CN107421992A - A kind of detection method of ozone and ozone precursor - Google Patents
A kind of detection method of ozone and ozone precursor Download PDFInfo
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- CN107421992A CN107421992A CN201710465574.XA CN201710465574A CN107421992A CN 107421992 A CN107421992 A CN 107421992A CN 201710465574 A CN201710465574 A CN 201710465574A CN 107421992 A CN107421992 A CN 107421992A
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Abstract
The present invention is the detection method of a kind of ozone and ozone precursor.A kind of detection method of ozone and ozone precursor, comprises the following steps：(1) ammonium molybdate, thiocarbamide and zinc acetate are dissolved completely in water, obtain mixed solution；(2) mixed solution is prepared into p-type molybdenum disulfide nano sheet powder；(3) repeating said steps (1) (2) are no less than 4 times, and each ammonium molybdate is different from the mol ratio of zinc acetate, obtain the p-type molybdenum disulfide nano sheet powder different no less than 5 kinds of zinc ion dopings；(4) no less than the 5 kinds different molybdenum disulfide nano sheet powder of zinc ion doping are prepared into sensor respectively, and are built into a sensor array；(5) ozone and ozone precursor, response signal of the collection sensor array to ozone and ozone precursor are detected respectively with sensor array.The detection method of a kind of ozone and ozone precursor of the present invention, operating temperature is low, preferable to ozone and ozone precursor identity, and the response time is short.
Description
Technical field
The invention belongs to the technical field of gas sensing detection field, and in particular to a kind of inspection of ozone and ozone precursor
Survey method.
Background technology
Ozone can almost react with any biological tissue, very strong to the destructiveness of health.Ozone can also be dirty with other
Contaminate thing integration of operation.For example ozone can strengthen harm of the pellet (PM) to human body, and PM can also aggravate the danger of ozone
Evil property.Increasing research has shown that, caused if long-time exposure (6-8 hours) even if ozone concentration is than relatively low
Harm is same serious.Environmental Protection Agency provides that the ozone mean concentration of 8 hours is no more than 80ppb in atmospheric environment
(Ebeling,D.,et al.,Electrochemical ozone sensor and instrument with
characterization of the electrode and gas flow effects.Sensors And Actuators
B-Chemical,2009.137(1):p.129-133；3.Policy,E.S.P.,Policy Assessment of
Scientific and Technical Information—Review of the National Ambient Air
Quality Standards(NAAQS)for Ozone.EPAHQ-OAR-2008-0318-0016,2008.).U.S. Jia Lifu
Buddhist nun Asia state is even more the indoor air purification equipment that regulation air cleaning facility manufacturer is produced should be by the ozone concentration control of interior
Make in level (California Environmental the Protection Agency, Air no more than 50ppb
Resources Board AB 2276 Air Cleaner Regulation,2007.).The rising of ozone concentration is motor vehicle
Exhaust emissions, chemical process and the coefficient result of meteorological condition.The near-earth ozone overwhelming majority from a small amount of natural source and
Substantial amounts of artificial source (nitrogen oxides NOXWith volatile organic matter VOCS) generated under illumination condition through a series of photochemical reactions
Secondary pollution, its concentration and meteorological condition are closely related.Reacted most under high temperature, strong sunshine, low humidity and lull wind conditions
To be violent, wherein ultraviolet radioactive is the factor of most critical.Therefore, increasingly highlighted in the summer ozone pollution problem of northern China.
And it is then the technology premise and base of ozone pollution control to ozone and its highly sensitive of preceding extract, high selection detection
Plinth.In recent years, summer ozone pollution alreadys exceed PM2.5 and turns into primary pollutant in most cities, in this context, right
The effective detection of ozone, control have more great meaning.But due to the high oxidative of ozone, unstability, (ozone exists
Half-life period in water and air is typically only 5-15 minutes) and air in other multiple pollutants presence and interference, at present
It is still a full of challenges sciences problems that highly sensitive, high selection detection is carried out to ozone.At present, the common method of ozone detection
Mainly have：Iodimetric titration, AAS, electrochemical process, fluorescence method etc..Wherein, because ultraviolet spectroscopy is to the detection machine of ozone
It is reliable and stable to manage clear and definite, technology maturation, detection performance, and is widely studied and applied.However, still there is set for ultraviolet spectroscopy
Standby the shortcomings of volume is big, cost is high, detection function is excessively single, its actual scope of application is restricted.
In order to meet the effective detection of ozone and its precursors, be badly in need of developing a kind of low cost, small volume, stability it is good,
The ozone sensor of high sensitivity, good in anti-interference performance.Metal Oxide Gas Sensors have small volume, high sensitivity, just
In the advantages of integrated, easy to use, huge potentiality are shown in ozone detection, are developed in recent years extremely rapid.But
In general, the selectivity of Metal Oxide Semiconductor Gas Sensing sensor is poor, response time length, generally a few minutes, and work
Make temperature higher (200-500 DEG C), it is necessary to which the heater element of auxiliary, power consumption is high, stability is not good enough.In addition, higher work temperature
Degree can also cause the thermal degradation of ozone, so as to influence the detection performance of gas sensor, cause to pass using metal oxide air-sensitive
The detection method less effective of sensor.The surface density of states of metal sulfide semiconductor is very low, and the change to surface electrical properties is non-
It is often sensitive, there are the potentiality as highly sensitive resistor-type gas sensitive.
In view of this, it is necessary to propose a kind of sensor made by molybdenum disulfide nano sheet to detect ozone and ozone
The detection method of precursor.
The content of the invention
It is an object of the invention to provide the detection method of a kind of ozone and ozone precursor, the detection method passes through doping
Modified ultra-thin molybdenum disulfide nano sheet and follow-up sensing data processing is combined, come realize at room temperature to ozone and ozone before
Body thing is sensitive, quick recognition detection, has that operating temperature is low, the response time selectively preferable to ozone and ozone precursor
The advantages of short.
To achieve these goals, scheme of the present invention is：
A kind of detection method of ozone and ozone precursor, comprises the following steps：
(1) ammonium molybdate, thiocarbamide and zinc acetate are dissolved completely in water, obtain mixed solution；The thiocarbamide, ammonium molybdate and second
The mol ratio of sour zinc is 3000:100:0-15；
(2) mixed solution is transferred in the reactor of sealing, and at 170-190 DEG C after reaction 22-26 hours, it is natural
After being cooled to room temperature, it is centrifuged, obtains the sediment of black；
With water or absolute ethyl alcohol washing precipitate to the aobvious neutrality of solution, the sediment after must washing；The washing refers to will be heavy
Starch ultrasonic disperse is in water or absolute ethyl alcohol, then centrifuges, and removes supernatant, isolated precipitation；
Sediment after washing is dried into 6-12 hours at 50-70 DEG C, obtains dried sediment；Will be dried heavy
Starch is fully ground, and obtains p-type molybdenum disulfide nano sheet powder；
(3) repeating said steps (1) (2) be no less than 4 times, each ammonium molybdate is different from the mol ratio of zinc acetate, and with step
Suddenly the ammonium molybdate in (1) is different from the mol ratio of zinc acetate, obtains the p-type curing different no less than 5 kinds of zinc ion dopings
Molybdenum nanometer sheet powder；
(4) the different p-type molybdenum disulfide nano sheet powder of no less than 5 kinds zinc ion dopings is prepared into sensing respectively
Device, and it is built into a sensor array for having no less than 5 sensors to form；
(5) ozone and ozone precursor are detected respectively with sensor array, before collection sensor array is to ozone and ozone
The response signal of body thing.
Further, in the step (1), ammonium molybdate, thiocarbamide and zinc acetate is added to the water, pass through magnetic agitation
Mode makes its dissolving.
Further, in the step (2), after being cooled to room temperature, the rotating speed of centrifugation is 8000-12000r/min,
Time is 3-5 minutes；
The washing times are 3-5 times；
The thickness of the p-type molybdenum disulfide nano sheet powder is 3-20nm.
Further, the washing in the step (2)：The rotating speed of centrifugation is 8000-12000r/min, and the time is
3-5 minutes.
Further, in the step (2), reaction temperature is 180 DEG C, and the reaction time is 24 hours；
The drying temperature is 60 DEG C.
Further, in the step (3), detection temperature is 20-30 DEG C, relative humidity 15-25%.
Further, the water is deionized water.
Compared with prior art, the beneficial effects of the present invention are：
The detection method of a kind of ozone and ozone precursor of the present invention, compared with prior art, operating temperature is low,
Selectively preferable to ozone and ozone precursor, the response time is short.The detection method is by controlling zinc ion in molybdenum disulfide
Doping regulates and controls the depleted of electrons layer of molybdenum disulfide nano sheet, so as to keep the constant condition of molybdenum disulfide nano sheet pattern
Under, the surface state of the big advantage of molybdenum disulfide nano sheet surface area and zinc ion doping regulation and control sensing material is combined, and then
Portable, economy, the gas sensor array of low-power consumption are constructed, is realized at room temperature to ozone, nitrogen dioxide, ethanol and formaldehyde
Quick, recognition detection.Meanwhile disclose the relation between structure, composition and the sensing capabilities of metal sulfide sensing material.
Brief description of the drawings
Fig. 1 is ultra-thin two sulphur that zinc ion doping is 0%, 1%, 3%, 5%, 9% and 15% in the embodiment of the present invention 1
Change the XRD of molybdenum nanometer sheet；
Fig. 2 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 0% in the step of the embodiment of the present invention 1 (1)
Penetrate electron microscope；
Fig. 3 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 1% in the step of the embodiment of the present invention 1 (2)
Penetrate electron microscope；
Fig. 4 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 3% in the step of the embodiment of the present invention 1 (3)
Penetrate electron microscope；
Fig. 5 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 5% in the step of the embodiment of the present invention 1 (4)
Penetrate electron microscope；
Fig. 6 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 9% in the step of the embodiment of the present invention 1 (5)
Penetrate electron microscope；
Fig. 7 is the saturating of the ultra-thin molybdenum disulfide nano sheet that zinc ion doping is 15% in the step of the embodiment of the present invention 1 (6)
Penetrate electron microscope；
Fig. 8 is that response of six kinds of ultra-thin molybdenum disulfide nano sheets of classification to formaldehyde at room temperature in the embodiment of the present invention 1 is bent
Line chart；
Fig. 9 is that response of six kinds of ultra-thin molybdenum disulfide nano sheets of classification to ethanol at room temperature in the embodiment of the present invention 1 is bent
Line chart；
Figure 10 is sound of the six kinds of ultra-thin molybdenum disulfide nano sheets of classification in the embodiment of the present invention 1 to nitrogen dioxide at room temperature
Answer curve map；
Figure 11 is that response of six kinds of ultra-thin molybdenum disulfide nano sheets of classification to ozone at room temperature in the embodiment of the present invention 1 is bent
Line chart；
Figure 12 is that zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% in the embodiment of the present invention 1
The response comparison diagram for the ozone sensor array PARA FORMALDEHYDE PRILLS(91,95) that ultra-thin molybdenum disulfide nano sheet makes；
Figure 13 is that zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% in the embodiment of the present invention 1
Response comparison diagram of the ozone sensor array that ultra-thin molybdenum disulfide nano sheet makes to ethanol.
Figure 14 is that zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% in the embodiment of the present invention 1
Response comparison diagram of the ozone sensor array that ultra-thin molybdenum disulfide nano sheet makes to ozone；
Figure 15 is that zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% in the embodiment of the present invention 1
Response comparison diagram of the ozone sensor array that ultra-thin molybdenum disulfide nano sheet makes to nitrogen dioxide.
Embodiment
In order to which the detection method of a kind of ozone of the present invention and ozone precursor is expanded on further, reach expected goal of the invention,
Below in conjunction with preferred embodiment, to the detection method according to a kind of ozone proposed by the present invention and ozone precursor, it is specific real
Mode, structure, feature and its effect are applied, is described in detail as after.In the following description, different " embodiment " or " embodiment "
What is referred to is not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by any suitable
Form combines.
Before the detection method of a kind of ozone of the present invention and ozone precursor is elaborated, it is necessary to being carried in the present invention
And associated materials and method be described further, to reach more preferable effect.
The principle of the present invention is：The molybdenum disulfide nano sheet of zinc ion doping is prepared using hydrothermal synthesis method, that is, is utilized
The ultra-thin molybdenum disulfide that the mixed solution that ammonium molybdate, thiocarbamide, zinc acetate and water form prepares the zinc ion doping of various concentrations is received
Rice piece, the big advantage of laminated structure nano material specific surface area is adulterated into regulation and control molybdenum disulfide depleted of electrons layer with zinc ion and mutually tied
Close, so as to improve the air-sensitive performance of molybdenum disulfide nano sheet, it is produced discrepant transducing signal to ozone at room temperature, and then
The different molybdenum disulfide nano sheet of zinc ion doping concentration is built into sensor array, finally believed the sensing of sensor array
Kinetic parameter (response magnitude) and thermodynamic parameter (response time) in number extract, as different analytes
Fingerprint parameter, reach the effect to ozone and ozone precursor recognition detection.
Molybdenum disulfide, chemical formula：MoS2, relative molecular mass：160.07, black solid powder, there is metallic luster.Chemistry
Formula is MoS2, 1185 DEG C of fusing point, density 4.80g/cm3(14 DEG C), 450 DEG C start to distil, and are dissolved in chloroazotic acid and hot concentrated sulfuric acid, insoluble
In water and diluted acid.
Raw material of the present invention：
Ammonium molybdate, alias have：Extraordinary ammonium molybdate, (T-4)-ammonium molybdate, ammonium tetramolybdate, the ammonium of molybdic acid two, ammonium molybdate are white
Or light green crystal, molecular formula H8MoN2O4, molecular weight 196.0145, density is (g/mL, 25/4 DEG C) 3.1, and fusing point is
300 DEG C, it is easy to purify, is easy to dissolve, is easy to thermal dissociation, moreover, the NH that pyrolysis separates out3Gas can be escaped fully with heating, no longer
Pollute molybdenum product.
Thiocarbamide, Chinese nickname thio urea, molecular formula CH4N2S, molecular weight 76.12, white and glossiness crystal,
Bitter, density 1.41,176-178 DEG C of fusing point are dissolved in water, decompose during heating, can be dissolved in ethanol during heating, atomic to be dissolved in ether.
Partly isomerization is played during melting and is formed sulphur cyanogen and is compared ammonium.
Zinc acetate, Chinese nickname：Zinc acetate, molecular formula are Zn (CH3COO)2, molecular weight 183.48, it is glossiness six
Face body scale or piece crystal, there is acetic acid odor, are acted on by zinc oxide and acetic acid and are obtained.
After the associated materials and method referred in having understood the present invention, below in conjunction with specific embodiments, to this
A kind of detection method of ozone and ozone precursor is invented to be further described in detail：
Embodiment 1.
(1)a：The thiocarbamide of 0.1960g ammonium molybdate and 2.2836g is added in the beaker of 35 ml deionized waters,
Magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 1；(the amount of the material of ammonium molybdate：
0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：2.2896 ÷ 76.12=
0.03007mol ≈ 0.0300mol=30mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 12000r/min, and the time is 3 minutes, removes supernatant, point
From being precipitated；
Sediment after washing is transferred in 100ml beaker, dried 8 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 0%, its thickness is 3-
20nm；As shown in Figure 2, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 0% is two-dimensional sheet structure；
(2)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0018g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 2；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0018÷183.48
=9.81 × 10-6mol=9.81 × 10-3mmol ≈ 0.01mmol)
b：Mixed solution 2 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
8000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 8000r/min, and the time is 5 minutes, removes supernatant, separation
Precipitated；
Sediment after washing is transferred in 100ml beaker, dried 8 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 1%, its thickness is 3-
20nm；As shown in Figure 3, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 1% is two-dimensional sheet structure；
(3)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0055g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 3；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0055÷183.48
=2.997 × 10-5mol=2.997 × 10-2mmol ≈ 0.03mmol)
b：Mixed solution 3 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 9000r/min, and the time is 4 minutes, removes supernatant, separation
Precipitated；
Sediment after washing is transferred in 100ml beaker, dried 6 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 3%, its thickness is 3-
20nm；As shown in Figure 4, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 3% is two-dimensional sheet structure；
(4)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0092g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 4；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0092÷183.48
=5.0141 × 10-5mol=5.0141 × 10-2mmol ≈ 0.05mmol)
b：Mixed solution 4 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 12000r/min, and the time is 5 minutes, removes supernatant, point
From being precipitated；
Sediment after washing is transferred in 100ml beaker, dried 12 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 5%, its thickness is 3-
20nm；As shown in Figure 5, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 5% is two-dimensional sheet structure；
(5)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0165g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 5；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0165÷183.48
=8.992 × 10-5mol=8.992 × 10-2 ≈ 0.09mmol)
b：Mixed solution 5 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
11000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 9000r/min, and the time is 3 minutes, removes supernatant, separation
Precipitated；
Sediment after washing is transferred in 100ml beaker, dried 9 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 9%, its thickness is 3-
20nm；As shown in Figure 6, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 9% is two-dimensional sheet structure；
(6)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0275g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 6；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0275÷183.48
=0.1498 × 10-3mol=0.1498mmol ≈ 0.15mmol)
b：Mixed solution 6 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 3 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasonic disperse in deionized water, then centrifuges, rotating speed 8000r/min, and the time is 3 minutes, removes supernatant, separation
Precipitated；
Sediment after washing is transferred in 100ml beaker, dried 10 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 15%, its thickness is 3-
20nm；As shown in Figure 7, it is known that the ultra-thin molybdenum disulfide nano sheet powder that zinc ion doping is 15% is two-dimensional sheet structure；
(7) sensor is prepared：
a：The zinc ion doping for taking 0.1g steps (1)-(6) to prepare respectively is 0%, 1%, 3%, 5%, 9% and 15%
Ultra-thin molybdenum disulfide nano sheet powder in agate mortar, be separately added into 3-5 drop deionized waters, be ground into pasty state；
b：Gained sample in step (7) a is applied on the electrode slice of 6 comb electrodes respectively with fine, soft fur pen, formed by zinc
Ions dosage is 0%, zinc ion doping is 1%, zinc ion doping is 3%, zinc ion doping is 5%, zinc ion
The sensor array that the ultra-thin molybdenum disulfide nano sheet powder that doping is 9% and zinc ion doping is 15% is formed；
(8) sensor array for having 6 sensors to form with preparing in Catherine's ammeter testing procedure (7) is to ozone and smelly
The response curve of oxygen precursor and volatile organic matter (formaldehyde, ethanol), collection sensor array is to ozone and ozone precursor
Response signal, and the kinetic parameter response magnitude in transducing signal and thermodynamic parameter response time are extracted, point
Each sensor in sensor array is not calculated, to the response magnitude and the ratio of response time of four kinds of analytes, to be made
For the fingerprint parameter of different analytes.
The detection of the saturated vapor of PARA FORMALDEHYDE PRILLS(91,95)：
Electrochemical workstation power supply is connected, under 1V bias, test sensor array (25 DEG C of test temperature, it is relatively wet
The response curve spent in the saturated vapor for 20%) PARA FORMALDEHYDE PRILLS(91,95), from response curve as can be seen that 0%, 1%, 3%, 5%, 9%
Respectively reach -2.94% with the response magnitude of 15% ultra-thin molybdenum disulfide nano sheet PARA FORMALDEHYDE PRILLS(91,95), -3.23%, -5.95%, -
7.73%th, -4.27%, -2.90%；Response time is respectively 2.87 seconds, 2.10 seconds, 3.38 seconds, 9.10 seconds, 4.55 seconds, 3.16
Second (as shown in figure 8, wherein corresponding from left to right zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and
15% ultra-thin molybdenum disulfide nano sheet, while the molybdenum disulfide that can illustrate to prepare is p-type semiconductor, is hole conduction).
Detection to the saturated vapor of ethanol：
Electrochemical workstation power supply is connected, under 1V bias, test sensor array (22 DEG C of test temperature, it is relatively wet
Spend for 20%) to the response curve in the saturated vapor of ethanol, from response curve as can be seen that at room temperature, 0%, 1%,
3%th, 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet respectively reach -3.54% to the response magnitude of ethanol, -
4.34%th, -6.40%, -10.27%, -6.84%, -4.41%；Response time is respectively 2.02 seconds, 1.70 seconds, 2.20 seconds,
4.44 seconds, 5.71 seconds and 3.82 seconds (as shown in figure 9, wherein corresponding from left to right zinc ion doping concentration be respectively 0%,
1%th, 3%, 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet, while the molybdenum disulfide that can illustrate to prepare is p-type half
Conductor, it is hole conduction).
Detection to nitrogen dioxide：
Connect electrochemical workstation power supply, under 1V bias, test by 0%, 1%, 3%, 5%, 9% and 15% it is super
Thin molybdenum disulfide nano sheet prepares sensor (25 DEG C of test temperature, relative humidity 20%) to NO2Ultra-thin molybdenum disulfide nano
Piece respectively reaches -2.26%, -4.41%, -5.33%, -7%, -4.46%, -2.96% to the response magnitude of nitrogen dioxide；Ring
Respectively 1.13 seconds, 1.13 seconds, 0.91 second, 1.57 seconds, 1.70 seconds and 2.42 seconds between seasonable (it is as shown in Figure 10, wherein by a left side extremely
Right corresponding zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet,
The molybdenum disulfide that can illustrate to prepare simultaneously is p-type semiconductor, is hole conduction).
Detection to ozone：
Connect electrochemical workstation power supply, under 1V bias, test by 0%, 1%, 3%, 5%, 9% and 15% it is super
Thin molybdenum disulfide nano sheet prepares sensor (25 DEG C of test temperature, relative humidity 20%) to the response in the saturated vapor of ozone
Curve, from response curve as can be seen that at room temperature, 0%, 1%, 3%, 5%, 9% and 15% ultra-thin molybdenum disulfide nano
Piece respectively reaches 1.70%, 2.28%, 3.38%, 6.48%, 3.71%, 2.81% to the response magnitude of ozone；Response time
Respectively 5.48 seconds, 4.53 seconds, 7.26 seconds, 11.83 seconds, 8.89 seconds and 3.18 seconds (as shown in figure 11, wherein from left to right pair
The ultra-thin molybdenum disulfide nano sheet that zinc ion doping concentration is respectively 0%, 1%, 3%, 5%, 9% and 15% is answered, while can
It is hole conduction using the molybdenum disulfide for illustrating to prepare as p-type semiconductor).
XRD phenograms as shown in Figure 1, zinc ion doping are ultra-thin the two of 0%, 1%, 3%, 5%, 9% and 15%
Molybdenum sulfide nanometer sheet does not have obvious peak and occurred, and illustrates that molybdenum disulfide nano sheet pattern is constant.
As shown in figure 12, for zinc ion doping concentration be respectively 0%, 1%, 3%, 5%, 9% and 15% ultra-thin two sulphur
Change the response comparison diagram for the sensor array PARA FORMALDEHYDE PRILLS(91,95) that molybdenum nanometer sheet makes, i.e., zinc ion doping concentration be respectively 0%, 1%,
3%th, the characteristic fingerprint for the sensor array PARA FORMALDEHYDE PRILLS(91,95) that 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet makes.Illustrate 6
Sensor has otherness, and sensor array has selectivity, with effective detection and can identify formaldehyde gas.
As shown in figure 13, for zinc ion doping concentration be respectively 0%, 1%, 3%, 5%, 9% and 15% ultra-thin two sulphur
Change the response comparison diagram of sensor array that molybdenum nanometer sheet makes to ethanol, i.e., zinc ion doping concentration be respectively 0%, 1%,
3%th, characteristic fingerprint of the sensor array that 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet makes to ethanol.Illustrate 6
Sensor has otherness, and sensor array has selectivity, with effective detection and can identify alcohol gas.
As shown in figure 14, for zinc ion doping concentration be respectively 0%, 1%, 3%, 5%, 9% and 15% ultra-thin two sulphur
Change the response comparison diagram of sensor array that molybdenum nanometer sheet makes to ozone, i.e., zinc ion doping concentration be respectively 0%, 1%,
3%th, characteristic fingerprint of the sensor array that 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet makes to ozone.Illustrate 6
Sensor has otherness, and sensor array has selectivity, with effective detection and can identify ozone.
As shown in figure 15, for zinc ion doping concentration be respectively 0%, 1%, 3%, 5%, 9% and 15% ultra-thin two sulphur
Change the response comparison diagram of sensor array that molybdenum nanometer sheet makes to nitrogen dioxide, i.e., zinc ion doping concentration be respectively 0%,
1%th, the sensor array that 3%, 5%, 9% and 15% ultra-thin molybdenum disulfide nano sheet makes refers to the feature of nitrogen dioxide
Line.Illustrate that 6 sensors have otherness, sensor array has selectivity, with effective detection and can identify nitrogen dioxide.
The detection method of a kind of ozone and ozone precursor described in the embodiment of the present invention, operating temperature is low, to ozone and
Ozone precursor is selectively preferable, and the response time, the response time was short within 1 minute.The detection method is by controlling curing
The doping of zinc ion regulates and controls the depleted of electrons layer of molybdenum disulfide nano sheet in molybdenum, so as to keep molybdenum disulfide nano sheet shape
Under conditions of looks are constant, by the big advantage of molybdenum disulfide nano sheet surface area and the surface state of zinc ion doping regulation and control sensing material
Be combined, so build by 6 sensor groups into gas sensor array, realize at room temperature to ozone, nitrogen dioxide,
Quick, the recognition detection of ethanol and formaldehyde.
Embodiment 2.
(1)a：The thiocarbamide of 0.1960g ammonium molybdate and 2.2836g is added in the beaker of 35 ml deionized waters,
Magnetic agitation 25 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 1；(the amount of the material of ammonium molybdate：
0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：2.2896 ÷ 76.12=
0.03007mol ≈ 0.0300mol=30mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 170 DEG C and react 26 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
8000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
With absolute ethyl alcohol washing precipitate 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is thoroughly dispersed in absolute ethyl alcohol, then is centrifuged, rotating speed 12000r/min, and the time is 5 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 6 hours in the baking oven that temperature is 50 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 0%, its thickness is 3-
20nm；
(2)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0073g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 28 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 2；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0073÷183.48
=3.978 × 10-6mol=3.978 × 10-3mmol ≈ 0.04mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 175 DEG C and react 23 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
8000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
With absolute ethyl alcohol washing precipitate 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is thoroughly dispersed in absolute ethyl alcohol, then is centrifuged, rotating speed 8000r/min, and the time is 3 minutes, removes supernatant,
Isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 8 hours in the baking oven that temperature is 55 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 4%, its thickness is 3-
20nm；
(3)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0147g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 29 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 3；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0147÷183.48
=0.8011 × 10-4mol=0.0801mmol ≈ 0.08mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 182 DEG C and react 23.5 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
11000r/min, time are 3 minutes, obtain the precipitate of molysulfides thing of black；
With absolute ethyl alcohol washing precipitate 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is thoroughly dispersed in absolute ethyl alcohol, then is centrifuged, rotating speed 8000r/min, and the time is 3 minutes, removes supernatant,
Isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 7 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 8%, its thickness is 3-
20nm；
(4)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0220g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 31 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 4；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0220÷183.48
=0.1199 × 10-3mol=0.1199mmol ≈ 0.12mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 174 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
8500r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
With absolute ethyl alcohol washing precipitate 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is thoroughly dispersed in absolute ethyl alcohol, then is centrifuged, rotating speed 10000r/min, and the time is 4 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 8 hours in the baking oven that temperature is 68 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 12%, its thickness is 3-
20nm；
(5)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0275g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 5；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0275÷183.48
=0.1498 × 10-3mol=0.1498mmol ≈ 0.15mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
With absolute ethyl alcohol washing precipitate 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is thoroughly dispersed in absolute ethyl alcohol, then is centrifuged, rotating speed 10000r/min, and the time is 4 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 11 hours in the baking oven that temperature is 55 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 15%, its thickness is 3-
20nm；
(6) sensor is prepared：
a：The zinc ion doping for taking 0.1g steps (1)-(5) to prepare respectively be 0%, 4%, 8%, 12% and 15% it is super
Thin molybdenum disulfide nano sheet powder is separately added into 3-5 drop deionized waters, is ground into pasty state in agate mortar；
b：Gained sample in step (7) a is applied on the electrode slice of 5 comb electrodes respectively with fine, soft fur pen, formed by zinc
Ions dosage is 0%, zinc ion doping is 4%, zinc ion doping is 8%, zinc ion doping is 12% and zinc from
The sensor array that the ultra-thin molybdenum disulfide nano sheet powder that sub- doping is 15% is formed；
(8) at 20 DEG C, under conditions of relative humidity is 15%, there are 5 with what is prepared in Catherine's ammeter testing procedure (6)
The sensor array that sensor is formed to ozone and the response curve of ozone precursor and volatile organic matter (formaldehyde, ethanol),
Gather response signal of the sensor array to ozone and ozone precursor.
The detection method of a kind of ozone and ozone precursor described in the embodiment of the present invention, operating temperature is low, to ozone and
Ozone precursor is selectively preferable, and the response time is short.The detection method by control the doping of zinc ion in molybdenum disulfide come
Regulate and control the depleted of electrons layer of molybdenum disulfide nano sheet, so that under conditions of keeping molybdenum disulfide nano sheet pattern constant, by two
The surface state of the big advantage of molybdenum sulfide nanometer sheet surface area and zinc ion doping regulation and control sensing material is combined, and then is built by 5
Individual sensor group into gas sensor array, realize at lower operating temperatures to ozone, nitrogen dioxide, ethanol and first
Quick, the recognition detection of aldehyde.
Embodiment 3.
(1)a：The thiocarbamide of 0.1960g ammonium molybdate and 2.2836g is added in the beaker of 35 ml deionized waters,
Magnetic agitation 32 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 1；(the amount of the material of ammonium molybdate：
0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：2.2896 ÷ 76.12=
0.03007mol ≈ 0.0300mol=30mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Reaction 22-26 hours in the air dry oven for 170-190 DEG C are spent, after it naturally cools to room temperature, are centrifuged, are turned
Speed is 8000-12000r/min, and the time is 3-5 minutes, obtains the precipitate of molysulfides thing of black；
Sediment is washed with deionized 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 8000r/min, and the time is 5 minutes, removes supernatant,
Isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 9 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 0%, its thickness is 3-
20nm；
(2)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0037g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 35 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 2；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0037÷183.48
=2.01 × 10-5mol=2.01 × 10-2mmol ≈ 0.02mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 184 DEG C and react 25 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
8000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 12000r/min, and the time is 3 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 7 hours in the baking oven that temperature is 65 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 1%, its thickness is 3-
20nm；
(3)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0073g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 33 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 3；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0073÷183.48
=3.978 × 10-6mol=3.978 × 10-3mmol ≈ 0.04mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 186 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
11000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 4 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 10000r/min, and the time is 4 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 11 hours in the baking oven that temperature is 68 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 4%, its thickness is 3-
20nm；
(4)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0110g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 4；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0110÷183.48
=5.995 × 10-5mol=5.998 × 10-2 ≈ 0.06mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 176 DEG C and react 25 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
9000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 9000r/min, and the time is 4 minutes, removes supernatant,
Isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 10 hours in the baking oven that temperature is 64 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 6%, its thickness is 3-
20nm；
(5)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0147g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 34 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 5；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0147÷183.48
=0.8011 × 10-4mol=0.0801mmol ≈ 0.08mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 188 DEG C and react 23 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 5 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 8000r/min, and the time is 4 minutes, removes supernatant,
Isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 7 hours in the baking oven that temperature is 65 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 8%, its thickness is 3-
20nm；
(6)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0220g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 31 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 6；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0220÷183.48
=0.1199 × 10-3mol=0.1199mmol ≈ 0.12mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 176 DEG C and react 25 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 3 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 12000r/min, and the time is 4 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 10 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 12%, its thickness is 3-
20nm；
(7)a：The zinc acetate of 0.1960g ammonium molybdate, 2.2836g thiocarbamide and 0.0275g 35 milliliters have been added to
In the beaker of ionized water, magnetic agitation 30 minutes, solute is completely dissolved, and forms uniform solution, obtains mixed solution 7；(ammonium molybdate
Material amount：0.1960 ÷ 196.0145=0.000999mol ≈ 0.001mol=1mmol；The amount of the material of thiocarbamide：
2.2896 ÷ 76.12=0.03007mol ≈ 0.0300mol=30mmol；The amount of the material of zinc acetate：0.0275÷183.48
=0.1498 × 10-3mol=0.1498mmol ≈ 0.15mmol)
b：Mixed solution 1 is transferred in the ptfe autoclave of 45 milliliters of sealings, reactor is put into temperature
Spend in the air dry oven for 180 DEG C and react 24 hours, after it naturally cools to room temperature, be centrifuged, rotating speed is
10000r/min, time are 4 minutes, obtain the precipitate of molysulfides thing of black；
Sediment is washed with deionized 5 times to the aobvious neutrality of solution, the sediment after must washing；The washing refers to and will precipitated
Thing ultrasound is completely dispersed in deionized water, then is centrifuged, rotating speed 10000r/min, and the time is 4 minutes, removes supernatant
Liquid, isolated precipitation；
Sediment after washing is transferred in 100ml beaker, dried 12 hours in the baking oven that temperature is 60 DEG C, is used
Agate mortar is fully ground, and obtains the ultra thin p-type molybdenum disulfide nano sheet powder that zinc ion doping is 15%, its thickness is 3-
20nm；
(8) sensor is prepared：
a：The zinc ion doping for taking 0.1g steps (1)-(7) to prepare respectively is 0%, 2%, 4%, 6%, 8%, 12% and
15% ultra-thin molybdenum disulfide nano sheet powder is separately added into 3-5 drop deionized waters, is ground into pasty state in agate mortar；
b：Gained sample in step (8) a is applied on the electrode slice of 7 comb electrodes respectively with fine, soft fur pen, formed by zinc
Ions dosage is 0%, zinc ion doping is 2%, zinc ion doping is 4%, zinc ion doping is 6%, zinc ion
The ultra-thin molybdenum disulfide nano sheet powder structure that doping is 8%, zinc ion doping is 12% and zinc ion doping is 15%
Into sensor array；
(8) at 30 DEG C, under conditions of relative humidity is 25%, there are 7 biographies with being prepared in Catherine's ammeter testing procedure (7)
The sensor array that sensor is formed is adopted to ozone and the response curve of ozone precursor and volatile organic matter (formaldehyde, ethanol)
Collect response signal of the sensor array to ozone and ozone precursor.
The detection method of a kind of ozone and ozone precursor described in the embodiment of the present invention, operating temperature is low, to ozone and
Ozone precursor is selectively preferable, and the response time is short.The detection method by control the doping of zinc ion in molybdenum disulfide come
Regulate and control the depleted of electrons layer of molybdenum disulfide nano sheet, so that under conditions of keeping molybdenum disulfide nano sheet pattern constant, by two
The surface state of the big advantage of molybdenum sulfide nanometer sheet surface area and zinc ion doping regulation and control sensing material is combined, and then is built by 7
Individual sensor group into gas sensor array, realize quick, the recognition detection to ozone, nitrogen dioxide, ethanol and formaldehyde.
It is described above, only it is 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 simply modification, the equivalent variations that the technical spirit according to the embodiment of the present invention is made to above example
With modification, in the range of still falling within technical scheme of the embodiment of the present invention.
Claims (7)
1. the detection method of a kind of ozone and ozone precursor, it is characterised in that comprise the following steps：
(1) ammonium molybdate, thiocarbamide and zinc acetate are dissolved completely in water, obtain mixed solution；The thiocarbamide, ammonium molybdate and zinc acetate
Mol ratio be 3000:100:0-15；
(2) mixed solution is transferred in the reactor of sealing, and at 170-190 DEG C after reaction 22-26 hours, natural cooling
To room temperature, it is centrifuged, obtains the sediment of black；
With water or absolute ethyl alcohol washing precipitate to the aobvious neutrality of solution, the sediment after must washing；The washing refers to sediment
Ultrasonic disperse is in water or absolute ethyl alcohol, then centrifuges, and removes supernatant, isolated precipitation；
Sediment after washing is dried into 6-12 hours at 50-70 DEG C, obtains dried sediment；By dried sediment
It is fully ground, obtains p-type molybdenum disulfide nano sheet powder；
(3) repeating said steps (1) (2) be no less than 4 times, each ammonium molybdate is different from the mol ratio of zinc acetate, and with step (1)
In ammonium molybdate it is different from the mol ratio of zinc acetate, obtain no less than the different p-type molybdenum disulfide nano of 5 kinds of zinc ion dopings
Piece powder；
(4) the different p-type molybdenum disulfide nano sheet powder of no less than 5 kinds zinc ion dopings is prepared into sensor respectively, and
It is built into a sensor array for there are no less than 5 sensors to form；
(5) ozone and ozone precursor are detected respectively with sensor array, collection sensor array is to ozone and ozone precursor
Response signal.
2. detection method according to claim 1, it is characterised in that wherein,
In the step (1), ammonium molybdate, thiocarbamide and zinc acetate are added to the water, its dissolving is made by way of magnetic agitation.
3. detection method according to claim 1, it is characterised in that wherein,
In the step (2), after being cooled to room temperature, the rotating speed of centrifugation is 8000-12000r/min, and the time is 3-5 minutes；
The washing times are 3-5 times；
The thickness of the p-type molybdenum disulfide nano sheet powder is 3-20nm.
4. detection method according to claim 3, it is characterised in that wherein,
Washing in the step (2)：The rotating speed of centrifugation is 8000-12000r/min, and the time is 3-5 minutes.
5. detection method according to claim 4, it is characterised in that wherein,
In the step (2), reaction temperature is 180 DEG C, and the reaction time is 24 hours；
The drying temperature is 60 DEG C.
6. detection method according to claim 1, it is characterised in that wherein,
In the step (3), detection temperature is 20-30 DEG C, relative humidity 15-25%.
7. according to the detection method described in claim 1-6, it is characterised in that wherein,
The water is deionized water.
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