CN114516656B - ZnO material and preparation method and application thereof - Google Patents
ZnO material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114516656B CN114516656B CN202011315116.6A CN202011315116A CN114516656B CN 114516656 B CN114516656 B CN 114516656B CN 202011315116 A CN202011315116 A CN 202011315116A CN 114516656 B CN114516656 B CN 114516656B
- Authority
- CN
- China
- Prior art keywords
- zinc
- reaction
- zno
- hours
- hydrothermal reaction
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title abstract description 41
- 239000002086 nanomaterial Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 120
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 82
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 230000007062 hydrolysis Effects 0.000 claims description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 150000003751 zinc Chemical class 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 239000013067 intermediate product Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 140
- 239000011787 zinc oxide Substances 0.000 description 70
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 239000007795 chemical reaction product Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011540 sensing material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The application discloses a ZnO material and a preparation method and application thereof. A ZnO nanomaterial having a particle size of 1-10 μm. The ZnO nano material has a porous mesoporous structure. The material is uniform and stable, has large specific surface area and is porous. The preparation method of the material is simple and harmless to operate, mild in reaction condition, low in cost and suitable for mass production. The ZnO material has good development and application prospects in the fields of gas sensing, optical and electrical devices and the like.
Description
Technical Field
The application relates to a ZnO material, a preparation method and application thereof, and belongs to the field of inorganic materials.
Background
ZnO is a common important n-type metal semiconductor, has good physical and chemical properties, such as a large energy band gap (about 3.37 eV) and exciton binding energy, and has high transparency and excellent normal-temperature luminescence property. In the production practice, znO has the advantages of low price, low toxicity, stable thermodynamic property, adjustable structure and the like, and has wide application prospect and application value in the fields of batteries, gas sensing, nano generators, photocatalysis and the like.
It is well known that morphology and porosity are closely related to performance. Porous materials with different morphologies exhibit better properties and performance than bulk materials by virtue of the large specific surface and high porosity. Compared with a compact structure, the interconnected pore network provides rich channels for gas diffusion and mass transport, is favorable for gas adsorption and dissociation, and provides larger contact area and reactive sites. Therefore, the preparation of a material with uniform and stable morphology and large gaps is one of important methods for improving the performance of the material. Two-dimensional porous Cd-Co 3 O 4 The nano-sheet is prepared by a microwave-assisted solvothermal method and in-situ annealing, and has NO at room temperature 2 Good response and fast recovery. Its enhanced sensing performance is attributed to the two-dimensional porous structure and the increased NO by the super-oxygen metal ion complex formed by Cd doping 2 Is a sorbent site of (2); three-dimensional netlike porous ZnO consisting of two-dimensional lamellar structure and prepared by hydrothermal method, wherein the pore diameter is 3-40nm, and the specific surface area is 36.4m 2 And/g, the sensor has good gas sensing performance on acetone and ethanol at a high temperature of 420 ℃; the ZnO nanowire or ZnO nanosheet is decorated on the trunk of the ZnO nanowire through continuous hydrothermal synthesis to create a layered three-dimensional nanostructure, so that the interface area between the electrode and the electrolyte is increased, and therefore, the capacity and the rate performance of the electrode are remarkably improved. Therefore, the development of a new method for preparing porous ZnO is of great significance in widening the application field and performance of the porous ZnO.
Disclosure of Invention
To prepare ZnO with a porous structure to improve the performance, the methodThe new preparation method of semiconductor ZnO is provided, and the nano microsphere with uniform and stable size is formed under the proper hydrothermal condition through the coordination of a zinc source and polyalcohol. And then placing the nano microspheres in a zinc nitrate aqueous solution with a certain concentration and stirring. Zn in solution 2+ With OH - The nano-sheets are formed on the surfaces of the microspheres, so that the hydrolysis of the nano-sheets is carried out by means of interface reaction, and the modification of the interfaces and the surfaces is carried out. Finally, washing and drying the hydrolysate, carrying out annealing treatment, removing polyol and other impurities, purifying and stabilizing ZnO.
According to a first aspect of the present application, there is provided a ZnO nanomaterial which is a white zinc oxide material which is uniform and stable, has a large specific surface area, and is porous.
A ZnO nanomaterial, the ZnO nanomaterial having a particle size of 1-20 μm.
Alternatively, the ZnO nanomaterial has a particle size of 1-10 μm.
Alternatively, the particle size of the ZnO nanomaterial is independently selected from any of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, or a range of values therebetween.
Optionally, the ZnO nanomaterial has a lamellar structure.
Optionally, the ZnO nanomaterial has a porosity.
Optionally, the ZnO nanomaterial has mesopores with a size of 2-50nm.
Alternatively, the mesoporous size is 2-40nm.
Alternatively, the mesoporous size is 2-30nm.
Alternatively, the mesoporous size of the ZnO nanomaterial is independently selected from any of 2nm, 5nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or a range of values therebetween.
Optionally, the specific surface area of the ZnO nano material is 10-200m 2 /g。
Optionally, the ZnO nanomaterialThe specific surface area is 15-150m 2 /g。
Alternatively, the specific surface area of the ZnO nanomaterial is independently selected from 10m 2 /g、50m 2 /g、20m 2 /g、30m 2 /g、40m 2 /g、50m 2 /g、60m 2 /g、80m 2 /g、100m 2 /g、120m 2 /g、140m 2 /g、150m 2 /g、160m 2 /g、180m 2 /g、200m 2 Any value in/g or a range of values between any two.
According to a second aspect of the application, a preparation method of ZnO nano material is provided, the preparation method is simple and harmless to operate, mild in reaction condition, low in cost and suitable for mass production, and the prepared material is high in purity, uniform and stable, large in specific surface area and porous.
The preparation method of the ZnO nano material comprises the following steps:
(1) Carrying out hydrothermal reaction on a mixture containing a zinc source and polyhydric alcohol to obtain an intermediate product;
(2) And (3) hydrolyzing the intermediate product in the step (1) in an aqueous solution of soluble zinc salt, and roasting the hydrolyzed product to obtain the ZnO nano material.
In the application, the zinc glycerol microsphere prepared in the first step is hydrolyzed in the water solution of soluble zinc salt.
In the application, the intermediate product is flower-shaped microsphere, and has the characteristic of uniform morphology.
Optionally, the molar ratio of the zinc source to the polyol is from 1:0.5 to 1:20.
Optionally, the molar ratio of zinc source to polyol is from 1:1 to 1:20.
Optionally, the molar ratio of the zinc source to the polyol is from 1:1.5 to 1:10.
Optionally, the molar ratio of the zinc source to the polyol is from 1:1.5 to 1:5.
Alternatively, the molar ratio of zinc source to polyol is independently selected from any value or range of values between any two of 1:0.5, 1:1, 1:1.25, 1:2, 1:5, 1:7, 1:10, 1:12, 1:15, 1:17, 1:20.
Optionally, the concentration of the zinc source in the mixture is 0.001-1mmol/mL.
Optionally, the concentration of the zinc source in the mixture is 0.0025 to 0.05mmol/mL.
Alternatively, the concentration of the zinc source is 0.008-0.8mmol/mL.
Alternatively, the concentration of the zinc source is 0.01-0.5mmol/mL.
Alternatively, the concentration of the zinc source is independently selected from any value or range of values between any two of 0.001mmol/mL, 0.0025mmol/mL, 0.005mmol/mL, 0.008mmol/mL, 0.01mmol/mL, 0.05mmol/mL, 0.08mmol/mL, 0.01mmol/mL, 0.05mmol/mL, 0.1mmol/mL, 0.2mmol/mL, 0.5mmol/mL, 0.8mmol/mL, 1mmol/mL.
Optionally, the polyol is selected from at least one of ethylene glycol, glycerol, xylose.
Optionally, the mixture includes an alcohol solvent selected from at least one of methanol, ethanol, isopropanol.
Optionally, the zinc source is selected from at least one of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate.
Alternatively, the reaction temperature of the hydrothermal reaction is 120-240 ℃.
Alternatively, the reaction temperature is 150-240 ℃.
Alternatively, the reaction temperature is 150-220 ℃.
Alternatively, the reaction temperature is 150-200 ℃.
Alternatively, the reaction temperature of the hydrothermal reaction is independently selected from any value or range of values between any two of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃.
Alternatively, the hydrothermal reaction has a reaction time of 3 to 48 hours.
Alternatively, the reaction time is 4-36h.
Alternatively, the reaction time is 6-24 hours.
Alternatively, the reaction time of the hydrothermal reaction is independently selected from any value or range of values between any two of 3h, 4h, 5h, 6h, 8h, 10h, 15h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, 48h.
Optionally, the mass ratio of the intermediate product to the soluble zinc salt is 1:0.1-1:10.
Optionally, the mass ratio of the intermediate product to the soluble zinc salt is 1:0.5-1:8.
Optionally, the mass ratio of the intermediate and the soluble zinc salt is independently selected from any value or range between any two values of 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.
Optionally, the concentration of zinc salt in the aqueous solution of soluble zinc salt is 0.001-0.8mol/L.
Optionally, the concentration of zinc salt in the aqueous solution of soluble zinc salt is 0.005-0.6mol/L.
Optionally, the concentration of zinc salt in the aqueous solution of the soluble zinc salt is 0.01-0.5mol/L.
Optionally, the concentration of zinc salt in the aqueous solution of the soluble zinc salt is 0.002-0.1mol/L.
Alternatively, the concentration of zinc salt in the aqueous solution of soluble zinc salt is independently selected from any of 0.001mol/L, 0.002mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, or a range of values between any two.
Optionally, the soluble zinc salt is selected from at least one of zinc nitrate and zinc chloride.
Optionally, the time of the hydrolysis is 2-24 hours;
optionally, the hydrolysis time is 3-18h
Alternatively, the time of hydrolysis is 5-12 hours.
Alternatively, the time of hydrolysis is independently selected from any value or range of values between any two of 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h.
Optionally, the temperature of the firing is 300-800 ℃.
Optionally, the firing temperature is 350-600 ℃.
Optionally, the firing temperature is 350-500 ℃.
Alternatively, the firing temperature is independently selected from any value or range of values between any two of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃.
Optionally, the temperature rising rate of the roasting is 1-5 ℃/min.
Optionally, the temperature rising rate of the roasting is 1-3 ℃/min.
Alternatively, the firing rate of temperature rise is independently selected from any value or range of values between any two of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min.
Optionally, the roasting time is 1-6h.
Optionally, the calcination time is 1-4 hours.
Optionally, the calcination time is 2-4 hours.
Alternatively, the time of calcination is independently selected from any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6h.
Optionally, the method comprises the following steps:
(1) Carrying out hydrothermal reaction on a mixture containing a zinc source and polyhydric alcohol to obtain an intermediate product, washing and drying;
(2) And (3) stirring and hydrolyzing the intermediate product obtained after the drying in the step (1) in a zinc nitrate aqueous solution, washing, drying and roasting the hydrolyzed product to obtain the ZnO nano material.
Specifically, zinc source and polyalcohol are fully mixed into homogeneous solution in alcohol solution according to a certain proportion, the homogeneous solution is transferred into a reaction kettle, and hydrothermal treatment is carried out at a certain temperature for a certain time. The product was washed with water and ethanol and dried in vacuo. And (3) stirring and hydrolyzing the product in zinc nitrate aqueous solution for a certain time to carry out surface modification, washing the product with ethanol, drying the product, and finally roasting at a high temperature to obtain the ZnO nano material.
According to a third aspect of the application, the application of the ZnO nanomaterial prepared by the preparation method in the fields of optical, electrical and gas sensing devices is provided.
The ZnO nano material porous mesoporous structure has uniform and stable morphology and large specific surface area, and is favorable for gas adsorption and diffusion. Has good development and application prospect in the fields of gas sensing, optical and electrical devices and the like.
According to a fourth aspect of the present application, there is provided a sensing material.
A sensing material comprises at least one of the ZnO nano-materials prepared by the preparation method and the ZnO nano-materials prepared by the preparation method.
According to a fifth aspect of the present application, a sensor is provided.
A sensor comprising at least one of the ZnO nanomaterial described above and the ZnO nanomaterial prepared by the preparation method described above.
According to a sixth aspect of the present application there is provided the use of a sensor as a substrate material for triethylamine sensing.
The application has the beneficial effects that:
1) The ZnO nano material provided by the application is uniform, stable and high in purity, and has good development and application prospects in the fields of gas sensing, optical and electrical devices and the like.
2) The preparation method of the ZnO nano material provided by the application has the advantages of simple operation, mild condition and low cost, and is suitable for mass production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a zinc oxide material prepared by the method of example 1.
FIG. 2 is an SEM image (10 μm) of a zinc glycerol intermediate material prepared by the method of example 1.
FIG. 3 is an SEM image (20 μm) of a zinc oxide material prepared by the method of example 1.
FIG. 4 is an SEM image (10 μm) of a zinc oxide material prepared by the method of example 1.
FIG. 5 is an SEM image (3 μm) of a zinc oxide material prepared by the method of example 1.
FIG. 6 is a graph showing the characterization of specific surface area of zinc oxide materials prepared by the method of example 1.
FIG. 7 is an SEM image (4 μm) of the zinc oxide material prepared in comparative example 1.
FIG. 8 shows the difference in the sample 1# and sample D1# in the example in the detection of triethylamine at 200 ℃.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially. If not specified, the test methods are all conventional methods, and the instrument settings are all recommended by manufacturers.
A process for preparing semiconductor ZnO includes such steps as fully mixing Zn source with polyol in alcohol solution, hydrothermal reaction at proper temp, and preparing uniform-size stable nanospheres. The nanospheres are hydrolyzed in a zinc salt solution under stirring to modify the surface morphology. And finally roasting the product at a certain temperature to obtain the high-purity porous ZnO material.
The analysis method in the embodiment of the application is as follows:
the topographical features of the samples were analyzed by Scanning Electron Microscope (SEM) testing with an analytical instrument of FEI Nova Nano SEM.
The structural characteristics of the sample are analyzed by X-ray diffraction (XRD) test, the analytical instrument is PANalytical X' pert Pro-1, and the test condition is 5-90 degrees and 6min.
The specific surface area of the sample is analyzed by BET test, the analysis instrument is MIC ASAP 2020, and the test condition is N 2 77K。
Example 1
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material, designated sample # 1.
Example 2
0.1mmol of zinc chloride solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 3
0.1mmol zinc acetate solid was weighed and dissolved in 40mL isopropyl alcohol, 1mmol glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 4
0.1mmol of zinc sulfate solid was weighed and dissolved in 40mL of isopropyl alcohol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 5
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of ethylene glycol was added while stirring, stirring and ultrasonic vibration were carried out to thoroughly mix them, the solution was transferred to a reaction vessel, and the reaction was carried out under hydrothermal conditions at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 6
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of xylose was added while stirring, stirring and ultrasonic vibration were carried out to thoroughly mix them, the solution was transferred to a reaction vessel, and the reaction was carried out under hydrothermal conditions at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 7
0.1mmol of zinc nitrate solid is weighed and dissolved in 40mL of ethanol, 1mmol of xylose is added while stirring, stirring and ultrasonic vibration are carried out to fully mix, the solution is transferred into a reaction kettle, and hydrothermal reaction is carried out for 10h at 180 ℃. The reaction product was washed with ethanol, dried in vacuo, and then put into 20ml of a 0.01mol/L aqueous zinc nitrate solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product is washed and dried by ethanol, and is heated to 400 ℃ in a tube furnace at 2 ℃/min and annealed for 3 hours to prepare the white zinc oxide material.
Example 8
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 2mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 9
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropyl alcohol, 0.5mmol of glycerol was added while stirring, stirring and ultrasonic vibration were carried out to thoroughly mix them, the solution was transferred to a reaction vessel, and the reaction was carried out under hydrothermal conditions at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20mL of a 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 10
0.8mmol zinc nitrate solid was weighed into 40mL isopropyl alcohol, 1mmol glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 11
2mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 12
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 150℃for 36 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 13
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 220℃for 6 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 14
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of a 0.002mol/L aqueous zinc nitrate solution and stirred for 24 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 15
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of a 0.1mol/L aqueous zinc nitrate solution and stirred for 4 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 400 ℃ in a tube furnace at 2 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 16
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 800 ℃ in a tube furnace at 5 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Example 17
0.1mmol of zinc nitrate solid was weighed and dissolved in 40mL of isopropanol, 1mmol of glycerol was added with stirring, stirring and ultrasonic vibration were carried out to thoroughly mix, the solution was transferred to a reaction kettle, and hydrothermal reaction was carried out at 180℃for 10 hours. The reaction product was washed with isopropyl alcohol, dried in vacuo, and then put into 20ml of 0.01mol/L zinc nitrate aqueous solution and stirred for 6 hours to hydrolyze. After hydrolysis, the product was washed with isopropanol and dried, and heated to 300 ℃ in a tube furnace at 1 ℃/min, and annealed for 3 hours to produce a white zinc oxide material.
Comparative example 1
The procedure is as in example 1 except that the aqueous solution of hydrolyzed zinc nitrate is replaced with ethanol and aqueous solution of zinc nitrate, the ethanol to water volume ratio is 1:1, and the resulting sample is designated sample D1#.
Example 18
The white zinc oxide materials obtained in examples 2-17 were designated as sample 2# 17. The samples prepared in the above examples and comparative examples were structurally characterized, and the X-ray powder diffraction pattern (XRD) of sample No. 1 is shown in FIG. 1, which is consistent with ZnO standard card 36-1451, and it can be seen that the material has a uniform phase and high purity. The XRD pattern of sample 2# -17# was similar to that of sample 1#.
The samples prepared in the above examples and comparative examples are subjected to morphology characterization, and the sample 1# is taken as a typical example, and SEM (20,10,3 μm) electron microscope characterization is shown in figures 3-5, and the samples are nano microspheres with mesoporous surfaces, and the particles are 1-10 μm and have a sheet-shaped structure; the samples prepared in the above examples and comparative examples were subjected to specific surface area characterization test, with sample #1 as a typical example, and pore size test as shown in FIG. 6, with specific surface area of 15-150m 2 And/g, the mesoporous size is 2-50nm. As shown in fig. 7, SEM images of sample d1# show that the surface thereof is wool-spherical, and that the morphology structure of sample d1# is greatly different. SEM images of sample 2# -17#, specific surface area characterization test images, and sample 1# are similar.
Example 19
Application experiment of ZnO nano material
Sample 1# is taken as an example.
Dispersing the sample No. 1 porous zinc oxide in a solvent, carrying out ultrasonic treatment to uniformly disperse the sample No. 1 porous zinc oxide, taking the uniformly dispersed suspension by using a pipette to prepare a film, and inserting electrodes to ensure that the electrode spacing is 3-5mm. Fixing the prepared sensor in a closed cavity with a known volume, and connecting with an external universal meter and a direct current power supply to enable the sensor to work at 50-300 ℃; taking a certain amount of triethylamine according to the volume of the cavity by using a microinjector, injecting the triethylamine into an electric heating block of the cavity, turning on an external heating power supply for heating to volatilize the triethylamine liquid in the air and fully diffusing the triethylamine liquid in the cavity so as to reach the set concentration of the triethylamine gas of 20ppm, and then turning off the external heating power supply, wherein the temperature in the cavity is maintained below 30 ℃; simultaneously starting timing, recording the resistance change value of the sensor in a set time, and observing the rapid decrease of the resistance change of the sensor; after the reaction is finished, the cavity cover is opened, the sensor is contacted with fresh air, and the resistance starts to recover.
The sample 1# is replaced by the sample D1#, the operation is the same as that of the sample 1#, the effect of the prepared sensor is similar to that of the sample 1#, but the sensing effect on triethylamine is lower than that of the sample 1#, the sample 1# is mainly because the microsphere surface of the sample 1 is flaky and has mesopores, and the sample D1# is in a wool sphere shape, so that the surface is firmer, and the diffusion and the response of gas molecules are not facilitated
The ZnO nano material is prepared into a sensor, the sensor using porous zinc oxide as a sensing material can be used as a substrate material for triethylamine sensing, the sheet mesoporous structure is beneficial to the diffusion and adsorption of gas molecules, and a large specific surface area provides more active sites.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (14)
1. A preparation method of ZnO nano material is characterized in that,
the particle size of the ZnO nano material is 1-20 mu m;
the ZnO nano material has a lamellar structure;
the ZnO nano material has mesopores with the size of 2-50nm;
the specific surface area of the ZnO nano material is 10-200m 2 /g；
The method comprises the following steps:
(1) Carrying out hydrothermal reaction on a mixture containing a zinc source and polyhydric alcohol to obtain an intermediate product;
(2) Hydrolyzing the intermediate product in the step (1) in a water solution of soluble zinc salt, and roasting the hydrolyzed product to obtain the ZnO nano material;
the molar ratio of the zinc source to the polyol is 1:0.5-1:20;
the concentration of the zinc source in the mixture is 0.001-1mmol/mL;
the reaction temperature of the hydrothermal reaction is 120-240 ℃;
the mass ratio of the intermediate product to the soluble zinc salt is 1:0.1-1:10;
the mixture is a homogeneous solution formed by fully mixing a zinc source and a polyol in an alcohol solvent;
the alcohol solvent is at least one selected from methanol, ethanol and isopropanol;
in the water solution of the soluble zinc salt, the concentration of the zinc salt is 0.002-0.01mol/L.
2. The method according to claim 1, wherein,
the molar ratio of the zinc source to the polyol is 1:1.5-1:10;
the polyalcohol is at least one selected from glycol, glycerol and xylose;
the zinc source is at least one selected from zinc chloride, zinc sulfate, zinc nitrate and zinc acetate.
3. The method according to claim 1, wherein,
the molar ratio of the zinc source to the polyol is 1:1.5-1:5.
4. The method according to claim 1, wherein,
the reaction temperature of the hydrothermal reaction is 150-240 ℃;
the reaction time of the hydrothermal reaction is 3-48h;
the mass ratio of the intermediate product to the soluble zinc salt is 1:0.5-1:8;
the soluble zinc salt is selected from at least one of zinc nitrate and zinc chloride;
the hydrolysis time is 2-24 hours;
the roasting temperature is 300-800 ℃;
the roasting time is 1-6h.
5. The method according to claim 1, wherein,
the reaction temperature of the hydrothermal reaction is 150-200 ℃.
6. The method according to claim 1, wherein,
the reaction time of the hydrothermal reaction is 4-36h.
7. The method according to claim 1, wherein,
the reaction time of the hydrothermal reaction is 6-24h.
8. The method according to claim 1, wherein,
the hydrolysis time is 3-18h.
9. The method according to claim 1, wherein,
the hydrolysis time is 5-12h.
10. The method according to claim 1, wherein,
the roasting temperature is 350-600 ℃.
11. The method according to claim 1, wherein,
the roasting temperature is 350-500 ℃.
12. The method according to claim 1, wherein,
the roasting time is 1-4h.
13. The method according to claim 1, wherein,
the roasting time is 2-4h.
14. The method of manufacturing according to claim 1, comprising the steps of:
(1) Carrying out hydrothermal reaction on a mixture containing a zinc source and polyhydric alcohol to obtain an intermediate product, washing and drying;
(2) And (3) stirring and hydrolyzing the intermediate product obtained after the drying in the step (1) in a zinc nitrate aqueous solution, washing, drying and roasting the hydrolyzed product to obtain the ZnO nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011315116.6A CN114516656B (en) | 2020-11-20 | 2020-11-20 | ZnO material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011315116.6A CN114516656B (en) | 2020-11-20 | 2020-11-20 | ZnO material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114516656A CN114516656A (en) | 2022-05-20 |
| CN114516656B true CN114516656B (en) | 2023-12-05 |
Family
ID=81594603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011315116.6A Active CN114516656B (en) | 2020-11-20 | 2020-11-20 | ZnO material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114516656B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979601A (en) * | 2014-05-21 | 2014-08-13 | 武汉理工大学 | Three-dimensional macroporous-mesoporous ZnO nano material used for gas sensor and preparation method thereof |
| CN105565366A (en) * | 2016-01-21 | 2016-05-11 | 山东科技大学 | Method for preparing porous zinc oxide with three-dimensional structure |
| CN109324092A (en) * | 2018-08-27 | 2019-02-12 | 天津理工大学 | Mesoporous polycrystalline ZnO nano piece and the preparation method and application thereof |
-
2020
- 2020-11-20 CN CN202011315116.6A patent/CN114516656B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979601A (en) * | 2014-05-21 | 2014-08-13 | 武汉理工大学 | Three-dimensional macroporous-mesoporous ZnO nano material used for gas sensor and preparation method thereof |
| CN105565366A (en) * | 2016-01-21 | 2016-05-11 | 山东科技大学 | Method for preparing porous zinc oxide with three-dimensional structure |
| CN109324092A (en) * | 2018-08-27 | 2019-02-12 | 天津理工大学 | Mesoporous polycrystalline ZnO nano piece and the preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114516656A (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019109831A1 (en) | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| US20130089739A1 (en) | Nanostructured metal oxides and mixed metal oxides, methods of making these nanoparticles, and methods of their use | |
| CN102745752A (en) | Method of synthesizing mesoporous nickel cobalt oxide nanowire using hydrothermal method and application thereof | |
| CN102942165B (en) | Graphene and ferrum diselenide composite material and method for preparing same | |
| Wang et al. | Controlled preparation and gas sensitive properties of two-dimensional and cubic structure ZnSnO3 | |
| CN105585043B (en) | Preparation method of flowerlike cerium oxide nano-material | |
| CN113740390B (en) | Nickel-doped indium oxide nano-particle and preparation method and application thereof | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN101704558A (en) | Preparation method of nickel oxide nano flake with uniform and mesoporous structure | |
| Zhang et al. | Porous ZnO/NiO microspherical structures prepared by thermolysis of heterobimetallic metal-organic framework as supercapacitor electrodes | |
| CN108996557B (en) | Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof | |
| CN110182856A (en) | A kind of preparation method of double shells hollow ball-shape nickel cobaltate nano particles | |
| CN1935662A (en) | Nano crystal constructed porous copper oxide aggregate and its preparing method | |
| CN101941731A (en) | Preparation method of void type nano-sheet zinc oxide and activated carbon load complex | |
| Hu et al. | Controllable hydrothermal-assisted synthesis of mesoporous Co 3 O 4 nanosheets | |
| Akbar et al. | Optimized structure and electrochemical properties of sulfonated carbon nanotubes/Co–Ni bimetallic layered hydroxide composites for high-performance supercapacitors | |
| CN111137927A (en) | Preparation method of nickel copper cobaltate nanoparticles and application of nickel copper cobaltate nanoparticles in catalyzing ammonia borane hydrolysis to produce hydrogen | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN113774429A (en) | ZIF-8/graphene composite aerogel and preparation method and application thereof | |
| CN114516656B (en) | ZnO material and preparation method and application thereof | |
| CN111135794B (en) | Alumina modified expanded graphite adsorbent and preparation method and application thereof | |
| CN116119707B (en) | Preparation method and application of ZnO nano-sheet for detecting N-methylpyrrolidone | |
| CN111899982A (en) | NiO nano-sheet and preparation method and application thereof | |
| CN114212829B (en) | Preparation method of zinc manganate nanosphere 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |