CN106066351B - A kind of intersection cobaltosic oxide nano chip arrays, gas sensor comprising the array and application thereof - Google Patents
A kind of intersection cobaltosic oxide nano chip arrays, gas sensor comprising the array and application thereof Download PDFInfo
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- CN106066351B CN106066351B CN201610362040.XA CN201610362040A CN106066351B CN 106066351 B CN106066351 B CN 106066351B CN 201610362040 A CN201610362040 A CN 201610362040A CN 106066351 B CN106066351 B CN 106066351B
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- cobaltosic oxide
- oxide nano
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- acetone
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 400
- 238000003491 array Methods 0.000 title claims abstract description 189
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 169
- 239000000758 substrate Substances 0.000 claims abstract description 101
- 230000035945 sensitivity Effects 0.000 claims abstract description 78
- 238000012360 testing method Methods 0.000 claims abstract description 77
- 238000001514 detection method Methods 0.000 claims abstract description 72
- 230000008859 change Effects 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003319 supportive effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 77
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 description 28
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- 230000000052 comparative effect Effects 0.000 description 25
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- 230000003647 oxidation Effects 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 229910017052 cobalt Inorganic materials 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- -1 nanometer sheet Substances 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000012456 homogeneous solution Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 9
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- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000000241 respiratory effect Effects 0.000 description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 235000014364 Trapa natans Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
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- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 206010016766 flatulence Diseases 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Classifications
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- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a kind of intersection cobaltosic oxide nano chip arrays, the gas sensor comprising the array and application thereof.It is intersected between each nanometer sheet in this special intersection cobaltosic oxide nano chip arrays across nanometer sheet is meso-hole structure, is 16.5 in the sensitivity highest of 111 DEG C or so selective enumeration method acetone.Intersection cobaltosic oxide nano chip arrays of the invention overcome traditional cobaltosic oxide nano piece can not be directly the problem of generating array in the insulating substrate only to play a supportive role, production cost is low, and high-efficient, operating process is simply controllable.The intersection cobaltosic oxide nano chip arrays, with Open architecture, biggish specific surface area and electron mobility, quick adsorption and disengaging of more spaces in favor of gas molecule can be provided, significantly improve the air-sensitive performance of material, with good stability, it surveys within every 3 days in 60 days and once carries out 20 tests altogether, 20 test performance change rates are only ± 8%, are highly suitable for sensor, acetone detection, medical detection.
Description
Technical field
The invention belongs to sensor fields, and in particular to a kind of intersection cobaltosic oxide nano chip arrays include the battle array
Gas sensor of column and application thereof.
Background technique
With the promotion of Chinese society economic level and living standard and the increase of life and work pressure, inferior health
Crowd is more and more, and the vulnerable groups of various diseases start extensiveization rejuvenation.In the gas of characteristics of contaminated respiratory droplets, in addition to nitrogen, oxygen and
It also include that other are permitted multiple compounds, the contents level of these compounds is judge physical condition one except carbon dioxide
A important indicator.For example, content of acetone is higher in exhaled gas, then mean there is great risk to suffer from diabetes；And if exhaling
Content of nitric oxide is higher than normal level in gas out, then is likely to asthma.Just because of this, the breathing of non-intrusion type
Analysis instrument has very big development potentiality in medical diagnosis and diseases monitoring field.Various respiratory analyzer has been developed at present
Device is used for medical diagnosis, but is analyzed in exhaled gas using mass spectrometric analysis method or laser mostly in these analysis instruments
Specific compound, analyst coverage very little, thus diagnose different diseases, it is necessary to use different equipment.
And semiconductive gas sensor meets that cost is small, low energy consumption, relying only on exhaled gas can be achieved with monitoring, analysis
Type is more, timely and easy to operate, to a series of indexs of human zero damage.And the volume of semiconductor-type gas sensor can
To be made sufficiently small, it can come into huge numbers of families as sphygmomanometer completely, extremely be suitable for preparing to meet the daily household of people and exhale
Diagnostic device is inhaled, our health status of real-time dynamic monitoring realizes the early detection and early intervention to disease.If this
A little physiological signal sensors and mobile communication, cloud computing and wearable device etc. combine, we can use " revolution " word completely
To describe its change to health of people life and medical market.
Metal-oxide semiconductor (MOS) gas sensor receives largely because of its excellent performance with due to being widely applied field
Concern.For the material for functioning as gas sensor, nano material is due to skin effect, small-size effect, quantum size
The characteristics such as effect and be widely noticed.From the angle of Spatial Dimension, nano material can be divided are as follows: zero dimensional nanometer materials, such as
Nanoparticle, elementide etc.；Monodimension nanometer material, such as nano wire, nanometer sheet, nanotube, nanometer rods etc.；Two-dimension nano materials,
Such as ultrathin membrane, superlattices etc..The physical and chemical properties of nano material are heavily dependent on the type, structure and shape of material
Looks.Monodimension nanometer material has greatly exploitation due to the advantage of its large specific surface area in terms of catalysis, energy storage, optics, sensing
Potential.Wherein, nanometer sheet is compared to nano wire, nanotube, for the materials such as nanometer rods, often has bigger specific surface area,
The bigger contact area with gas.But traditional nanometer sheet material is when being used to prepare gas sensor, is often in unordered accumulation
Shape, this can not only reduce effective gas absorption active site, and be unfavorable for electronics between nanometer sheet and nanometer sheet and electricity
Transmitting between pole.
Current Metal oxide semiconductor gas-sensitiveness material sensor usually prepares powder gas sensitive first, is applied
It overlays in prefabricated insulating substrate, using the final obtained gas sensor of annealing aging.This kind of gas sensor
Effect is transmitted in the absorption and electricity for often greatly reducing material, so that large specific surface area is lost, the advantages such as high length-diameter ratio.Cause
This, it is particularly important to gas sensor to prepare the nano material that can be directly grown in insulating substrate.
For the gas sensor using functional material manufacture, performance depends on type, the structure of functional material
Comprehensive with pattern acts synergistically.For Metal oxide semiconductor gas-sensitiveness material sensor, performance is aoxidized depending on metal
Type, structure and the comprehensive of pattern of object act synergistically.
Sensitivity, selectivity and stability are to judge the most important index of gas sensor performance, for gas sensing
For device, these three indexs carry out the index of Comprehensive Evaluation to gas sensor as a whole.The sensitivity of sensor is
Refer to, the resistance Rg after being passed through object gas, the ratio (S=Rg/Ra) with aerial initial resistance Ra.When sensor compared with
When working under low temperature, the negative oxygen ion of material surface absorption is less, and the active site that can carry out gas-sensitive reaction is also less, institute
It is universal lower or even without gas sensitive detection performance with sensitivity.Selection has large specific surface area or exposure active site more
Material be used for gas sensitive detection, the sensitivity of sensor can be promoted.
The selectivity of sensor refers to, in the environment for having interference gas, sensor only has reaction to certain gas,
Or other gases are significantly larger than to the sensitivity of such gas.Good selectivity is that gas sensor can be used for detecting correspondence
The premise of gas when gas sensitive has good selectivity, could exclude the interference of other atmosphere in detection environment, guarantee inspection
Survey the reliability of result.The height of sensor selectivity can by the ratio of object gas sensitivity and interference gas sensitivity come
Characterization, ratio is higher, illustrates that the selectivity of sensor is better.
The stability of sensor refers to that sensor its sensitivity and selectivity after working or placing a period of time do not have
It significantly reduces, is still in confidence band.Can sensor put into practical application, and stability is a crucial factor.Such as
Fruit stability is bad, though the sensitivity of sensor and selectivity are very well, and can not actually be promoted and applied.Usual feelings
Condition, the sensitivity of gas sensor will receive the influence of humidity and time, humidity is bigger or work or the time placed more
Long, stability is poorer；It is, humidity it is bigger or work or place time it is longer, the sensitivity of gas sensor and
Selectivity is lower.Not only testing result reliability is low in practical applications but also can greatly mention for the gas sensor of stability difference
High preparation cost.
Operating temperature appropriate is the necessary condition that gas sensor is effectively worked, and conventional gas sensor is especially
Gas sensor of the metal oxide as functional material, generally require higher optimum working temperature (200 DEG C or more, very
Extremely will be to 400 DEG C or more) it can be only achieved highest detection sensitivity, and work at high temperature will lead to the spirit of sensor for a long time
Sensitivity reduces, and selectivity is deteriorated, and bad stability even fails.It therefore, can be at a lower temperature for sensor field
The functional material of work has very important significance, i.e., the enabled temperature for reducing the several years, also to the sensitivity of sensor, choosing
Selecting property and stability have important influence.
In the prior art, the optimum working temperature that the gas sensor of acetone can be detected be usually 200 DEG C or more (for example,
Fig. 4 report of CN104950017A is when operating temperature is 200 DEG C, sensitivity of the high sensitivity under other operating temperatures,
200 DEG C of optimum working temperatures as device) or when reducing temperature detection, sensitivity it is very poor (such as J Mater Sci:
Mater Electron, 2015,15,3995 reports, the Co of preparation3O4Nanometer sheet, at 160 DEG C to 100ppm acetone
6.1) sensitivity is only.
Thus, preparation can be used for the research emphasis that the gas sensitive that low temperature detects is current sensor material, it is for passing
Sensor is widely used in the detection in industrial environment and daily life with great impetus.
Summary of the invention
In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of novel oxidations of intersection four
Three cobalt nano-chip arrays, gas sensor comprising the array and application thereof.
The technical solution adopted by the invention is as follows:
A kind of intersection cobaltosic oxide nano chip arrays are intersected across described between each nanometer sheet in the array
Nanometer sheet be meso-hole structure, the nano-chip arrays 90 DEG C~111 DEG C or so selective enumeration method acetone sensitivity most
It is high.
The sensitivity highest of the selective enumeration method acetone, be not intended to limit the nano-chip arrays has in other temperature
The performance of selective enumeration method acetone, only in 90 DEG C~111 DEG C or so sensitivity highests.Described 90 DEG C~111 DEG C or so are
Refer to that (for example, ± 1 DEG C) is all sensitive with selective enumeration method acetone within the scope of the detection error that those skilled in the art allow
Spend highest.Described 90 DEG C~111 DEG C or so are the best effort temperature of the present invention for intersecting cobaltosic oxide nano chip arrays
Degree.
It further, is mutually perpendicular cross through between each nanometer sheet.As shown in Figure 2 and Figure 3, described
Vertically refer to angle that can be in 90 ° in space any position shape between each nanometer sheet.
Further, the aperture of the meso-hole structure is 2nm~50nm.
Further, the nano-chip arrays are the intersection cobaltosic oxide nano chip arrays of metal-modified.
Further, the metal be selected from group ib, group VIII any one or it is any a variety of, it is preferred that it is described
Metal in platinum, gold, silver and palladium any one or it is any a variety of.
Further, ratio shared by the metal is 0.01wt%~0.5wt%, ratio shared by the preferred metal
For 0.05wt%~0.5wt%, more preferably ratio shared by the metal is 0.1wt%~0.4wt%.
Further, the nano-chip arrays are used to detect acetone in 200 DEG C of property chosen below；Preferably, described
Nano-chip arrays are used to detect acetone in 160 DEG C of property chosen below；Preferably, the nano-chip arrays be used for 60 DEG C~
160 DEG C of selective enumeration method acetone；It is furthermore preferred that the nano-chip arrays are used in 90 DEG C~130 DEG C selective enumeration method acetone,
It is furthermore preferred that the nano-chip arrays are used in 90 DEG C~111 DEG C selective enumeration method acetone.
Further, the acetone that the nano-chip arrays are able to achieve that concentration is 10~1000ppm detects.
Further, the nano-chip arrays have good stability, survey within every 3 days in 60 days primary progress 20 times altogether
It tests, in first five test, the change rate of performance comparing with intial value is ± 3%；In preceding ten tests, performance and initial value phase
The change rate of ratio is ± 4%；In preceding 15 tests, the change rate of performance comparing with intial value is ± 5%；In 20 tests,
The change rate of performance comparing with intial value is ± 8%.
A second object of the present invention is to provide a kind of gas sensor, the gas sensor is comprising substrate and as before
The intersection cobaltosic oxide nano chip arrays of any one form, the substrate are only used for supporting the nano-chip arrays,
The material of the substrate is insulating materials, and the nano-chip arrays are directly grown on the substrate.
Further, for the nano-chip arrays vertical-growth on the substrate, described vertically refers to nanometer sheet and lining
Bottom can be in 90 ° in space any position shape angle.
Further, the substrate is selected from insulating ceramics, glass, material.
Third object of the present invention is to provide a kind of methods for preparing intersection cobaltosic oxide nano chip arrays, including such as
Lower step:
A kind of preparation method for intersecting cobaltosic oxide nano chip arrays, includes the following steps:
(1) two citric acid monohydrate trisodiums, ammonium fluoride, urea, cobalt salt and water are stirred to get into uniform solution, then will done
Net substrate is placed in the solution, is carried out hydro-thermal reaction, is obtained cobaltosic oxide precursor；
(2) cobaltosic oxide precursor is heat-treated to get intersection cobaltosic oxide nano chip arrays are arrived.
Further, further include step (3) after step (2): being deposited in the intersection cobaltosic oxide nano chip arrays
The step of upper metal, is to get the intersection cobaltosic oxide nano chip arrays for arriving metal-modified.
Further, the substrate in the step (1) is insulating substrate；Preferably, the substrate is selected from insulation pottery
Porcelain, glass, material；
Further, the cobalt salt in the step (1) is selected from cobalt nitrate, cobalt acetate, cobalt chloride；
Further, the cobalt salt in the step (1), urea, ammonium fluoride, two citric acid monohydrate trisodiums molar ratio be
10:5:5:1~5:3:2:1；
Further, the temperature of hydro-thermal reaction is 90 DEG C~120 DEG C in the step (1), and the time of hydro-thermal reaction is
12h or more；Preferably, the time of the hydro-thermal reaction is 12h~for 24 hours.
Further, the hydro-thermal reaction of the step (1) carries out in a kettle, it is preferred that the reaction kettle is filled out
Dress degree is 60%~80%.Preferably, the reaction kettle is stainless steel cauldron.
Further, the temperature being heat-treated in the step (2) is 350 DEG C~550 DEG C, heat treatment time is 2~
4h, heating rate are 5~20 DEG C/min.
Further, for the nano-chip arrays vertical-growth on the substrate, described vertically refers to nanometer sheet and lining
Bottom can be in 90 ° in space any position shape angle.
Further, the metal be selected from group ib, group VIII any one or it is any a variety of, it is preferred that it is described
Metal in gold, silver and palladium any one or it is any a variety of.
Further, ratio shared by the metal is 0.01wt%~0.5wt%, ratio shared by the preferred metal
For 0.05wt%~0.5wt%, more preferably ratio shared by the metal is 0.1wt%~0.4wt%.
Method provided by the invention can prepare above-mentioned intersection cobaltosic oxide nano chip arrays.Different from conventional four
The preparation method of Co 3 O nanometer sheet, applicant are found surprisingly that, a kind of special appearance has been made using method of the invention
Intersection cobaltosic oxide nano chip arrays, intersect between each nanometer sheet in the array across passing through ammonium fluoride, urine
Element, two citric acid monohydrate trisodiums, the synergistic effect between four kinds of substances of cobalt salt as a whole, occur direct complex reaction,
Directly forming core on substrate, generates the intersection cobaltosic oxide nano chip arrays of special appearance, in the array each nanometer sheet it
Between to intersect across, the nanometer sheet be meso-hole structure.
Intersection cobaltosic oxide nano chip arrays provided by the invention have biggish specific surface area and electron mobility.
Wherein, intersect the desorption reaction that is adsorbed in that the gap between cobaltosic oxide nano chip arrays is conducive to gas molecule, improve anti-
The sensitivity answered simultaneously reduces reaction duration.Intersection cobaltosic oxide nano array of the invention is directly to exist in the synthesis process
The growth of substrate surface crystallization nucleation, traditional coating procedure is not needed, and there is better performance (to significantly reduce best
Operating temperature, and improve detection sensitivity).The intersection cobaltosic oxide nano chip arrays directly forming core on substrate
Growth, does not need first to grow seed crystal yet, and reducing reaction step reduces production cost, but also entire reaction process more may be used
Control.Open structure caused by crossed array pattern is conducive to that the coming into full contact with of gas and nanometer sheet surface, to have it larger
Specific surface area and electron mobility, and the gap between crossing nanotube chip arrays be conducive to gas molecule be adsorbed in desorption
Reaction, increases the gas sensitivity of material, and accelerates the rate adsorbed and be desorbed.
Fourth object of the present invention is to provide the intersection cobaltosic oxide nano piece battle array of any form as previously described
It is listed in sensor, acetone detects, the purposes of medical context of detection.
Fifth object of the present invention is to provide the gas sensors to detect in sensor, acetone, medical detection side
The purposes in face, for example detected whether by the content of acetone in characteristics of contaminated respiratory droplets gas with diabetes.Breathing diagnosis diabetes
Device may include gas sensor of the present invention, and the breathing diagnosis diabetes device can be portable.
Intersection cobaltosic oxide nano chip arrays and gas sensor of the present invention can be used under a variety of environment detecting
The acetone of various concentration, for example, in characteristics of contaminated respiratory droplets gas detection, for detecting the acetone (≤10ppm) of low concentration, with detection
Whether diabetes are suffered from, detects the acetone (>=500ppm) of high concentration, in industrial environment to detect whether Environmental insults have
It is harmful.
Sixth object of the present invention is to provide a kind of acetone detection device, the acetone detection device includes such as preceding institute
It states such as preceding any a form of intersection cobaltosic oxide nano chip arrays or gas sensor.
Since the present invention considerably reduces optimum working temperature than the prior art, testing cost is reduced, is also beneficial to
Prepare portable acetone detection device.
Beneficial effects of the present invention are as follows:
1) intersection cobaltosic oxide nano chip arrays provided by the invention have biggish specific surface area and electron transfer
Rate, what the gap between crossing nanotube chip arrays was conducive to gas molecule is adsorbed in desorption reaction, can provide more gases
Molecular Adsorption active site and faster electron transfer rate improve the sensitivity of reaction and reduce reaction duration, hence it is evident that improve
Gas sensing performance；
2) reaction process of the present invention carries out in a kettle, product good crystallinity, with short production cycle, at low cost, to environment
It is pollution-free；
3) preparation method of the invention is simply controllable, and reaction temperature is low, and the consumption energy is few, lower to equipment requirement, favorably
In progress large-scale industrial production；
4) preparation method of the invention does not need growth cobaltosic oxide seed layer, and directly forming core is grown on substrate, saves
Traditional coating step has been removed, it is at low cost, it is high-efficient；
5) intersection cobaltosic oxide nano chip arrays of the invention overcome traditional cobaltosic oxide nano piece can not be straight
It connects the problem of generating array in the insulating substrate only to play a supportive role, production cost is low, and high-efficient, operating process simply may be used
Control；
6) gas sensor cocoa made from intersection cobaltosic oxide nano chip arrays provided by the invention is in lower temperature
Under (60 DEG C~160 DEG C), test the acetone of big concentration range (10~1000ppm)；The sensor has good selectivity, inspection
The sensitivity for surveying acetone is pentane, ammonia, methanol, the 3.43 of formaldehyde and ethyl alcohol, 2.95,2.7,2.58,1.89 times；And the biography
Sensor is with good stability, survey within every 3 days in 60 days it is primary carry out 20 tests altogether, in first five test, performance and initial
The change rate that value is compared is ± 3%；In preceding ten tests, the change rate of performance comparing with intial value is ± 4%；Preceding 15 tests
In, the change rate of performance comparing with intial value is ± 5%；20 times test in, the change rate of performance comparing with intial value be ±
8%；
Intersection cobaltosic oxide nano chip arrays provided by the present invention can be used for preparing breathing diagnosis diabetes device.
Detailed description of the invention
Fig. 1, which is that embodiment 1 is obtained, intersects cobaltosic oxide nano chip arrays X-ray diffraction (XRD) figure piece；
Fig. 2, which is that embodiment 1 is obtained, intersects cobaltosic oxide nano chip arrays high power scanning electron microscope (SEM) figure
Piece；
Fig. 3, which is that embodiment 1 is obtained, intersects cobaltosic oxide nano chip arrays low power scanning electron microscope (SEM) figure
Piece；
Fig. 4 is high power transmission electron microscope (HRTEM) figure obtained for intersecting cobaltosic oxide nano piece of embodiment 1；
Fig. 5, which is that embodiment 1 is obtained, intersects cobaltosic oxide nano chip arrays Current Voltage (I-V) characteristic curve；
Fig. 6 is the obtained specific surface area-Pore Diameter Detection figure for intersecting cobaltosic oxide nano chip arrays of embodiment 1, in figure
Curve a be specific surface area figure (corresponding Relative Pressure-Volume Adsorption coordinate), curve b is aperture
Distribution map (corresponding Pore diameter-dV/dlog (D) coordinate)；
Fig. 7 is that the cobaltosic oxide nano chip arrays obtained that intersect of embodiment 1 detect the sensitive of acetone at different temperatures
Degree；
Fig. 8 be embodiment 1 it is obtained intersect cobaltosic oxide nano chip arrays to the remolding sensitivity of various concentration acetone compared with
Table；
Fig. 9 is the gaseousness selection detection comparison sheet obtained for intersecting cobaltosic oxide nano chip arrays of embodiment 1；
Figure 10 is the cobaltosic oxide nano chip arrays obtained that intersect of embodiment 1 in the 20 resulting detection of survey of test in 2 months
The sensitivity of acetone；
Figure 11 is cobaltosic oxide nano needle array low power scanning electron microscope (SEM) figure made from comparative example 1
Piece；
Figure 12 is low power scanning electron microscope (SEM) picture of cobaltosic oxide nano piece made from comparative example 2.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and examples.Following embodiment is merely to illustrate the present invention and does not have to
In limiting the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art can be with
The present invention is made various changes or modifications, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Embodiment 1
The production method of intersection cobaltosic oxide nano chip arrays of the invention, comprising the following steps:
1) cobalt nitrate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 10:5:5:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 80%；
3) and it will clean up and be coated with the insulating substrate of electrode and be placed in solution, control hydrothermal temperature is 95
DEG C, when reaction, is 12 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 2 hours in the air that temperature is 450 DEG C, heating rate
It is 10 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, the intersection cobaltosic oxide nano chip arrays are direct
Growth is on an insulating substrate.
Using step 1)~5) it can be made on an insulating substrate and intersect cobaltosic oxide nano chip arrays, obtained sample
It is used directly for carrying out gas sensing detection.For the XRD diagram of gained sample as shown in Figure 1, showing in Fig. 1, gained peak position is corresponding
Pure cobaltosic oxide, without miscellaneous peak, it is seen that preparation is pure cobaltosic oxide, without miscellaneous phase.The pattern of obtained product is such as
Shown in Fig. 2 and Fig. 3, it is seen then that be mutually perpendicular friendship between each nanometer sheet obtained for intersecting cobaltosic oxide nano chip arrays
Fork across, it is described vertically refer to can be in 90 ° in space any position shape between each nanometer sheet angle.
The high power transmission electron microscope figure obtained for intersecting cobaltosic oxide nano piece is shown in Fig. 4, can from Fig. 4
To find out, gained cobaltosic oxide is polycrystalline material.The oxidation of intersection four three being grown directly upon in insulating substrate is shown in Fig. 5
Current Voltage (I-V) characteristic curve of cobalt nano-chip arrays, as shown in Figure 5, electric current and voltage linear relationship, it is seen that intersect
It is Ohmic contact between cobaltosic oxide nano piece and electrode, so that it is guaranteed that gas-sensitive reaction later is material gas sensing capabilities
Embodiment, rather than variation caused by contact between material and electrode.Fig. 6 is intersection cobaltosic oxide nano piece battle array obtained
The specific surface area of column-Pore Diameter Detection figure, from curve a as it can be seen that the specific surface area of sample is 83 m2·g–1, from curve b as it can be seen that sample
The hole average-size of product is 8.5nm, and biggish specific surface area, open structure are conducive to the abundant of gas and sample surfaces
Contact, increases the gas sensitivity of material, and accelerates the rate adsorbed and be desorbed.Fig. 7 is that intersection cobaltosic oxide obtained is received
Rice chip arrays under different test temperatures (60 DEG C~160 DEG C) to the detection sensitivity of acetone, although its optimum working temperature is
111 DEG C, but the intersection cobaltosic oxide nano chip arrays have good Gas Detection Performance of thermal at 60 DEG C~160 DEG C, it can work
It is wide to make temperature range, optimum working temperature is low, reduces operating power consumption, is conducive to be used for a long time.Fig. 8 is to intersect cobaltosic oxide to receive
Rice chip arrays are to the detection sensitivity of the acetone of various concentration, and detectable concentration range is wide (10~1000ppm), detection sensitivity
High (detection sensitivity to 100ppm acetone is 16.5).Fig. 9 is to intersect cobaltosic oxide nano chip arrays to gas with various
Different detection sensitivity testing results, intersecting cobaltosic oxide nano chip arrays is detection penta respectively to the detection sensitivity of acetone
Alkane, ammonia, formaldehyde, methanol, the 3.34 of ethyl alcohol sensitivity, 2.95,2.7,2.58 and 1.89 times, it is seen that intersect cobaltosic oxide and receive
Rice chip arrays detection acetone has fabulous selectivity.Figure 10 is to intersect cobaltosic oxide nano chip arrays to survey within every 3 days in 60 days
Once carry out the sensitivity (the 60th day survey the 20th time) of the resulting detection acetone of 20 tests altogether, in first five test, performance with
The change rate that initial value is compared is ± 3%；In preceding ten tests, the change rate of performance comparing with intial value is ± 4%；First 15 times
In test, the change rate of performance comparing with intial value is ± 5%；In 20 tests, the change rate of performance comparing with intial value is
± 8%, it is seen then that intersection cobaltosic oxide nano chip arrays obtained have good stability, are conducive to practical application.
Comparative example 1
The production method of cobaltosic oxide nano needle array, comprising the following steps:
1) cobalt nitrate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 10:5:5:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 80%；
3) it and by the insulating substrate for being coated with electrode cleaned up being placed in solution, control hydrothermal temperature is 95 DEG C,
A length of 6 hours when reaction, the substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
It 5) is carries out heat treatment in 2 hours in 450 DEG C of air to get to four in temperature by gained cobaltosic oxide precursor
Co 3 O nano needle arrays.
The SEM picture of 1 gained sample of comparative example is as shown in figure 11, and gained sample is nano needle arrays pattern.Detection
The acetone detection sensitivity of cobaltosic oxide nano needle array made from comparative example 1, optimum working temperature are 130 DEG C,
Lower (the S of sensitivity of 100ppm acetone is detected at 130 DEG CAcetone=8.1), cobaltosic oxide nano needle array obtained is carried out steady
Qualitative test surveys primary progress altogether 20 times for every 3 days in 60 days and tests the sensitivity for detecting acetone, in first five test, performance
Change rate comparing with intial value is ± 5%；In preceding ten tests, the change rate of performance comparing with intial value is ± 8%；Preceding 15
In secondary test, the change rate of performance comparing with intial value is ± 15%；In 20 tests, the variation of performance comparing with intial value
Rate is ± 20%, illustrates that the stability of cobaltosic oxide nano needle array is poor.The difference of comparative example 1 and embodiment 1 is just
Be the hydro-thermal reaction of step 3) time it is short (only 6 hours), only grow up to cobaltosic oxide nano needle array, do not generate friendship also
Cobaltosic oxide nano chip arrays are pitched, air-sensitive performance is poor, and optimum working temperature height (for 130 DEG C), sensitivity is low, and stability
Difference illustrates that the pattern of crossing nanotube chip arrays has decisive role for air-sensitive performance.
Comparative example 2(is referring to RSC Advances, and 2015,5,59976)
The production method of cobaltosic oxide nano piece, comprising the following steps:
1) by 0.02mmol polyethylene glycol-polypropylene glycol-polyethylene glycol copolymer (ethylene glycol)-block-
Poly (propylene glycol)-block-poly (ethylene glycol)) it is dissolved in 16.5mL ethyl alcohol and 1mL deionization
Homogeneous solution is stirred to obtain in water；
2) urotropine of 0.5mmol, the cobalt acetate of 0.5mml and 13mL ethylene glycol are dissolved in obtained by step 1)
Solution in stir evenly；
3) homogeneous solution obtained by step 2) is stood into 12h；
4) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), control hydro-thermal is anti-
Answering temperature is 170 DEG C, and when reaction is 2 hours a length of；
5) after the reaction was completed, gained turbid solution is centrifuged to obtain sample, gained sample with ethanol and deionized water are cleaned；
6) gained cobaltosic oxide precursor is carried out being heat-treated for 2 hours in the air that temperature is 450 DEG C, gained is
Cobaltosic oxide nano piece；
7) powder obtained by step 6) is exhausted coated in having cleaned up after mixing according to a certain percentage with ethyl alcohol
In edge potsherd, silicon wafer or glass substrate.
The SEM picture of cobaltosic oxide nano piece made from comparative example 2 is as shown in figure 12, is four oxidations three of accumulation
Cobalt nanometer sheet detects the acetone detection sensitivity of the resulting cobaltosic oxide nano piece of comparative example 2, optimum working temperature
It is 150 DEG C, the poor (S of sensitivity of 100ppm acetone is detected at 150 DEG CAcetone=11.4).This comparative example and embodiment 1 are not
It is to test the entirely different preparation method of drug used not having to place, although obtained is cobaltosic oxide nano piece,
Embodiment 1 and the difference of cobaltosic oxide nano piece pattern made from comparative example 2.Intersect cobaltosic oxide obtained by embodiment 1
Directly forming core is grown nano-chip arrays on substrate, and cobaltosic oxide nano piece obtained in comparative example 2 can not be direct
On substrate, needing to coat could be used to carry out gas sensing detection on substrate for growth.Also, such as Figure 12 and Fig. 2, Fig. 3 couple
Than shown, compared with intersecting cobaltosic oxide nano chip arrays obtained by embodiment 1, the nanometer sheet of comparative example 2 is on substrate
Mutually accumulation superposition, so that its effective area contacted with gas is small, and poorly conductive, so its gas sensitive detection performance is poor.It is right
Illustrate than result, gained nanometer sheet is grown directly upon on substrate and is in the pattern of array, for the gas sensing property of gas sensor
There can be decisive role.
Comparative example 3(is referring to Chinese patent CN 103217460A)
The production method of diamond shape cobaltosic oxide nano linear array, comprising the following steps:
1) cobalt nitrate, ammonium fluoride, hexa and the deionized water that molar ratio is 1:1:5 are mixed uniformly
Solution；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 50%；
3) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 95 DEG C, when reaction is 24 hours a length of；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the argon gas that temperature is 450 DEG C to get water chestnut is arrived
Shape cobaltosic oxide nano linear array.
3 gained sample of comparative example is diamond shape cobaltosic oxide nano linear array, detects the resulting water chestnut of comparative example 3
The acetone detection sensitivity of shape cobaltosic oxide array, optimum working temperature is 160 DEG C, at 160 DEG C to 500ppm acetone
Detection sensitivity is only 20.1.Comparative example 3 and the difference of embodiment 1 are exactly that the pattern of gained nano-array is different,
Cause the optimum working temperature of the comparative example selective enumeration method acetone higher, detection sensitivity is lower.Comparing result explanation,
The pattern for intersecting cobaltosic oxide nano chip arrays has decisive role for the air-sensitive performance of gas sensor.
Comparative example 4(is referring to Sensors and Actuators B, and 2015,208 112-121)
The production method of diamond shape zinc oxide nano-array, comprising the following steps:
1) zinc nitrate, hexa, ammonium fluoride and the 40mL deionized water that molar ratio is 1:2:4 are mixed
Homogeneous solution；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 80%；
3) it and by the insulating substrate for being coated with electrode cleaned up being placed in solution, control hydrothermal temperature is 95 DEG C,
A length of 24 hours when reaction, the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains zinc oxide
Presoma；
6) gained zinc oxide presoma is carried out being heat-treated for 4 hours in the argon gas that temperature is 450 DEG C to get diamond shape is arrived
Zinc oxide nano-array.
4 gained sample of comparative example is diamond shape zinc oxide nano-array, detects the resulting diamond shape two of comparative example 4
The acetone detection sensitivity of zinc oxide nano array, discovery to acetone without response, to the selective enumeration method sensitivity highest of ethyl alcohol,
Its optimum working temperature is 300 DEG C, and obtained diamond shape zinc oxide nano-array is in 300 DEG C of detection spirits to 100ppm ethyl alcohol
Sensitivity is only 11.8.Comparative example 4 and the difference of embodiment 1 are exactly that material category is different, and embodiment 1 is four oxidations
Three cobalts and comparative example 4 are zinc oxide, and gained sample topography is different, and embodiment 1 is to intersect cobaltosic oxide nano
Chip arrays, comparative example 4 are diamond shape zinc oxide array.Gas detected is ethyl alcohol and to acetone in the comparative example
Without response, and required detection temperature is very high.Comparing result explanation, the type and pattern of functional material are for gas sensing
The air-sensitive performance of device all has decisive role.
Embodiment 2
The production method of intersection cobaltosic oxide nano chip arrays of the invention, comprising the following steps:
1) cobalt acetate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 6:3:3:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 70%；
3) and it will clean up and be coated with the insulating substrate of electrode and be placed in solution, control hydrothermal temperature is 90
DEG C, when reaction, is 14 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 350 DEG C, heating rate
It is 5 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, the intersection cobaltosic oxide nano chip arrays are directly raw
Length is on an insulating substrate.
2 gained sample of embodiment is to intersect cobaltosic oxide nano chip arrays.Detect resulting four oxidation of intersection of embodiment 2
The acetone detection sensitivity of three cobalt nano-chip arrays, optimum working temperature is 111 DEG C, to the detection sensitivity of 100ppm acetone
It is 16.3.It pitches to survey for cobaltosic oxide nano chip arrays every 3 days in 60 days and once carries out testing resulting detection acetone 20 times altogether
Sensitivity (the 60th day survey the 20th time), in first five test, the change rate of performance comparing with intial value is ± 3%；Preceding ten surveys
In examination, the change rate of performance comparing with intial value is ± 4%；In preceding 15 tests, the change rate of performance comparing with intial value is
±4%；In 20 tests, the change rate of performance comparing with intial value is ± 8%, it is seen then that intersection cobaltosic oxide obtained is received
Rice chip arrays have good stability, are conducive to practical application.
Embodiment 3
The production method of intersection cobaltosic oxide nano chip arrays of the invention, comprising the following steps:
1) cobalt chloride, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 5:3:2:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 60%；
3) and it will clean up and be coated with the insulating substrate of electrode and be placed in solution, control hydrothermal temperature is 110
DEG C, when reaction, is 13 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 3 hours in the air that temperature is 550 DEG C, heating rate
It is 15 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, the intersection cobaltosic oxide nano chip arrays are direct
Growth is on an insulating substrate.
3 gained sample of embodiment is to intersect cobaltosic oxide nano chip arrays.Detect resulting four oxidation of intersection of embodiment 3
The acetone detection sensitivity of three cobalt nano-chip arrays, optimum working temperature is 110 DEG C, to the detection sensitivity of 100ppm acetone
It is 16.7.It pitches to survey for cobaltosic oxide nano chip arrays every 3 days in 60 days and once carries out testing resulting detection acetone 20 times altogether
Sensitivity (the 60th day survey the 20th time), in first five test, the change rate of performance comparing with intial value is ± 2%；Preceding ten surveys
In examination, the change rate of performance comparing with intial value is ± 4%；In preceding 15 tests, the change rate of performance comparing with intial value is
±5%；In 20 tests, the change rate of performance comparing with intial value is ± 7%, it is seen then that intersection cobaltosic oxide obtained is received
Rice chip arrays have good stability, are conducive to practical application.
Embodiment 4
The production method of intersection cobaltosic oxide nano chip arrays of the invention, comprising the following steps:
6) cobalt acetate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 8:5:5:1 are existed
It is mixed under room temperature；
7) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 70%；
8) and it will clean up and be coated with the insulating substrate of electrode and be placed in solution, control hydrothermal temperature is 115
DEG C, when reaction, is 15 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
9) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
10) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 450 DEG C, heating speed
Rate is 20 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, and the intersection cobaltosic oxide nano chip arrays are straight
Length deliver a child on an insulating substrate.
4 gained sample of embodiment is to intersect cobaltosic oxide nano chip arrays.Detect resulting four oxidation of intersection of embodiment 4
The acetone detection sensitivity of three cobalt nano-chip arrays, optimum working temperature is 112 DEG C, to the detection sensitivity of 100ppm acetone
It is 16.6.It pitches to survey for cobaltosic oxide nano chip arrays every 3 days in 60 days and once carries out testing resulting detection acetone 20 times altogether
Sensitivity (the 60th day survey the 20th time), in first five test, the change rate of performance comparing with intial value is ± 3%；Preceding ten surveys
In examination, the change rate of performance comparing with intial value is ± 3%；In preceding 15 tests, the change rate of performance comparing with intial value is
±5%；In 20 tests, the change rate of performance comparing with intial value is ± 8%, it is seen then that intersection cobaltosic oxide obtained is received
Rice chip arrays have good stability, are conducive to practical application.
Embodiment 5
The production method that gold modification of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
1) cobalt acetate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 10:5:5:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 60%；
3) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 90 DEG C, when reaction is 14 hours a length of, and the insulating substrate can be insulating ceramics, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 550 DEG C, heating rate
It is 5 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, the intersection cobaltosic oxide nano chip arrays are directly raw
Length is on an insulating substrate；
6) gained be grown into the substrate for intersecting cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersected
The gold of upper 0.05wt% is deposited to get the intersection cobaltosic oxide nano for arriving gold modification in the surface of cobaltosic oxide nano chip arrays
Chip arrays.
5 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of gold modification.Detect the resulting gold of embodiment 5
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of modification, optimum working temperature is 105 DEG C, to 100ppm
The detection sensitivity of acetone is 18.7.Gold intersects to survey for cobaltosic oxide nano chip arrays every 3 days in 60 days once carries out 20 altogether
The sensitivity (the 60th day survey the 20th time) of the secondary resulting detection acetone of test, in first five test, performance is comparing with intial value
Change rate is ± 2%；In preceding ten tests, the change rate of performance comparing with intial value is ± 4%；In preceding 15 tests, performance
Change rate comparing with intial value is ± 5%；In 20 tests, the change rate of performance comparing with intial value is ± 7%, it is seen then that
Gold obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Embodiment 6
The production method that gold modification of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
7) cobalt nitrate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 10:8:7:1 are existed
It is mixed under room temperature；
8) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 70%；
9) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 90 DEG C, when reaction is 18 hours a length of, and the insulating substrate can be insulating ceramics, silicon wafer or glass substrate；
10) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations
Three cobalt precursors；
11) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 550 DEG C, heating speed
Degree is 8 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, and the intersection cobaltosic oxide nano chip arrays are direct
Growth is on an insulating substrate；
12) gained be grown into the substrate for intersecting cobaltosic oxide nano chip arrays as on electron beam evaporation platform, handed over
The surface of fork cobaltosic oxide nano chip arrays is deposited the gold of upper 0.01wt% and receives to get the intersection cobaltosic oxide to gold modification
Rice chip arrays.
6 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of gold modification.Detect the resulting gold of embodiment 6
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of modification, optimum working temperature is 108 DEG C, to 100ppm
The detection sensitivity of acetone is 18.9.Gold intersects to survey for cobaltosic oxide nano chip arrays every 3 days in 60 days once carries out 20 altogether
The sensitivity (the 60th day survey the 20th time) of the secondary resulting detection acetone of test, in first five test, performance is comparing with intial value
Change rate is ± 2%；In preceding ten tests, the change rate of performance comparing with intial value is ± 3%；In preceding 15 tests, performance
Change rate comparing with intial value is ± 5%；In 20 tests, the change rate of performance comparing with intial value is ± 7%, it is seen then that
Gold obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Embodiment 7
The production method that modified by silver of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
1) cobalt chloride, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 6:4:2:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 70%；
3) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 100 DEG C, when reaction is 13 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 3 hours in the air that temperature is 550 DEG C, heating rate
It is 20 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, the intersection cobaltosic oxide nano chip arrays are direct
Growth is on an insulating substrate；
6) substrate by gained with intersection cobaltosic oxide nano chip arrays is intersecting four as on electron beam evaporation platform
The silver of upper 0.1wt% is deposited to get the intersection cobaltosic oxide nano piece battle array for arriving modified by silver in the surface of Co 3 O nano-chip arrays
Column.
7 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of modified by silver.Detect the resulting silver of embodiment 7
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of modification, optimum working temperature is 100 DEG C, to 100ppm
The detection sensitivity of acetone is 29.5.Modified by silver intersect survey within cobaltosic oxide nano chip arrays every 3 days in 60 days it is primary altogether into
The sensitivity (the 60th day survey the 20th time) of the resulting detection acetone of row 20 times tests, in first five test, performance and initial value phase
The change rate of ratio is ± 2%；In preceding ten tests, the change rate of performance comparing with intial value is ± 3%；In preceding 15 tests,
The change rate of performance comparing with intial value is ± 5%；In 20 tests, the change rate of performance comparing with intial value is ± 8%, can
See, modified by silver obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Embodiment 8
The production method that modified by silver of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
7) cobalt acetate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 8:6:3:1 are existed
It is mixed under room temperature；
8) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 80%；
9) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 120 DEG C, when reaction is 12 hours a length of, and the insulating substrate can be insulating ceramic film, silicon wafer or glass substrate；
10) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations
Three cobalt precursors；
11) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 450 DEG C, heating speed
Degree is 10 DEG C/min to get to cobaltosic oxide nano chip arrays are intersected, and the intersection cobaltosic oxide nano chip arrays are straight
Length deliver a child on an insulating substrate；
12) substrate by gained with intersection cobaltosic oxide nano chip arrays is intersecting as on electron beam evaporation platform
The silver of upper 0.5wt% is deposited to get the intersection cobaltosic oxide nano piece for arriving modified by silver in the surface of cobaltosic oxide nano chip arrays
Array.
8 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of modified by silver.Detect the resulting silver of embodiment 8
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of modification, optimum working temperature is 92 DEG C, to 100ppm
The detection sensitivity of acetone is 30.1.Modified by silver intersect survey within cobaltosic oxide nano chip arrays every 3 days in 60 days it is primary altogether into
The sensitivity (the 60th day survey the 20th time) of the resulting detection acetone of row 20 times tests, in first five test, performance and initial value phase
The change rate of ratio is ± 2%；In preceding ten tests, the change rate of performance comparing with intial value is ± 2%；In preceding 15 tests,
The change rate of performance comparing with intial value is ± 4%；In 20 tests, the change rate of performance comparing with intial value is ± 7%, can
See, modified by silver obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Embodiment 9
The production method that palladium modification of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
1) cobalt nitrate, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 5:3:3:1 are existed
It is mixed under room temperature；
2) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 70%；
3) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 115 DEG C, when reaction is 24 hours a length of；
4) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations three
Cobalt precursor；
5) gained cobaltosic oxide precursor is carried out being heat-treated for 4 hours in the air that temperature is 350 DEG C, heating rate
It obtains intersecting cobaltosic oxide nano chip arrays for 10 DEG C/min；
6) substrate by gained with intersection cobaltosic oxide nano chip arrays is intersecting four as on electron beam evaporation platform
The palladium of upper 0.4wt% is deposited to get the intersection cobaltosic oxide nano piece battle array modified to palladium in the surface of Co 3 O nano-chip arrays
Column.
9 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of palladium modification.Detect the resulting palladium of embodiment 9
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of modification, optimum working temperature is 90 DEG C, to 100ppm
The detection sensitivity of acetone is 29.8.It surveys within palladium modification fork cobaltosic oxide nano chip arrays every 3 days in 60 days and once carries out altogether
The sensitivity (the 60th day survey the 20th time) of the resulting detection acetone of 20 tests, in first five test, performance is comparing with intial value
Change rate be ± 3%；In preceding ten tests, the change rate of performance comparing with intial value is ± 3%；In preceding 15 tests, property
Can change rate comparing with intial value be ± 4%；In 20 tests, the change rate of performance comparing with intial value is ± 7%, can
See, palladium modification obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Embodiment 10
The production method that platinum modification of the invention intersects cobaltosic oxide nano chip arrays, comprising the following steps:
7) cobalt chloride, urea, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water that molar ratio is 8:5:6:1 are existed
It is mixed under room temperature；
8) obtained homogeneous solution is moved into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reaction kettle loads
Degree is 60%；
9) it and by the insulating ceramic film cleaned up, silicon wafer or glass substrate is placed in solution, controls hydrothermal temperature
It is 120 DEG C, when reaction is 20 hours a length of；
10) it after the reaction was completed, takes out substrate and is rinsed respectively with deionized water and ethyl alcohol and drying obtains four oxidations
Three cobalt precursors；
11) gained cobaltosic oxide precursor is carried out being heat-treated for 2 hours in the air that temperature is 550 DEG C, heating speed
Degree is that 20 DEG C/min obtains intersecting cobaltosic oxide nano chip arrays；
12) substrate by gained with intersection cobaltosic oxide nano chip arrays is intersecting as on electron beam evaporation platform
The platinum of upper 0.5wt% is deposited to get the intersection cobaltosic oxide nano piece modified to platinum in the surface of cobaltosic oxide nano chip arrays
Array.
10 gained sample of embodiment is the intersection cobaltosic oxide nano chip arrays of palladium modification.It is resulting to detect embodiment 10
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays of palladium modification, optimum working temperature is 95 DEG C, right
The detection sensitivity of 100ppm acetone is 28.9.It surveys within palladium modification fork cobaltosic oxide nano chip arrays every 3 days in 60 days primary
Carry out the sensitivity (the 60th day survey the 20th time) of the resulting detection acetone of 20 tests altogether, in first five test, performance and initial
The change rate that value is compared is ± 2%；In preceding ten tests, the change rate of performance comparing with intial value is ± 3%；Preceding 15 tests
In, the change rate of performance comparing with intial value is ± 3%；20 times test in, the change rate of performance comparing with intial value be ±
7%, it is seen then that platinum modification obtained, which intersects cobaltosic oxide nano chip arrays, has good stability, is conducive to practical application.
Claims (39)
1. a kind of intersection cobaltosic oxide nano chip arrays, which is characterized in that intersect between each nanometer sheet in the array
It passes through, the nanometer sheet is meso-hole structure, and the nano-chip arrays are in 90 DEG C~111 DEG C or so selective enumeration method acetone
Sensitivity highest, the nano-chip arrays are directly grown in insulating substrate.
2. intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that each nanometer sheet it
Between be it is mutually perpendicular cross through, described vertically referring to can be in 90 ° in space any position shape between each nanometer sheet
Angle.
3. intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that the meso-hole structure
Aperture is 2nm~50nm.
4. intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that the nano-chip arrays
For the intersection cobaltosic oxide nano chip arrays of metal-modified.
5. intersection cobaltosic oxide nano chip arrays according to claim 4, which is characterized in that the metal is selected from the
IB race, group VIII any one or it is any a variety of.
6. intersection cobaltosic oxide nano chip arrays according to claim 4, which is characterized in that the metal is selected from
In gold, silver, palladium and platinum any one or it is any a variety of.
7. intersection cobaltosic oxide nano chip arrays according to claim 4, which is characterized in that ratio shared by the metal
Example is 0.01wt%~0.5wt%.
8. intersection cobaltosic oxide nano chip arrays according to claim 4, which is characterized in that ratio shared by the metal
Example is 0.05wt%~0.5wt%.
9. intersection cobaltosic oxide nano chip arrays according to claim 4, which is characterized in that ratio shared by the metal
Example is 0.1wt%~0.4wt%.
10. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are used to detect acetone in 200 DEG C of property chosen below.
11. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are used to detect acetone in 160 DEG C of property chosen below.
12. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are used in 60 DEG C~160 DEG C selective enumeration method acetone.
13. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are used in 90 DEG C~130 DEG C selective enumeration method acetone.
14. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are used in 90 DEG C~111 DEG C selective enumeration method acetone.
15. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays have good stability, survey within every 3 days in 60 days primary progress altogether 20 times and test, in first five test, performance
Change rate comparing with intial value is ± 3%；In preceding ten tests, the change rate of performance comparing with intial value is ± 4%；Preceding 15
In secondary test, the change rate of performance comparing with intial value is ± 5%；In 20 tests, the change rate of performance comparing with intial value
It is ± 8%.
16. -9 described in any item intersection cobaltosic oxide nano chip arrays according to claim 1, which is characterized in that described
Nano-chip arrays are able to achieve the acetone that concentration is 10~1000ppm and detect.
17. intersecting the preparation method of cobaltosic oxide nano chip arrays described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) two citric acid monohydrate trisodiums, ammonium fluoride, urea, cobalt salt and water are stirred to get into uniform solution, it then will be clean
Substrate is placed in the solution, is carried out hydro-thermal reaction, is obtained cobaltosic oxide precursor；
(2) cobaltosic oxide precursor is heat-treated to get intersection cobaltosic oxide nano chip arrays are arrived.
18. preparation method according to claim 17, which is characterized in that further include step (3) after step (2): in institute
It states and intersects the step of upper metal is deposited in cobaltosic oxide nano chip arrays to get the intersection cobaltosic oxide nano for arriving metal-modified
Chip arrays.
19. preparation method described in 7 or 18 according to claim 1, which is characterized in that cobalt salt, urine in the step (1)
Element, ammonium fluoride, two citric acid monohydrate trisodiums molar ratio be 10:5:5:1~5:3:2:1.
20. preparation method described in 7 or 18 according to claim 1, which is characterized in that the cobalt salt in the step (1) is selected from
Cobalt nitrate, cobalt acetate, cobalt chloride.
21. preparation method described in 7 or 18 according to claim 1, which is characterized in that hydro-thermal reaction in the step (1)
Temperature is 90 DEG C~120 DEG C, and the time of hydro-thermal reaction is 12h or more.
22. preparation method according to claim 21, which is characterized in that the time of the hydro-thermal reaction be 12h~
24h。
23. preparation method described in 7 or 18 according to claim 1, which is characterized in that the substrate in the step (1) is exhausted
Edge substrate.
24. preparation method according to claim 23, which is characterized in that the substrate is selected from insulating ceramics, glass, contains
Silicon materials.
25. preparation method described in 7 or 18 according to claim 1, which is characterized in that the hydro-thermal reaction of the step (1) exists
It is carried out in reaction kettle.
26. preparation method according to claim 25, which is characterized in that the filling degree of the reaction kettle is 60%~80%.
27. preparation method according to claim 25, which is characterized in that the reaction kettle is stainless steel cauldron.
28. preparation method described in 7 or 18 according to claim 1, which is characterized in that the temperature being heat-treated in the step (2)
Degree is 350 DEG C~550 DEG C, and heat treatment time is 2~4h, and heating rate is 5~20 DEG C/min.
29. preparation method described in 7 or 18 according to claim 1, which is characterized in that the nano-chip arrays vertical-growth is in institute
It states on substrate, the described angle for vertically referring to that nanometer sheet and substrate can be in 90 ° in space any position shape.
30. preparation method according to claim 18, which is characterized in that the metal is selected from group ib, group VIII
Any one is any a variety of.
31. preparation method according to claim 30, which is characterized in that the metal appointing in gold, silver and palladium
It anticipates a kind of or any a variety of.
32. preparation method according to claim 18, which is characterized in that ratio shared by the metal be 0.01wt%~
0.5wt%。
33. preparation method according to claim 18, which is characterized in that ratio shared by the metal be 0.05wt%~
0.5wt%。
34. preparation method according to claim 18, which is characterized in that ratio shared by the metal be 0.1wt%~
0.4wt%。
35. a kind of gas sensor, which is characterized in that the gas sensor includes any one of substrate and claim 1-16
The intersection cobaltosic oxide nano chip arrays, the substrate are only used for supporting the nano-chip arrays, the material of the substrate
Material is insulating materials, and the nano-chip arrays are directly grown on the substrate.
36. gas sensor according to claim 35, which is characterized in that the nano-chip arrays vertical-growth is in described
On substrate, the described angle for vertically referring to that nanometer sheet and substrate can be in 90 ° in space any position shape.
37. gas sensor according to claim 35, which is characterized in that the substrate be selected from insulating ceramics, glass,
Material.
38. any one of the described in any item intersection cobaltosic oxide nano chip arrays of claim 1-16 or claim 35-37
The gas sensor sensor, acetone detection, medical context of detection purposes.
39. a kind of acetone detection device, it is characterised in that: the acetone detection device includes any one of claim 1-16 institute
The intersection cobaltosic oxide nano chip arrays or the described in any item gas sensors of claim 35-37 stated.
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| CN107337473B (en) * | 2017-07-25 | 2020-07-07 | 济南大学 | In-situ growth of MoO on ceramic tubes3Nanosheet method and gas sensor |
| CN107589153A (en) | 2017-10-23 | 2018-01-16 | 京东方科技集团股份有限公司 | Gas sensor and its manufacture method, detection device |
| CN110887890A (en) * | 2019-12-12 | 2020-03-17 | 淮北师范大学 | Method for electrochemically detecting heavy metal ions by doping modified reinforced nano material |
| CN111334818A (en) * | 2020-02-28 | 2020-06-26 | 浙江糖能科技有限公司 | Device for electrolytic catalytic oxidation and method for preparing 2, 5-furandicarboxylic acid |
| CN113219011B (en) * | 2021-05-19 | 2022-08-09 | 吉林大学 | Co-doped SnO 2 Formaldehyde-acetone gas sensor and preparation method thereof |
| CN114487020B (en) * | 2022-02-08 | 2023-12-22 | 扬州大学 | Gas-sensitive material for lung cancer breathing mark gas methanol and preparation method thereof |
| CN114460144B (en) * | 2022-03-10 | 2024-07-30 | 浙江大学 | Co-MOF array film derived cobalt oxide prototype gas sensor and large-area batch preparation method and application thereof |
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