CN110104678A - To the cobalt titanate gas sensitive and preparation method thereof of low-concentration ethanol high sensitivity - Google Patents
To the cobalt titanate gas sensitive and preparation method thereof of low-concentration ethanol high sensitivity Download PDFInfo
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- CN110104678A CN110104678A CN201910406352.XA CN201910406352A CN110104678A CN 110104678 A CN110104678 A CN 110104678A CN 201910406352 A CN201910406352 A CN 201910406352A CN 110104678 A CN110104678 A CN 110104678A
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- concentration ethanol
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 230000035945 sensitivity Effects 0.000 title claims abstract description 43
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229960004756 ethanol Drugs 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000005352 clarification Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- 238000009825 accumulation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 abstract description 11
- 235000019441 ethanol Nutrition 0.000 description 30
- 238000000034 method Methods 0.000 description 13
- 238000003795 desorption Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910019096 CoTiO3 Inorganic materials 0.000 description 1
- 241000627951 Osteobrama cotio Species 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 206010036067 polydipsia Diseases 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer 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
- C01G23/003—Titanates
-
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
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- 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
- C01P2006/14—Pore volume
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- 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
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- General Health & Medical Sciences (AREA)
- Immunology (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Biochemistry (AREA)
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- General Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Pathology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The cobalt titanate gas sensitive and preparation method thereof of a kind of pair of low-concentration ethanol high sensitivity, 25~100nm of partial size of gas sensitive, the three-dimensional structure that powder accumulation is constituted have mesoporous, mesoporous 0.1~0.3cm of average pore size 30~40nm, Kong Rong3/ g, 5~21m of specific surface area2/g；The preparation method comprises the following steps: (1) using dehydrated alcohol as solvent, or using the mixed liquor of ethylene glycol and dehydrated alcohol as solvent；(2) butyl titanate and cobalt nitrate are added in solvent, are stirred to form red clarification mixed solution；(3) 150~220 DEG C of progress solvent thermal reactions, are centrifugated out solid phase；(4) 600~750 DEG C of roastings after drying.For product prepared by the present invention to the high sensitivity of low-concentration ethanol gas, the response time is short；Preparation process is simple, at low cost, is suitble to promote and apply.
Description
Technical field
The invention belongs to Metal oxide semiconductor gas-sensitiveness material technical fields, and in particular to a kind of pair of low-concentration ethanol height
Cobalt titanate gas sensitive of sensitivity and preparation method thereof.
Background technique
With the improvement of people's life quality, health and safety problem is particularly important；Ethyl alcohol is the main of various wine
Ingredient, and there is combustibility, chance open fire, high temperature can cause combustion explosion, and excessive drinking, drunk driving and the leakage of ethyl alcohol can be brought
Great health and safety hidden danger；Cobalt titanate belongs to P-type semiconductor oxide, and chemical stability is good, inexpensive, is widely used in
The detection of alcohol gas；However, response recovery time narrow to poor sensitivity, the operating temperature range of low-concentration ethanol gas compared with
The big resistance for becoming it in practical applications such as long；Due to sensor sensitivity dependent on sensitive material porosity, have
The factors such as surface area are imitated, therefore the important research that its sensitivity is gas sensitive is improved by the porosity of raising material
Direction.If the sensitive material of gas sensor is made the structure of nanoporous, the height of original nano material is not only remained
The advantages that specific surface area and more active site, also has flourishing pore structure, not only gas molecule is promoted quickly to expand in hole
It dissipates, effectively improves the mass-transfer performance of material, shorten the response-recovery time, and provide more quality under test gas
The inlet of transmission space, object gas increases, and the sensitivity of material improves.
The preparation method of traditional cobalt titanate gas sensitive mainly includes magnetron sputtering method, sol-gel method, hydro-thermal method etc.,
These methods there are energy consumptions it is high, time-consuming, and the prices of raw materials are expensive the disadvantages of, and the cobalt titanate gas sensitive sensitivity prepared is not
Enough height, operating temperature range need further expansion；For the sensitivity for improving cobalt titanate gas sensitive, researcher has done a large amount of works
Make, such as ion doping, with other metal oxides it is compound, exploitation new material；And cobalt titanate is doped or by itself and its
Its substance is compound, so that preparation process complicates, and technological parameter is more uncontrollable；Fundamentally to solve current cobalt titanate
Poor sensitivity present in gas sensitive responds the problems such as recovery is not fast enough and operating temperature range is narrow, needs to be strengthened to novel
The developmental research of gas sensitive.
Chinese patent CN201610583835.3 discloses a kind of New Co TiO3The preparation method and application of gas sensitive,
For this method using cabaltous nitrate hexahydrate and tetra-n-butyl titanate as initial feed, ethylene glycol monomethyl ether is solvent, and citric acid is complexing agent,
CoTiO has been made using sol-gel method3Gas sensitive；This method preparation process is complicated, and obtained colloidal sol need to be by for a long time
It stands, redrying and secondary clacining processing, energy consumption is high, and time-consuming, pollution environment is easy in preparation process, and obtained
CoTiO3Gas sensitive is longer to the response time of alcohol gas, needs 15s；Thus, preparing with simple method has height
Sensitivity, quick response and the wider gas sensitive of operating temperature range become the key of research.
Summary of the invention
The purpose of the present invention is intended to provide the cobalt titanate gas sensitive and its preparation of a kind of pair of low-concentration ethanol high sensitivity
Method improves the ingredient and proportion of solvent, simplifies preparation process, and pore structure prosperity is made, and specific surface area effective rate of utilization is high
Gas sensitive.
Cobalt titanate gas sensitive to low-concentration ethanol high sensitivity of the invention is cobalt titanate nanocrystalline powder, partial size 25
~100nm, the three-dimensional structure that the accumulation of cobalt titanate nanocrystalline powder is constituted have mesoporous, mesoporous 30~40nm of average pore size, hole
Hold in 0.1~0.3cm3Between/g, 5~21m of specific surface area2/g。
Above-mentioned is mesoporous including big mesoporous, intermediary hole and small mesoporous, wherein big mesoporous 100~200nm of aperture, intermediary hole
20~100nm of aperture, small mesoporous 2~10nm of aperture.
The preparation method of cobalt titanate gas sensitive to low-concentration ethanol high sensitivity of the invention sequentially includes the following steps:
(1) using dehydrated alcohol as solvent, or using the mixed liquor of ethylene glycol and dehydrated alcohol as solvent；Second in solvent
Volume ratio≤2 of glycol and dehydrated alcohol；
(2) butyl titanate and cobalt nitrate are added sequentially in solvent, are stirred to form red clarification mixed solution；
Wherein the molar ratio of butyl titanate and cobalt nitrate is 1:1, the molar ratio of butyl titanate and dehydrated alcohol be 1:(65~
195)；
(3) red clarification mixed solution is placed in reaction kettle, is heated to 150~220 DEG C of progress solvent thermal reactions, reacts
Time 15~for 24 hours, room temperature is then naturally cooled to, the material after reaction is centrifugated out sediment solid phase；
(4) 600~750 DEG C of 1.5~3h of roasting after the washed drying of sediment solid phase, will be heated to, be made to low concentration
The cobalt titanate gas sensitive of ethyl alcohol high sensitivity.
In above-mentioned step (2), being stirred is to carry out at room temperature.
In above-mentioned step (2), water is added for promoting hydrolysis condensation reaction, the dosage of water to red clarification mixed solution
≤2mL。
In above-mentioned step (3), solvent thermal reaction is to carry out in confined conditions.
In above-mentioned step (4), roasting is carried out in air atmosphere.
In above-mentioned step (4), washing is washed using dehydrated alcohol.
In above-mentioned step (4), drying temperature is 50~100 DEG C.
The invention has the following beneficial effects:
1, flourishing to the pore structure of the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity, it is transported with gas diffusion
It is easy to carry out, the advantages that specific surface area effective rate of utilization is high, is applied to gas sensor to the sensitive of low-concentration ethanol gas
Degree is high, and the response time is short；
2, preparation process is simple to operation, low in cost, equipment investment is few, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is the scanning electron microscope of the cobalt titanate gas sensitive to low-concentration ethanol high sensitivity in the embodiment of the present invention 3
Figure；In figure, (a) is low power, (b) is high power；
Fig. 2 is that hole is desorbed in the BJH of the cobalt titanate gas sensitive to low-concentration ethanol high sensitivity in the embodiment of the present invention 3
Diameter distribution curve and absorption/desorption isotherm figure；
Fig. 3 is the cobalt titanate gas sensitive to low-concentration ethanol high sensitivity in the embodiment of the present invention 3 in different temperatures
Under to the dynamic response curve figure of 20ppm ethyl alcohol；In figure, A is response initial value, and B is to restore initial value；
Fig. 4 is the cobalt titanate gas sensitive to low-concentration ethanol high sensitivity in the embodiment of the present invention 3 in different temperatures
Under to the sensitivity curve figure of 20ppm ethyl alcohol.
Specific embodiment
Butyl titanate, cobalt nitrate, ethylene glycol and the dehydrated alcohol used in the embodiment of the present invention is the commercially available pure examination of analysis
Agent.
The water used in the embodiment of the present invention is deionized water.
It is using centrifuge separation that solid phase is isolated in the embodiment of the present invention.
In the embodiment of the present invention to sediment solid phase washing be using dehydrated alcohol wash twice it is above.
Drying temperature is 50~100 DEG C in the embodiment of the present invention.
Roasting uses Muffle furnace in the embodiment of the present invention.
Solvent thermal reaction uses the reaction kettle of inner liner polytetrafluoroethylene in the embodiment of the present invention.
The scanning electron microscope model Hitachi SU8010 field emission scanning electron microscope used in the embodiment of the present invention.
The equipment that the detection of central hole structure of the embodiment of the present invention uses is V-Sorb 2800P specific surface area and Porosimetry.
The equipment that air-sensitive performance detection uses in the embodiment of the present invention is WS-60A Testing system of gas-sensor built.
Using static volumetric method measurement cobalt titanate heater-type gas sensor to the sensitivity of alcohol gas in the embodiment of the present invention
Characteristic, the sensitivity definition of gas sensor element are S=Rg/Ra, wherein RaAnd RgIt is that gas sensor is aerial respectively
Resistance value and the resistance value in object gas；Response time is defined as the response after test gas is injected and reaches final
Time needed for the 80% of equilibrium valve.
Embodiment 1
Using the mixed liquor of ethylene glycol and 66mL dehydrated alcohol as solvent；The volume ratio of ethylene glycol and dehydrated alcohol in solvent
=0.1；
Butyl titanate and cobalt nitrate are added sequentially in solvent, at room temperature, be stirred to be formed it is red clear
Clear mixed solution；Water is added for promoting hydrolysis condensation reaction, the dosage 1.5mL of water to red clarification mixed solution；Wherein titanium
The molar ratio of sour four butyl esters and cobalt nitrate is 1:1, and the molar ratio of butyl titanate and dehydrated alcohol is 1:65；
Red clarification mixed solution is placed in reaction kettle, is heated to 160 DEG C of progress solvent thermal reactions in confined conditions,
Reaction time 18h, then naturally cools to room temperature, and the material after reaction is centrifugated out sediment solid phase；
After sediment solid phase is washed and dried using dehydrated alcohol, 600 DEG C of roastings are heated in air atmosphere
The cobalt titanate gas sensitive to low-concentration ethanol high sensitivity is made in 3h；
It is cobalt titanate nanocrystalline powder to the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity, 25~100nm of partial size,
The three-dimensional structure that the accumulation of cobalt titanate nanocrystalline powder is constituted has mesoporous, mesoporous average pore size 34.51nm, Kong Rong 0.14cm3/
G, specific surface area 6.2m2/g；It is mesoporous including big mesoporous, intermediary hole and small mesoporous, wherein big mesoporous 100~200nm of aperture, in
Mesoporous 20~100nm of aperture, small mesoporous 2~10nm of aperture.
Embodiment 2
With embodiment 1, difference is method:
(1) using 100mL dehydrated alcohol as solvent；
(2) water is not added to red clarification mixed solution；The molar ratio of butyl titanate and dehydrated alcohol is 1:85；
(3) 170 DEG C of progress solvent thermal reactions, reaction time 16h；
(4) 650 DEG C of roasting 2h；
(5) average pore size 38.43nm, Kong Rong mesoporous to the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity
0.3cm3/ g, specific surface area 7.4m2/g。
Embodiment 3
With embodiment 1, difference is method:
(1) using the mixed liquor of ethylene glycol and 48mL dehydrated alcohol as solvent；The body of ethylene glycol and dehydrated alcohol in solvent
Product ratio=0.5；
(2) water 0.5mL is added to red clarification mixed solution；The molar ratio of butyl titanate and dehydrated alcohol is 1:110；
(3) 200 DEG C of progress solvent thermal reactions, reaction time 18h；
(4) 700 DEG C of roasting 2h；
(5) to the cobalt titanate gas sensitive electron-microscope scanning result of low-concentration ethanol high sensitivity as shown in Figure 1, from Fig. 1 (a)
In as it can be seen that powder is in irregular shape, by Fig. 1 (b) as it can be seen that the three-dimensional structure that constitutes of powder accumulation is with multiple dimensioned meso-hole structure,
Big mesopore diameter is 100~200nm；Crystal grain is based on near-spherical, having a size of 25~100nm, there are also seldom take measurements 150~
Near-spherical particle and draw ratio between 300nm are 2~4 and vermiform particle interconnected, and particle packing is more loose, shape
The meso-hole structure for being 2~10nm and 20~100nm at pore diameter；
Pore size distribution curve and absorption/desorption isotherm figure is desorbed as shown in Fig. 2, the specific surface area that BET is calculated in BJH
For 8.7m2/g；Aperture integrated distribution is near 2.2nm and 54nm on BJH desorption pore size distribution curve, and average pore size is
31.26nm Kong Rongwei 0.27cm3/ g shows that the product is mesoporous material；Absorption/desorption isotherm belongs to III type thermoisopleth, and
With H3 type hysteresis loop, show that there are the mesoporous of slit-shaped；Absorption/desorption isotherm hysteresis loop is from lower pressure spot (P/P0
=0.22) it begins to be formed, arrives higher pressure spot (P/P0=0.957) adsorbance is significantly raised, illustrates the product except mesoporous
Outside, the macropore of 100nm is also greater than containing a certain number of sizes；
To the dynamic response curve of 20ppm ethyl alcohol as shown in figure 3, can by figure at being 260~500 DEG C in operating temperature range
See, obtained cobalt titanate gas sensor is to the sensitivity with higher of low-concentration ethanol gas, and in the operating temperature model
In enclosing, response time only 7s；
To the sensitivity test result of 20ppm ethyl alcohol as shown in figure 4, by scheming at being 260~500 DEG C in operating temperature range
As it can be seen that the sensitivity presentation of made gas sensor first increases the trend reduced afterwards, in operating temperature with the raising of operating temperature
Sensitivity reaches peak when being 370 DEG C, is 18.5.
Embodiment 4
With embodiment 1, difference is method:
(1) using the mixed liquor of ethylene glycol and 90mL dehydrated alcohol as solvent；The body of ethylene glycol and dehydrated alcohol in solvent
Product ratio=0.72；
(2) water 0.8mL is added to red clarification mixed solution；The molar ratio of butyl titanate and dehydrated alcohol is 1:130；
(3) 180 DEG C of progress solvent thermal reactions, the reaction time is for 24 hours；
(4) 650 DEG C of roasting 2.5h；
(5) average pore size 37.26nm, Kong Rong mesoporous to the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity
0.26cm3/ g, specific surface area 11.5m2/g。
Embodiment 5
With embodiment 1, difference is method:
(1) using the mixed liquor of ethylene glycol and 78mL dehydrated alcohol as solvent；The body of ethylene glycol and dehydrated alcohol in solvent
Product ratio=1；
(2) water 1.4mL is added to red clarification mixed solution；The molar ratio of butyl titanate and dehydrated alcohol is 1:155；
(3) 200 DEG C of progress solvent thermal reactions, reaction time 20h；
(4) 750 DEG C of roasting 1.5h；
(5) average pore size 35.15nm, Kong Rong mesoporous to the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity
0.19cm3/ g, specific surface area 16.4m2/g。
Embodiment 6
With embodiment 1, difference is method:
(1) using the mixed liquor of ethylene glycol and 55mL dehydrated alcohol as solvent；The body of ethylene glycol and dehydrated alcohol in solvent
Product ratio=2；
(2) water 2mL is added to red clarification mixed solution；The molar ratio of butyl titanate and dehydrated alcohol is 1:195；
(3) 220 DEG C of progress solvent thermal reactions, reaction time 22h；
(4) 700 DEG C of roasting 2.5h；
(5) average pore size 38.37nm, Kong Rong mesoporous to the cobalt titanate gas sensitive of low-concentration ethanol high sensitivity
0.22cm3/ g, specific surface area 20.3m2/g。
Claims (7)
1. the cobalt titanate gas sensitive of a kind of pair of low-concentration ethanol high sensitivity is cobalt titanate nanocrystalline powder, it is characterised in that
25~100nm of partial size, the three-dimensional structure that the accumulation of cobalt titanate nanocrystalline powder is constituted have it is mesoporous, mesoporous average pore size 30~
40nm, Kong Rong are in 0.1~0.3cm3Between/g, 5~21m of specific surface area2/g。
2. the cobalt titanate gas sensitive according to claim 1 to low-concentration ethanol high sensitivity, it is characterised in that described
It is mesoporous include big mesoporous, intermediary hole and small mesoporous, wherein big mesoporous 100~200nm of aperture, the aperture 20 of intermediary hole~
100nm, small mesoporous 2~10nm of aperture.
3. a kind of preparation method of the cobalt titanate gas sensitive described in claim 1 to low-concentration ethanol high sensitivity, special
Sign is to sequentially include the following steps:
(1) using dehydrated alcohol as solvent, or using the mixed liquor of ethylene glycol and dehydrated alcohol as solvent；Ethylene glycol in solvent
With volume ratio≤2 of dehydrated alcohol；
(2) butyl titanate and cobalt nitrate are added sequentially in solvent, are stirred to form red clarification mixed solution；Wherein
The molar ratio of butyl titanate and cobalt nitrate is 1:1, and the molar ratio of butyl titanate and dehydrated alcohol is 1:(65~195)；
(3) red clarification mixed solution is placed in reaction kettle, is heated to 150~220 DEG C of progress solvent thermal reactions, reaction time
15~for 24 hours, room temperature is then naturally cooled to, the material after reaction is centrifugated out sediment solid phase；
(4) 600~750 DEG C of 1.5~3h of roasting after the washed drying of sediment solid phase, will be heated to, be made to low-concentration ethanol
Highly sensitive cobalt titanate gas sensitive.
4. the preparation method of the cobalt titanate gas sensitive according to claim 3 to low-concentration ethanol high sensitivity, special
Sign is in step (2) that being stirred is to carry out at room temperature.
5. the preparation method of the cobalt titanate gas sensitive according to claim 3 to low-concentration ethanol high sensitivity, special
Sign is in step (2), and water is added for promoting hydrolysis condensation reaction, dosage≤2mL of water to red clarification mixed solution.
6. the preparation method of the cobalt titanate gas sensitive according to claim 3 to low-concentration ethanol high sensitivity, special
Sign is in step (4) that roasting is carried out in air atmosphere.
7. the preparation method of the cobalt titanate gas sensitive according to claim 3 to low-concentration ethanol high sensitivity, special
Sign is in step (4) that washing is washed using dehydrated alcohol.
Priority Applications (1)
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| CN113238005A (en) * | 2021-05-12 | 2021-08-10 | 陕西科技大学 | N/CoTiO with alcohol-sensitive aldehyde-sensitive dual functions3@g-C3N4Composite material and preparation method and application thereof |
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| CN113238005B (en) * | 2021-05-12 | 2024-01-23 | 深圳万知达科技有限公司 | N/CoTiO with alcohol-sensitive aldehyde-sensitive dual functions 3 @g-C 3 N 4 Composite material, preparation method and application thereof |
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