CN111675238A - Method for preparing multi-morphology nano zinc oxide by solid phase method - Google Patents
Method for preparing multi-morphology nano zinc oxide by solid phase method Download PDFInfo
- Publication number
- CN111675238A CN111675238A CN202010566955.9A CN202010566955A CN111675238A CN 111675238 A CN111675238 A CN 111675238A CN 202010566955 A CN202010566955 A CN 202010566955A CN 111675238 A CN111675238 A CN 111675238A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- solid
- preparing
- phase method
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
-
- 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
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a method for preparing multi-morphology nano zinc oxide by a solid phase method, which comprises the following steps: (1) weighing zinc sulfate heptahydrate and ammonium bicarbonate into a ceramic mortar, (2) manually grinding a solid mixture, (3) after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifuge tube, adding 10 mL-30 mL deionized water, stirring the suspension by using a glass rod for 3 min-5 min, centrifuging the suspension, filtering, continuously adding deionized water, repeating the washing and centrifuging steps for 3-5 times, (4) drying the centrifuged solid, (5) placing a precursor into a muffle furnace for calcination, and (6) filling the calcined powder into a sample bag. The preparation method of the zinc oxide has the advantages of simple solid phase method process conditions, low cost, low requirement on equipment, environmental protection, high zinc oxide yield, continuous and adjustable operation program, and easy control of the experimental process, so the preparation method of the zinc oxide is easy for industrial production.
Description
Technical Field
The invention relates to a preparation method of zinc oxide, in particular to a method for preparing multi-morphology nano zinc oxide by a solid phase method.
Background
The zinc oxide is a direct band gap oxide semiconductor material with excellent performance and has higher thermal stability and chemical stability. The material has larger energy band gap and exciton constraint energy, high transparency, excellent normal temperature luminescence performance and ultraviolet and blue-green light emission capability, and is widely applied to the aspects of gas sensors, surface acoustic wave devices, light emitters and the like.
The preparation method of the nano zinc oxide mainly comprises a chemical method and a physical method. Chemical method controls reaction condition to make atom (or molecule) nucleate and grow into nano particle method [ trellis, fanhuli, xiaojunping, etc. research progress of nano material surface modification, material report 2006,20(S1):5-7 ]. The common preparation methods include homogeneous precipitation, direct precipitation, hydrothermal synthesis, sol-gel method and template preparation [ Jiaomeng, Gong Ding Chung, plum-Yong. Research on preparation of nano zinc oxide by a uniform precipitation method, inorganic material science, 2006,21(1): 65-69; guaran, Xupeng, Zhongji, etc. The direct precipitation method is used for preparing the special-shaped zinc oxide microcrystal and the characterization thereof, and the material report is 2012,26(8):44-46 ]. In addition, solid phase grinding is also a rapid and simple method for synthesizing nano zinc oxide [ Shujian, Xinxin spring, new method for synthesizing nano nickel oxide, zinc oxide, inorganic chemistry report, 1999,15(1):95-98], research shows that oxalic acid and zinc acetate dihydrate are weighed according to a molar ratio of 1:1, ground for 30min and then dried, and then the precursor zinc oxalate dihydrate is thermally decomposed at 460 ℃ to obtain spherical zinc oxide with an average particle size of 20 nm. The precipitant added by the uniform precipitation method can slowly generate the precipitant in the whole solution through chemical reaction, solves the problem of local nonuniformity of the precipitant caused by directly adding the precipitant from the outside, is the most common preparation method at present, and has the advantages of high purity of the obtained product, simple process, long reaction time and complex reaction process. The direct precipitation method is a method of adding a precipitant into a soluble zinc salt solution to generate another water-insoluble zinc salt or basic salt of zinc, zinc hydroxide and the like, and obtaining the nano zinc oxide through filtration, washing, drying, roasting and the like, and is also a more common preparation method. In a specially manufactured closed reaction container, an aqueous solution is used as a reaction medium, the reaction container is heated, then a high-temperature and high-pressure reaction environment is created, so that a method for dissolving and recrystallizing a generally insoluble substance is a hydrothermal method, and the product obtained by the method has the advantages of high purity, uniform size, no agglomeration, low cost, high requirement on equipment, harsh preparation conditions and easiness in waste. The sol-gel method uses inorganic salt or metal alkoxide as precursor, and through hydrolysis and polycondensation, the precursor is gradually gelled, and then through sintering, the nano powder is obtained. The template preparation method is a method for depositing related materials into holes or surfaces of a template by a physical or chemical method and then removing the template to obtain the nano material with the morphology and the size of the template tissue, and the material prepared by the template method is widely applied in the field of gas sensors because the microscopic fine porous structure of a biological template is copied. The physical method is a method for preparing nano particles by mutual grinding and impact between a medium and a material [ Zhangwei, Wanfengzhu, research on preparing ultrafine powder by utilizing a vertical vibration mill, functional materials 1997,28(5):511-513], common mechanical crushing methods, deep plastic deformation methods and the like, but the application degree is not high because the nano grade and the purity of the material prepared by the physical method are low.
The solid phase method for preparing zinc oxide is a simple and controllable synthesis method, wherein zinc salt and ammonium bicarbonate (solid) are subjected to ball milling or manual grinding to obtain a zinc precursor, and then the zinc precursor is subjected to high-temperature calcination to obtain the zinc oxide. The solid phase method used in the method is to quickly and simply prepare the nano-grade zinc oxide powder with good dispersity and multi-shape structure by utilizing a manual grinding mode. The method for preparing the zinc oxide mainly comprises the following two steps:
5ZnSO4·7H2O+10NH4HCO3→Zn5(CO3)2(OH)6+5(NH4)2SO4+8CO2+37H2O (1)
Zn5(CO3)2(OH)6→5ZnO+2CO2(g)+3H2O (2)
reaction (1) is a process of forming basic zinc carbonate precursor during grinding; the reaction (2) is a process in which the basic zinc carbonate precursor is gradually decomposed into zinc oxide during the high-temperature calcination. The essence of the solid phase method is similar to that of the liquid phase method, but the innovation point is that the solid reactant is manually ground, so that the solid reactant absorbs mechanical energy to induce chemical reaction, and the solid reactant is simple, quick and easy to operate; meanwhile, through orthogonal experimental design, the influence of calcination time, a dispersion medium, the quantity ratio of zinc sulfate heptahydrate to ammonium bicarbonate (hereinafter referred to as zinc-ammonium ratio) and calcination temperature on the particle size, the crystal type and the particle morphology of zinc oxide is systematically researched, basic zinc carbonate is rarely used in the general solid-phase synthesis of zinc oxide, zinc hydroxide, zinc oxalate or zinc carbonate is mostly used as a precursor, the influence of the factors on the crystal form and the morphology of nano zinc oxide is not studied in detail in most documents, and nano zinc oxide with various morphology structures is rarely obtained in the same system. Therefore, the method can provide brand new theoretical basis and practical reference for preparing the zinc oxide by the solid phase.
There are many patents that have been published to prepare zinc oxide, including: a preparation process of high-purity nano zinc oxide (publication number: CN109399693A), a preparation method of self-assembled hexagonal prism zinc oxide (publication number: CN109399692A), a preparation and particle size regulation method of zinc oxide (publication number: CN109133149A), a preparation method of nano zinc oxide (publication number: CN108821328A), a preparation method of active zinc oxide (publication number: CN108455656A), a preparation method of feed-grade active zinc oxide (publication number: CN108467055A), polyhedral zinc oxide and a preparation method thereof (publication number: CN108163884A) and the like, but the nano zinc oxide is synthesized by utilizing a solid phase method, particularly manually grinding and taking basic zinc carbonate as a precursor, but related documents are rare.
Disclosure of Invention
The invention aims to provide a method for preparing multi-morphology nano zinc oxide by a solid phase method, wherein the solid phase method in the preparation method of the zinc oxide has the advantages of simple process conditions, low cost, low requirement on equipment, environmental protection, high zinc oxide yield, continuous and adjustable operation program, easy control of the experimental process and easy industrial production; the basic zinc carbonate is used as a precursor, and the good-dispersity multi-shape (needle-shaped, rod-shaped, flower-shaped and spherical) nano-grade zinc oxide can be prepared by adjusting experimental parameters (calcining time, dispersion medium, zinc-ammonium ratio and calcining temperature); the method adopts simpler manual grinding, has obvious difference with common mechanical ball milling (solid phase reaction), and can simply and quickly prepare the multi-shape (needle-shaped, rod-shaped, flower-shaped and spherical) nano-grade zinc oxide.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing multi-morphology nano zinc oxide by a solid phase method comprises the following steps:
(1) weighing zinc sulfate heptahydrate and ammonium bicarbonate into a ceramic mortar with the caliber of 160mm, and adding or not adding a dispersion medium, wherein the dispersion medium is 5mL of water or 5mL of absolute ethyl alcohol.
(2) The solid mixture was ground by hand for 30 min-90 min.
(3) After the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifuge tube, adding 10 mL-30 mL deionized water, stirring the suspension with a glass rod for 3 min-5 min, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 3-5 times to remove the unreacted reactants and ammonium sulfate.
(4) And drying the solid after the centrifugation to obtain a precursor basic zinc carbonate.
(5) And placing the precursor in a muffle furnace for calcining.
(6) And filling the calcined powder into a sample bag to obtain the zinc oxide powder.
Further, the molar ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1: (1-3).
Further, the solid mixture was manually ground for 60min in the step (2).
Further, the number of washing times in the step (3) is 4.
Further, the drying temperature in the step (4) is 60-80 ℃, and the drying time is 0.5-2 h.
Further, the calcining temperature in the step (5) is 300-500 ℃, and the time is 1-3 h.
The invention has the beneficial effects that:
1. the preparation method of the zinc oxide has the advantages of simple solid phase method process conditions, low cost, low requirements on equipment, environmental protection, high zinc oxide yield, continuous and adjustable operation procedures, easy control of experimental processes and easy industrial production;
2. the preparation method of the zinc oxide takes basic zinc carbonate as a precursor, and can prepare the multi-morphology (needle-shaped, rod-shaped, flower-shaped and spherical) nano-grade zinc oxide with good dispersibility by adjusting experimental parameters (calcining time, dispersion medium, zinc-ammonium ratio and calcining temperature);
3. the preparation method of the zinc oxide adopts simpler manual grinding, has obvious difference with common mechanical ball milling (solid phase reaction), and simply and quickly prepares the multi-shape (needle-shaped, rod-shaped, flower-shaped and spherical) nano-scale zinc oxide.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction (XRD) pattern of a precursor basic zinc carbonate of the present invention;
FIG. 2 is an XRD pattern of a sample of zinc oxide of the present invention;
FIG. 3 is a field emission scanning electron microscope (FE-SEM) image of inventive No. 1 zinc oxide;
FIG. 4 is an FE-SEM photograph of zinc oxide No. 2 of the present invention;
FIG. 5 is an FE-SEM photograph of zinc oxide No. 3 of the present invention;
FIG. 6 is an FE-SEM photograph of zinc oxide No. 4 of the present invention;
FIG. 7 is an FE-SEM photograph of zinc oxide No. 5 of the present invention;
FIG. 8 is an FE-SEM photograph of zinc oxide No. 6 of the present invention;
FIG. 9 is an FE-SEM photograph of zinc oxide No. 7 of the present invention;
FIG. 10 is an FE-SEM photograph of zinc oxide No. 8 of the present invention;
FIG. 11 is an FE-SEM photograph of zinc oxide No. 9 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. Weighing 11.52g of zinc sulfate heptahydrate (0.04mol) and 3.17g of ammonium bicarbonate (0.04mol) in a ceramic mortar with the caliber of 160mm, wherein the ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1:1, and no dispersion medium is added;
2. manually grinding the solid mixture for 30 min;
3. after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifugal bottle, adding 10mL deionized water, stirring the suspension for 3min by using a glass rod, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 3 times to remove the unreacted reactants (zinc sulfate heptahydrate and ammonium bicarbonate) and ammonium sulfate;
4. drying the centrifuged solid at the temperature of 60 ℃ for 0.5h to obtain a precursor basic zinc carbonate;
5. and (3) calcining the precursor in a muffle furnace at the temperature of 300 ℃ for 1h, and filling calcined powder into a sample bag to obtain the zinc oxide powder.
XRD analysis of the precursor thus obtained (as in the case of the No. 1-9 sample zinc oxide precursor, here, the No. 5 precursor was used as a test sample) showed that the precursor was basic zinc carbonate and had a chemical formula of Zn, as shown in FIG. 15(CO3)2(OH)6(ii) a XRD examination of the obtained zinc oxide powder was carried out, as shown in FIG. 2, and the results showed that four factors (calcination time, dispersion medium, zinc-ammonium ratio and calcination) in the orthogonal table were changedFiring temperature), and the crystal forms of the zinc oxide are all hexagonal wurtzite structures. The XRD patterns of zinc oxide samples from No. 1 to No. 9 are respectively shown in sequence in (a) - (i) in FIG. 2 of the zinc oxide samples from No. 1 to No. 9, the FE-SEM images of the zinc oxide samples from No. 1 to No. 9 are respectively shown in sequence in FIGS. 3 to 11 of the zinc oxide samples, the particle sizes of the zinc oxide samples are constantly changed (FIG. 3-11 and Table 2), the minimum particle size is 19.1nm, the maximum particle size is 50.9nm, and the zinc oxide samples are all nano-scale sizes, which indicates that the zinc oxide prepared by the method is. The FE-SEM results showed that zinc oxide had a typical rod-like structure, was uniformly dispersed, and had a small particle size, as shown in fig. 3.
Analyzing orthogonal data by a range method, wherein four factors (calcining time, dispersion medium, zinc-ammonium ratio and calcining temperature) have influence on the particle size of the nano zinc oxide, the influence degrees of the four factors are calcining temperature, dispersion medium, calcining time and zinc-ammonium ratio from large to small, the optimal scheme is determined that the calcining temperature is 300 ℃, the dispersion medium is 5mL of absolute ethyl alcohol, the calcining time is 1h, the zinc-ammonium ratio is 1:3, and the particle size of the zinc oxide prepared according to the parameters is theoretically lower than 25.4 nm; as shown in fig. 3-11, it was found that zinc oxide exhibits various morphologies by varying four factors (calcination time, dispersion medium, zinc-ammonium ratio, and calcination temperature): needle-like, rod-like, flower-like, spherical.
Example 2
1. Weighing 5.76g of zinc sulfate heptahydrate (0.02mol) and 3.17g of ammonium bicarbonate (0.04mol) in a ceramic mortar with the caliber of 160mm, wherein the ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1:2, and adding a dispersion medium which is 5mL of ultrapure water;
2. the solid mixture was ground by hand for 60 min;
3. after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifugal bottle, adding 20mL deionized water, stirring the suspension for 4min by using a glass rod, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 4 times to remove the unreacted reactants (zinc sulfate heptahydrate and ammonium bicarbonate) and ammonium sulfate;
4. drying the centrifuged solid at the temperature of 70 ℃ for 1h to obtain a precursor basic zinc carbonate;
5. and (3) calcining the precursor in a muffle furnace at 400 ℃ for 1h, and filling calcined powder into a sample bag to obtain the zinc oxide powder.
XRD detection is carried out on the obtained product, as shown in figure 2, the result shows that the grain diameter of the zinc oxide is 30.5nm, and the crystal form is a hexagonal wurtzite structure. As shown in fig. 4, zinc oxide is mainly rod-shaped under this condition.
Example 3
1. Weighing 3.75g of zinc sulfate heptahydrate (0.013mol) and 3.17g of ammonium bicarbonate (0.04mol) in a ceramic mortar with the caliber of 160mm, wherein the ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1:3, and adding a dispersion medium, wherein the dispersion medium is 5mL of absolute ethyl alcohol;
2. the solid mixture was ground by hand for 90 min;
3. after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifugal bottle, adding 30mL deionized water, stirring the suspension for 5min by using a glass rod, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 5 times to remove the unreacted reactants (zinc sulfate heptahydrate and ammonium bicarbonate) and ammonium sulfate;
4. drying the centrifuged solid at the temperature of 80 ℃ for 2h to obtain a precursor basic zinc carbonate;
5. and (3) calcining the precursor in a muffle furnace at 500 ℃ for 1h, and filling calcined powder into a sample bag to obtain the zinc oxide powder.
XRD detection is carried out on the obtained product, as shown in figure 2, the result shows that the grain diameter of the zinc oxide is 25.4nm, and the crystal form is a hexagonal wurtzite structure. As shown in fig. 5, zinc oxide is mainly acicular under this condition.
Example 4
1. Weighing 3.75g of zinc sulfate heptahydrate (0.013mol) and 3.17g of ammonium bicarbonate (0.04mol) in a ceramic mortar with the caliber of 160mm, wherein the ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1:3, and adding a dispersion medium, wherein the dispersion medium is 5mL of ultrapure water;
2. manually grinding the solid mixture for 30 min;
3. after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifugal bottle, adding 30mL deionized water, stirring the suspension for 3min by using a glass rod, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 3 times to remove the unreacted reactants (zinc sulfate heptahydrate and ammonium bicarbonate) and ammonium sulfate;
4. drying the centrifuged solid at the temperature of 60 ℃ for 0.5h to obtain a precursor basic zinc carbonate;
5. and (3) calcining the precursor in a muffle furnace at the temperature of 300 ℃ for 2h, and filling calcined powder into a sample bag to obtain the zinc oxide powder.
XRD detection is carried out on the obtained product, as shown in figure 2, the result shows that the grain diameter of the zinc oxide is 21.8nm, and the crystal form is a hexagonal wurtzite structure. As shown in fig. 7, zinc oxide is predominantly (rosette) in this condition.
Example 5
1. Weighing 11.52g of zinc sulfate heptahydrate (0.04mol) and 3.17g of ammonium bicarbonate (0.04mol) in a ceramic mortar with the caliber of 160mm, wherein the ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1:1, and adding a dispersion medium, wherein the dispersion medium is 5mL of absolute ethyl alcohol;
2. the solid mixture was ground by hand for 90 min;
3. after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifugal bottle, adding 30mL deionized water, stirring the suspension for 5min by using a glass rod, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the steps of washing and centrifuging for 5 times to remove the unreacted reactants (zinc sulfate heptahydrate and ammonium bicarbonate) and ammonium sulfate;
4. drying the centrifuged solid at the temperature of 80 ℃ for 0.5h to obtain a precursor basic zinc carbonate;
5. and (3) calcining the precursor in a muffle furnace at the temperature of 400 ℃ for 2h, and filling calcined powder into a sample bag to obtain the zinc oxide powder.
XRD detection is carried out on the obtained product, as shown in figure 2, the result shows that the grain diameter of the zinc oxide is 19.1nm, and the crystal form is a hexagonal wurtzite structure. As shown in fig. 8, zinc oxide is mainly spherical under this condition.
TABLE 1 orthogonal experiment parameter table
TABLE 2 analysis table of orthogonal experimental data results calculated by range method
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (6)
1. A method for preparing multi-morphology nano zinc oxide by a solid phase method is characterized by comprising the following steps:
(1) weighing zinc sulfate heptahydrate and ammonium bicarbonate into a ceramic mortar with the caliber of 160mm, and adding or not adding a dispersion medium, wherein the dispersion medium is 5mL of water or 5mL of absolute ethyl alcohol;
(2) manually grinding the solid mixture for 30 min-90 min;
(3) after the reaction is finished, transferring the mixture in the ceramic mortar into a 50mL centrifuge tube, adding 10 mL-30 mL deionized water, stirring the suspension with a glass rod for 3 min-5 min, centrifuging the suspension, filtering, continuously adding deionized water, and repeating the washing and centrifuging steps for 3-5 times to remove unreacted reactants and ammonium sulfate;
(4) drying the centrifuged solid to obtain a precursor basic zinc carbonate;
(5) placing the precursor in a muffle furnace for calcining;
(6) and filling the calcined powder into a sample bag to obtain the zinc oxide powder.
2. The method for preparing the multi-morphology nano zinc oxide by the solid-phase method according to claim 1, wherein the molar ratio of the zinc sulfate heptahydrate to the ammonium bicarbonate is 1: (1-3).
3. The method for preparing the multi-morphology nano zinc oxide through the solid-phase method according to claim 1, wherein the solid mixture is manually ground for 60min in the step (2).
4. The method for preparing the multi-morphology nano zinc oxide by the solid-phase method according to claim 1, wherein the number of washing times in the step (3) is 4.
5. The method for preparing the multi-morphology nano zinc oxide by the solid-phase method according to claim 1, wherein the drying temperature in the step (4) is 60-80 ℃, and the drying time is 0.5-2 h.
6. The solid-phase method for preparing the multi-morphology nano zinc oxide according to claim 1, wherein the calcining temperature in the step (5) is 300-500 ℃ and the calcining time is 1-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010566955.9A CN111675238A (en) | 2020-08-03 | 2020-08-03 | Method for preparing multi-morphology nano zinc oxide by solid phase method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010566955.9A CN111675238A (en) | 2020-08-03 | 2020-08-03 | Method for preparing multi-morphology nano zinc oxide by solid phase method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111675238A true CN111675238A (en) | 2020-09-18 |
Family
ID=72455952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010566955.9A Pending CN111675238A (en) | 2020-08-03 | 2020-08-03 | Method for preparing multi-morphology nano zinc oxide by solid phase method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111675238A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112320825A (en) * | 2020-10-26 | 2021-02-05 | 安徽景成新材料有限公司 | Method for preparing nano magnesium oxide by solid phase method |
| CN112357955A (en) * | 2020-10-16 | 2021-02-12 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide powder with different morphologies by solid phase method |
| CN112645366A (en) * | 2020-12-14 | 2021-04-13 | 安徽景成新材料有限公司 | Preparation method of nano magnesium oxide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433966A (en) * | 2002-01-22 | 2003-08-06 | 大连三科科技发展有限公司 | Process for preparing nano zinc oxide material |
| CN1994892A (en) * | 2006-11-27 | 2007-07-11 | 华南理工大学 | Microwave method for preparing nanometer zinc oxide |
| CN102659170A (en) * | 2012-05-03 | 2012-09-12 | 西北工业大学 | Room temperature solid-phase synthesis method for platy zinc oxide nanometer powder |
| FR2972440A1 (en) * | 2011-03-07 | 2012-09-14 | Commissariat Energie Atomique | PROCESS FOR FORMING DOPED METAL OXIDE |
| CN103183372A (en) * | 2013-04-07 | 2013-07-03 | 江苏大学 | Solid-phase preparation method for nano zinc oxide through template |
| CN104843764A (en) * | 2015-03-31 | 2015-08-19 | 南京工业大学 | Method for preparing nano zinc oxide by using fluidized calcinated alkali zinc carbonate |
| CN106064828A (en) * | 2016-07-29 | 2016-11-02 | 柳州豪祥特科技有限公司 | Solid phase method prepares the method for Zinc oxide powder |
| CN110194480A (en) * | 2019-06-11 | 2019-09-03 | 宜昌三峡中润纳米材料有限公司 | A kind of nano-cerium oxide and preparation method thereof |
-
2020
- 2020-08-03 CN CN202010566955.9A patent/CN111675238A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433966A (en) * | 2002-01-22 | 2003-08-06 | 大连三科科技发展有限公司 | Process for preparing nano zinc oxide material |
| CN1994892A (en) * | 2006-11-27 | 2007-07-11 | 华南理工大学 | Microwave method for preparing nanometer zinc oxide |
| FR2972440A1 (en) * | 2011-03-07 | 2012-09-14 | Commissariat Energie Atomique | PROCESS FOR FORMING DOPED METAL OXIDE |
| CN102659170A (en) * | 2012-05-03 | 2012-09-12 | 西北工业大学 | Room temperature solid-phase synthesis method for platy zinc oxide nanometer powder |
| CN103183372A (en) * | 2013-04-07 | 2013-07-03 | 江苏大学 | Solid-phase preparation method for nano zinc oxide through template |
| CN104843764A (en) * | 2015-03-31 | 2015-08-19 | 南京工业大学 | Method for preparing nano zinc oxide by using fluidized calcinated alkali zinc carbonate |
| CN106064828A (en) * | 2016-07-29 | 2016-11-02 | 柳州豪祥特科技有限公司 | Solid phase method prepares the method for Zinc oxide powder |
| CN110194480A (en) * | 2019-06-11 | 2019-09-03 | 宜昌三峡中润纳米材料有限公司 | A kind of nano-cerium oxide and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 俞建群等: "纳米氧化镍、氧化锌的合成新方法", 《无机化学学报》 * |
| 姜伟等: "以常温固相反应合成纳米氧化锌的研究", 《现代盐化工》 * |
| 谭国进等: "碱式碳酸锌前驱体合成纳米氧化锌及数据挖掘", 《无机盐工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112357955A (en) * | 2020-10-16 | 2021-02-12 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide powder with different morphologies by solid phase method |
| WO2022078015A1 (en) * | 2020-10-16 | 2022-04-21 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide powder in different morphologies by using solid-phase process |
| CN112357955B (en) * | 2020-10-16 | 2022-07-26 | 安徽景成新材料有限公司 | Method for preparing titanium dioxide powder with different morphologies by solid phase method |
| CN112320825A (en) * | 2020-10-26 | 2021-02-05 | 安徽景成新材料有限公司 | Method for preparing nano magnesium oxide by solid phase method |
| CN112645366A (en) * | 2020-12-14 | 2021-04-13 | 安徽景成新材料有限公司 | Preparation method of nano magnesium oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111675238A (en) | Method for preparing multi-morphology nano zinc oxide by solid phase method | |
| CN100443414C (en) | Production of nanometer copper oxide with controllable microstructure | |
| CN103395826B (en) | Preparation method of aluminum doped zinc oxide nano powder | |
| CN106186008B (en) | Boehmite for lithium battery diaphragm coating and hydrothermal preparation method thereof | |
| CN109942012B (en) | Nanoscale flaky boehmite and preparation method thereof | |
| CN112357955B (en) | Method for preparing titanium dioxide powder with different morphologies by solid phase method | |
| CN109336143B (en) | Method for preparing nano magnesium oxide by one-step pyrolysis method | |
| CN108483474A (en) | A kind of preparation method of nano-level sphere aluminium oxide | |
| JP2010105892A (en) | Zirconia fine particle and method for producing the same | |
| CN111747441A (en) | Method for solid-phase synthesis of nano zinc oxide by utilizing alcohol amine compound | |
| CN112745105A (en) | High-sintering-activity alumina ceramic powder and preparation method thereof | |
| CN108640145B (en) | Preparation method of flower-ball-shaped yttrium oxide nano material with controllable appearance | |
| CN1321942C (en) | Method for preparing Nano crystal of metal oxide of anti agglomeration | |
| KR101438121B1 (en) | Method of manufacturing barium titanate nanowire | |
| JPH01133939A (en) | Production of fine titanium oxide particles | |
| CN109422293B (en) | Preparation method of micron-sized spherical cobaltosic oxide material | |
| CN103482672B (en) | Preparation method of hexagonal-prism-shaped Sm(OH)3 nanocrystalline | |
| Fu et al. | A general synthesis strategy for hierarchical porous metal oxide hollow spheres | |
| CN113479897B (en) | Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof | |
| CN110371941B (en) | Preparation method of morphology-adjustable copper hydroxyphosphate multi-level micron material | |
| Ernst et al. | Enhanced hydrothermal conversion of surfactant-modified diatom microshells into barium titanate replicas | |
| CN108946796A (en) | A kind of doped titanate and preparation method thereof | |
| Cheng et al. | Synthesis of sealed sponge ZnO nanospheres through a novel NH3-evaporation method | |
| CN110203956B (en) | Method for preparing vaterite-phase-containing calcium carbonate by using calcium ethylene glycol wet ball milling | |
| CN112047383A (en) | Method for preparing nano iron oxide by solid phase method and iron oxide material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220124 Address after: 232000 standardized workshop B1 of Zhenxing intelligent industrial park, Zhenxing South Road, Huainan Economic and Technological Development Zone, Anhui Province Applicant after: Huainan prospect new material Co.,Ltd. Address before: 230031 room 1305, Jinqian Plaza, 4680 Jinzhai South Road, Shushan District, Hefei City, Anhui Province Applicant before: Anhui Jingcheng New Material Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200918 |