CN107010657A - Anatase TiO with high-energy {001} crystal face selectively eroded2Hierarchical microsphere and preparation method and application thereof - Google Patents
Anatase TiO with high-energy {001} crystal face selectively eroded2Hierarchical microsphere and preparation method and application thereof Download PDFInfo
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- CN107010657A CN107010657A CN201710229823.5A CN201710229823A CN107010657A CN 107010657 A CN107010657 A CN 107010657A CN 201710229823 A CN201710229823 A CN 201710229823A CN 107010657 A CN107010657 A CN 107010657A
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- 239000013078 crystal Substances 0.000 title claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004005 microsphere Substances 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 230000003628 erosive effect Effects 0.000 claims abstract 3
- 230000001105 regulatory effect Effects 0.000 claims abstract 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 40
- 238000012360 testing method Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 3
- 238000003466 welding Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 46
- 238000011160 research Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- 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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- 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
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/30—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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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Pathology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Catalysts (AREA)
Abstract
The invention discloses anatase TiO with high-energy {001} crystal face selectively eroded2Hierarchical microspheres and a preparation method and application thereof. The preparation is completed through one-step hydrothermal reaction, and the method is simple and convenient, has high product yield and is easy for large-scale production. The anatase TiO with high-energy {001} crystal face selectively eroded2Is a microspherical structure with the diameter of 1-5 mu m, and the microsphere is made of anatase TiO selectively eroded by high-energy {001} crystal face2The nano-sheets are assembled, the transverse size of the nano-sheets is 100-500nm, and the degree of erosion of the high-energy {001} crystal faces in the nano-sheets can be simply and conveniently regulated and controlled by the pH value of a reaction system. The TiO can be prepared by adopting a flat plate type thick film gas sensing device process2And coating, welding and aging the graded microsphere material to prepare the semiconductor type gas sensing device. Due to the selective erosion of the high-energy {001} crystal face and the unique graded porous morphology of the material, the device shows enhanced gas-sensitive performance to acetone.
Description
Technical field
The present invention relates to the anatase TiO that a kind of high energy { 001 } crystal face-selective corrodes2It is classified microballoon, more particularly to one
Plant the anatase TiO that high energy { 001 } crystal face-selective corrodes2It is classified microballoon and its preparation method and application.
Background technology
Industry and expanding economy provide great material for the production and living of the mankind and facilitated, but various environment simultaneously
Problem also comes one after another.Vehicle exhaust, plant gas, liquefied gas, natural gas and coal gas etc. is not all the time in prestige
Coerce poisonous, harmful, inflammable, explosion hazard gases effective monitoring and early warning in the health and lives of people, environment has turned into necessary
One of the problem of solution.The appearance of gas sensor provides approach to solve this problem.Passed in resistive memory gas
In terms of sensor research, TiO2Due to having the advantages that with low cost, property stabilization and bio-compatible, have become a kind of extensive
The gas sensitive of research, particularly in terms of automobile oxygen sensor, TiO2Serial gas sensitive is metal oxide materials
Middle most study and the most maturation.But, generally, current TiO2Gas-sensitive nano material still has that sensitivity is low, work
The problems such as making high temperature, response turnaround time length and poor selectivity.
Because gas-sensitive reaction is a kind of surface reaction, therefore the crystal face of nano material exposure is to influence the weight of its gas-sensitive property
Want factor.Due to different crystal faces surface can and Electronic Structure difference, cause its adsorption capacity and surface to gas
React difference very big, SnO has been related to so as to cause in the difference of gas-sensitive property, documents and materials2、In2O3、ZnO、Fe2O3With
WO3Report in terms of gas-sensitive property " crystal face dependence effect ".Such as, research shows, cubic Rutile Type SnO2High energy { 221 }
Crystal face shows the gas-sensitive property being remarkably reinforced relative to { 110 } crystal face to ethanol, has benefited from { 221 } crystal face with higher
Surface energy and surface-active.On the other hand, it is sudden and violent with high energy crystal face (including { 001 }, { 100 }, { 110 } and { 111 } crystal face etc.)
The Anatase TiO of dew2Nanocrystalline material is due to especially noticeable in recent years with higher surface reaction activity.But,
On the whole, the research at present on its application mainly all concentrates on its control synthesis and photocatalysis, lithium ion battery, solar energy
In terms of battery applications, and also compare shortage at present on its application study in terms of air-sensitive detection.Exploitation has special form
Looks and the TiO of crystal face exposure2Nano structural material, not only for " the crystal face dependence effect " of further investigation gas-sensitive property, so that
It is significant in terms of the gas sensing mechanism of abundant metal oxide semiconductor material, it is also actual high sensitivity gas sensor
Construct there is provided a new direction.
The content of the invention
It is an object of the invention to solve the existing TiO exposed with special appearance and crystal face2The system of nano structural material
There is provided the anatase TiO that a kind of high energy { 001 } crystal face-selective corrodes for standby problem2It is classified microballoon and its preparation method and application
Method.
What the present invention was realized in：
The anatase TiO that a kind of high energy { 001 } crystal face-selective corrodes2The preparation method of microballoon, including hydro-thermal method are classified,
It is characterized in that：The 0.025-0.075mol/L titanium tetrafluoride aqueous solution is prepared first, is adjusted with dilute sulfuric acid and sodium hydroxide solution
The pH value for controlling reaction system is 2-4, and it is stand-by that stirring 2-4h obtains reaction precursor liquid；A certain amount of reaction precursor liquid is taken to be added to poly- four
In PVF autoclave to inner bag compactedness be 30~70%, polytetrafluoroethylene (PTFE) autoclave is put into air dry oven
In, reaction temperature is set as 180 DEG C, and soaking time is 3-15h；Question response is finished, after autoclave natural cooling, takes out reaction production
Thing, with deionized water cyclic washing to the aqueous solution in neutrality, is finally put into baking oven by product and 2-10h is dried at 70 DEG C, produce
Final product.
The anatase TiO that high energy { 001 } crystal face-selective as made from above-mentioned preparation method corrodes2Microballoon is classified, its is straight
Footpath is 1-5 μm, the anatase TiO that the microballoon is corroded by high energy { 001 } crystal face-selective2Nanometer sheet assembles, nanometer sheet
Lateral dimension is 100-500nm, the degree that high energy { 001 } crystal face is etched in the nanometer sheet can by reaction system pH value
Simply and easily regulate and control.
The anatase TiO that high energy { 001 } crystal face-selective corrodes2Classification microballoon can be used for making gas sensor
Part, is fabricated to the process of gas sensor, is mainly cleaned by substrate, gas sensitive coating and the step of device aging three are constituted.Its
The cleaning of middle substrate is exactly that the plate ceramic substrate for being coated with sensing electrode and heating electrode is sequentially placed into and is marked with ethanol, acetone
In the beaker of deionized water, remove the impurity on surface by ultrasonic procedure, it is to be cleaned it is clean after, dry stand-by.Gas sensitive
Coating is exactly the anatase TiO for corroding high energy { 001 } crystal face-selective2It is classified microballoon powder ultrasonic disperse in deionized water
Slurry is formed, a certain amount of slurry is then coated with to plate ceramic substrate.After after air-sensitive slurry drying, placed at 450 DEG C
24h formation thick film gas sensors.The thick film gas sensor carries out air-sensitive test using static testing.
The solution have the advantages that：First, the anatase TiO that this high energy { 001 } crystal face-selective corrodes2Classification is micro-
The preparation method of ball material is simple and convenient, it is only necessary to first adds predecessor and further walks hydro-thermal reaction, without subsequent treatment；Its
Two, the micro-sphere material that above-mentioned preparation method is obtained is the anatase TiO corroded by high energy { 001 } crystal face-selective2Nanometer sheet group
Dress is formed, with good graded porous structure, and the degree that is etched of high energy { 001 } crystal face can by reaction system pH
Value simply and easily regulates and controls；Third, the anatase TiO corroded by this high energy { 001 } crystal face-selective2It is classified what microballoon made
Gas sensor can be applied to the detection of acetone gas, and it is simple that gas sensing device makes the flat thick-film technique used
Practicality, beneficial to actual large-scale production；Fourth, because the selectivity of high energy { 001 } crystal face corrodes and the unique classification of material
Porous pattern, this TiO2Micro-sphere material shows the enhanced air-sensitive performance of structure to acetone, has opened up resistive memory
The Research Thinking of gas sensor.
Brief description of the drawings
The anatase TiO that Fig. 1 corrodes for prepared high energy { 001 } crystal face-selective2The X-ray of classification micro-sphere material is spread out
Penetrate curve.
The anatase TiO that Fig. 2 corrodes for prepared high energy { 001 } crystal face-selective2It is classified the Flied emission of micro-sphere material
SEM pattern photo.
Fig. 3 is the field emission scanning electron microscope pattern photo of prepared contrast material under different pH condition.
The anatase TiO that Fig. 4 corrodes for prepared high energy { 001 } crystal face-selective2The transmitted electron for being classified microballoon shows
Micro mirror pattern photo.
Fig. 5 is the anatase TiO corroded by high energy { 001 } crystal face-selective2The gas sensing that classification micro-sphere material is made
The gas-sensitive property test device and test circuit of device.
Fig. 6 is the test result of different materials gas-sensitive property.
In Figure 5,1. reaction chambers, 2. air inlet needle tubings, 3. computers, 4. sensors, 5 fans.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing, embodiment and had the advantage that, it is intended to help reader more
The essence of the present invention is understood well, but implementation that can not be to the present invention and protection domain constitute any limit.
The anatase TiO that high energy { 001 } crystal face-selective corrodes2The preparation process for being classified microballoon is to complete according to the following steps
's：The 0.025-0.075mol/L titanium tetrafluoride aqueous solution is prepared first, and the dilute sulfuric acid and sodium hydroxide for being 0.01M with concentration are molten
Liquid regulates and controls its pH value for 2-4, and it is stand-by that stirring 2-4h obtains reaction precursor liquid；A certain amount of reaction precursor liquid is taken to be added to polytetrafluoroethyl-ne
In alkene autoclave to inner bag compactedness be 30~70%, autoclave is put into air dry oven, set reaction temperature as
180 DEG C, soaking time is 3-15h；Question response is finished, after autoclave natural cooling, takes out reaction product, with deionized water repeatedly
Product, in neutrality, is finally put into baking oven and 2-10h is dried at 70 DEG C, produce final product by washing to the aqueous solution.
The anatase TiO that obtained high energy { 001 } crystal face-selective corrodes2For microspheroidal structure, its a diameter of 1-5 μm,
The anatase TiO that the microballoon is corroded by high energy { 001 } crystal face-selective2Nanometer sheet assembles, and nanometer sheet lateral dimension is
The degree that high energy { 001 } crystal face is etched in 100-500nm, the nanometer sheet can by reaction system pH value simply and easily
Regulation and control.
The anatase TiO that high energy { 001 } crystal face-selective corrodes2Classification microballoon its be fabricated to the mistake of gas sensor
Journey, is mainly cleaned, gas sensitive coating and the step of device aging three are constituted by substrate.Wherein substrate cleaning is exactly to be coated with passing
The plate ceramic substrate of sense electrode and heating electrode, which is sequentially placed into, to be marked with the beaker of ethanol, acetone and deionized water, is passed through
Ultrasonic procedure removes the impurity on surface, it is to be cleaned it is clean after, dry stand-by.Gas sensitive coating is exactly by high energy { 001 } crystal face
The anatase TiO that selectivity corrodes2Microballoon powder ultrasonic disperse formation slurry in deionized water is classified, is then coated with a certain amount of
Slurry is on plate ceramic substrate.After after air-sensitive slurry drying, placement 24h forms thick film gas sensor at 450 DEG C.Institute
State thick film gas sensor and air-sensitive test is carried out using static testing.
Fig. 1 is the anatase TiO corroded high energy { 001 } crystal face-selective2It is classified microballoon and uses X-ray diffraction (XRD)
The result that instrument is characterized.Anatase TiO will be obvious by it2Diffraction maximum (JCPDS card No.21-1272).
Fig. 2 is the anatase TiO to prepared high energy { 001 } crystal face-selective erosion2Classification microballoon is swept with Flied emission
Retouch the photo for shooting and obtaining after electron microscope observation.Should be apparent that product is microspheroidal structure, microsphere diameter distribution
In 1-5 μm, the anatase TiO that microsphere surface is corroded by high energy { 001 } crystal face-selective2Nanometer sheet assembles, and nanometer sheet is horizontal
It is 100-500nm to size.
Fig. 3 is to reacting obtained TiO under different pH condition2It is classified the field emission scanning electron microscope pattern of microballoon
Photo.Fig. 3 a and 3b are the TiO that high energy { 001 } crystal face is not etched2Classification microballoon (is designated as Intact-TiO2), it is in pH value
For what is prepared under conditions of 4.Fig. 3 c and 3d are the TiO that high energy { 001 } crystal face is somewhat corroded2Classification microballoon (is designated as
Slightly-etched-TiO2), it is prepared under conditions of pH value is 3.The above results illustrate the entirety of microballoon
Pattern does not have significant change.But the degree that high energy { 001 } crystal face is etched in the nanometer sheet of composition microballoon can be by reactant
The pH value of system simply and easily regulates and controls.
Fig. 4 is the anatase TiO to prepared high energy { 001 } crystal face-selective erosion2It is classified microballoon transmitted electron
Obtained photo is shot after microscopic, Fig. 4 a and 4b should be apparent that microballoon is strictly to be selected by high energy { 001 } crystal face
The anatase TiO that selecting property corrodes2Nanometer sheet assembles.Being characterized by high-resolution lattice fringe and selection electronic diffraction can be true
Fixed this nanometer sheet is mono-crystalline structures, and has Anatase TiO really2The exposure of high energy { 001 } crystal face.
Fig. 5 left sides are the gas-sensitive property test devices of gas sensor, and measuring circuit is also as shown in Fig. 5 the right.During test
Sensor 4 is put into reaction chamber 1, gas injects reaction chamber 1 by air inlet needle tubing 2, and gas is uniformly distributed by fan 5.
The operating temperature of device by through Ni-Cr alloy heater strip heated current control, the response of gas sensor 4 is basis
The change of its resistance under different atmosphere is determined, and data are collected with LabVIEW softwares.
The research of air-sensitive detection application is carried out to the gas sensing device after aging, acetone is chosen as object gas,
Test is carried out using Fig. 5 gas-sensitive property test device, and the sensitivity definition of gas sensitive device is the aerial resistance of device
(Ra) with resistance (R under test gasg) ratio, i.e. Ra/Rg, it is to be measured that response turnaround time is defined as device exposure/disengaging
During gas, required time when its resistance reaches 90%.
Fig. 6 is the anatase TiO that above-mentioned high energy { 001 } crystal face-selective corrodes using acetone as object gas2It is classified microballoon
(it is designated as Etched-TiO2) air-sensitive performance.Can significantly it find out compared to contrast material Intact-TiO2And Slightly-
etched-TiO2(Intact-TiO2And Slightly-etched-TiO2Pattern is shown in that Fig. 3 field emission scanning electron microscope shines
Piece), Etched-TiO2Optimal performance is shown, has benefited from its unique graded porous structure and high energy { 001 } is brilliant
The selectivity in face corrodes.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
In various modifications and improvement that case is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (5)
1. the anatase TiO that a kind of high energy { 001 } crystal face-selective corrodes2The preparation method of microballoon, including hydro-thermal method are classified, its
It is characterised by：The 0.025-0.075mol/L titanium tetrafluoride aqueous solution is prepared first, is regulated and controled with dilute sulfuric acid and sodium hydroxide solution
The pH value of reaction system is 2-4, and it is stand-by that stirring 2-4h obtains reaction precursor liquid；A certain amount of reaction precursor liquid is taken to be added to polytetrafluoro
In ethylene high pressure reactor to inner bag compactedness be 30~70%, polytetrafluoroethylene (PTFE) autoclave is put into air dry oven
In, reaction temperature is set as 180 DEG C, and soaking time is 3-15h；Question response is finished, after autoclave natural cooling, takes out reaction production
Thing, with deionized water cyclic washing to the aqueous solution in neutrality, is finally put into baking oven by product and 2-10h is dried at 70 DEG C, produce
Final product.
2. the anatase TiO that high energy { 001 } crystal face-selective that preparation method according to claim 1 is obtained corrodes2Classification is micro-
Ball, it is characterised in that：The anatase TiO that high energy { 001 } crystal face-selective corrodes2For microspheroidal structure, its a diameter of 1-5
μm, the anatase TiO corroded by high energy { 001 } crystal face-selective2Nanometer sheet assembles；High energy { 001 } crystal face selection
Property corrode anatase TiO2Nanometer sheet lateral dimension is 100-500nm, the anatase that high energy { 001 } crystal face-selective corrodes
TiO2The degree that high energy { 001 } crystal face is etched in nanometer sheet can simply and easily be regulated and controled by the pH value of reaction system.
3. the anatase TiO that high energy { 001 } crystal face-selective described in claim 2 corrodes2Microballoon is classified in gas sensing device
The application in field.
4. application according to claim 3, it is characterised in that：The construction method of gas sensing device is main clear by substrate
Wash, gas sensitive coating and the step of device aging three are constituted；Wherein substrate cleaning is exactly to be coated with sensing electrode and heating electricity
The plate ceramic substrate of pole, which is sequentially placed into, to be marked with the beaker of ethanol, acetone and deionized water, and table is removed by ultrasonic procedure
The impurity in face, it is to be cleaned it is clean after, dry stand-by；Gas sensitive coating is exactly by the sharp of high energy { 001 } crystal face-selective erosion
Titanium ore TiO2Microballoon powder ultrasonic disperse formation slurry in deionized water is classified, a certain amount of slurry is then coated with to plate pottery
On ceramic chip；After after air-sensitive slurry drying, placement 24h forms thick film gas sensor at 450 DEG C；The thick film gas sensing
Device carries out air-sensitive test using static testing.
5. application according to claim 4, it is characterised in that：The object gas for carrying out air-sensitive test is acetone.
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