CN110530941A - A kind of Cu doping Sn3O4Gas sensitive and its formaldehyde gas sensor and preparation method, application - Google Patents
A kind of Cu doping Sn3O4Gas sensitive and its formaldehyde gas sensor and preparation method, application Download PDFInfo
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- CN110530941A CN110530941A CN201910646516.6A CN201910646516A CN110530941A CN 110530941 A CN110530941 A CN 110530941A CN 201910646516 A CN201910646516 A CN 201910646516A CN 110530941 A CN110530941 A CN 110530941A
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Abstract
The present invention relates to gas sensor technical fields more particularly to a kind of Cu to adulterate Sn3O4Gas sensitive and its formaldehyde gas sensor and preparation method, application.The gas sensitive includes: Sn3O4Nanometer sheet and copper ion, the Sn3O4Nanometer sheet heap poststack forms three-dimensional flower-like structure, and the copper ion is present in Sn3O4Replace Sn among lattice3O4Part tin ion and Sn in lattice3O4In nanometer sheet and Sn3O4In interstitial void.The Sn with flower-like structure that the present invention is adulterated with Cu3O4For formaldehyde gas sensor sensitive material, the gas sensor of preparation at lower operating temperatures, has big response, good formaldehyde gas selectivity and fast-response and resume speed, and can be effectively reduced experimental implementation complexity, saves experimental cost.
Description
Technical field
The present invention relates to gas sensor technical fields more particularly to a kind of Cu to adulterate Sn3O4Gas sensitive and its formaldehyde
Gas sensor and preparation method, application.
Background technique
In background of invention, it is only intended to increase understanding of the overall background of the invention for disclosed information, without
Necessarily it is considered as recognizing or imply that information composition has become in any form to show well known to persons skilled in the art
There is technology.
With the emergence of artificial intelligence and Internet of Things information age, in the acquisition to information-transmission-processing chain,
Sensor plays very important effect as the front end device for obtaining information in information technology chain.Society in recent years
Rapid development that can be economic also gives our living environment band while bringing great riches and endless convenience to the mankind
Some indelible damages are carried out.The exhaust gas generated in industrial processes, the tail gas of vehicular emission, house decoration generate
The various air pollutions such as formaldehyde, the eyes and skin of people can be stimulated, make inflammatory eye skin allergy, moreover it is possible to stimulate exhaling for people
Desorption system causes the diseases such as cough, asthma, or even can cause the fatal diseases such as lung cancer, cutaneum carcinoma, causes to people's health huge
Big threat.So ensureing people's life wealth in order to inflammable and explosive, poisonous and hazardous gases various in real-time monitoring environment
Safety is produced, gas sensor plays vital effect in the production and living of people.
Compared to separated using form and aspect, the equipment such as ultraviolet-uisible spectrophotometer and infrared absorption instrument sample gas
Analysis, metal-oxide semiconductor (MOS) gas sensor have many advantages, such as that structure is simple, cheap, easy to use.It is generally used for
The metal oxide materials of gas sensor have SnO2、In2O3、Fe2O3、Co3O4, CuO etc., present inventors believe that common system
The method of standby metal-oxide semiconductor (MOS), such as pulse laser deposition, magnetron sputtering, chemical vapor deposition etc., it usually needs complicated
Operating procedure, and need expensive experimental facilities；And the gas sensor of single metal oxide materials, usually have
The disadvantages of operating temperature height (200-400 DEG C), response is small, poor selectivity, slow response and resume speed.
Summary of the invention
For above-mentioned problem, the present invention is intended to provide a kind of Cu adulterates Sn3O4Gas sensitive and its formaldehyde gas sensing
Device and preparation method, application.The present invention constructs Cu/Sn by metal ion mixing3O4Semiconductor material of composite metal oxide,
The selectivity of metal-oxide semiconductor (MOS) gas sensor effectively can be enhanced at lower operating temperatures, accelerate sensor
Response and resume speed, significantly improve sensor to test gas response.
The first object of the present invention is to provide Cu doping Sn3O4Gas sensitive and preparation method thereof.
The second object of the present invention is to provide and adulterates Sn based on Cu3O4The formaldehyde gas sensor of gas sensitive and its preparation
Method.
The third object of the present invention is to provide the Cu doping Sn3O4Gas sensitive and its formaldehyde gas sensor and system
The application of Preparation Method.
For achieving the above object, the invention discloses following technical proposals:
Firstly, the present invention discloses a kind of Cu doping Sn3O4Gas sensitive, comprising: Sn3O4Nanometer sheet and copper ion, it is described
Sn3O4Nanometer sheet heap poststack forms three-dimensional flower-like structure, and the copper ion is present in Sn3O4Replace Sn among lattice3O4Lattice
In part tin ion and Sn3O4In nanometer sheet and Sn3O4In interstitial void.
As further technical solution, the Sn3O4The thickness of nanometer sheet between 10-25nm, diameter 1-4 μm it
Between.
Cu proposed by the present invention adulterates Sn3O4Gas sensitive the characteristics of be: (1) this Sn with flower-like structure3O4Gas
Quick material is compared with ordinary granular or block-like oxide semiconductor material, and specific surface area is obviously improved, and is had micro-
Pore structure can provide good absorption and diffusion path for gas, improve the response speed and resume speed of sensor.(2)
By adulterating copper ion, Sn further reduced3O4The structure size of nanometer sheet increases the specific surface area of material, thus, into
One step improves the response and response and resume speed of gas sensor.(3) doping metals copper ion can be such that material generates
A large amount of atom defect, such defect are conducive to the absorption of oxygen molecule in air, increase the initial resistance of sensor, improve gas
Quick response.(4) Cu ion in part is present in Sn3O4Interstitial void between, the Cu in these gaps is capable of providing a large amount of catalysis
Active site is conducive to formaldehyde gas molecule and is chemically reacted on sense film surface, is also beneficial to the correlation of film surface
Electronics transfer improves transducer sensitivity.
Secondly, the present invention provides a kind of Cu doping Sn3O4Gas sensitive preparation method, step are as follows:
(1) by stannous chloride, citrate stirring soluble in water to abundant dissolution, copper ion is then added, stirs evenly,
It is designated as solution A；
(2) aqueous slkali is slowly poured into the solution A, obtained solution is subjected to hydro-thermal reaction after stirring, completed
After be cooled to room temperature, isolate solid product, as Cu adulterates Sn3O4Gas sensitive.
As further technical solution, in step (1), the stannous chloride, citrate (such as sodium citrate), copper
The adding proportion of ion is sequentially 1mmol:(2-3) mmol:(0.1-0.3) mmol, the dosage of water guarantees stannous chloride
It is sufficiently dissolved with citrate.
As further technical solution, in step (1), form of the addition of the copper ion using inorganic mantoquita, example
Such as common mantoquita of copper nitrate, copper chloride, copper sulphate.
As further technical solution, in step (2), the aqueous slkali includes sodium hydroxide, ammonium hydroxide etc., by adjusting
The pH value of precursor solution, can control synthesis has the tin-oxide of different valence state of specific morphology.
As further technical solution, in step (2), the adding proportion of the lye are as follows: stannous chloride: lye=1:
0.5-1.2, molar ratio.
As further technical solution, in step (2), the condition of the hydro-thermal reaction are as follows: anti-between 160-200 DEG C
It answers 12-15 hours.
As further technical solution, in step (2), include the steps that washing solid product and being dried,
Specially use deionized water and ethanol washing, it may be necessary to which repeatedly washing dries 12-14 at 60-80 DEG C after the completion of washing
Hour adulterates Sn to get Cu3O4Gas sensitive.
Again, the present invention discloses a kind of based on Cu doping Sn3O4The formaldehyde gas sensor of gas sensitive, the sensor are
Heater-type structure comprising: pedestal, ceramic tube, heater strip, circular metal electrode, gas sensitive and conducting wire；Wherein, the gas
The above-mentioned Cu of quick material adulterates Sn3O4Gas sensitive, heater strip, and the both ends difference of heater strip are provided in the ceramic tube
Extend to the outside of two ports of ceramic tube；The circular metal electrode is two, is covered along the circumferential direction of ceramic tube
On the outer surface of ceramic tube, and two circular metal electrode interval settings；The gas sensitive setting is being provided with endless metal
On the outer surface of the ceramic tube of electrode, and ceramic tube and circular metal electrode are wrapped up wherein；The extension of the heater strip
Both ends outside to ceramic tube are connect with pedestal；The conducting wire is four, for connecting circular metal electrode and pedestal, wherein often
The corresponding one group of circular metal electrode of two conducting wires, and two conducting wires are arranged a circular metal electrode two sides.
For further technical solution, the material of the ceramic tube is aluminium oxide etc..
As further technical solution, the material of the heater strip is Ni-Cr alloy, any one in Fe-Cr alloy
Kind.
As further technical solution, the material of the metal electrode is noble metal, such as gold, platinum, palladium, silver.
As further technical solution, the material of the conducting wire is noble metal, such as gold, platinum, palladium, silver.
As further technical solution, it is spiral shape that the heater strip, which is located at the part in ceramic tube,.In order to more
Temperature needed for sensor function work is rapidly provided.
Thirdly, the present invention provides described based on Cu doping Sn3O4The preparation side of the formaldehyde gas sensor of gas sensitive
Method includes the following steps:
S1, the Cu is adulterated into Sn3O4Gas sensitive is prepared into finely dispersed paste；
S2, the paste in step S1 is uniformly coated on the ceramic pipe surface with a pair of metal electrodes, dried in the air naturally
It is dried after dry；
S3, will it is dry in step S2 after ceramic tube in heating wire, metal electrode be respectively welded at connecing for six leg bases
On terminal, aging is carried out then to get the formaldehyde gas sensor of heater-type structure.
As further technical solution, in step S1, the paste the preparation method comprises the following steps: Cu is adulterated Sn3O4Air-sensitive
Material powder is mixed with deionized water by mass volume ratio (mg/ml) 185-230:1-1.5, and then grinding and ultrasound, are divided
Dissipate uniform paste, wherein the milling time is 15-30min, ultrasonic time 30-60min.
As further technical solution, in step S2, the drying condition are as follows: the dry 10-12h between 60-80 DEG C.
As further technical solution, in step S2, the time of the aging is 22-25 hours.
Finally, the present invention discloses the Cu doping Sn3O4Gas sensitive and preparation method thereof, Sn adulterated based on Cu3O4Gas
The formaldehyde gas sensor of quick material and the application in the fields such as monitored gas environment, industrial gasses analysis.
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) Sn with flower-like structure that the present invention is adulterated with Cu3O4For formaldehyde gas sensor sensitive material, preparation
Gas sensor at lower operating temperatures (160 DEG C), has big response, good formaldehyde gas selectivity and fast-response
And resume speed, and can be effectively reduced experimental implementation complexity, save experimental cost.
(2) present invention reduces flower-shaped Sn by doping copper ion3O4The structure size of nanometer sheet, increases Sn3O4It receives
The specific surface area of rice piece further improves the response and response and resume speed of gas sensor.
(3) present invention makes Sn by doping copper ion3O4A large amount of atom defect is generated in nanometer sheet, such defect has
Conducive to the absorption of oxygen molecule in air, increase the initial resistance of sensor, improves air-sensitive response.
(4) present invention has part copper ion and is present in Sn by doping copper ion3O4Interstitial void between, and these
Cu in gap is capable of providing a large amount of active site, is conducive to formaldehyde gas molecule on sense film surface and carries out chemistry
Reaction is also beneficial to the associated electrical transfer of film surface, improves transducer sensitivity.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is to adulterate Sn based on Cu in the embodiment of the present invention 43O4The structural representation of the formaldehyde gas sensor of gas sensitive
Figure.
Fig. 2 is to adulterate Sn based on Cu in the embodiment of the present invention 13O4The sectional view of the formaldehyde gas sensor of gas sensitive.
Fig. 3 is the Sn of difference Cu doping in the embodiment of the present invention 13O4X-ray diffraction (XRD) figure of material.
Fig. 4 is the Sn of difference Cu doping in the embodiment of the present invention 13O4Scanning of materials electron microscope (SEM) figure.
Fig. 5 is the Sn of difference Cu doping in the embodiment of the present invention 13O4The sensor of material preparation is in different operating temperature
Under at a temperature of 100ppm formaldehyde gas response test and different operating response and recovery time test result figure.
Fig. 6 is the Sn of difference Cu doping in the embodiment of the present invention 13O4The sensor of material preparation is in 160 DEG C of operating temperatures
Under to formaldehyde (1-300ppm) response test result figure of various concentration.
Fig. 7 is the Sn of difference Cu doping in the embodiment of the present invention 13O4The sensor of material preparation is in 160 DEG C of operating temperatures
Under to the selectivity test result figure of 100ppm gas with various.
Fig. 8 is the Sn of difference Cu doping in the embodiment of the present invention 13O4The sensor of material preparation is in 160 DEG C of operating temperatures
Under to the repeatability test of 100ppm formaldehyde gas and stability test figure in 40 days.
Attached drawing acceptance of the bid note respectively represents: 1- pedestal, 2- ceramic tube, 3- heater strip, 4- circular metal electrode, 5- air-sensitive material
Material, 6- conducting wire.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As described in background, the common method for preparing metal-oxide semiconductor (MOS), such as pulse laser deposition, magnetic control
Sputtering, chemical vapor deposition etc., it usually needs complicated operating procedure, and need expensive experimental facilities；And single gold
Belong to the gas sensor of oxide material, usually have that operating temperature is high (200-400 DEG C), response is small, poor selectivity, response
The disadvantages of slow with resume speed.Therefore, the invention proposes a kind of Cu to adulterate Sn3O4Gas sensitive and its formaldehyde gas sensing
Device and preparation method, application are further illustrated the present invention now in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of Cu doping Sn3O4Gas sensitive preparation method, include the following steps:
(1) by the SnCl of 5mmol2·2H2The Na of O and 12.5mmol3C6H5O7·2H2O is dissolved in the deionized water of 12.5mL
In, uniform solution is formed, Cu (NO is separately added into obtained solution3)2, obtain Cu (NO3)2Mass concentration is respectively
Four kinds of mixed solutions of 0wt%, 2wt%, 4wt%, 6wt%, the magnetic agitation mixed solution, successively by obtain four kinds of solution
Sequence is designated as solution A 1, A2, A3 and A4；
(2) NaOH of 2.5mmol is dissolved in the deionized water of 12.5ml, magnetic agitation make it dissolve to be formed it is uniform molten
Liquid is designated as solution B；
(3) Xiang Suoshu solution A 1, the solution B being slowly added in A2, A3, A4 in step (2), it is small to continue magnetic agitation 2
When, obtained solution is sequentially denoted as C1, C2, C3, C4.
(4) described C1, C2, C3, C4 are transferred in the autoclave of 50mL Teflon lining respectively, are added at 180 DEG C
Heat 12 hours, cooled to room temperature, obtained precipitating deionized water and ethyl alcohol is cleaned 6 times, then at 80 DEG C later
Drying 12 hours, obtains the Sn of four kinds of Cu dopings3O4Gas sensitive；
2, Sn is adulterated based on Cu3O4The preparation method of the formaldehyde gas sensor of gas sensitive, includes the following steps:
The Sn of S1, the four kinds of Cu dopings manufactured in the present embodiment taken3O4Each 210mg of gas sensitive powder, respectively at
The deionized water of 1.5ml mixes, and grinds 20min with agate mortar respectively, respectively ultrasound 40min, and four kinds of acquisition is finely dispersed
Cu adulterates Sn3O4Gas sensitive paste.
S2, the paste that step S1 is obtained is dipped with hooking pen be uniformly coated on the Al with a pair of of gold electrode2O3Ceramics
Pipe surface obtains four kinds of ceramic tubes for being coated with paste.
S3, four kinds of ceramic tubes for being coated with paste for obtaining step S2 place 12h naturally dry, then 60
Dry 10h under the conditions of DEG C.
S4, the resistance heating wire of four kinds of obtained ceramic tubes of the step S3 and Ni-Cr alloy is successively welded on pedestal
On, aging 24 hours on agingtable, obtain the Sn of four kinds of Cu dopings later3O4The formaldehyde gas sensing of gas sensitive preparation
Device, for testing its performance.
Embodiment 2
A kind of Cu doping Sn3O4Gas sensitive preparation method, include the following steps:
(1) by the SnCl of 5mmol2·2H2The Na of O and 10mmol3C6H5O7·2H2O is dissolved in the deionized water of 12.0mL,
Uniform solution is formed, Cu (NO is separately added into obtained solution3)2, obtain Cu (NO3)2Mass concentration is the mixed of 3wt%
Solution is closed, obtained solution is designated as solution A by the magnetic agitation mixed solution；
(2) NaOH of 5mmol is dissolved in the deionized water of 12.5ml, magnetic agitation make it dissolve to be formed it is uniform molten
Liquid is designated as solution B；
(3) solution B being slowly added in Xiang Suoshu solution A in step (2) continues magnetic agitation 2 hours, molten by what is obtained
Liquid is designated as C.
(4) C is transferred in the autoclave of 50mL Teflon lining, heats 15 hours at 160 DEG C, later from
It is so cooled to room temperature, obtained precipitating deionized water and ethyl alcohol is cleaned 5 times, then dries 14 hours, obtains at 70 DEG C
Cu adulterates Sn3O4Gas sensitive；
2, Sn is adulterated based on Cu3O4The preparation method of the formaldehyde gas sensor of gas sensitive, includes the following steps:
S1, the Cu manufactured in the present embodiment taken adulterate Sn3O4Gas sensitive powder 185mg, mixes with the deionized water of 1ml
15min is ground with agate mortar afterwards, then ultrasound 60min, obtains evenly dispersed Cu doping Sn3O4Gas sensitive paste.
S2, the paste that step S1 is obtained is dipped with hooking pen be uniformly coated on the Al with a pair of of gold electrode2O3Ceramics
Pipe surface obtains the ceramic tube coated with paste.
S3, the ceramic tube coated with paste for obtaining step S2 place 12h naturally dry, then in 80 DEG C of items
Dry 12h under part.
S4, the resistance heating wire of the obtained ceramic tube of step S3 and Ni-Cr alloy is successively welded on the base, it
Aging 22 hours on agingtable afterwards obtain the Sn of Cu doping3O4The formaldehyde gas sensor of gas sensitive preparation.
Embodiment 3
A kind of Cu doping Sn3O4Gas sensitive preparation method, include the following steps:
(1) by the SnCl of 5mmol2·2H2The Na of O and 15mmol3C6H5O7·2H2O is dissolved in the deionized water of 13.0mL,
Uniform solution is formed, Cu (NO is separately added into obtained solution3)2, obtain Cu (NO3)2Mass concentration is the mixed of 5wt%
Solution is closed, obtained solution is designated as solution A by the magnetic agitation mixed solution；
(2) NaOH of 6mmol is dissolved in the deionized water of 13.0ml, magnetic agitation make it dissolve to be formed it is uniform molten
Liquid is designated as solution B；
(3) solution B being slowly added in Xiang Suoshu solution A in step (2) continues magnetic agitation 2.5 hours, by what is obtained
Solution is designated as C.
(4) C is transferred in the autoclave of 50mL Teflon lining, heats 12 hours at 200 DEG C, later from
It is so cooled to room temperature, obtained precipitating deionized water and ethyl alcohol is cleaned 7 times, then dries 14 hours, obtains at 60 DEG C
Cu adulterates Sn3O4Gas sensitive；
2, Sn is adulterated based on Cu3O4The preparation method of the formaldehyde gas sensor of gas sensitive, includes the following steps:
S1, the Cu manufactured in the present embodiment taken adulterate Sn3O4Gas sensitive powder 230mg, it is mixed with the deionized water of 1.5ml
30min is ground with agate mortar after conjunction, then ultrasound 30min, obtains evenly dispersed Cu doping Sn3O4Gas sensitive paste.
S2, the paste that step S1 is obtained is dipped with hooking pen be uniformly coated on the Al with a pair of of gold electrode2O3Ceramics
Pipe surface obtains the ceramic tube coated with paste.
S3, the ceramic tube coated with paste for obtaining step S2 place 12h naturally dry, then in 70 DEG C of items
Dry 12h under part.
S4, the resistance heating wire of the obtained ceramic tube of step S3 and Ni-Cr alloy is successively welded on the base, it
Aging 25 hours on agingtable afterwards obtain the Sn of Cu doping3O4The formaldehyde gas sensor of gas sensitive preparation.
Embodiment 4
With reference to Fig. 1 and 2, one kind adulterating Sn based on Cu3O4The formaldehyde gas sensor of gas sensitive, the sensor are indirect heat
Formula structure comprising: pedestal 1, alumina ceramic tube 2, heater strip 3 (Ni-Cr alloy), annular gold electrode 4,5 and of gas sensitive
Pt conducting wire 6；Wherein, the gas sensitive 5 is that Cu prepared by embodiment 2 adulterates Sn3O4Gas sensitive 5, the aluminium oxide ceramics
Heater strip 3 is provided in pipe 2, and the both ends of heater strip 3 extend respectively to the outside of 2 two ports of alumina ceramic tube；It is described
Annular gold electrode 4 is two, is covered on the outer surface of ceramic tube along the circumferential direction of alumina ceramic tube 2, and two rings
The setting of the interval of shape gold electrode 4；The outer surface for being provided with the alumina ceramic tube 2 of annular gold electrode 4 is arranged in the gas sensitive 5
On, and alumina ceramic tube 2 and annular gold electrode 4 are wrapped up wherein；The heater strip 3 extends to alumina ceramic tube
Both ends outside 2 are connect with pedestal 1；The Pt conducting wire is four, for connecting circular metal electrode 4 and pedestal 1, wherein every two
The corresponding one group of circular metal electrode of a conducting wire, and the two sides of a circular metal electrode are arranged in two conducting wires.
Performance test:
(1) Fig. 3 is the Sn that embodiment 1 prepares different Cu dopings by one step hydro thermal method3O4The X-ray diffraction of material
(XRD) figure, as can be seen from the figure: all samples all have good crystallinity, for the sample of no Cu doping, diffraction
It peak can be with the Sn of anorthic system3O4Standard card (JCPDS No16-0737) is good fit, it was demonstrated that has synthesized high-purity
Sn3O4, it is the sample of 4wt% and 6wt% for Cu doping, can detecte to a lesser peak, corresponds to Cu (JCPDS
Card No.04-0836) (111) face.
(2) Fig. 4 is the Sn of difference Cu doping in embodiment 13O4Scanning of materials electron microscope (SEM) figure, wherein scheming
(a) Cu (NO when-(d) respectively indicates preparation3)2Mass concentration is respectively 0wt%, 2wt%, 4wt%, the gas sensitive of 6wt%,
As can be seen from the figure: all samples of synthesis are all shown stacked as nanometer sheet made of flower-like structure, with Cu doping
Increase, the diameter of nano flower is being gradually reduced, and flower-like structure size reduces, and can increase the specific surface area of material, be conducive to
Sensor material is improved to the sensing response of gas.
(3) Cu doping content and operating temperature influence the sensing capabilities of metal-oxide semiconductor (MOS) gas sensor, will be real
Apply the Sn based on different Cu dopings of the preparation of example 13O4Sensor be respectively placed in 120 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170,
Under the conditions of 180 DEG C, 200 DEG C, 220 DEG C, susceptibility test is carried out to the formaldehyde gas of 100ppm, test results are shown in figure 5.From
As can be seen that adulterating Sn based on 4wt%Cu in Fig. 5 (a)3O4The sensor PARA FORMALDEHYDE PRILLS(91,95) of material shows highest response, so this
Invention selects optimum doping concentration of the 4wt% as Cu.Although simultaneously it can also be seen that the sensor is in lower operating temperature
At 120 DEG C, the response of PARA FORMALDEHYDE PRILLS(91,95) is bigger, and still, the recovery time of sensor is long at a lower temperature, can not be to test
The variation of gas concentration, which is made, timely to be responded.In the higher situation of temperature, the response of sensor PARA FORMALDEHYDE PRILLS(91,95) is again smaller.
Binding test Fig. 5 (b), when operating temperature is less than 160 DEG C, the recovery time of sensor quickly reduces as the temperature increases, when
When operating temperature is higher than 160 DEG C, the recovery time of sensor slowly reduces as the temperature increases, it is contemplated that practical situations,
Select 160 DEG C of optimum working temperatures as sensor.
(4) quantity sensor (Cu (NO is adulterated for different Cu prepared by testing example 13)2Mass concentration be respectively 0wt% and
4wt%, i.e. 0wt% are comparative example) the detectable concentration range of PARA FORMALDEHYDE PRILLS(91,95) gas, at 160 DEG C to the formaldehyde of 1-300ppm into
Sensing testing is gone, as a result as shown in Figure 6, it was demonstrated that gas sensor PARA FORMALDEHYDE PRILLS(91,95) proposed by the present invention has biggish detection model
It encloses.
(5) quantity sensor (Cu (NO is adulterated for different Cu prepared by testing example 13)2Mass concentration be respectively 0wt% and
4wt%, i.e. 0wt% are comparative example) sensor is respectively placed in by the selectivity of PARA FORMALDEHYDE PRILLS(91,95) gas in the case where temperature is 160 DEG C
The formaldehyde of 100ppm, ethyl alcohol, triethylamine, in dimethylbenzene, tests the selectivity of the sensor PARA FORMALDEHYDE PRILLS(91,95), as a result such as Fig. 7 institute at acetone
Show, from test result as can be seen that under identical test temperature, tests gas in formaldehyde, acetone, ethyl alcohol, triethylamine, dimethylbenzene
In body, the response of the gas sensor PARA FORMALDEHYDE PRILLS(91,95) is apparently higher than other gases, shows good formaldehyde gas selectivity.
(6) sensor (Cu (NO prepared by testing example 13)2Mass concentration is 4wt%) repeatability and long-term
Stability test, wherein Fig. 8 (a) is repeatable test result, and Fig. 8 (b) is long term stability tests result, the results showed that
The sensor has superior repeatability and good long-time stability.
Sensor prepared by the present invention can obtain above-mentioned excellent technical effect, the main reason is that: preparation has
The Sn of flower-like structure3O4Gas sensitive is compared with ordinary granular or block-like oxide semiconductor material, and specific surface area is shown
It writes and is promoted, and there is microcellular structure, good absorption and diffusion path can be provided for gas, improve the response speed of sensor
And resume speed because the response mechanism of the gas sensor based on metal oxide materials be sensor in gas with various when
Resistance variations.When sensor exposes in air, the oxygen molecule of surface of sensing materials absorption will capture oneself in conduction band
By electronics, increase the resistance of sensor, when sensor is exposed in reducibility gas, test gas molecule will and inhale
Attached oxygen chemically reacts, and discharges electronics, reduces the resistance of sensor, and more adsorption sites and good absorption are expanded
Channel is dissipated, the response of sensor can be improved, accelerates response and resume speed.In addition, being further decreased by doping copper ion
Sn3O4The structure size of nanometer sheet increases the specific surface area of material, thus, further improve the response of gas sensor
Value and response and resume speed.Meanwhile doping metals copper ion, material can be made to generate a large amount of atom defect, it is such to lack
The absorption for being conducive to oxygen molecule in air is fallen into, the initial resistance of sensor is increased, improves air-sensitive response；Because in Sn3O4Lattice
In, Cu2+Sn can be replaced3O4Part Sn in lattice4+, process can accord with by Kroger-Ming Ke (Kroger-Vink) defect
Number indicate, as shown in formula (1):
Wherein, Cu "SnRepresent Cu2+Replace Sn4+Substituent group defect,The oxonium ion of oxygen lattice position is represented,Generation
There are two the Lacking oxygens of positive charge for table tool.The Lacking oxygen of high concentration is conducive to surface of sensing materials adsorption of oxygen, when sensor is sudden and violent
When being exposed in air atmosphere, due to the introducing of gaseous oxygen, Lacking oxygen will subtract lower and generate positively charged hole, cause in conduction band
Electron concentration reduces, and increases the resistance of sensor, as shown in formula (2).The resistance of sensor increases, and is conducive to improve doping sample
The sensing capabilities of product.In addition, part Cu is present in Sn3O4Interstitial void between, the Cu in gap is capable of providing a large amount of catalysis
Active site is conducive to formaldehyde gas molecule and is chemically reacted on sense film surface, is also beneficial to the correlation of film surface
Electronics transfer improves transducer sensitivity.
In conclusion proposed by the present invention adulterate Sn based on Cu3O4The formaldehyde gas of metal oxide semiconductor material senses
Device has operating temperature low, and response is high, and selectivity is strong, and it is excellent that response and resume speed are fast, and reproducible and stability is high etc.
Gesture can be used for the detection of pernicious gas formaldehyde in actual production and life.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of Cu adulterates Sn3O4Gas sensitive characterized by comprising Sn3O4Nanometer sheet and copper ion, the Sn3O4It receives
Rice piece heap poststack forms three-dimensional flower-like structure, and the copper ion is present in Sn3O4Replace Sn among lattice3O4Portion in lattice
Divide tin ion and Sn3O4In nanometer sheet and Sn3O4In interstitial void.
2. Cu as described in claim 1 adulterates Sn3O4Gas sensitive, which is characterized in that the Sn3O4The thickness of nanometer sheet exists
Between 10-25nm, diameter is between 1-4 μm.
3. a kind of Cu adulterates Sn3O4Gas sensitive preparation method, which comprises the steps of:
(1) then stannous chloride, citrate stirring soluble in water are added copper ion, stirred evenly, is designated as to abundant dissolution
Solution A；
(2) aqueous slkali is slowly poured into the solution A, obtained solution is subjected to hydro-thermal reaction after stirring, it is cold after the completion
But to room temperature, solid product is isolated, as Cu adulterates Sn3O4Gas sensitive.
4. Cu as claimed in claim 3 adulterates Sn3O4Gas sensitive preparation method, which is characterized in that in step (1), institute
State stannous chloride, citrate (preferably sodium citrate), copper ion adding proportion be sequentially 1mmol:(2-3) mmol:
(0.1-0.3) mmol, the dosage of water guarantee sufficiently to dissolve stannous chloride and citrate；
Preferably, in step (1), the addition of the copper ion is using the form of inorganic mantoquita, more preferably copper nitrate, chlorination
Any one in copper, copper sulphate；
Preferably, in step (2), the aqueous slkali includes sodium hydroxide, any one in ammonium hydroxide；
Preferably, in step (2), the adding proportion of the aqueous slkali are as follows: stannous chloride: lye=1:0.5-1.2, molar ratio；
Preferably, in step (2), the condition of the hydro-thermal reaction are as follows: reacted 12-15 hours between 160-200 DEG C；
Preferably, in step (2), include the steps that washing solid product and being dried, specially with deionized water and
Ethanol washing, it may be necessary to which repeatedly washing dries 12-14 hours at 60-80 DEG C after the completion of washing and adulterates Sn to get Cu3O4
Gas sensitive.
5. one kind adulterates Sn based on Cu3O4The formaldehyde gas sensor of gas sensitive, which is characterized in that the sensor is heater-type
Structure, comprising: pedestal, ceramic tube, heater strip, circular metal electrode, gas sensitive and conducting wire；Wherein, the gas sensitive power
The Cu doping Sn that benefit requires method described in 1 or 2 and/or claim 3 or 4 to prepare3O4Gas sensitive, in the ceramic tube
It is provided with heater strip, and the both ends of heater strip extend respectively to the outside of two ports of ceramic tube；The circular metal electrode is
It two, is covered on the outer surface of ceramic tube along the circumferential direction of ceramic tube, and two circular metal electrode interval settings；Institute
It states gas sensitive to be arranged on the outer surface for being provided with the ceramic tube of circular metal electrode, and by ceramic tube and circular metal electrode
It wraps up wherein；The both ends of the heater strip extended to outside ceramic tube are connect with pedestal；The conducting wire is four, is used for
Circular metal electrode and pedestal are connected, wherein the corresponding one group of circular metal electrode of every two conducting wire, and two conducting wire settings exist
One circular metal electrode two sides.
6. adulterating Sn based on Cu as claimed in claim 53O4The formaldehyde gas sensor of gas sensitive, which is characterized in that described
The material of ceramic tube is aluminium oxide；
Preferably, the material of the heater strip is Ni-Cr alloy, any one in Fe-Cr alloy；
Preferably, the material of the metal electrode is noble metal, such as any one in gold, platinum, palladium, silver；
Preferably, the material of the conducting wire is noble metal, such as any one in gold, platinum, palladium, silver.
7. adulterating Sn based on Cu as described in claim 5 or 63O4The formaldehyde gas sensor of gas sensitive, which is characterized in that
It is spiral shape that the heater strip, which is located at the part in ceramic tube,.
8. one kind adulterates Sn based on Cu3O4The preparation method of the formaldehyde gas sensor of gas sensitive, which is characterized in that including such as
Lower step:
S1, Cu of any of claims 1 or 2 is adulterated into Sn3O4The preparation of method described in gas sensitive and/or claim 3 or 4
Cu adulterate Sn3O4Gas sensitive is prepared into finely dispersed paste；
S2, the paste in step S1 is uniformly coated on the ceramic pipe surface with a pair of metal electrodes, after natural drying
It is dried；
S3, will it is dry in step S2 after ceramic tube in heating wire, metal electrode be respectively welded at the binding posts of six leg bases
On, carry out aging then to get the formaldehyde gas sensor of heater-type structure.
9. adulterating Sn based on Cu as claimed in claim 83O4The preparation method of the formaldehyde gas sensor of gas sensitive, it is special
Sign is, in step S1, the paste the preparation method comprises the following steps: Cu is adulterated Sn3O4Gas sensitive powder and deionized water press matter
Measure volume ratio 185-230:1-1.5 mixing, mg/ml；Then grinding and ultrasound, obtain finely dispersed paste, wherein described
Milling time is 15-30min, ultrasonic time 30-60min；
Preferably, in step S2, the drying condition are as follows: the dry 10-12h between 60-80 DEG C；
Preferably, in step S2, the time of the aging is 22-25 hours.
10. Cu as claimed in claim 1 or 2 adulterates Sn3O4Gas sensitive and/or claim 3 or 4 described in method system
Standby Cu adulterates Sn3O4Gas sensitive and/or such as described in any item formaldehyde gas sensors of claim 5-7 and in environment
Application in gas-monitoring, industrial gasses analysis field.
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