CN109030588A - A kind of preparation method of ozone gas sensor array - Google Patents
A kind of preparation method of ozone gas sensor array Download PDFInfo
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- CN109030588A CN109030588A CN201810520398.XA CN201810520398A CN109030588A CN 109030588 A CN109030588 A CN 109030588A CN 201810520398 A CN201810520398 A CN 201810520398A CN 109030588 A CN109030588 A CN 109030588A
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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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- G—PHYSICS
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- 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
- G01N27/27—Association of two or more measuring systems or cells, each measuring a different parameter, where the measurement results may be either used independently, the systems or cells being physically associated, or combined to produce a value for a further parameter
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The present invention is a kind of preparation method of ozone gas sensor array.A kind of preparation method of ozone gas sensor array, comprising: (1) prepare modifier solution；(2) carbon nano tube dispersion liquid is prepared；(3) carbon nano tube dispersion liquid is stood, centrifugation, obtains sediment；(4) it after mixing sediment with water, is coated in interdigital electrode and dry, obtains sensing chip；Sensing chip is fabricated to sensor, obtains sensor 1；(5) it repeats step (1)-(4) 5 times, obtains sensor 2-6；(6) by after sensor 1-6 energization aging, sensor array is formed, the ozone gas sensor array is obtained.A kind of preparation method of ozone gas sensor array of the present invention, physical modification is carried out to carbonyl multi-walled carbon nanotube using a variety of small molecule modifiers, and then the sensor array of carbon nanotube base has been prepared, realize the high sensitivity to ozone and its common interference object, recognition detection at room temperature.
Description
Technical field
The invention belongs to the technical fields of gas sensing detection field, and in particular to a kind of ozone gas sensor array
Preparation method.
Background technique
It is shown according to the information that China Environmental Monitoring General Station issues, since 2013, three big key area (Jing-jin-ji regions, length
Triangle, Pearl River Delta) in, Jing-jin-ji region and Yangtze River Delta ozone concentration have significant trend, especially 2017 year of rising year by year to rise most
It is significant.Subsequent monitoring data is shown: in May, 2017, the ozone in 74 cities be averaged exceeding standard rate be 32.7%, and from this
Start within a month, the primary pollutant of the continuous 5 months exceeded number of days in 74 cities is ozone.Since the near-earth ozone overwhelming majority is come
From a large amount of artificial source (nitrogen oxides NOXWith volatile organic matter VOCs), through a series of photochemical reactions under illumination condition
The secondary pollution of generation, concentration are closely related with meteorological condition.It is anti-under high temperature, strong sunshine, low humidity and lull wind conditions
Should the most acutely, wherein ultraviolet radioactive is the factor of most critical.Xinjiang region belongs to typical continental arid climate, and photo-thermal is rich
Richness, dry weather, ultraviolet light is strong, in addition the lineament of Xinjiang " three mountains press from both sides two basins " is unfavorable for the diffusion of pollutant, equally
Severe ozone pollution is faced with to threaten.Chief component of the ozone as photochemical fog, drastically influences local air
Quality, the increase of concentration will directly endanger the health of human and animal, damage the growth of plant.Moreover, ozone can also be with it
His pollutant combined operation, for example, ozone can reinforce harm of the PM (pellet) to human body, and PM can also reinforce ozone
Harmfulness.2008, Environmental protection administration regulation: the per day maximum value of 8h ozone was not above 75ppb, indoor 8h
Per day maximum value is not above 50ppb.More stringent requirements are proposed for this detection technique to ozone and ozone precursor.Mesh
Before, the common method of ozone detection mainly has: iodimetric titration, spectrophotometry, electrochemical process, ultraviolet spectroscopy etc..Wherein, due to
Ultraviolet spectroscopy clear, technology maturation, stable and reliable for performance to the detection mechanism of ozone, and be widely studied and applied.However,
Ultraviolet spectroscopy still has the disadvantages of equipment volume is big, cost is high, detection function is excessively single, the practical scope of application by
Limitation.
Gas sensor is a kind of device for measuring gas type, concentration, ingredient.Currently, chemical-electrical resistance type gas sensing
Device due to prepare it is simple, small in size, be widely used convenient for the advantages such as integrated, high sensitivity, low to operating environment requirements.Its
In, most typical metal oxide base gas sensor because there is sufficiently wide band gap that can react with many object gas, but
The defects of there is operating temperature high (200-500 DEG C), power consumptions for this gas sensor greatly, poor selectivity.And conducting polymer
Sensor is although at low cost, but there is sensitivity and selectivity are lower, and stability, weatherability are poor, to object gas
Response time longer (generally 2-10 minutes or so) the shortcomings that.Carbon nanotube is due to big specific surface area, abundant
Reaction site, good electric conductivity, weatherability and stability and the feature more sensitive to environment, these features make carbon receive
Mitron becomes ideal gas sensing materials.In general, atmosphere pollution is varied, such as ethyl alcohol, formaldehyde, vapor
Presence the highly sensitive detection of ozone can be caused greatly to interfere.
In view of this, the present invention proposes the ozone gas sensor array and its system of a kind of carbon nanotube base of high sensitivity
Preparation Method, the gas sensor array can carry out recognition detection to ozone and its common interference object at room temperature.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of ozone gas sensor array, and the preparation method is simple,
The ozone gas sensor array prepared can at room temperature, for the recognition detection to ozone and common interference object, spirit
Sensitivity is high.
To achieve the goals above, used technical solution are as follows:
A kind of preparation method of ozone gas sensor array, comprising the following steps:
(1) in deionized water by small molecule modifier dissolution, and after ultrasonic disperse, obtaining molar concentration is 0.8-
The modifier solution of 1.2mmol/L；Wherein, the small molecule modifier is hydroxylamine hydrochloride；
(2) carboxylic carbon nano-tube powder and modifier solution are mixed according to the mass volume ratio of 0.02g:3-5ml equal
It is even, obtain carbon nano tube dispersion liquid；
(3) after carbon nano tube dispersion liquid being stood 46-50h at room temperature, centrifugation obtains sediment；
(4) by sediment and deionized water according to 1:3.5-4.5 mass ratio after mixing, obtain paste；
Paste is uniformly applied in interdigital electrode, and is dried at room temperature for 12-24h, obtains sensing chip；
Sensing chip is fabricated to sensor, obtains sensor 1；
(5) it repeats step (1)-(4) 5 times, successively obtains sensor 2, sensor 3, sensor 4, sensor 5 and sensor 6；
Wherein, the small molecule modifier is followed successively by amion acetic acid, succinic acid, cetyl trimethylammonium bromide, 8- hydroxyl quinaldine
And pyrene；
(6) both ends of sensor 1-6 persistently add to the voltage of 0.1V, after energization aging 22-26h, form sensor array
Column, obtain the ozone gas sensor array.
Further, in the step (1), the time of ultrasonic disperse is 8-12min.
Further, in the step (1), the molar concentration of the modifier solution is 1mmol/L；
The time of the ultrasonic disperse is 10min.
Further, it in the step (2), after the carboxylic carbon nano-tube powder and modifier solution mixing, then passes through
The ultrasonic disperse for crossing 30-60min, obtains carbon nano tube dispersion liquid.
Further, in the step (2), the base carbon nano tube powder and modifier solution are according to 0.02g:
The mass volume ratio of 4ml mixes.
Further, in the step (3), carbon nano tube dispersion liquid static placement 48h at room temperature.
Further, in the step (4), substrate of the sensing chip as sensor.
Further, in the step (6), the voltage is DC voltage.
Further, in the step (6), the ageing time is for 24 hours.
It is another object of the present invention to provide the detection method of a kind of ozone and its common interference object, the detection methods
Dynamics and thermodynamic parameter are combined analysis by the ozone gas sensor array being prepared using above-mentioned preparation method
Data are handled, the detection method stability is good, the response time is short, selectivity is good.
Compared with prior art, the beneficial effects of the present invention are:
1, the preparation method of a kind of ozone gas sensor array of the present invention, under mild conditions using a variety of
Small molecule modifier has carried out physical modification to carbonyl multi-walled carbon nanotube, and then has prepared the ozone air-sensitive of carbon nanotube base
Sensor array realizes the high sensitivity to ozone and its common interference object, recognition detection at room temperature, and prepare
Ozone gas sensor array stability is good, the response time is short, selectivity is good, strong interference immunity, is also mainly useful pair
The detection of the chaff interferents such as the measurement of ozone and PARA FORMALDEHYDE PRILLS(91,95), alcohol, nitrogen dioxide.
2, the detection method of a kind of ozone and its common interference object of the present invention utilizes this hair under mild conditions
The bright ozone gas sensor array realizes the high sensitivity to ozone and its common interference object, identification at room temperature
Detection, the detection method stability is good, the response time is short, selectivity is good.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the carbon nanotube not being modified used in the present invention；
Fig. 2 is the transmission electron microscope picture for the carbon nanotube not being modified used in the present invention；
Fig. 3 be embodiment 1 in sensor 1 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 4 be embodiment 1 in sensor 2 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 5 be embodiment 1 in sensor 3 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 6 be embodiment 1 in sensor 4 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 7 be embodiment 1 in sensor 5 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 8 be embodiment 1 in sensor 6 to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve
Figure；
Fig. 9 is fingerprint region component of the ozone gas sensor array to 6 kinds of target analytes of carbon nanotube base；
Wherein, in Fig. 3-8: 1 is ozone, and 2 be formaldehyde, and 3 be alcohol, and 4 be acetone, and 5 be vapor, and 6 be nitrogen dioxide.
Specific embodiment
In order to which the present invention is further explained, a kind of preparation method of ozone gas sensor array, reaches expected invention mesh
, in conjunction with the preferred embodiment, to a kind of preparation method of ozone gas sensor array proposed according to the present invention, tool
Body embodiment, structure, feature and its effect, detailed description is as follows.In the following description, different " embodiment " or " real
Apply example " refer to be not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by appointing
What suitable form combination.
Before elaborating a kind of preparation method of ozone gas sensor array of the present invention, it is necessary to in the present invention
The raw material etc. referred to is described further, to reach better effect.
Hydroxylamine hydrochloride, molecular formula ClH4NO, molecular weight 69.49 are a kind of colourless crystallizations, and hygroscopicity is strong, are easily deliquesced,
The chemical substance of white, is dissolved in water, and ethyl alcohol, glycerol do not dissolve in ether, density 1.67g/cm3(17 DEG C), are mainly used as reducing agent
And imaging agent, oxime is used to prepare in organic synthesis, also serves as synthesis anticarcinogen (hydroxycarbamide), sulfa drug (radonil) and pesticide
The raw material of (Methomyl).
The skeleton symbol of amion acetic acid is NH2CH2COOH is commonly called as glycine, glycocoll, white monoclinic system or hexagonal crystal system
Crystal or white crystalline powder, it is odorless, have special sweet taste, it is soluble easily in water, be slightly soluble in methanol, ethyl alcohol, be practically insoluble in acetone,
Ether.
Succinic acid also known as succinic acid, molecular formula C4H6O4, molecular weight 118.09, colourless crystallization body is sour, and it is flammable,
It is dissolved in water, is slightly soluble in ethyl alcohol, ether, acetone, glycerol.
Cetyl trimethylammonium bromide (abbreviation CTMAB), molecular formula C19H42BrN, molecular weight 364.446, white
Microcrystalline powder is a kind of quaternary ammonium salt；There is hygroscopicity, it is stable in an acidic solution；10 parts of water are dissolved in, ethyl alcohol is soluble in, is slightly soluble in
Acetone is practically insoluble in ether and benzene.
8- hydroxyl quinaldine also known as 8- hydroxy-2-methylquinoline, molecular formula are C10H9NO, molecular weight 159.1846 are white
Color prismatic crystal, 266-270 DEG C of boiling point, is dissolved in hot alcohol, ether and benzene by 74 DEG C of fusing point, not soluble in water, can wave with vapor
Hair distils at 100 DEG C, has phenol smell, is used as analytical reagent.
Pyrene, molecular formula C16H10, molecular weight 202.26, faint yellow monoclinic crystal (sterling is colourless) has fragrance,
Boiling point be 393.5 DEG C, relative density be 1.271 (22/4 DEG C), it is not soluble in water, be soluble in ethyl alcohol, ether, carbon disulfide, benzene and
The organic solvents such as toluene, tetrahydrofuran.Pyrene is primarily present in the distillation of coal tar asphalt.Pyrene is organic synthesis raw material, warp
Oxidation can produce Isosorbide-5-Nitrae, and 5,8- naphthalenetetracarbacidic acidics are used for dyestuff, synthetic resin, disperse dyes and engineering plastics；It can be made after acylation
The gorgeous orange GR of reducing dye and other a variety of dyestuffs.
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of the carboxylic carbon nano-tube powder used in the present invention are as shown in Figs. 1-2,
Known to carbon nanotube have the characteristics that big specific surface area, reaction site abundant, these features make carbon nanotube as compared with
For ideal gas sensing materials.
After having understood above-mentioned raw materials, below in conjunction with specific embodiment to a kind of ozone gas sensor battle array of the present invention
The preparation method of column is further described in detail:
Embodiment 1.
Specific steps are as follows:
(1) in deionized water, and after ultrasonic disperse 10min by small molecule modifier dissolution, molar concentration is obtained
For the modifier solution of 1mmol/L；Wherein, the small molecule modifier is hydroxylamine hydrochloride；
(2) 0.02g carboxylic carbon nano-tube powder is added to 4ml modifier solution to be uniformly mixed, using 50min's
Ultrasonic disperse obtains stable carbon nano tube dispersion liquid；
(3) by after carbon nano tube dispersion liquid at room temperature static placement 48h, small molecule modifier is allowed to pass through supermolecular mechanism
Or the suction-operated physical bond of carbon nanotube forms the carbon nanometer of small molecule modifier physical modification on carbon nanotube wall
Pipe, then using centrifugation, the sediment of the carbon nanotube after collecting physical modification obtains sediment；
(4) by sediment and deionized water according to 1:4 mass ratio after mixing, uniform slurry is formed after grinding
Object is pasted, paste is obtained；
Few paste is dipped with sample brush to be uniformly applied in interdigital electrode, and is dried at room temperature for 18h, is obtained primary
The sensing chip of carbon nanotube base；
Sensing chip is fabricated to sensor, substrate of the sensing chip as sensor obtains sensor 1；
(5) it repeats step (1)-(4) 5 times, successively obtains sensor 2, sensor 3, sensor 4, sensor 5 and sensor 6；
Wherein, the small molecule modifier is followed successively by amion acetic acid, succinic acid, cetyl trimethylammonium bromide, 8- hydroxyl quinaldine
And pyrene；
(6) DC voltage that the both ends of sensor 1-6 are persistently added to 0.1V after energization aging for 24 hours, obtains performance and stablizes
Carbon nano tube sensor, then form sensor array, obtain the ozone gas sensor array, can be used to that test its right
The air-sensitive response performance of ozone, nitrogen dioxide and common interference object.
Ozone, formaldehyde, alcohol, acetone, water are steamed with the sensor 1-6 prepared in electrochemical workstation testing example 1
The response curve of gas, nitrogen dioxide, as shown in figures 3-8.
Energization chem workstation power supply, under the bias of 0.1V, with hydroxylamine hydrochloride for small point obtained in testing example 1
Carbon nanotube base ozone gas sensor 1 obtained by sub- dispersing agent at room temperature (25 DEG C of temperature, relative humidity 25%) to smelly
Oxygen, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in figure 3, can be seen that from response curve in room
It is carbon nanotube base ozone gas sensor obtained by small molecule dispersing agent to ozone response magnitude point using hydroxylamine hydrochloride under temperature
Do not reach 19.91%, 20.99%, 22.07%；Response time is respectively 22.7 seconds, 14.8 seconds, 22.1 seconds.PARA FORMALDEHYDE PRILLS(91,95) response is big
It is small to respectively reach -15.67%, -16.25%, -17.60%；Response time is respectively 14.7 seconds, 11.7 seconds, 13.4 seconds.To wine
Smart response magnitude respectively reaches -49.24%, -48.58%, -46.99%；Response time is respectively 6 seconds, 6.6 seconds, 6.4 seconds.It is right
Acetone response magnitude respectively reaches -4.07%, -4.62%, -5.09%；Response time is respectively 3.59 seconds, 3.83 seconds, 5.06
Second: -0.19%, -0.17%, -0.17% is respectively reached to vapor response magnitude；Response time is respectively 11.04 seconds, 5.59
Second, 7.28 seconds.1.13%, 1.23%, 1.23% is respectively reached to nitrogen dioxide response magnitude；Response time is respectively as follows: 10.34
Second, 8.5 seconds, 10.35 seconds.
Connect electrochemical workstation power supply, under the bias of 0.1V, obtained in testing example 1 with amion acetic acid be it is small
Carbon nanotube base ozone gas sensor 2 obtained by dispersal agent molecule is right at room temperature (25 DEG C of temperature, relative humidity 25%)
Ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in figure 4, can be seen that from response curve
It at room temperature, is carbon nanotube base ozone gas sensor obtained by small molecule dispersing agent to ozone response magnitude using amion acetic acid
Respectively reach 6.10%, 6.21%, 6.76%；Response time is respectively 29.5 seconds, 23.2 seconds, 29.5 seconds.PARA FORMALDEHYDE PRILLS(91,95) response is big
It is small to respectively reach -2.87%, -3.01%, -2.98%；Response time is respectively 3.6 seconds, 3.4 seconds, 3 seconds.It is big to alcohol response
It is small to respectively reach -25.12%, -24.76%, -24.26%；Response time is respectively 8.1 seconds, 8.4 seconds, 8.7 seconds.Acetone is rung
Size is answered to respectively reach -4.71%, -4.94%, -4.96%；Response time is respectively 3.62 seconds, 8.39 seconds, 10.98 seconds.It is right
Vapor response magnitude respectively reaches: -0.63%, -0.62%, 0.17%.Response time is respectively 8.59 seconds, 5.0 seconds 5.89
Second: 0.81%, 0.81%, 0.94% is respectively reached to nitrogen dioxide response magnitude；Response time is respectively as follows: 8.0 seconds, 10.63
Second, 10.69 seconds.
Electrochemical workstation power supply is connected, under the bias of 0.1V, with succinic acid for small point obtained in testing example 1
Carbon nanotube base ozone gas sensor 3 obtained by sub- dispersing agent at room temperature (25 DEG C of temperature, relative humidity 25%) to smelly
Oxygen, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in figure 5, can be seen that from response curve in room
It is carbon nanotube base ozone gas sensor obtained by small molecule dispersing agent to ozone response magnitude point using succinic acid under temperature
Do not reach 16.62%, 15.71%, 16.14%；Response time is respectively 6.6 seconds, 7.8 seconds, 5.3 seconds.PARA FORMALDEHYDE PRILLS(91,95) response magnitude
Respectively reach -5.98%, -5.91%, -5.74%；Response time is respectively 8.7 seconds, 8.7 seconds, 7.4 seconds.It is big to alcohol response
It is small to respectively reach -22.68%, -21.85%, -22.44%；Response time is respectively 4.6 seconds, 5.3 seconds, 4.6 seconds.Acetone is rung
Size is answered to respectively reach -5.25%, -4.97%, -4.79%；Response time is respectively 6.67 seconds, 6.33 seconds, 5.47 seconds.To water
Steam response magnitude respectively reaches -0.29%, -0.40%, -0.46；Response time is respectively as follows: 8.81 seconds, 5.17 seconds, 4.29
Second.1.77%, 1.57%, 1.84% is respectively reached to nitrogen dioxide response magnitude；Response time is respectively as follows: 12.3 seconds, 4.9
Second, 4.6 seconds.
Electrochemical workstation power supply is connected, under the bias of 0.1V, with cetyl front three obtained in testing example 1
Base ammonium bromide be small molecule dispersing agent obtained by carbon nanotube base ozone gas sensor 4 at room temperature (25 DEG C of temperature, relatively
Humidity 25%) to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in fig. 6, from response curve
As can be seen that at room temperature, using cetyl trimethylammonium bromide as carbon nanotube base ozone obtained by small molecule dispersing agent
Gas sensor respectively reaches 29.24%, 29.10%, 29.99% to ozone response magnitude；Response time is respectively 14.3
Second, 11.2 seconds, 12.4 seconds.PARA FORMALDEHYDE PRILLS(91,95) response magnitude respectively reaches -6.07%, -6.15%, -6.91%；Response time is respectively
16.4 seconds, 15 seconds, 15.7 seconds.- 3.62%, -3.57%, -3.62% is respectively reached to alcohol response magnitude；Response time difference
It is 8.5 seconds, 5.9 seconds, 4.9 seconds.- 4.54%, -4.65%, -4.54% is respectively reached to acetone response magnitude；Response time point
It Wei not be 3.93 seconds, 10.81 seconds, 8.91 seconds.0.08%, 0.92%, 1.4% is respectively reached to vapor response magnitude；When response
Between be respectively as follows: 6.07 seconds, 4.01 seconds, 5.15 seconds.1.75%, 2.09%, 1.73% is respectively reached to nitrogen dioxide response magnitude；
Response time is respectively as follows: 11.47 seconds, 10.27 seconds, 8.71 seconds.
Electrochemical workstation power supply is connected, under the bias of 0.1V, with 8- hydroxyl quinaldine obtained in testing example 1
For carbon nanotube base ozone gas sensor 5 obtained by small molecule dispersing agent at room temperature (25 DEG C of temperature, relative humidity
25%) to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in fig. 7, can be with from response curve
Find out, at room temperature, using 8- hydroxyl quinaldine as carbon nanotube base ozone gas sensor pair obtained by small molecule dispersing agent
31.01%, 28.74%, 26.93% is respectively reached to ozone response magnitude；Response time is respectively 9.2 seconds, 9.4 seconds, 10.7
Second.PARA FORMALDEHYDE PRILLS(91,95) response magnitude respectively reaches -26.61%, -27.93%, -30.32%；Response time is respectively 12.2 seconds, 13.7
Second, 12.1 seconds.- 18.10%, -17.20%, -16.71% is respectively reached to alcohol response magnitude；Response time is respectively 8.2
Second, 8.4 seconds, 9.3 seconds.- 6.56%, -6.38%, -6.38% is respectively reached to acetone response magnitude；Response time is respectively
3.1 seconds, 2.8 seconds 3.0 seconds.0.31%, 0.59%, 0.94% is respectively reached to vapor response magnitude；Response time is respectively as follows:
3.08 seconds, 9.47 seconds, 11.29 seconds.1.44%, 1.47%, 1.44% is respectively reached to nitrogen dioxide response magnitude；Response time
It is respectively as follows: 9.73 seconds, 10.57 seconds, 11.49 seconds.
Electrochemical workstation power supply is connected, under the bias of 0.1V, using pyrene as small molecule point obtained in testing example 1
Carbon nanotube base ozone gas sensor 6 obtained by powder at room temperature (25 DEG C of temperature, relative humidity 25%) to ozone, first
Aldehyde, alcohol, acetone, vapor, nitrogen dioxide response curve, as shown in figure 8, can be seen that at room temperature from response curve,
It is respectively reached by carbon nanotube base ozone gas sensor obtained by small molecule dispersing agent of pyrene to ozone response magnitude
32.28%, 35.63%, 35.31%；Response time is respectively 19 seconds, 14.8 seconds, 21.3 seconds.PARA FORMALDEHYDE PRILLS(91,95) response magnitude reaches respectively
To -13.10%, -13.96%, -14.41%；Response time is respectively 16.5 seconds, 15.7 seconds, 15.0 seconds.It is big to alcohol response
It is small to respectively reach -4.55%, -4.76%, -4.56%；Response time is respectively 10.1 seconds, 11.9 seconds, 12.5 seconds.Acetone is rung
Size is answered to respectively reach -8.94%, -8.90%, -8.79%；Response time is respectively 2.79 seconds, 3.3 seconds, 3.1 seconds.Water is steamed
Gas response magnitude respectively reaches 0.04%, -0.05%, -0.58%；Response time is respectively as follows: 6.11 seconds, 8.33 seconds, 2.92 seconds.
1.22%, 1.42%, 1.44% is respectively reached to nitrogen dioxide response magnitude；Response time be respectively as follows: 0.91 second, 1.98 seconds,
4.85 the second.
A kind of preparation method of ozone gas sensor array, utilizes under mild conditions described in the embodiment of the present invention
A variety of small molecule modifiers have carried out physical modification to carbonyl multi-walled carbon nanotube, and then have prepared the ozone of carbon nanotube base
Gas sensor array realizes the high sensitivity to ozone and its common interference object, recognition detection at room temperature, and prepares
Ozone gas sensor array stability out is good, the response time is short, selectivity is good.
Embodiment 2.
Specific steps are as follows:
(1) in deionized water, and after ultrasonic disperse 8min by small molecule modifier dissolution, obtaining molar concentration is
The modifier solution of 0.8mmol/L；Wherein, the small molecule modifier is hydroxylamine hydrochloride；
(2) 0.02g carboxylic carbon nano-tube powder is added to 5ml modifier solution to be uniformly mixed, using 30min's
Ultrasonic disperse obtains stable carbon nano tube dispersion liquid；
(3) by after carbon nano tube dispersion liquid at room temperature static placement 46h, small molecule modifier is allowed to pass through supermolecular mechanism
Or the suction-operated physical bond of carbon nanotube forms the carbon nanometer of small molecule modifier physical modification on carbon nanotube wall
Pipe, then using centrifugation, the sediment of the carbon nanotube after collecting physical modification obtains sediment；
(4) by sediment and deionized water according to 1:3.5 mass ratio after mixing, formed after grinding uniform
Paste object, obtains paste；
Few paste is dipped with sample brush to be uniformly applied in interdigital electrode, and is dried at room temperature for 12h, is obtained primary
The sensing chip of carbon nanotube base；
Sensing chip is fabricated to sensor, substrate of the sensing chip as sensor obtains sensor 1；
(5) it repeats step (1)-(4) 5 times, successively obtains sensor 2, sensor 3, sensor 4, sensor 5 and sensor 6；
Wherein, the small molecule modifier is followed successively by amion acetic acid, succinic acid, cetyl trimethylammonium bromide, 8- hydroxyl quinaldine
And pyrene；
(6) both ends of sensor 1-6 persistently add to the DC voltage of 0.1V, after energization aging 22h, obtains performance and stablizes
Carbon nano tube sensor, then form sensor array, obtain the ozone gas sensor array, can be used to that test its right
The air-sensitive response performance of ozone, nitrogen dioxide and common interference object.
A kind of preparation method of ozone gas sensor array, utilizes under mild conditions described in the embodiment of the present invention
A variety of small molecule modifiers have carried out physical modification to carbonyl multi-walled carbon nanotube, and then have prepared the air-sensitive of carbon nanotube base
Sensor array realizes the high sensitivity to ozone and its common interference object, recognition detection at room temperature, and prepare
Ozone gas sensor array stability is good, the response time is short, selectivity is good.
Embodiment 3.
Specific steps are as follows:
(1) in deionized water, and after ultrasonic disperse 12min by small molecule modifier dissolution, molar concentration is obtained
For the modifier solution of 1.2mmol/L；Wherein, the small molecule modifier is hydroxylamine hydrochloride；
(2) 0.02g carboxylic carbon nano-tube powder is added to 3ml modifier solution to be uniformly mixed, using 60min's
Ultrasonic disperse obtains stable carbon nano tube dispersion liquid；
(3) by after carbon nano tube dispersion liquid at room temperature static placement 50h, small molecule modifier is allowed to pass through supermolecular mechanism
Or the suction-operated physical bond of carbon nanotube forms the carbon nanometer of small molecule modifier physical modification on carbon nanotube wall
Pipe, then using centrifugation, the sediment of the carbon nanotube after collecting physical modification obtains sediment；
(4) by sediment and deionized water according to 1:4.5 mass ratio after mixing, formed after grinding uniform
Paste object, obtains paste；
Few paste is dipped with sample brush to be uniformly applied in interdigital electrode, and is dried at room temperature for for 24 hours, obtaining primary
The sensing chip of carbon nanotube base；
Sensing chip is fabricated to sensor, substrate of the sensing chip as sensor obtains sensor 1；
(5) it repeats step (1)-(4) 5 times, successively obtains sensor 2, sensor 3, sensor 4, sensor 5 and sensor 6；
Wherein, the small molecule modifier is followed successively by amion acetic acid, succinic acid, cetyl trimethylammonium bromide, 8- hydroxyl quinaldine
And pyrene；
(6) both ends of sensor 1-6 persistently add to the DC voltage of 0.1V, after energization aging 26h, obtains performance and stablizes
Carbon nano tube sensor, then form sensor array, obtain the ozone gas sensor array, can be used to that test its right
The air-sensitive response performance of ozone, nitrogen dioxide and common interference object.
A kind of preparation method of ozone gas sensor array, utilizes under mild conditions described in the embodiment of the present invention
A variety of small molecule modifiers have carried out physical modification to carbonyl multi-walled carbon nanotube, and then have prepared the air-sensitive of carbon nanotube base
Sensor array realizes the high sensitivity to ozone and its common interference object, recognition detection at room temperature, and prepare
Ozone gas sensor array stability is good, the response time is short, selectivity is good.
Embodiment 4.
A kind of detection method of ozone and its common interference object:
Using radar fingerprint analysis method, using in the ozone gas sensor array of embodiment 1 sensor 1,
Sensor 2, sensor 3, sensor 4, sensor 5, sensor 6 are to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide
It is detected, then is combined dynamics and thermodynamic parameter at analysis come analyzing and processing data with Principal Component Analysis
It manages data (radar map analytic approach), specifically: it is removed respectively with thermodynamic parameter response magnitude of 6 sensors to every kind of analyte
It with the kinetic parameter response time, responses to which that size and response time are handled, realizes to ozone and its common interference object
Highly sensitive, recognition detection obtains the radar finger-print of 6 kinds of analytes.
It can be realized the differentiation to ozone, formaldehyde, alcohol, acetone, vapor, nitrogen dioxide, such as Fig. 9 according to finger-print
It is shown, it is known that embodiment 1 prepare ozone gas sensor array can at room temperature recognition detection go out ozone, formaldehyde, alcohol,
Acetone, vapor, nitrogen dioxide, and strong interference immunity, high sensitivity, selectivity are high.
The detection method of a kind of ozone and its common interference object described in the embodiment of the present invention, mainly for atmosphere pollution
The detection of the chaff interferents such as the anti-interference of ozone, recognition detection and PARA FORMALDEHYDE PRILLS(91,95), alcohol, nitrogen dioxide, vapor, mild
Under the conditions of utilize gas sensor array of the present invention, realize at room temperature to the Gao Ling of ozone and its common interference object
Sensitivity, recognition detection, the detection method stability is good, the response time is short, selectivity is good.
The above is only the preferred embodiment of the embodiment of the present invention, not makees any shape to the embodiment of the present invention
Limitation in formula, any simple modification to the above embodiments of technical spirit according to an embodiment of the present invention, equivalent variations
With modification, in the range of still falling within technical solution of the embodiment of the present invention.
Claims (10)
1. a kind of preparation method of ozone gas sensor array, which comprises the following steps:
(1) in deionized water by small molecule modifier dissolution, and after ultrasonic disperse, obtaining molar concentration is 0.8-
The modifier solution of 1.2mmol/L；Wherein, the small molecule modifier is hydroxylamine hydrochloride；
(2) carboxylic carbon nano-tube powder and modifier solution are uniformly mixed according to the mass volume ratio of 0.02g:3-5ml, are obtained
Carbon nano tube dispersion liquid；
(3) by after carbon nano tube dispersion liquid at room temperature static placement 46-50h, centrifugation obtains sediment；
(4) by sediment and deionized water according to 1:3.5-4.5 mass ratio after mixing, obtain paste；
Paste is uniformly applied in interdigital electrode, and is dried at room temperature for 12-24h, obtains sensing chip；
Sensing chip is fabricated to sensor, obtains sensor 1；
(5) it repeats step (1)-(4) 5 times, successively obtains sensor 2, sensor 3, sensor 4, sensor 5 and sensor 6；Its
In, the small molecule modifier be followed successively by amion acetic acid, succinic acid, cetyl trimethylammonium bromide, 8- hydroxyl quinaldine and
Pyrene；
(6) both ends of sensor 1-6 persistently add to the voltage of 0.1V, after energization aging 22-26h, forms sensor array, obtains
The ozone gas sensor array.
2. preparation method according to claim 1, which is characterized in that wherein,
In the step (1), the time of ultrasonic disperse is 8-12min.
3. preparation method according to claim 2, which is characterized in that wherein,
In the step (1), the molar concentration of the modifier solution is 1mmol/L；
The time of the ultrasonic disperse is 10min.
4. preparation method according to claim 1, which is characterized in that wherein,
In the step (2), after the carboxylic carbon nano-tube powder and modifier solution mixing, using the super of 30-60min
Sound dispersion, obtains carbon nano tube dispersion liquid.
5. the preparation method according to claim 4, which is characterized in that wherein,
In the step (2), the base carbon nano tube powder and modifier solution are mixed according to the mass volume ratio of 0.02g:4ml
It closes.
6. preparation method according to claim 1, which is characterized in that wherein,
In the step (3), carbon nano tube dispersion liquid static placement 48h at room temperature.
7. preparation method according to claim 1, which is characterized in that wherein,
In the step (4), substrate of the sensing chip as sensor.
8. preparation method according to claim 1, which is characterized in that wherein,
In the step (6), the voltage is DC voltage.
9. preparation method according to claim 8, which is characterized in that wherein,
In the step (6), the ageing time is for 24 hours.
10. the detection method of a kind of ozone and its common interference object, which is characterized in that use claim 1-9 any one institute
The ozone gas sensor array that preparation method is prepared is stated, dynamics and thermodynamic parameter are combined at analysis
Manage data.
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