Zinc oxide nanoparticle.By scanning electron photomicrograph, the height of known this rescinded angle hecaprismo shape Zinc oxide nanoparticle is 50-150nm, and end face diameter is 160-240nm, and bottom surface diameter is 280-320nm; And measured its xps energy spectrum.
Embodiment 7
The DMF that adds 98.8ml in the glass containers of 150ml, then adds the H of 0.2ml
2zn (the NO of O and 0.75g
3)
26H
2o, obtains reactant mixing solutions after fully mixing.By the mixing solutions obtaining stirring reaction 9 hours at 120 ℃, naturally cool to after room temperature, supernatant liquid in sucking-off reaction system, obtain multilayer plate-like zinc oxide precipitation nano particle, the dehydrated alcohol that adds 6mL, after ultrasonic cleaning 20 minutes, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, 4mL dehydrated alcohol will be added in the precipitation obtaining again, ultrasonic cleaning again, with 13000rpm centrifugal 3 minutes, remove after supernatant liquor, the precipitation obtaining is put into thermostat container and at 85 ℃, be dried 15 hours, obtain dried multilayer plate-like Zinc oxide nanoparticle, pass through scanning electron photomicrograph, the diameter of known this multilayer plate-like Zinc oxide nanoparticle is 300-400nm, the number of plies is 8-20 layer, every layer thickness is 20nm-40nm, and measured its xps energy spectrum.
By the x-ray photoelectron power spectrum (XPS) to resulting Zinc oxide nanoparticle in embodiment 1-7, characterize known, the difference of the surperficial O1s state of the zinc oxide nanocrystalline particle of different-shape is comparatively remarkable, by Gauss curve fitting swarming, the O1s state of zinc oxide can be divided into three peaks, wherein Oa can be classified as lattice surface oxygen, Ob can be classified as Surface Oxygen defect, oxygen carrier that Oc can be classified as surface adsorption such as OH group, carbonate negative ion and negative oxygen ion etc.From the x-ray photoelectron power spectrum (XPS) to resulting Zinc oxide nanoparticle embodiment 1-7, characterize, can obviously observe multilayer disc zinc oxide and contain more oxygen defect, rescinded angle hecaprismo takes second place, bar-shaped minimum.Visible, by method of the present invention, not only can well control the pattern of prepared Zinc oxide nanoparticle, and can effectively control the defect density of the Zinc oxide nanoparticle of different-shape, thereby meet the needs of various materials.
Claims (6)
1. a method of controlling Zinc oxide nanoparticle pattern, it is at 110-140 ℃ that the method is included in temperature, by N, dinethylformamide, water and zinc nitrate hexahydrate contact, it is characterized in that, by controlling DMF and the ratio of water and the Zinc oxide nanoparticle that obtains different-shape duration of contact of DMF, water and zinc nitrate hexahydrate;
Wherein, described Zinc oxide nanoparticle is bar-shaped, and the diameter of this bar-shaped Zinc oxide nanoparticle is 100-150nm, and length is 800-1000nm; The volume ratio of DMF and water is 6-25:1, and be 1-4 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate;
Or described Zinc oxide nanoparticle is rescinded angle hecaprismo shape, the height of this rescinded angle hecaprismo shape Zinc oxide nanoparticle is 50-150nm, and end face diameter is 160-240nm, and bottom surface diameter is 280-320nm; The volume ratio of DMF and water is 45-110:1, and be 5-8 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate;
Or, described Zinc oxide nanoparticle is multilayer plate-like, the diameter of this multilayer plate-like Zinc oxide nanoparticle is 300-400nm, the number of plies is 8-20 layer, the thickness of every layer is 20-40nm, and the volume ratio of described DMF and water is greater than 500:1, be 8-20 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
2. method according to claim 1, wherein, the temperature of described contact is 115-125 ℃, the total volume ratio of the quality of described zinc nitrate hexahydrate and DMF and water is 5-10:1g/L.
3. method according to claim 2, wherein, the total volume ratio of the quality of described zinc nitrate hexahydrate and DMF and water is 7-8:1g/L.
4. method according to claim 1, wherein, described Zinc oxide nanoparticle is bar-shaped, the diameter of this bar-shaped Zinc oxide nanoparticle is 100-150nm, length is 800-1000nm, and the volume ratio of described DMF and water is 9-19:1, be 2-3 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
5. method according to claim 1, wherein, described Zinc oxide nanoparticle is rescinded angle hecaprismo shape, the height of this rescinded angle hecaprismo shape Zinc oxide nanoparticle is 50-150nm, and when end face diameter is 160-240nm, bottom surface diameter is 280-320nm, described N, the volume ratio of dinethylformamide and water is 49-100:1, and be 5-7 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
6. method according to claim 1, wherein, described Zinc oxide nanoparticle is multilayer plate-like, the diameter of this multilayer plate-like Zinc oxide nanoparticle is 300-400nm, the number of plies is 8-20 layer, the thickness of every layer is 20-40nm, and be 9-15 hour the duration of contact of described DMF, water and zinc nitrate hexahydrate.
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| CN107032386B (en) * | 2017-04-12 | 2018-07-03 | 济南大学 | Tetrahedral Zinc oxide single crystal particle and preparation method thereof |
| CN107032387B (en) * | 2017-04-12 | 2018-07-31 | 济南大学 | Six prism-frustum-shaped Zinc oxide particles of one kind and preparation method thereof |
| CN107089677B (en) * | 2017-06-07 | 2018-07-10 | 首都医科大学宣武医院 | Zinc oxide nanoparticle preparation method based on the regulation and control of fibroin albumen biological template |
| CN109576900A (en) * | 2018-11-22 | 2019-04-05 | 四川大学 | A method of promoting composite material piezoelectric property |
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| 商祥淑.纳米氧化锌的制备及其光催化性能研究.《中国优秀硕士学位论文数据库》.2009,第35-36页. |
| 纳米氧化锌的制备及其光催化性能研究;商祥淑;《中国优秀硕士学位论文数据库》;20090831;第35-36页 * |
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