CN106976903B - A kind of flower-shaped CuO method for preparing microsphere and its in formaldehyde gas sensor application - Google Patents
A kind of flower-shaped CuO method for preparing microsphere and its in formaldehyde gas sensor application Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000004005 microsphere Substances 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
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- 238000013019 agitation Methods 0.000 claims description 6
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
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- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 206010070834 Sensitisation Diseases 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000008313 sensitization Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 2
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- 230000008569 process Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 239000010949 copper Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 52
- 239000007789 gas Substances 0.000 description 38
- 239000002086 nanomaterial Substances 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
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- 239000006185 dispersion Substances 0.000 description 2
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- 239000002057 nanoflower Substances 0.000 description 2
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- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
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- 230000015689 metaplastic ossification Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 210000002700 urine Anatomy 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
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- 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
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- 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
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- 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
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- 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
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Abstract
A kind of flower-shaped CuO method for preparing microsphere and its in formaldehyde gas sensor application, is related to a kind of flower-shaped CuO microballoon preparation and its in gas sensor application, the present invention is with Cu (NO3)2·3H2O is copper source, and urea and PEG20000 are auxiliary addition agent, and the flower-shaped CuO microballoon assembled by nano strip is obtained by hydro-thermal reaction.The advantages of this preparation method, is that entire production process is simple and easy, product purity is high, low in cost, is suitable for large-scale industrial production.The flower-shaped CuO microballoon that the present invention is prepared has unique space structure, not only increase the specific surface area of material, flourishing classification hole path can also be constructed simultaneously, be conducive to the quick adsorption and desorption of formaldehyde gas molecule, sensor sheet is set to reveal higher sensitivity, good response-recovery characteristics and selectivity have broad application prospects in terms of manufacturing gas sensor.
Description
Technical field
The present invention relates to a kind of CuO method for preparing microsphere and its in gas sensor application, more particularly to a kind of flower-shaped
CuO method for preparing microsphere and its in formaldehyde gas sensor application.
Background technique
Copper oxide (CuO) is a kind of typical p-type narrow-band semiconductor material, forbidden bandwidth 1.2eV.Since CuO has
Unique electricity, magnetic, catalysis characteristics can be used as widely used multifunctional inorganic material: mutually converting in gas sensing, magnetic, surpass
The fields such as leading and be catalyzed has extensive purposes.As nanometer material science reaches its maturity with what technology developed, nanotechnology
It has applied in the more excellent CuO nano material of processability.Compared with the CuO of stock size, nanoscale CuO material exhibition
Reveal some unique performances, such as small-size effect and quantum tunneling effect, hence it is evident that improve the physics and chemistry of the material
Property has significantly widened the application space of the material.In the preparation method of numerous CuO nano materials, hydrothermal synthesis method due to
Equipment is simple, and cost is relatively low, and controllability is good, the material purity height of preparation, advantages of good crystallization, good dispersion, can primary reconstruction etc. it is excellent
Point, it is considered to be the preparation most potential method of nano material.In hydro-thermal method, soaking time, temperature, etc. factors CuO is received
The morphology and size of rice material all has a significant impact.Therefore, the controllable preparation of nano material how is realized, accurate control experiment item
Part, reduction prepare production cost, and exploitation CuO applications to nanostructures performance is had a very important significance.
With the development of society, more and more air pollutants such as industrial waste gas, life fire coal, vehicle exhaust, finishing
Building materials etc. are threatening the health of the mankind.Especially indoor polluted gas-volatile organic compounds is largely present in finishing
In material, furniture, lead to the illnesss such as lung cancer, leukaemia, fetal anomaly, cutaneum carcinoma.Currently, to volatile organic compounds
Common detection method is the off-line checking method that solid extraction and gas phase chromatogram binding assay are used referring to national standard, to operation
Personnel have very high technical requirements, and detection device is expensive, can not large-scale application.Therefore, it utilizes with semiconductor gold
Belong to gas sensor of the oxide nano structure as sensitive material, in due course, accurately detects environment for human survival pernicious gas
Concentration has great importance in fields such as daily life, medical environment, workers and peasants' military affairs.CuO as semiconductor functional material,
Excellent performance makes it increasingly by the attention of researchers in terms of gas detection.Therefore, using CuO nanostructure as
Gas sensitive, which studies it, has important research significance to the sensing capabilities of volatile organic compound.
Summary of the invention
The purpose of the present invention is to provide a kind of flower-shaped CuO method for preparing microsphere and its in formaldehyde gas sensor application,
The present invention prepares the flower-shaped CuO microballoon assembled by nanometer sheet using hydrothermal synthesis method, and device therefor is simple, low in cost, produces
Product purity is high, is suitable for large-scale industrial production.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of flower-shaped CuO microballoon has process below and step:
(1) Cu (NO is weighed3)2·3H2O, urea, PEG20000 are dissolved in 80 mL deionized waters；Magnetic agitation at room temperature
30 minutes, it is configured to hydrothermal synthesis presoma reaction solution；
(2) hydrothermal synthesis presoma reaction solution is transferred in inner liner polytetrafluoroethylene stainless steel autoclave, is loaded
Degree is 80%, sealing；12 hours are kept the temperature at a temperature of 120-200 DEG C, room temperature is then cooled to the furnace, obtains reaction product；
(3) the solution centrifuge separation after reaction is obtained into reaction product, reuses distilled water, dehydrated alcohol washs repeatedly；
(4) reaction product after washing is put into the drying box of steady temperature, 80 DEG C, is dried within 24 hours,
It is cooling after the completion of dry；
(5) product after drying is put into clean crucible and is placed in Muffle furnace, 400 DEG C are calcined 3 hours, and CuO is obtained
Black powder saves it in drier with pending analysis detection.
The preparation step of the flower-shaped CuO microballoon includes: step 1: 0.483 g Cu (NO3) 23H2O, 0.36 g urine
Element, 1.784 g PEG20000 are dissolved in 80 mL deionized waters, at room temperature magnetic agitation 30 minutes, before being configured to hydrothermal synthesis
Drive precursor reactant solution；
Step 2: presoma reaction solution made from step 1 is transferred to inner liner polytetrafluoroethylene stainless steel autoclave
In, filling degree is 80%, sealing；
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 180 DEG C, is then cooled down；
Step 4: reactant solution made from step 3 is centrifugated, obtain black precipitate, reuse distilled water,
Dehydrated alcohol washs repeatedly；
Step 5: the product of step 4 is placed in the drying box of steady temperature, 80 DEG C, is dried within 24 hours；
Step 6: product of the step 5 after dry is put into clean crucible and is placed in Muffle furnace, 400 DEG C of calcinings 3 are small
When, CuO black powder is obtained, is saved it in drier with pending analysis detection.
The preparation step of the flower-shaped CuO microballoon includes: that the reaction kettle of step 2 is placed in baking oven in step 3,
12 hours are kept the temperature at a temperature of 120 DEG C, is then cooled down.
The preparation step of the flower-shaped CuO microballoon includes: that the reaction kettle of step 2 is placed in baking oven in step 3,
12 hours are kept the temperature at a temperature of 140 DEG C, is then cooled down.
The preparation step of the flower-shaped CuO microballoon includes: that the reaction kettle of step 2 is placed in baking oven in step 3,
12 hours are kept the temperature at a temperature of 160 DEG C, is then cooled down.
The preparation step of the flower-shaped CuO microballoon includes: step 3) in the reaction kettle of step 2 is placed in baking oven,
12 hours are kept the temperature at a temperature of 200 DEG C, is then cooled down.
Flower-shaped CuO microballoon is put into mortar in formaldehyde gas sensor application and grinds 20 points by a kind of flower-shaped CuO microballoon
Clock；Then deionized water is added, is further continued for grinding 20 minutes, slurry is made；A small amount of slurry is picked with hairbrush, is coated in aluminium oxide
On ceramic substrate, then dries, ceramic substrate is welded on four leg bases, and place it on agingtable under the conditions of 80 DEG C
Aging 48 hours, gas sensor element is made；Using WS-30A air-sensitive tester, the gas sensitization characteristic of sensor is tested i.e.
It can.
The advantages and effects of the present invention are:
(1) present invention is with Cu (NO3)2·3H2O copper source, prepared by hydrothermal synthesis technology assembled by nano strip it is flower-shaped
CuO microballoon has the advantages of cost is relatively low, and controllability is good, material purity height of preparation, advantages of good crystallization, good dispersion, is suitable for greatly
Technical scale metaplasia produces.
(2) flower-shaped CuO microballoon produced by the present invention not only increases the specific surface of material because having unique space structure
Product, while flourishing classification hole path can also be constructed, make material that there is better permeability, the gas as gas sensitive preparation
Sensor PARA FORMALDEHYDE PRILLS(91,95) shows higher sensitivity, good response-recovery characteristics and selectivity and stability, is detecting
It has broad application prospects in terms of toxic and harmful gas in environment.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of product prepared by embodiment 1；
Fig. 2 is the electron scanning micrograph of product prepared by embodiment 1；
Fig. 3 (a) is the electron scanning micrograph of product prepared by embodiment 2, (b) product prepared for embodiment 3
Electron scanning micrograph, (c) for embodiment 4 prepare product electron scanning micrograph, (d) be embodiment 5
The electron scanning micrograph of the product of preparation；
Gas sensor element schematic diagram prepared by Fig. 4 present invention；
Fig. 5 (a) is that gas sensor is bent with temperature change to the sensitivity of 100 ppm formaldehyde gas in embodiment 1
Line chart, (b) for gas sensor at 300 DEG C to the dynamic response curve figure of various concentration formaldehyde gas, (c) be gas sensing
Device PARA FORMALDEHYDE PRILLS(91,95) gas concentration (d) restores 100 ppm differences at 300 DEG C for gas sensor with change of sensitivity curve graph
The selective figure of property gas.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The starting material of preparation method of the present invention is Cu (NO cheap and easy to get3)2·3H2O, urea, PEG20000 pass through
Hydro-thermal reaction, by centrifugation, washing, the processing such as drying and calcining.Prepared flower-shaped CuO microballoon by 100 nm of diameter nanometer
Item assembles, and the diameter of microballoon is 2-6 μm.Flower-shaped CuO microballoon is prepared into gas sensor, because its unique space is tied
Structure, PARA FORMALDEHYDE PRILLS(91,95) show higher sensitivity, good response-recovery characteristics and selectivity.
(1) the flower-shaped CuO method for preparing microsphere, comprising the following steps:
Step 1: by a certain amount of Cu (NO3)2•3H2O, urea, PEG20000 are dissolved in 80 mL deionized waters.At room temperature
Magnetic agitation 30 minutes, it is configured to hydrothermal synthesis presoma reaction solution.
Step 2: presoma reaction solution made from step 1 is transferred to inner liner polytetrafluoroethylene stainless steel autoclave
In, filling degree is 80%, sealing.12 hours are kept the temperature at a temperature of 120-200 DEG C, room temperature is then cooled to the furnace, is reacted
Product.
Step 3: reaction product made from centrifugation step two, and washed repeatedly with distilled water, dehydrated alcohol, it carries out later
It is dried.
Step 4: product of the step 3 after dry is placed in Muffle furnace, and 400 DEG C are calcined 3 hours to get flower-shaped CuO is arrived
Microballoon.
(2) described the step of preparing gas sensor using flower-shaped CuO microballoon:
Step 1: flower-shaped CuO microballoon is put into mortar and is ground 20 minutes.Then deionized water is added, is further continued for grinding
20 minutes, slurry is made.
Step 2: picking a small amount of slurry with hairbrush, is coated on aluminium oxide ceramic substrate, then dries under the conditions of 80 DEG C
It is dry.
Step 3: ceramic substrate is welded on four leg bases, and places it in aging 48 hours on agingtable, and gas is made
Body sensor element.
Step 4: WS-30A air-sensitive tester is used, the gas sensitization characteristic of sensor is tested.Test temperature is 100-
300℃。
Embodiment 1
(1) flower-shaped CuO microballoon is prepared:
Step 1: 0.483 g Cu (NO3)2·3H2O, 0.36 g urea, 1.784 g PEG20000 be dissolved in 80 mL go from
In sub- water, magnetic agitation 30 minutes, are configured to hydrothermal synthesis presoma reaction solution at room temperature.
Step 2: presoma reaction solution made from step 1 is transferred to inner liner polytetrafluoroethylene stainless steel autoclave
In, filling degree is 80%, sealing.
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 180 DEG C, is then cooled down.
Step 4: reactant solution made from step 3 is centrifugated, obtain black precipitate, reuse distilled water,
Dehydrated alcohol washs repeatedly.
Step 5: the product of step 4 is placed in the drying box of steady temperature, 80 DEG C, is dried within 24 hours.
Step 6: product of the step 5 after dry is put into clean crucible and is placed in Muffle furnace, 400 DEG C of calcinings 3 are small
When, CuO black powder is obtained, is saved it in drier with pending analysis detection.
(2) structural characterization of flower-shaped CuO microballoon
Crystalline product structure is characterized using XRD powder diffractometer (XRD, PANalytical X ' Pert Pro).
As shown in Figure 1, diffractive features peak is all very sharp, no any miscellaneous peak occurs, and shows that the sample purity prepared and crystallinity are very high.
Diffraction maximum is complied fully with NO.48-1548 in standard PDF card rod, therefore the sample is monoclinic phase CuO.
Product morphology is characterized using scanning electron microscope (FESEM, ZEISS Ultra Plus).As shown in Fig. 2, institute
Synthetic product is flower type structure, and nano flower pattern is good, diameter distribution is more uniform.The petal of these flowers is by nano strip
Neatly assemble.It will be apparent that a kind of tightly packed, formation of these nano strips by way of self assembly in layer
Radial floriform appearance, to finally evolve into this layered structure.It can be seen that group from the single nano flower of amplification
Diameter at the nanometer rods of these flowers is 100 nm, and colored diameter is 6 μm of 2- or so.This unique layering flower-like structure
There are many holes, gap, may be played an important role to air-sensitive performance is improved.
Embodiment 2
(1) flower-shaped CuO microballoon is prepared:
Step 1: two the same as embodiment 1.
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 120 DEG C, is then cooled down.
Step 4: five, six the same as embodiment 1.
(2) structural characterization of flower-shaped CuO microballoon
Product morphology is characterized using scanning electron microscope.As shown in Fig. 3 (a), product is aggregative by nanometer blocks
Bulk material.
Embodiment 3
(1) flower-shaped CuO microballoon is prepared:
Step 1: two the same as embodiment 1.
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 140 DEG C, is then cooled down.
Step 4: five, six the same as embodiment 1.
(2) structural characterization of flower-shaped CuO microballoon
Product morphology is characterized using scanning electron microscope.As shown in Fig. 3 (b), product is by micron chip and nano strip group
The loose flower-shaped CuO microballoon dressed up.
Embodiment 4
(1) flower-shaped CuO microballoon is prepared:
Step 1: two the same as embodiment 1.
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 160 DEG C, is then cooled down.
Step 4: five, six the same as embodiment 1.
(2) structural characterization of flower-shaped CuO microballoon
Product morphology is characterized using scanning electron microscope.As shown in Fig. 3 (c), product is dredged for what is be assembled by nano strip
The flower-shaped CuO microballoon of pine.
Embodiment 5
(1) flower-shaped CuO microballoon is prepared:
Step 1: two the same as embodiment 1.
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 200 DEG C, is then cooled down.
Step 4: five, six the same as embodiment 1.
(2) structural characterization of flower-shaped CuO microballoon
Product morphology is characterized using scanning electron microscope.As shown in Fig. 3 (d), product is the CuO being assembled by nano strip
Microballoon, sphere diameter increased, and nano strip is assembled closer.
Gas sensor is made with flower-shaped CuO micro-sphere material made from embodiment 1, PARA FORMALDEHYDE PRILLS(91,95) has carried out relevant gas sensing property
It can test:
Flower-shaped CuO microballoon is put into mortar and is ground 20 minutes.Then deionized water is added, is further continued for grinding 20 minutes,
Slurry is made.A small amount of slurry is picked with hairbrush, is coated on aluminium oxide ceramic substrate, is then dried under the conditions of 80 DEG C, it will
Ceramic substrate is welded on four leg bases, and places it in aging 48 hours on agingtable, and gas sensor element is made.Using
WS-30A air-sensitive tester tests the gas sensitization characteristic of sensor.
100 ppm formaldehyde gas sensitivity with shown in temperature change curve graph such as Fig. 5 (a), we can see that
In 100 DEG C to 350 DEG C temperature ranges, sensitivity increases with temperature and is increased, and it is 4.2 that maximum value is reached at 300 DEG C, then with temperature
Degree continues to increase and reduce.Fig. 5 (b) show the response-recovery curve of 10-500 ppm formaldehyde gas, flower-shaped as seen from the figure
CuO microballoon all has quick response-recovery speed to various concentration formaldehyde, shows there is good point to various concentration formaldehyde
Distinguish ability.It can be seen that (Fig. 5 (c)) on from the graph of relation of sensitivity and concentration, sensitivity with the increase of concentration of formaldehyde and
Increase.5 (d) show the sensitivity when operating temperature is 300 DEG C to 100 ppm gas with various, are being tested as seen from the figure
6 kinds of gases in, the sensitivity of flower-shaped CuO microballoon PARA FORMALDEHYDE PRILLS(91,95) is higher than ethyl alcohol, methanol, acetone, toluene, benzene, show preferably
Selectivity.
Claims (7)
1. a kind of preparation method of flower-shaped CuO microballoon, which is characterized in that have process below and step:
Weigh Cu (NO3)2·3H2O, urea, PEG20000 are dissolved in 80 mL deionized waters；Magnetic agitation 30 minutes at room temperature,
It is configured to hydrothermal synthesis presoma reaction solution；
Hydrothermal synthesis presoma reaction solution is transferred in inner liner polytetrafluoroethylene stainless steel autoclave, filling degree is 80%,
Sealing；12 hours are kept the temperature at a temperature of 120-200 DEG C, room temperature is then cooled to the furnace, obtains reaction product；
Solution centrifuge separation after reaction is obtained into reaction product, reuses distilled water, dehydrated alcohol washs repeatedly；
Reaction product after washing is put into the drying box of steady temperature, 80 DEG C, is dried within 24 hours, it is dry to complete
After cool down；
Product after drying is put into clean crucible and is placed in Muffle furnace, 400 DEG C are calcined 3 hours, and CuO black powder is obtained
End saves it in drier with pending analysis detection.
2. a kind of preparation method of flower-shaped CuO microballoon according to claim 1, which is characterized in that the flower-shaped CuO microballoon
Preparation step includes:
Step 1: 0.483 g Cu (NO3)2·3H2O, 0.36 g urea, 1.784 g PEG20000 are dissolved in 80 mL deionized waters
In, magnetic agitation 30 minutes, are configured to hydrothermal synthesis presoma reaction solution at room temperature；
Step 2: presoma reaction solution made from step 1 is transferred in inner liner polytetrafluoroethylene stainless steel autoclave,
Filling degree is 80%, sealing；
Step 3: the reaction kettle of step 2 is placed in baking oven, is kept the temperature 12 hours at a temperature of 180 DEG C, is then cooled down；
Step 4: reactant solution made from step 3 is centrifugated, and obtains black precipitate, reuses distilled water, anhydrous
Ethyl alcohol washs repeatedly；
Step 5: the product of step 4 is placed in the drying box of steady temperature, 80 DEG C, is dried within 24 hours；
Step 6: product of the step 5 after dry being put into clean crucible and is placed in Muffle furnace, and 400 DEG C are calcined 3 hours, are obtained
To CuO black powder, save it in drier with pending analysis detection.
3. a kind of preparation method of flower-shaped CuO microballoon according to claim 2, which is characterized in that the flower-shaped CuO microballoon
Preparation step includes: that the reaction kettle of step 2 is placed in baking oven in step 3, keeps the temperature 12 hours at a temperature of 120 DEG C, then
It is cooling.
4. a kind of preparation method of flower-shaped CuO microballoon according to claim 2, which is characterized in that the flower-shaped CuO microballoon
Preparation step includes: that the reaction kettle of step 2 is placed in baking oven in step 3, keeps the temperature 12 hours at a temperature of 140 DEG C, then
It is cooling.
5. a kind of preparation method of flower-shaped CuO microballoon according to claim 2, which is characterized in that the flower-shaped CuO microballoon
Preparation step includes: that the reaction kettle of step 2 is placed in baking oven in step 3, keeps the temperature 12 hours at a temperature of 160 DEG C, then
It is cooling.
6. a kind of preparation method of flower-shaped CuO microballoon according to claim 2, which is characterized in that the flower-shaped CuO microballoon
Preparation step includes: that the reaction kettle of step 2 is placed in baking oven in step 3, keeps the temperature 12 hours at a temperature of 200 DEG C, then
It is cooling.
7. using a kind of flower-shaped CuO microballoon described in claim 1 in formaldehyde gas sensor application, which is characterized in that will be flower-shaped
CuO microballoon is put into mortar and grinds 20 minutes；Then deionized water is added, is further continued for grinding 20 minutes, slurry is made；Use hairbrush
A small amount of slurry is picked, is coated on aluminium oxide ceramic substrate, is then dried under the conditions of 80 DEG C, ceramic substrate is welded on four feet
On pedestal, and aging 48 hours on agingtable are placed it in, gas sensor element is made；Using WS-30A air-sensitive tester,
Test the gas sensitization characteristic of sensor.
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| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN105174299A (en) * | 2015-08-28 | 2015-12-23 | 云南大学 | Preparation of CuO flakes and application of CuO flakes serving as gas sensitive materials |
| CN105439190A (en) * | 2014-09-28 | 2016-03-30 | 天津工业大学 | Method for preparing pompon-like copper oxide |
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| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN105439190A (en) * | 2014-09-28 | 2016-03-30 | 天津工业大学 | Method for preparing pompon-like copper oxide |
| CN105174299A (en) * | 2015-08-28 | 2015-12-23 | 云南大学 | Preparation of CuO flakes and application of CuO flakes serving as gas sensitive materials |
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