CN106066351A - A kind of cobaltosic oxide nano chip arrays, the gas sensor comprising described array and application thereof of intersecting - Google Patents
A kind of cobaltosic oxide nano chip arrays, the gas sensor comprising described array and application thereof of intersecting Download PDFInfo
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- CN106066351A CN106066351A CN201610362040.XA CN201610362040A CN106066351A CN 106066351 A CN106066351 A CN 106066351A CN 201610362040 A CN201610362040 A CN 201610362040A CN 106066351 A CN106066351 A CN 106066351A
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Abstract
The invention discloses a kind of cobaltosic oxide nano chip arrays, the gas sensor comprising described array and application thereof of intersecting.This special intersection cobaltosic oxide nano chip arrays intersects between each nanometer sheet through, nanometer sheet is meso-hole structure, the highest in the sensitivity of about 111 DEG C selective enumeration method acetone, is 16.5.The intersection cobaltosic oxide nano chip arrays of the present invention overcomes traditional cobaltosic oxide nano sheet and directly cannot generate the problem of array in the most passive dielectric substrate, and production cost is low, and efficiency is high, and operating process is the most controlled.Described intersection cobaltosic oxide nano chip arrays, there is Open architecture, bigger specific surface area and electron mobility, quick adsorption and disengaging that more space is beneficial to gas molecule can be provided, significantly improve the air-sensitive performance of material, there is good stability, within in 60 days every 3 days, surveying and carry out 20 tests the most altogether, 20 times test performance rate of change is only ± 8%, is highly suitable for sensor, acetone detection, medical treatment detection.
Description
Technical field
The invention belongs to sensor field, be specifically related to a kind of intersection cobaltosic oxide nano chip arrays, comprise described battle array
Gas sensor of row and application thereof.
Background technology
Along with Chinese society economic level and the lifting of living standard, and the increase of live and work pressure, subhealth state
Crowd gets more and more, and the vulnerable groups of various diseases starts extensively to change rejuvenation.In the gas of characteristics of contaminated respiratory droplets, except nitrogen, oxygen and
Outside carbon dioxide, also comprising other and permitted multiple compounds, the contents level of these compounds is judge health one
Individual important indicator.Such as, in exhaled gas, content of acetone is higher, then mean have great risk to suffer from diabetes；And if exhaling
Go out content of nitric oxide in gas and higher than normal level, be then likely to asthma.Just because of this, the breathing of non-intrusion type
Analytical tool has the biggest development potentiality in medical diagnosis and diseases monitoring field.Develop various respiratory analyser at present
Device is used for medical diagnosis, but is to use mass spectrometric analysis method or laser to analyze in exhaled gas mostly in these analytical tool
Specific compound, analyst coverage is the least, thus diagnoses different diseases, it is necessary to use different equipment.
And semiconductive gas sensor meets that cost is little, energy consumption is low, rely only on exhaled gas and can be achieved with monitoring, analyze
Kind is many, timely and simple to operate, a series of indexs to human zero damage.And the volume of semiconductor-type gas sensor can
Sufficiently small to be made, it can come into huge numbers of families completely as sphygomanometer, and extremely suitable preparation meets the daily domestic of people and exhales
Inhale the diagnostic equipment, our health status of real-time dynamic monitoring, it is achieved the early stage of disease is detected and early intervention.If this
A little physiological signal sensors combine with mobile communication, cloud computing and Wearable etc., and we can use " revolution " word completely
Describe that it is to health of people life and the change of medical market.
Metal-oxide semiconductor (MOS) gas sensor receives a large amount of because of the performance of its excellence with being widely applied field
Pay close attention to.For functioning as the material of gas sensor, nano material is owing to having skin effect, small-size effect, quantum size
The characteristics such as effect and the most concerned.From the angle of Spatial Dimension, nano material can be divided into: zero dimensional nanometer materials, 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 process based prediction model of nano material is heavily dependent on the kind of material, structure and shape
Looks.Monodimension nanometer material, due to the big advantage of its specific surface area, has exploitation greatly in terms of catalysis, energy storage, optics, sensing
Potential.Wherein, nanometer sheet, compared to nano wire, nanotube, for the material such as nanometer rods, often has bigger specific surface area,
The contact area bigger with gas.When but traditional nanometer sheet material is used for preparing gas sensor, often in unordered accumulation
Shape, this not only can reduce effective gas absorption avtive spot, and between nanometer sheet and nanometer sheet is with electric to be unfavorable for electronics
Transmission between pole.
Current Metal oxide semiconductor gas-sensitiveness material sensor is typically first to prepare powder gas sensitive, is coated with
Overlay in prefabricated dielectric substrate, the more annealed step such as aging finally prepares gas sensor.This kind of gas sensor
The advantages such as the absorption and the electricity that are often greatly reduced material transmit effect, thus lose specific surface area greatly, high length-diameter ratio.Cause
This, the nano material that preparation can be directly grown in dielectric substrate is particularly important to gas sensor.
For the gas sensor utilizing functional material to manufacture, its performance depends on the kind of functional material, structure
Comprehensive synergism with pattern.For Metal oxide semiconductor gas-sensitiveness material sensor, its performance depends on burning
The kind of thing, structure and the comprehensive synergism of pattern.
Sensitivity, selectivity and stability are to pass judgment on the most important index of gas sensor performance, for gas sensing
For device, these three index carries out the index of Comprehensive Evaluation as an entirety to gas sensor.The sensitivity of sensor is
Refer to, be passed through the resistance Rg after object gas, with the ratio (S=Rg/Ra) of aerial initial resistance Ra.When sensor is relatively
When working under low temperature, the negative oxygen ion of its material surface absorption is less, and the avtive spot that can carry out gas-sensitive reaction is the most less, institute
Even performance is detected without air-sensitive so that sensitivity is the most relatively low.Selection has large specific surface area or exposure avtive spot is more
Material for air-sensitive detect, the sensitivity of sensor can be promoted.
The selectivity of sensor refers to, in the environment having interference gas, certain gas is only responded by sensor,
Or the sensitivity to this kind of gas is significantly larger than other gas.Good selectivity is that gas sensor can be used for detection correspondence
The premise of gas, when gas sensitive has good selectivity, could get rid of the interference of other atmosphere in detection environment, it is ensured that inspection
Survey the reliability of result.The height of sensor selectivity can be come by the ratio of object gas sensitivity with interference gas sensitivity
Characterizing, ratio is the highest, illustrates that the selectivity of sensor is the best.
The stability of sensor refers to, sensor its sensitivity and selectivity after working or placing a period of time do not have
Significantly reduce, be still in confidence band.Can sensor put into actual application, and stability is a crucial factor.As
Really stability is bad, even if the sensitivity of sensor and selectivity are fine, also cannot be carried out actual popularization and application.Generally feelings
Condition, the sensitivity of gas sensor can be affected by humidity and time, humidity is the biggest or work or time of placing more
Long, stability is the poorest；It is, humidity is the biggest or work or place time the longest, the sensitivity of gas sensor and
Selectivity is the lowest.The gas sensor of poor stability the most not only testing result reliability is low but also can carry greatly
High preparation cost.
Suitable operating temperature is the essential condition that gas sensor effectively works, and conventional gas sensor is particularly
Metal-oxide as the gas sensor of functional material, generally require higher optimum working temperature (more than 200 DEG C, very
Extremely will be to more than 400 DEG C) can be only achieved the highest detection sensitivity, and at high temperature work for a long time and can cause the spirit of sensor
Sensitivity reduces, and selectivity is deteriorated, and bad stability even lost efficacy.Therefore, for sensor field, can be at a lower temperature
The functional material of work has very important significance, and i.e. enables the temperature reducing the several years, also sensitivity, the choosing to sensor
Selecting property and stability have important impact.
In prior art, (such as, the optimum working temperature of the gas sensor that can detect acetone is usually more than 200 DEG C
Fig. 4 of CN104950017A reports when operating temperature is 200 DEG C, its highly sensitive sensitivity under other operating temperatures,
200 DEG C of optimum working temperatures as device) or reduce temperature detection time, sensitivity very poor (such as J Mater Sci:
Mater Electron, 2015,15,3995 reports, its Co prepared3O4Nanometer sheet, at 160 DEG C to 100ppm acetone
Sensitivity is only 6.1).
Thus, preparation can be used for the research emphasis that the gas sensitive of low temperature detection is current sensor material, and it is for passing
The detection that sensor is widely used in industrial environment and daily life has great impetus.
Summary of the invention
For the deficiencies in the prior art, the technical problem to be solved is to provide a kind of novel intersection four oxidation
Three cobalt nano-chip arrays, the gas sensor comprising described array and application thereof.
The technical solution used in the present invention is as follows:
A kind of cobaltosic oxide nano chip arrays that intersects, described array intersects between each nanometer sheet through, described receives
Rice sheet is meso-hole structure, and described nano-chip arrays is the highest in the sensitivity of 90 DEG C～about 111 DEG C selective enumeration method acetone.
The sensitivity of described selective enumeration method acetone is the highest, is not limiting as described nano-chip arrays and has in other temperature
The performance of selective enumeration method acetone is the highest at 90 DEG C～about 111 DEG C sensitivity.Described 90 DEG C～about 111 DEG C are
Refer to that (such as, ± 1 DEG C) all has the sensitive of selective enumeration method acetone in the detection range of error that those skilled in the art allow
Spend the highest.Described 90 DEG C～about 111 DEG C are the best effort temperature of intersection cobaltosic oxide nano chip arrays of the present invention
Degree.
Further, it is mutually perpendicular crossing through between described each nanometer sheet.As shown in Figure 2 and Figure 3, described
Vertically referring between each nanometer sheet can be at optional position, space shape angle in 90 °.
Further, the aperture of described meso-hole structure is 2nm～50nm.
Further, described nano-chip arrays is the intersection cobaltosic oxide nano chip arrays of metal-modified.
Further, described metal selected from group ib, group VIII any one or the most multiple, it is preferred that described
Metal in platinum, gold, silver and palladium any one or the most multiple.
Further, the ratio shared by described metal is 0.01wt%～0.5wt%, the ratio shared by preferred described metal
For 0.05wt%～0.5wt%, the ratio shared by preferred described metal is 0.1wt%～0.4wt%.
Further, described nano-chip arrays is for detecting acetone 200 DEG C of property chosen below；Preferably, described
Nano-chip arrays is for detecting acetone 160 DEG C of property chosen below；Preferably, described nano-chip arrays at 60 DEG C～
160 DEG C of selective enumeration method acetone；It is furthermore preferred that described nano-chip arrays is used at 90 DEG C～130 DEG C of selective enumeration method acetone,
It is furthermore preferred that described nano-chip arrays is at 90 DEG C～111 DEG C of selective enumeration method acetone.
Further, described nano-chip arrays can realize the acetone detection that concentration is 10～1000ppm.
Further, described nano-chip arrays has good stability, within 60 days every 3 days, surveys and carries out the most altogether 20 times
Test, in first five test, performance rate of change compared with initial value is ± 3%；In front ten tests, performance and initial value phase
The rate of change of ratio is ± 4%；In front 15 tests, performance rate of change compared with initial value is ± 5%；In 20 tests,
Performance rate of change compared with initial value is ± 8%.
Second object of the present invention is to provide a kind of gas sensor, and described gas sensor comprises substrate and as front
The intersection cobaltosic oxide nano chip arrays of described any form, described substrate is only used for supporting described nano-chip arrays,
The material of described substrate is insulant, and described nano-chip arrays is directly grown on described substrate.
Further, described nano-chip arrays vertical-growth is on described substrate, and described vertically refers to nanometer sheet and lining
The end, can be at optional position, space shape angle in 90 °.
Further, described substrate is selected from insulating ceramics, glass, material.
Third object of the present invention is to provide a kind of method preparing intersection cobaltosic oxide nano chip arrays, including such as
Lower step:
A kind of preparation method intersecting cobaltosic oxide nano chip arrays, comprises the steps:
(1) by two citric acid monohydrate trisodiums, ammonium fluoride, carbamide, cobalt salt and water stirring obtain uniform solution, then by clean
Substrate is placed in described solution, carries out hydro-thermal reaction, obtains cobaltosic oxide precursor；
(2) described cobaltosic oxide precursor is carried out heat treatment, i.e. obtain intersection cobaltosic oxide nano chip arrays.
Further, after step (2), step (3) is also included: be deposited with at described intersection cobaltosic oxide nano chip arrays
The step of upper metal, i.e. obtains the intersection cobaltosic oxide nano chip arrays of metal-modified.
Further, the described substrate in step (1) is dielectric substrate；Preferably, described substrate is selected from insulation pottery
Porcelain, glass, material；
Further, the described cobalt salt in step (1) is selected from cobalt nitrate, cobaltous acetate, cobaltous chloride；
Further, the described cobalt salt in step (1), carbamide, ammonium fluoride, the mol ratio of two citric acid monohydrate trisodiums are 10:
5:5:1～5:3:2:1；
Further, in described step (1), the temperature of hydro-thermal reaction is 90 DEG C～120 DEG C, and the time of hydro-thermal reaction is 12h
Above；Preferably, the time of described hydro-thermal reaction is 12h～24h.
Further, the hydro-thermal reaction of described step (1) is carried out in a kettle., it is preferred that filling out of described reactor
Dress degree is 60%～80%.Preferably, described reactor is stainless steel cauldron.
Further, in described step (2), the temperature of heat treatment is 350 DEG C～550 DEG C, heat treatment time be 2～
4h, programming rate is 5～20 DEG C/min.
Further, described nano-chip arrays vertical-growth is on described substrate, and described vertically refers to nanometer sheet and lining
The end, can be at optional position, space shape angle in 90 °.
Further, described metal selected from group ib, group VIII any one or the most multiple, it is preferred that described
Metal in gold, silver and palladium any one or the most multiple.
Further, the ratio shared by described metal is 0.01wt%～0.5wt%, the ratio shared by preferred described metal
For 0.05wt%～0.5wt%, the ratio shared by preferred described metal is 0.1wt%～0.4wt%.
The method that the present invention provides can prepare above-mentioned intersection cobaltosic oxide nano chip arrays.It is different from the four of routine
The preparation method of Co 3 O nanometer sheet, applicant is found surprisingly that, uses the method for the present invention to prepare a kind of special appearance
Intersection cobaltosic oxide nano chip arrays, described array intersects between each nanometer sheet through, by ammonium fluoride, urine
As an overall synergism between element, two citric acid monohydrate trisodiums, four kinds of materials of cobalt salt, there is direct complex reaction,
Directly forming core on substrate, generates the intersection cobaltosic oxide nano chip arrays of special appearance, in described array each nanometer sheet it
Between intersect through, described nanometer sheet is meso-hole structure.
The intersection cobaltosic oxide nano chip arrays that the present invention provides, has bigger specific surface area and electron mobility.
Wherein, intersect the desorption reaction that is adsorbed in of the space beneficially gas molecule between cobaltosic oxide nano chip arrays, improve anti-
The sensitivity answered also reduces reaction duration.The intersection cobaltosic oxide nano array of the present invention, in building-up process, is directly to exist
The growth of substrate surface crystallization nucleation, it is not necessary to traditional coating procedure, and there is better performance (significantly reduce optimal
Operating temperature, and improve detection sensitivity).Described intersection cobaltosic oxide nano chip arrays directly forming core on substrate
Growth, it is not required that first grow seed crystal, decrease reactions steps and reduce production cost, also make whole course of reaction more may be used
Control.Being fully contacted of the open structure beneficially gas that crossed array pattern causes and nanometer sheet surface, to make it have bigger
Specific surface area and electron mobility, and crossing nanotube chip arrays between space beneficially gas molecule be adsorbed in desorption
Reaction, increases the gas sensitivity of material, and accelerates absorption and the speed of desorption.
Fourth object of the present invention is to provide the intersection cobaltosic oxide nano sheet battle array of any form as previously mentioned
It is listed in sensor, acetone detection, the purposes of medical treatment context of detection.
5th purpose of the present invention is to provide described gas sensor in sensor, acetone detection, medical treatment detection side
The purposes in face, such as detects whether suffer from diabetes by the content of acetone in characteristics of contaminated respiratory droplets gas.Breathe diagnosis diabetes
Device can comprise gas sensor of the present invention, and described breathing diagnosis diabetes device can be portable.
Intersection cobaltosic oxide nano chip arrays of the present invention and gas sensor can be used for detecting under multiple environment
The acetone of variable concentrations, such as, in characteristics of contaminated respiratory droplets gas detecting, for detecting the acetone (≤10ppm) of low concentration, with detection
Whether suffer from diabetes, industrial environment detects the acetone (>=500ppm) of high concentration, to detect whether Environmental insults has
There is harm.
6th purpose of the present invention is to provide a kind of acetone detection device, and described acetone detection device comprises such as front institute
State the intersection cobaltosic oxide nano chip arrays such as front any form or gas sensor.
Owing to the present invention considerably reduces optimum working temperature than prior art, reduce testing cost, be also beneficial to
Prepare portable acetone detection equipment.
Beneficial effects of the present invention is as follows:
1) the intersection cobaltosic oxide nano chip arrays that the present invention provides, has bigger specific surface area and electron mobility, hands over
That pitches the space beneficially gas molecule between nano-chip arrays is adsorbed in desorption reaction, it is provided that more gas molecule is inhaled
Attached avtive spot and faster electron transfer rate, improve the sensitivity of reaction and reduce reaction duration, hence it is evident that improves gas and passes
Perception energy；
2) course of reaction of the present invention is carried out in a kettle., product good crystallinity, with short production cycle, and low cost, to environment without dirt
Dye；
3) preparation method of the present invention is the most controlled, and reaction temperature is low, consume the energy few, relatively low to equipment requirements, be conducive to into
Row large-scale industrial production；
4) preparation method of the present invention need not grow Cobalto-cobaltic oxide inculating crystal layer, directly forming core growth on substrate, eliminates
Traditional coating step, low cost, efficiency is high；
5) the cobaltosic oxide nano chip arrays that intersects of the present invention overcomes traditional cobaltosic oxide nano sheet and cannot directly exist
The problem generating array in the most passive dielectric substrate, production cost is low, and efficiency is high, and operating process is the most controlled；
6) what the present invention provided intersect gas sensor cocoa at a lower temperature (60 that cobaltosic oxide nano chip arrays prepares
DEG C～160 DEG C), test the acetone of big concentration range (10～1000ppm)；This sensor has good selectivity, detects third
The sensitivity of ketone is pentane, ammonia, methanol, formaldehyde and the 3.43 of ethanol, 2.95,2.7,2.58,1.89 times；And this sensor
There is good stability, within 60 days every 3 days, survey and carry out 20 tests the most altogether, in first five test, performance and initial value phase
The rate of change of ratio is ± 3%；In front ten tests, performance rate of change compared with initial value is ± 4%；In front 15 tests,
Performance rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is ± 8%；
Intersection cobaltosic oxide nano chip arrays provided by the present invention can be used for preparation and breathes diagnosis diabetes device.
Accompanying drawing explanation
Fig. 1 is intersection cobaltosic oxide nano chip arrays X-ray diffraction (XRD) picture that embodiment 1 prepares；
Fig. 2 is intersection cobaltosic oxide nano chip arrays high power scanning electron microscope (SEM) picture that embodiment 1 prepares；
Fig. 3 is intersection cobaltosic oxide nano chip arrays low power scanning electron microscope (SEM) picture that embodiment 1 prepares；
Fig. 4 is high power transmission electron microscope (HRTEM) figure of the intersection cobaltosic oxide nano sheet that embodiment 1 prepares；
Fig. 5 is intersection cobaltosic oxide nano chip arrays current/voltage (I-V) characteristic curve that embodiment 1 prepares；
Fig. 6 is the specific surface area-Pore Diameter Detection figure of the intersection cobaltosic oxide nano chip arrays that embodiment 1 prepares, the song in figure
Line a is specific surface area figure (corresponding Relative Pressure-Volume Adsorption coordinate), and curve b is pore-size distribution
Figure (corresponding Pore diameter-dV/dlog (D) coordinate)；
Fig. 7 is the sensitivity that the intersection cobaltosic oxide nano chip arrays that embodiment 1 prepares detects acetone at different temperatures；
Fig. 8 is the intersection cobaltosic oxide nano chip arrays sensitivity comparison sheet to variable concentrations acetone that embodiment 1 prepares；
Fig. 9 is that the gaseousness of the intersection cobaltosic oxide nano chip arrays that embodiment 1 prepares selects detection comparison sheet；
Figure 10 is that the cobaltosic oxide nano chip arrays that intersects that embodiment 1 prepares tested the 20 detection acetone surveying gained at 2 months
Sensitivity；
Figure 11 is cobaltosic oxide nano pin array low power scanning electron microscope (SEM) picture that comparative example 1 prepares；
Figure 12 is low power scanning electron microscope (SEM) picture of the cobaltosic oxide nano sheet that comparative example 2 prepares.
Detailed description of the invention
The present invention is further illustrated below in conjunction with drawings and Examples.Following example are merely to illustrate the present invention and need not
In limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art are permissible
Making various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
Embodiment 1
The manufacture method of the intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
1) it is that the cobalt nitrate of 10:5:5:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
80%；
3) and by the dielectric substrate cleaning up and being coated with electrode being placed in solution, controlling hydrothermal temperature is 95 DEG C, instead
The most a length of 12 hours, described dielectric substrate can be insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 450 DEG C 2 hours heat treatments, heating rate is 10
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate.
Use step 1)～5) intersection cobaltosic oxide nano chip arrays, the sample obtained can be prepared on an insulating substrate
It is used directly for carrying out gas sensing detection.The XRD figure of gained sample is as it is shown in figure 1, show in Fig. 1, and gained peak position is corresponding
Pure Cobalto-cobaltic oxide, does not has miscellaneous peak, it is seen that preparation for pure Cobalto-cobaltic oxide, there is no dephasign.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 of the intersection cobaltosic oxide nano chip arrays prepared
Pitch through, described vertically refer between each nanometer sheet can be at optional position, space shape angle in 90 °.
Fig. 4 is shown that the high power transmission electron microscope figure of the intersection cobaltosic oxide nano sheet prepared, can from Fig. 4
To find out, gained Cobalto-cobaltic oxide is polycrystalline material.Fig. 5 is shown that direct growth intersection four on an insulating substrate and aoxidizes three
Current/voltage (I-V) characteristic curve of cobalt nano-chip arrays, as shown in Figure 5, electric current and voltage linear relation, it is seen that intersect
It is Ohmic contact between cobaltosic oxide nano sheet and electrode, so that it is guaranteed that gas-sensitive reaction afterwards is material gas sensing capabilities
Embodiment rather than material with electrode between contact the change caused.Fig. 6 is prepared intersection cobaltosic oxide nano sheet battle array
Specific surface area-Pore Diameter Detection the figure of row, from curve a, the specific surface area of sample is 83 m2·g–1, from curve b, sample
The hole average-size of product is 8.5nm, and bigger specific surface area, open structure are conducive to the abundant of gas and sample surfaces
Contact, increases the gas sensitivity of material, and accelerates absorption and the speed of desorption.The intersection Cobalto-cobaltic oxide that Fig. 7 is prepared is received
Rice chip arrays detection sensitivity to acetone under difference tests temperature (60 DEG C～160 DEG C), although its optimum working temperature is
111 DEG C, but all there is good Gas Detection Performance of thermal at 60 DEG C～160 DEG C these intersection cobaltosic oxide nano chip arrays, can work
Making temperature range wide, optimum working temperature is low, reduces operating power consumption, beneficially life-time service.Fig. 8 receives for intersection Cobalto-cobaltic oxide
The rice chip arrays detection sensitivity to the acetone of variable concentrations, its detectable concentration scope 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, the cobaltosic oxide nano chip arrays that intersects is detection penta to the detection sensitivity of acetone respectively
Alkane, ammonia, formaldehyde, methanol, the 3.34 of ethanol sensitivity, 2.95,2.7,2.58 and 1.89 times, it is seen that intersect Cobalto-cobaltic oxide receive
Rice chip arrays detection acetone has fabulous selectivity.Figure 10 is that intersection cobaltosic oxide nano chip arrays is surveyed for every 3 days in 60 days
Carry out the sensitivity (the 60th day survey the 20th time) of the detection acetone of 20 test gained the most altogether, in first five test, performance with
The rate of change that initial value is compared is ± 3%；In front ten tests, performance rate of change compared with initial value is ± 4%；First 15 times
In test, performance rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is
± 8%, it is seen then that the intersection cobaltosic oxide nano chip arrays prepared has good stability, be conducive to reality application.
Comparative example 1
The manufacture method of cobaltosic oxide nano pin array, comprises the following steps:
1) it is that the cobalt nitrate of 10:5:5:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
80%；
3) and by the dielectric substrate being coated with electrode cleaned up being placed in solution, controlling hydrothermal temperature is 95 DEG C, reaction
Shi Changwei 6 hours, described substrate can be insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor is carried out in the air that temperature is 450 DEG C 2 hours heat treatments, i.e. obtain four oxidations
Three cobalt nano needle arrays.
As shown in figure 11, gained sample is nano needle arrays pattern to the SEM picture of comparative example 1 gained sample.Detection
The acetone detection sensitivity of the cobaltosic oxide nano pin array that comparative example 1 prepares, its optimum working temperature is 130 DEG C,
Relatively low (the S of sensitivity at 130 DEG C of detection 100ppm acetoneAcetone=8.1), prepared cobaltosic oxide nano pin array is carried out surely
Qualitative test, surveys the sensitivity carrying out 20 test detection acetone the most altogether, in first five test, performance for every 3 days in 60 days
Rate of change compared with initial value is ± 5%；In front ten tests, performance rate of change compared with initial value is ± 8%；Front 15
In secondary test, performance rate of change compared with initial value is ± 15%；In 20 tests, performance change compared with initial value
Rate is ± 20%, and the poor stability of cobaltosic oxide nano pin array is described.The difference of comparative example 1 and embodiment 1 is just
It is the time short (only 6 hours) in the hydro-thermal reaction of step 3), only grows up to cobaltosic oxide nano pin array, also do not generate friendship
Fork cobaltosic oxide nano chip arrays, air-sensitive performance is poor, and optimum working temperature is high (being 130 DEG C), and 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(sees RSC Advances, and 2015,5,59976)
The manufacture method of cobaltosic oxide nano sheet, comprises the following steps:
1) by 0.02mmol PEO-PPO-PEO (ethylene glycol)-block-poly
(propylene glycol)-block-poly (ethylene glycol)) it is dissolved in 16.5mL ethanol and 1mL deionized water
Stir to obtain homogeneous solution；
2) urotropine of 0.5mmol, the cobaltous acetate of 0.5mml and 13mL ethylene glycol are dissolved in step 1) gained molten
Liquid stirs；
3) by step 2) gained homogeneous solution standing 12h；
4) homogeneous solution obtained is moved in the rustless steel autoclave that liner is politef, control hydro-thermal reaction temperature
Degree is 170 DEG C, during reaction a length of 2 hours；
5), after having reacted, obtain sample by centrifugal for gained turbid solution, gained sample with ethanol and deionized water are cleaned；
6) gained cobaltosic oxide precursor carrying out in the air that temperature is 450 DEG C 2 hours heat treatments, gained is four oxygen
Change three cobalt nanometer sheet；
7) by step 6) gained powder be coated in after mixing homogeneously according to a certain percentage with ethanol cleaned up insulation pottery
In ceramics, silicon chip or glass substrate.
The SEM picture of the cobaltosic oxide nano sheet that comparative example 2 prepares as shown in figure 12, is four oxidations three piled up
Cobalt nanometer sheet, the acetone detection sensitivity of the cobaltosic oxide nano sheet of detection comparative example 2 gained, its optimum working temperature
It it is 150 DEG C, at the poor (S of sensitivity of 150 DEG C of detection 100ppm acetoneAcetone=11.4).This comparative example is with embodiment 1 not
It is that the experiment entirely different preparation method of medicine used need not with part, although the obtained cobaltosic oxide nano sheet that is, but
The cobaltosic oxide nano sheet pattern that embodiment 1 prepares with comparative example 2 is different.Embodiment 1 gained intersection Cobalto-cobaltic oxide
Nano-chip arrays directly forming core growth on substrate, and the cobaltosic oxide nano sheet obtained in comparative example 2 cannot be direct
It is grown on substrate, needs to be coated in and could be used on substrate carrying out gas sensing detection.Further, as Figure 12 and Fig. 2, Fig. 3 pair
Ratio is shown, intersects with embodiment 1 gained compared with cobaltosic oxide nano chip arrays, and the nanometer sheet of comparative example 2 is on substrate
Mutually pile up superposition so that its effective area contacted with gas is little, and poorly conductive, so its air-sensitive detection poor performance.Right
Illustrating than result, gained nanometer sheet is grown directly upon on substrate and pattern in array, for the gas sensing property of gas sensor
Can have decisive role.
Comparative example 3(sees Chinese patent CN 103217460A)
The manufacture method of rhombus cobaltosic oxide nano linear array, comprises the following steps:
1) it is that the cobalt nitrate of 1:1:5, ammonium fluoride, hexamethylenetetramine and deionized water mix and blend obtain the most molten mol ratio
Liquid；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
50%；
3) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 95
DEG C, during reaction a length of 24 hours；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor is carried out in the argon that temperature is 450 DEG C 4 hours heat treatments, i.e. obtain rhombus four
Co 3 O nano-wire array.
Comparative example 3 gained sample is rhombus cobaltosic oxide nano linear array, the Pedicellus et Pericarpium Trapae of detection comparative example 3 gained
The acetone detection sensitivity of shape Cobalto-cobaltic oxide array, its optimum working temperature is 160 DEG C, at 160 DEG C to 500ppm acetone
Detection sensitivity is only 20.1.Comparative example 3 with the difference of embodiment 1 is exactly, and the pattern of gained nano-array is different,
The optimum working temperature causing this comparative example's selective enumeration method acetone is higher, and detection sensitivity is lower.Comparing result illustrates,
The pattern of intersection cobaltosic oxide nano chip arrays has decisive role for the air-sensitive performance of gas sensor.
Comparative example 4(sees Sensors and Actuators B, and 2015,208 112 121)
The manufacture method of rhombus zinc oxide nano-array, comprises the following steps:
1) it is that the zinc nitrate of 1:2:4, hexamethylenetetramine, ammonium fluoride and 40mL deionized water mix and blend obtain uniformly mol ratio
Solution；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
80%；
3) and by the dielectric substrate being coated with electrode cleaned up being placed in solution, controlling hydrothermal temperature is 95 DEG C, reaction
Shi Changwei 24 hours, described dielectric substrate can be insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and drying obtains zinc oxide forerunner
Body；
6) gained zinc oxide presoma is carried out in the argon that temperature is 450 DEG C 4 hours heat treatments, i.e. obtain rhombus dioxy
Change zinc nano-array.
Comparative example 4 gained sample is rhombus zinc oxide nano-array, the rhombus two of detection comparative example 4 gained
The acetone detection sensitivity of zinc oxide nano array, finds to acetone without response, the selective enumeration method sensitivity to ethanol is the highest,
Its optimum working temperature is 300 DEG C, and obtained rhombus zinc oxide nano-array is 300 DEG C of detection spirits to 100ppm ethanol
Sensitivity is only 11.8.Comparative example 4 with the difference of embodiment 1 is exactly, and material category is different, and embodiment 1 is four oxidations
Three cobalts and comparative example 4 is zinc oxide, and gained sample topography is different, and embodiment 1 is for intersecting cobaltosic oxide nano
Chip arrays, comparative example 4 is rhombus zinc oxide array.The gas detected in this comparative example is ethanol and to acetone
Without response, and required detection temperature is the highest.Comparing result illustrates, the kind of functional material and pattern are for gas sensing
The air-sensitive performance of device is respectively provided with decisive role.
Embodiment 2
The manufacture method of the intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
1) it is that the cobaltous acetate of 6:3:3:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
70%；
3) and by the dielectric substrate cleaning up and being coated with electrode being placed in solution, controlling hydrothermal temperature is 90 DEG C, instead
The most a length of 14 hours, described dielectric substrate can be insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 350 DEG C 4 hours heat treatments, heating rate is 5
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate.
Embodiment 2 gained sample is for intersecting cobaltosic oxide nano chip arrays.The intersection four of detection embodiment 2 gained aoxidizes
The acetone detection sensitivity of three cobalt nano-chip arrays, its optimum working temperature is 111 DEG C, the detection sensitivity to 100ppm acetone
It is 16.3.Fork cobaltosic oxide nano chip arrays surveys the detection acetone carrying out 20 test gained the most altogether in every 3 days in 60 days
Sensitivity (the 60th day survey the 20th time), in first five test, performance rate of change compared with initial value is ± 3%；Survey for front ten times
In examination, performance rate of change compared with initial value is ± 4%；In front 15 tests, performance rate of change compared with initial value is
±4%；In 20 tests, performance rate of change compared with initial value is ± 8%, it is seen then that the intersection Cobalto-cobaltic oxide prepared is received
Rice chip arrays has good stability, is conducive to reality application.
Embodiment 3
The manufacture method of the intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
1) it is that the cobaltous chloride of 5:3:2:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
60%；
3) and by the dielectric substrate cleaning up and being coated with electrode being placed in solution, controlling hydrothermal temperature is 110 DEG C, instead
The most a length of 13 hours, described dielectric substrate can be insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 550 DEG C 3 hours heat treatments, heating rate is 15
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate.
Embodiment 3 gained sample is for intersecting cobaltosic oxide nano chip arrays.The intersection four of detection embodiment 3 gained aoxidizes
The acetone detection sensitivity of three cobalt nano-chip arrays, its optimum working temperature is 110 DEG C, the detection sensitivity to 100ppm acetone
It is 16.7.Fork cobaltosic oxide nano chip arrays surveys the detection acetone carrying out 20 test gained the most altogether in every 3 days in 60 days
Sensitivity (the 60th day survey the 20th time), in first five test, performance rate of change compared with initial value is ± 2%；Survey for front ten times
In examination, performance rate of change compared with initial value is ± 4%；In front 15 tests, performance rate of change compared with initial value is
±5%；In 20 tests, performance rate of change compared with initial value is ± 7%, it is seen then that the intersection Cobalto-cobaltic oxide prepared is received
Rice chip arrays has good stability, is conducive to reality application.
Embodiment 4
The manufacture method of the intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
6) it is that the cobaltous acetate of 8:5:5:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
7) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
70%；
8) and by the dielectric substrate cleaning up and being coated with electrode being placed in solution, controlling hydrothermal temperature is 115 DEG C, instead
The most a length of 15 hours, described dielectric substrate can be insulating ceramic film, silicon chip or glass substrate；
9), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
10) gained cobaltosic oxide precursor carrying out in the air that temperature is 450 DEG C 4 hours heat treatments, heating rate is
20 DEG C/min, i.e. obtaining intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays is directly given birth to
Length is on an insulating substrate.
Embodiment 4 gained sample is for intersecting cobaltosic oxide nano chip arrays.The intersection four of detection embodiment 4 gained aoxidizes
The acetone detection sensitivity of three cobalt nano-chip arrays, its optimum working temperature is 112 DEG C, the detection sensitivity to 100ppm acetone
It is 16.6.Fork cobaltosic oxide nano chip arrays surveys the detection acetone carrying out 20 test gained the most altogether in every 3 days in 60 days
Sensitivity (the 60th day survey the 20th time), in first five test, performance rate of change compared with initial value is ± 3%；Survey for front ten times
In examination, performance rate of change compared with initial value is ± 3%；In front 15 tests, performance rate of change compared with initial value is
±5%；In 20 tests, performance rate of change compared with initial value is ± 8%, it is seen then that the intersection Cobalto-cobaltic oxide prepared is received
Rice chip arrays has good stability, is conducive to reality application.
Embodiment 5
The gold of the present invention modifies the manufacture method of intersection cobaltosic oxide nano chip arrays, comprises the following steps:
1) it is that the cobaltous acetate of 10:5:5:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
60%；
3) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 90
DEG C, during reaction a length of 14 hours, described dielectric substrate can be insulating ceramics, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 550 DEG C 4 hours heat treatments, programming rate is 5
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate；
6) gained be grown intersect the substrate of cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersect four oxygen
Change the gold of the upper 0.05wt% of surface evaporation of three cobalt nano-chip arrays, i.e. obtain the intersection cobaltosic oxide nano sheet battle array of gold modification
Row.
Embodiment 5 gained sample is the intersection cobaltosic oxide nano chip arrays that gold is modified.The gold of detection embodiment 5 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays modified, its optimum working temperature is 105 DEG C, to 100ppm
The detection sensitivity of acetone is 18.7.Gold intersection cobaltosic oxide nano chip arrays is surveyed and is carried out 20 the most altogether for every 3 days in 60 days
The sensitivity (surveying the 20th time for the 60th day) of the detection acetone of secondary test gained, in first five test, performance is compared with initial value
Rate of change is ± 2%；In front ten tests, performance rate of change compared with initial value is ± 4%；In front 15 tests, performance
Rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is ± 7%, it is seen then that
The gold intersection cobaltosic oxide nano chip arrays prepared has good stability, is conducive to reality application.
Embodiment 6
The gold of the present invention modifies the manufacture method of intersection cobaltosic oxide nano chip arrays, comprises the following steps:
7) it is that the cobalt nitrate of 10:8:7:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
8) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
70%；
9) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 90
DEG C, during reaction a length of 18 hours, described dielectric substrate can be insulating ceramics, silicon chip or glass substrate；
10), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and drying obtains Cobalto-cobaltic oxide
Presoma；
11) gained cobaltosic oxide precursor carrying out in the air that temperature is 550 DEG C 4 hours heat treatments, programming rate is 8
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate；
12) gained be grown intersect the substrate of cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersect four
The gold of the upper 0.01wt% of surface evaporation of Co 3 O nano-chip arrays, i.e. obtains the intersection cobaltosic oxide nano sheet of gold modification
Array.
Embodiment 6 gained sample is the intersection cobaltosic oxide nano chip arrays that gold is modified.The gold of detection embodiment 6 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays modified, its optimum working temperature is 108 DEG C, to 100ppm
The detection sensitivity of acetone is 18.9.Gold intersection cobaltosic oxide nano chip arrays is surveyed and is carried out 20 the most altogether for every 3 days in 60 days
The sensitivity (surveying the 20th time for the 60th day) of the detection acetone of secondary test gained, in first five test, performance is compared with initial value
Rate of change is ± 2%；In front ten tests, performance rate of change compared with initial value is ± 3%；In front 15 tests, performance
Rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is ± 7%, it is seen then that
The gold intersection cobaltosic oxide nano chip arrays prepared has good stability, is conducive to reality application.
Embodiment 7
The manufacture method of the modified by silver intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
1) it is that the cobaltous chloride of 6:4:2:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
70%；
3) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 100
DEG C, during reaction a length of 13 hours, but described dielectric substrate insulating ceramic film, silicon chip or glass substrate；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 550 DEG C 3 hours heat treatments, programming rate is 20
DEG C/min, i.e. obtain intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays direct growth
On an insulating substrate；
6) gained length is had the substrate of intersection cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersecting four oxidations
The silver of the upper 0.1wt% of surface evaporation of three cobalt nano-chip arrays, i.e. obtains the intersection cobaltosic oxide nano chip arrays of modified by silver.
Embodiment 7 gained sample is the intersection cobaltosic oxide nano chip arrays of modified by silver.The silver of detection embodiment 7 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays modified, its optimum working temperature is 100 DEG C, to 100ppm
The detection sensitivity of acetone is 29.5.Modified by silver intersection cobaltosic oxide nano chip arrays is surveyed to enter the most altogether for every 3 days in 60 days
The sensitivity (surveying the 20th time for the 60th day) of the detection acetone of 20 test gained of row, in first five test, performance and initial value phase
The rate of change of ratio is ± 2%；In front ten tests, performance rate of change compared with initial value is ± 3%；In front 15 tests,
Performance rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is ± 8%, can
Seeing, the modified by silver intersection cobaltosic oxide nano chip arrays prepared has good stability, is conducive to reality application.
Embodiment 8
The manufacture method of the modified by silver intersection cobaltosic oxide nano chip arrays of the present invention, comprises the following steps:
7) it is that the cobaltous acetate of 8:6:3:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
8) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
80%；
9) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 120
DEG C, during reaction a length of 12 hours, but described dielectric substrate insulating ceramic film, silicon chip or glass substrate；
10), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and drying obtains Cobalto-cobaltic oxide
Presoma；
11) gained cobaltosic oxide precursor carrying out in the air that temperature is 450 DEG C 4 hours heat treatments, programming rate is
10 DEG C/min, i.e. obtaining intersection cobaltosic oxide nano chip arrays, described intersection cobaltosic oxide nano chip arrays is directly given birth to
Length is on an insulating substrate；
12) gained length is had the substrate of intersection cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersecting four oxygen
Change the silver of the upper 0.5wt% of surface evaporation of three cobalt nano-chip arrays, i.e. obtain the intersection cobaltosic oxide nano sheet battle array of modified by silver
Row.
Embodiment 8 gained sample is the intersection cobaltosic oxide nano chip arrays of modified by silver.The silver of detection embodiment 8 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays modified, its optimum working temperature is 92 DEG C, to 100ppm
The detection sensitivity of acetone is 30.1.Modified by silver intersection cobaltosic oxide nano chip arrays is surveyed to enter the most altogether for every 3 days in 60 days
The sensitivity (surveying the 20th time for the 60th day) of the detection acetone of 20 test gained of row, in first five test, performance and initial value phase
The rate of change of ratio is ± 2%；In front ten tests, performance rate of change compared with initial value is ± 2%；In front 15 tests,
Performance rate of change compared with initial value is ± 4%；In 20 tests, performance rate of change compared with initial value is ± 7%, can
Seeing, the modified by silver intersection cobaltosic oxide nano chip arrays prepared has good stability, is conducive to reality application.
Embodiment 9
The palladium of the present invention modifies the manufacture method of intersection cobaltosic oxide nano chip arrays, comprises the following steps:
1) it is that the cobalt nitrate of 5:3:3:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
2) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
70%；
3) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 115
DEG C, during reaction a length of 24 hours；
4), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and before drying obtains Cobalto-cobaltic oxide
Drive body；
5) gained cobaltosic oxide precursor carrying out in the air that temperature is 350 DEG C 4 hours heat treatments, programming rate is 10
DEG C/min i.e. obtain intersect cobaltosic oxide nano chip arrays；
6) gained length is had the substrate of intersection cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersecting four oxidations
The palladium of the upper 0.4wt% of surface evaporation of three cobalt nano-chip arrays, i.e. obtains the intersection cobaltosic oxide nano chip arrays that palladium is modified.
Embodiment 9 gained sample is the intersection cobaltosic oxide nano chip arrays that palladium is modified.The palladium of detection embodiment 9 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays modified, its optimum working temperature is 90 DEG C, to 100ppm
The detection sensitivity of acetone is 29.8.Palladium is modified the survey in every 3 days in 60 days of fork cobaltosic oxide nano chip arrays and is carried out the most altogether
The sensitivity (surveying the 20th time for the 60th day) of the detection acetone of 20 test gained, in first five test, performance is compared with initial value
Rate of change be ± 3%；In front ten tests, performance rate of change compared with initial value is ± 3%；In front 15 tests, property
Can the rate of change compared with initial value be ± 4%；In 20 tests, performance rate of change compared with initial value is ± 7%, can
Seeing, the palladium prepared is modified intersection cobaltosic oxide nano chip arrays and is had good stability, is conducive to reality application.
Embodiment 10
The platinum of the present invention modifies the manufacture method of intersection cobaltosic oxide nano chip arrays, comprises the following steps:
7) it is that the cobaltous chloride of 8:5:6:1, carbamide, ammonium fluoride, two citric acid monohydrate trisodiums and deionized water are at room temperature by mol ratio
Lower mix and blend；
8) being moved in the rustless steel autoclave that liner is politef by the homogeneous solution obtained, reactor filling degree is
60%；
9) and by the insulating ceramic film cleaned up, silicon chip or glass substrate being placed in solution, controlling hydrothermal temperature is 120
DEG C, during reaction a length of 20 hours；
10), after having reacted, take out substrate and be rinsed respectively with deionized water and ethanol and drying obtains Cobalto-cobaltic oxide
Presoma；
11) gained cobaltosic oxide precursor carrying out in the air that temperature is 550 DEG C 2 hours heat treatments, programming rate is
20 DEG C/min i.e. obtains intersection cobaltosic oxide nano chip arrays；
12) gained length is had the substrate of intersection cobaltosic oxide nano chip arrays as on electron beam evaporation platform, intersecting four oxygen
Change the platinum of the upper 0.5wt% of surface evaporation of three cobalt nano-chip arrays, i.e. obtain the intersection cobaltosic oxide nano sheet battle array that platinum is modified
Row.
Embodiment 10 gained sample is the intersection cobaltosic oxide nano chip arrays that palladium is modified.Detection embodiment 10 gained
The acetone detection sensitivity of the intersection cobaltosic oxide nano chip arrays that palladium is modified, its optimum working temperature is 95 DEG C, right
The detection sensitivity of 100ppm acetone is 28.9.Palladium is modified fork cobaltosic oxide nano chip arrays and is surveyed once for every 3 days in 60 days
Carrying out the sensitivity (surveying the 20th time for the 60th day) of the detection acetone of 20 test gained altogether, in first five test, performance is with initial
The rate of change that value is compared is ± 2%；In front ten tests, performance rate of change compared with initial value is ± 3%；Front 15 tests
In, performance rate of change compared with initial value is ± 3%；In 20 tests, performance rate of change compared with initial value is ±
7%, it is seen then that the platinum prepared is modified intersection cobaltosic oxide nano chip arrays and had good stability, is conducive to reality application.
Claims (10)
1. an intersection cobaltosic oxide nano chip arrays, it is characterised in that intersect between each nanometer sheet in described array
Passing, described nanometer sheet is meso-hole structure, and described nano-chip arrays is at 90 DEG C～about 111 DEG C selective enumeration method acetone
Sensitivity is the highest.
Intersection cobaltosic oxide nano chip arrays the most according to claim 1, it is characterised in that described nano-chip arrays
Intersection cobaltosic oxide nano chip arrays for metal-modified.
Intersection cobaltosic oxide nano chip arrays the most according to claim 2, it is characterised in that described metal is selected from the
IB race, group VIII any one or the most multiple, it is preferred that any one in gold, silver, palladium and platinum of described metal
Or it is the most multiple.
Intersection cobaltosic oxide nano chip arrays the most according to claim 3, it is characterised in that the ratio shared by described metal
Example is 0.01wt%～0.5wt%, and the ratio shared by preferred described metal is 0.05wt%～0.5wt%, preferred described gold
Ratio shared by genus is 0.1wt%～0.4wt%.
5. according to the intersection cobaltosic oxide nano chip arrays described in any one of claim 1-4, it is characterised in that described receives
Rice chip arrays is for detecting acetone 200 DEG C of property chosen below；Preferably, described nano-chip arrays is for below 160 DEG C
Selective enumeration method acetone；Preferably, described nano-chip arrays is at 60 DEG C～160 DEG C of selective enumeration method acetone；More preferably
, described nano-chip arrays is used at 90 DEG C～130 DEG C of selective enumeration method acetone, it is furthermore preferred that described nano-chip arrays
For at 90 DEG C～111 DEG C of selective enumeration method acetone.
6. according to the intersection cobaltosic oxide nano chip arrays described in any one of claim 1-4, it is characterised in that described receives
Rice chip arrays there is good stability, in 60 days every 3 days survey carry out the most altogether 20 times test, first five time test in, performance with
The rate of change that initial value is compared is ± 3%；In front ten tests, performance rate of change compared with initial value is ± 4%；First 15 times
In test, performance rate of change compared with initial value is ± 5%；In 20 tests, performance rate of change compared with initial value is
±8%。
7. the preparation method of intersection cobaltosic oxide nano chip arrays described in claim 1, comprises the steps:
(1) by two citric acid monohydrate trisodiums, ammonium fluoride, carbamide, cobalt salt and water stirring obtain uniform solution, then by clean
Substrate is placed in described solution, carries out hydro-thermal reaction, obtains cobaltosic oxide precursor；
(2) described cobaltosic oxide precursor is carried out heat treatment, i.e. obtain intersection cobaltosic oxide nano chip arrays.
8. a gas sensor, it is characterised in that: described gas sensor comprises substrate and any one of claim 1-7 institute
The intersection cobaltosic oxide nano chip arrays stated, described substrate is only used for supporting described nano-chip arrays, the material of described substrate
For insulant, described nano-chip arrays is directly grown on described substrate.
9. the gas described in cobaltosic oxide nano chip arrays or claim 8 that intersects described in any one of claim 1-7 passes
Sensor is in sensor, acetone detection, the purposes of medical treatment context of detection.
10. an acetone detection device, it is characterised in that: described acetone detection device comprises any one of claim 1-7 institute
Gas sensor described in the intersection cobaltosic oxide nano chip arrays stated or claim 8.
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| CN107356639A (en) * | 2017-06-21 | 2017-11-17 | 中国科学院合肥物质科学研究院 | Cobaltosic oxide nano piece hollow ball and its production and use |
| CN107356639B (en) * | 2017-06-21 | 2019-05-31 | 中国科学院合肥物质科学研究院 | Cobaltosic oxide nano piece hollow sphere and its preparation method and application |
| CN107337473A (en) * | 2017-07-25 | 2017-11-10 | 济南大学 | The growth in situ MoO on earthenware3The method and gas sensor of nanometer sheet |
| CN107337473B (en) * | 2017-07-25 | 2020-07-07 | 济南大学 | In-situ growth of MoO on ceramic tubes3Nanosheet method and gas sensor |
| US10809216B2 (en) | 2017-10-23 | 2020-10-20 | Boe Technology Group Co., Ltd. | Gas sensor and method for manufacturing the same, and detection device |
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| 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 |
| CN113219011A (en) * | 2021-05-19 | 2021-08-06 | 吉林大学 | Co-doped SnO2Formaldehyde-acetone gas sensor and preparation method thereof |
| CN114487020A (en) * | 2022-02-08 | 2022-05-13 | 扬州大学 | Gas-sensitive material for lung cancer breath marker gas methanol 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 |
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