CN108732207A - A kind of sensitive material used in formaldehyde examination and preparation method and application - Google Patents
A kind of sensitive material used in formaldehyde examination and preparation method and application Download PDFInfo
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Abstract
The present invention discloses sensitive material and preparation method and application used in a kind of formaldehyde examination, the sensitive material is after using graphene oxide to make its adsorption tin ligand for template, the tin oxide nano piece that there is the redox graphene of meso-hole structure to adulterate on surface is obtained by heat treatment, the meso-hole structure that ultra-thin surfaces and surface have so that specific surface area reaches 69.8m2∙g‑1‑105.7m2∙g‑1, surface has more active sites.Therefore, the gas sensor PARA FORMALDEHYDE PRILLS(91,95) in the gas sensor used in formaldehyde examination using its preparation has that high sensitivity, response/recovery capability selectively good to interference gas be strong, detection limits low, steady performance, therefore its in formaldehyde gas sensor in application, sensitivity and the selectivity of formaldehyde gas sensor can be improved effectively.The detection that can be used for indoor and outdoor concentration of formaldehyde carries out the assessment of air quality, to ensure the health of the mankind.
Description
Technical field
The present invention relates to the sensitive materials and preparation method and application used in a kind of formaldehyde examination, belong to semi-conducting material neck
Domain.
Technical background
Formaldehyde (HCHO) is as the carcinogenic volatile organic compounds (VOC) in room air pollution, to health structure
At seriously threatening.It is widely used in manufacturing construction material, can be released from household products.Low HCHO levels (1-
The stimulation of nose and eyes, the level higher than 15ppm can 3ppm) be caused to may result in death.Therefore, effective HCHO detections
Method is extremely important, to health and environmental protection.In recent decades, a variety of sensings with different sensor mechanisms have been developed
Device is for detecting formaldehyde gas.Conductor oxidate sensor is a kind of gas sensor most widely used at present.Semiconductor
When sensitive oxide material is used for the detection of formaldehyde gas, it is generally basede on formaldehyde gas molecule and sensitive material surface adsorbed oxygen object
Kind redox reaction occurs, by regulating and controlling nanostructure or surface-functionalized can improve the effective specific surface of metal oxide
Product improves its air-sensitive performance in turn.For example, the SnO that Wang etc. is prepared by solvent-thermal method2Microballoon is sensitive to 100ppm formaldehyde
Degree is 38.3.Its good air-sensitive performance is attributed to special chondritic, big specific surface area and surface composition particle with suitable
These three factors of suitable grain size；Sun etc. is successfully prepared SnO with sacrifice template2/Zn2SnO4Porous hollow microballoon, at 330 DEG C
Under be 131.6 to the sensitivity of 500ppm formaldehyde；Gu etc. is obtained using simple chemical solution route in conjunction with subsequent calcination process
Obtain porous NiO/SnO2Microballoon is 27.6 to the sensitivity of 100ppm formaldehyde at 200 DEG C；In addition, various nanostructured metals
Oxide material such as Co3O4Nanocube and In2O3Nanometer sheet also has been reported that as formaldehyde examination.
These novel nano structures respectively have advantage and disadvantage in aspect of performance such as susceptibility, selectivity, for example above-mentioned formaldehyde passes
Low, the easy to operate advantage of some development costs in sensor, but there is a problem of that operating temperature is high, sensitivity is low.And some
Formaldehyde sensor operating temperature is low or even can reach room temperature and detectable limit is low, but there are development cost height, from it is practical still
There is relatively large distance.
It is generally too high for highly sensitive formaldehyde sensor price at present on the market, and cheap sensitivity compared with
Low, poor anti jamming capability cannot be satisfied the great market demand of household environment-friendlywater industry.Compared to zero dimension, a peacekeeping three-dimensional formaldehyde
The features such as sensitive material, two dimensional oxidation object sensitive material is by feat of high-specific surface area, active site is abundant, electronics orientation conduction and
It is concerned.
Bibliography
[1] Zhou Zeyi, Gai Liangjing, beam Jianping the research of Calibration Gases Prepared by Static Volumetric Method [J] measure journal,
2003,24(3):236-239。
[2] structure of the south Xiong Li, Wang Jincheng, Zhu Jun semiconductor gas sensors and preparation process [J] meteorological models ocean
Instrument, 2000:22-24.
Invention content
An object of the present invention is in order to solve above-mentioned highly sensitive formaldehyde sensor price at present on the market generally too
Height, and cheap sensitivity is relatively low, poor anti jamming capability, cannot be satisfied great market demand of household environment-friendlywater industry etc.
The technical issues of aspect and the gas sensor in the gas sensor used in a kind of formaldehyde examination is provided and prepares sensitive material used
Material, i.e. sensitive material used in formaldehyde examination.
The second object of the present invention is to provide the preparation method of the sensitive material used in a kind of above-mentioned formaldehyde examination, the system
Preparation Method has the advantages that preparation process is simple and is suitable for large-scale production.
The third object of the present invention is to provide for the gas sensor in the gas sensor used in a kind of formaldehyde examination, should
Gas sensor have cheap and PARA FORMALDEHYDE PRILLS(91,95) high sensitivity, operating temperature are low, selectivity is good, strong antijamming capability, respond it is extensive
The features such as multiple fast.
The fourth object of the present invention is to provide the system of the quick element in the gas sensor used in a kind of above-mentioned formaldehyde examination
Preparation Method, the preparation method is with simple for process, element is cheap, reproducible, making easy to produce.
Technical scheme of the present invention
A kind of sensitive material used in formaldehyde examination, is prepared by a method comprising the following steps:：
1., add graphene oxide into absolute ethyl alcohol, control power be 400W, frequency be 32KHz be ultrasonically treated
30min obtains graphene oxide dispersion so that graphene oxide is dispersed in absolute ethyl alcohol；
The dosage of above-mentioned graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 10-200mg：20-
The ratio of 200mL calculates, preferably graphene oxide：Absolute ethyl alcohol is 100mg:200mL；
2., tin source is added to step 1. in the graphene oxide dispersion of gained, controlled at 10~50 DEG C, rotating speed
It is stirred 12-18h for 1000r/min, obtains mixed solution, the purpose is to make tin source uniform adsorption to graphene oxide mould
On plate；
The tin source is four N-butyl of butter of tin, dibutyl tin laurate or stannic acid；The addition of tin source, by body
Product is than calculating, graphene oxide dispersion：Tin source is 1：4-16, preferably 1：16；
3., the mixed solution control rotating speed 10000r/min of step 2. gained is subjected to centrifugation 15min, the precipitation of gained is used
Absolute ethyl alcohol, which is washed, not to be had into efflux subject to tin source, and then control rotating speed 10000r/min is centrifuged again
The precipitation of centrifugation gained again is dried controlled at 60 DEG C, collects the product after drying by 15min；
4., product of the step after 3. gained is dry be put into Muffle furnace, be warming up to 450 with the rate of 1-5 DEG C/min~
500 DEG C, preferably 475 DEG C carry out calcination processing 2-12h to get the sensitive material used in formaldehyde examination；
Sensitive material used in the formaldehyde examination of above-mentioned gained is surface, and there is the redox graphene of meso-hole structure to mix
Miscellaneous tin oxide nano piece, after testing, count by weight percentage, wherein the content of redox graphene is 0.5-
50wt%, preferably 0.5-3.7wt%, tin oxide are tetragonal crystalline structure；After measured, thickness 3-15nm, length 5-
20 μm, width is 5-15 μm, and it is 3~10nm that surface, which has uniform meso-hole structure, mesoporous aperture, and specific surface area is reachable
69.8m2·g-1-105.7m2·g-1。
Sensitive material used in the formaldehyde examination of above-mentioned gained is for the air-sensitive in the gas sensor used in formaldehyde examination
The preparation of element, preparation process specifically comprise the following steps：
(1), deionized water or absolute ethyl alcohol are added in the sensitive material used in the formaldehyde examination of above-mentioned gained, mixing is equal
Pasty slurry is obtained after even；
The dosage of sensitive material and deionized water or absolute ethyl alcohol used in formaldehyde examination, by the sensitivity used in formaldehyde examination
Material：Deionized water or absolute ethyl alcohol are 20mg:The ratio of 1ml calculates；
(2) pasty slurry obtained by step (1) is coated uniformly on to the surface of semiconductor element, control coating thickness is
Then 0.5-1.5mm is dried controlled at 60 DEG C, then carry out heat treatment 2h controlled at 400 DEG C, had
The semiconductor element of dry coating；
The semiconductor element is alumina ceramic tube；
Then, above-mentioned gained is had dry coating half by heater-type semiconductor gas sensor manufacture craft routinely
Conductor element and base material welded, aging and encapsulation, referring in particular to bibliography[2], finally obtain used in formaldehyde examination
Gas sensor in gas sensor；
The base material is plastic-metal electrode base.
It is low to meet PARA FORMALDEHYDE PRILLS(91,95) detection simultaneously for the gas sensor in gas sensor used in the formaldehyde examination of above-mentioned gained
Cost, highly sensitive requirement, highly selective requirement, being expected to can be in household electrical appliance, mobile electronic equipment, automobile etc.
Field is integrated to be used.
The advantageous effects of the present invention
The gas sensor in gas sensor used in a kind of formaldehyde examination of the present invention, due to used in its preparation process
Formaldehyde examination used in sensitive material be after using and making its adsorption tin ligand by graphene oxide for template, to pass through heat
Processing acquisition surface has the tin oxide nano piece that the redox graphene of meso-hole structure adulterates, should going back with meso-hole structure
The content of redox graphene is 0.5-50wt%, preferably 0.5- in the tin oxide nano piece of former graphene oxide doped
The thickness of 3.7wt%, nanometer sheet are 3-15nm, and length is 5-20 μm, and width is 5-15 μm, surface mesoporous uniform, mesoporous pore size
For 3-10nm, due to meso-hole structure, there is big specific surface area, specific surface area is up to 69.8m2·g-1-
105.7m2·g-1, surface has more active sites, therefore utilizes in the gas sensor used in the formaldehyde examination of its preparation
Gas sensor there is high sensitivity, response/recovery capability selectively good to interference gas are strong, detection limit is low, performance is stablized etc.
Advantage.It is tested using CGS-8 Testing system of gas-sensor built, gas concentration 0.25ppm-100ppm, operating temperature can be 40-90
DEG C, 2200 is reached to 100ppm formaldehyde sensitivity, the response time is less than 70s, and recovery time is less than 90s, therefore it is in formaldehyde
In application, sensitivity and the selectivity of formaldehyde gas sensor can be improved effectively in detection gas sensor used, to
Solve detection sensitivity in the prior art and the more low technical problem of selectivity.The gas used in formaldehyde examination due to the present invention
There is gas sensor PARA FORMALDEHYDE PRILLS(91,95) in body sensor high sensitivity, quick response resume speed, these characteristics to make it easy to be in
The fields such as electrical appliance, mobile electronic equipment, automobile are integrated, keep the intelligent monitoring of formaldehyde ubiquitous.
Further, the gas sensor in the gas sensor used in a kind of formaldehyde examination of the invention, by preparing its institute
Graphene oxide is reduced into reduction by calcining heat treatment process in the preparation process of the sensitive material used in formaldehyde examination
Graphene oxide remains in metal oxide, regulates and controls gas sensitive semiconducting behavior using the redox graphene of trace
So as to reduce formaldehyde sensor operating temperature, to meet the needs of low cost detection.
In conclusion the present invention a kind of formaldehyde examination used in gas sensor in gas sensor, can meet simultaneously
PARA FORMALDEHYDE PRILLS(91,95) detection low cost, highly sensitive requirement, being expected to can be in necks such as household electrical appliance, mobile electronic equipment, automobiles
Domain is integrated, keeps the intelligent monitoring of formaldehyde ubiquitous, will generate huge economic and social benefits.
Description of the drawings
The X-ray diffractogram of sensitive material in Fig. 1, embodiment 1 used in the formaldehyde examination of gained；
The Raman spectrogram of sensitive material in Fig. 2, embodiment 1 used in the formaldehyde examination of gained；
The SEM figures of sensitive material in Fig. 3, embodiment 1 used in the formaldehyde examination of gained；
The TEM figures of sensitive material in Fig. 4, embodiment 1 used in the formaldehyde examination of gained；
The thermogravimetric phenogram of sensitive material in Fig. 5, embodiment 1 used in the formaldehyde examination of gained；
Calcination temperature is the first that the gas sensitive used in 475 DEG C of obtained formaldehyde examinations is prepared in Fig. 6, embodiment 1
Aldehyde detects optimum working temperature figure of the gas sensor in gas sensor used to 100ppm formalins；
Calcination temperature is the first that the gas sensitive used in 475 DEG C of obtained formaldehyde examinations is prepared in Fig. 7, embodiment 1
Aldehyde detects selective figure of the gas sensor in gas sensor used to interference gas；
Calcination temperature is the first that the gas sensitive used in 475 DEG C of obtained formaldehyde examinations is prepared in Fig. 8, embodiment 1
Response of the gas sensor to various concentration formaldehyde gas in aldehyde detection gas sensor used；
Calcination temperature is the first that the gas sensitive used in 475 DEG C of obtained formaldehyde examinations is prepared in Fig. 9, embodiment 1
Gas sensor in aldehyde detection gas sensor used is to various concentration under conditions of 10ppm, 30ppm, 50ppm, 100ppm
The linear relationship chart of formaldehyde gas response；
Figure 10, the corresponding calcination temperatures of embodiment 1-3 are used in the formaldehyde examination of 450 DEG C, 475 DEG C, 500 DEG C difference gained
The formaldehyde examination that is prepared of sensitive material used in gas sensor in gas sensor be respectively in concentration of formaldehyde
Graph of relation under 10ppm, 30ppm, 50ppm, 100ppm between the sensitivity and concentration of formaldehyde of the PARA FORMALDEHYDE PRILLS(91,95) of gained.
Specific implementation mode
Keep present disclosure more clear and easy to understand, below in conjunction with Figure of description, present disclosure is made further
Explanation.Certainly the invention is not limited to the specific embodiment, and the general replacement known to those skilled in the art is also contained
Lid is within the scope of the present invention.
Conventional heater-type semiconductor gas sensor manufacture craft described in various embodiments of the present invention, see reference text
It offers[2]。
Semiconductor element used in various embodiments of the present invention is alumina ceramic tube, belongs to heater-type gas sensor and matches
Part is bought in Beijing Ai Lite Science and Technology Ltd.s；Base material used is plastic-metal electrode base, belongs to heater-type
Gas sensor accessory is bought in Beijing Ai Lite Science and Technology Ltd.s.
Embodiment 1
A kind of sensitive material used in formaldehyde examination, is prepared by a method comprising the following steps:：
1., by 100mg graphene oxides be added 200ml absolute ethyl alcohols in, control power be 400W, frequency for 32KHz into
Row is ultrasonically treated 30min and obtains graphene oxide dispersion so that graphene oxide is dispersed in absolute ethyl alcohol；
The dosage of above-mentioned graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 100mg：The ratio of 200mL
Example calculates；
2., 2.47mmol dibutyl tin laurates are added to step 1. in the graphene oxide dispersion of gained, control
Temperature processed is that 25 DEG C of rotating speeds are that 1000r/min is stirred 16h, obtains mixed solution, the purpose is to organotin is uniformly inhaled
It is attached in graphene oxide template；It calculates by volume, graphene oxide dispersion：Dibutyl tin laurate is 1：16；
3., the mixed solution control rotating speed 10000r/min of step 2. gained is subjected to centrifugation 15min, the precipitation of gained is used
Absolute ethyl alcohol, which is washed, not to be had into efflux subject to dibutyl tin laurate, then controls rotating speed 10000r/min again
Centrifugation 15min is carried out, the precipitation of centrifugation gained again is dried controlled at 60 DEG C, collects the product after drying；
4., product of the step after 3. gained is dry be put into Muffle furnace, with the rate of 2 DEG C/min be warming up to 475 DEG C into
Row calcination processing 2h is to get the sensitive material used in formaldehyde examination；
The D8-ADVANCE model x-ray diffractometers produced using German Bruker-AXS companies, to the first of above-mentioned gained
Aldehyde detection sensitivity used is measured, and the x-ray diffraction pattern of gained is as shown in Figure 1, be as can be seen from Figure 1 used for formaldehyde
Detection sensitive material used is mainly tin oxide, and diffraction maximum is mainly tetragonal crystal system tin oxide (JCPDS 41-1445), thus
The main component for showing the sensitive material used in formaldehyde examination is tin oxide；
The Labram HR Evolution spectrometers produced using Japanese HORIBA companies examine the formaldehyde of above-mentioned gained
It surveys sensitive material used to be measured, the Raman spectrogram of gained is as shown in Fig. 2, from figure 2 it can be seen that Raman peaks prove
Sensitive material used in formaldehyde examination is the tin oxide of redox graphene doping；
The QuantaFEG450 type field emission scanning electron microscopes produced using FEI Co. of the U.S., to above-described embodiment 1
Sensitive material used in the formaldehyde examination of gained is scanned, and the SEM figures of gained are as shown in figure 3, obtained by as can be seen from Figure 3
Sensitive material, that is, redox graphene doping tin oxide nano piece be large-sized nanometer of chip architecture, length is in 15-20 μ
M, width are 10-15 μm, thickness 3-5nm.
Using the Tecnai G2F30 type transmission electron microscopes of FEI Co. of the U.S., to the formaldehyde examination institute of above-mentioned gained
Sensitive material is scanned, and the TEM figures of gained are as shown in figure 4, as can be seen from Figure 4 used in the formaldehyde examination of gained
The tin oxide nano piece of sensitive material, that is, redox graphene doping, surface has meso-hole structure, mesoporous to be evenly distributed, mesoporous
Aperture be about 3nm, specific surface area 69.8m2·g-1。
The Pyris 1TGA calorimetric analysis instrument produced using PerkinElme companies of the U.S., to the formaldehyde examination of above-mentioned gained
Sensitive material used is roasted, and the mass change and temperature of the sensitive material in roasting process used in detection formaldehyde examination are detected
The relationship of degree, sensitive material quality-temperature relation figure of gained is as shown in figure 5, as can be drawn from Figure 5, wherein reduction-oxidation
The content of graphene is 1.6wt% count by weight percentage；
In conclusion the sensitive material used in the formaldehyde examination of above-mentioned gained, after measured, thickness 3-5nm, length exist
15-20 μm, width is 10-15 μm, and surface has meso-hole structure, and mesoporous pore size 3-5nm, specific surface area is up to 69.8m2·g-1, the tin oxide in tin oxide nano piece be tetragonal crystal system tin oxide, the wherein content of redox graphene by weight percentage
It is calculated as 1.6wt%.
Sensitive material used in the formaldehyde examination of above-mentioned gained is for the air-sensitive in the gas sensor used in formaldehyde examination
The preparation of element, preparation process specifically comprise the following steps：
(1), deionized water is added in the sensitive material used in the formaldehyde examination of above-mentioned gained, is pasted after mixing
Shape slurry；
The dosage of sensitive material and deionized water used in formaldehyde examination, by the sensitive material used in formaldehyde examination：Go from
Sub- water is 20mg:The ratio of 1mL calculates；
(2), the pasty slurry obtained by step (1) is coated uniformly on to the surface of semiconductor element, control coating thickness is
Then 2h is dried controlled at 60 DEG C in 1mm, then carry out heat treatment 2h for 400 DEG C, obtains partly leading with dry coating
Volume elements part；
The semiconductor element is alumina ceramic tube；
Then, above-mentioned gained is had dry coating half by heater-type semiconductor gas sensor manufacture craft routinely
Conductor element and base material welded, aging and encapsulation, finally obtains gas sensor used in formaldehyde gas sensor；
The base material is plastic-metal electrode base.
It is specific to join by the gas sensor in the gas sensor used in the formaldehyde examination of above-mentioned gained according to static volumetric method
Air-sensitive performance test is carried out according to bibliography [1], and using CGS-8 Testing system of gas-sensor built, test curve is respectively such as Fig. 5-8
It is shown；
Fig. 6 is the optimum working temperature figure measured under conditions of 40-90 DEG C of operating temperature, as can be seen from Figure 6 right
It is 60 DEG C to answer the optimum temperature of the gas sensor in the gas sensor used in the formaldehyde examination that calcination temperature is 475 DEG C of gained,
The gas sensor being indicated above in the gas sensor used in formaldehyde examination has lower operating temperature.It is to 100ppm first
The peak of formaldehyde air-sensitive performance in aldehyde aqueous solution reaches 2200 or so；
It is 60 DEG C that Fig. 7, which is in operating temperature, the gas used in formaldehyde examination that gas concentration measures under conditions of being 100ppm
The selective figure of the gases such as gas sensor PARA FORMALDEHYDE PRILLS(91,95), ethyl alcohol, acetone, methanol, ammonia, toluene in body sensor, can from Fig. 7
The sensitivity with the gas sensor PARA FORMALDEHYDE PRILLS(91,95) found out in the gas sensor used in the formaldehyde examination of the present invention with superelevation, to second
The sensitivity of other gases such as alcohol, acetone, methanol, ammonia, toluene is sensitive well below PARA FORMALDEHYDE PRILLS(91,95), or even basic no response,
The gas sensor PARA FORMALDEHYDE PRILLS(91,95) being indicated above in the gas sensor used in the formaldehyde examination of the present invention has good selectivity；
It is 60 DEG C that Fig. 8, which is in operating temperature, and formaldehyde gas concentration is respectively the item of 10ppm, 30ppm, 50ppm, 100ppm
The formaldehyde gas response recovery curve figure measured under part, as can be seen from Figure 7 with the increase formaldehyde examination institute of concentration of formaldehyde
The sensitivity of gas sensor PARA FORMALDEHYDE PRILLS(91,95) in gas sensor is consequently increased；
It is 60 DEG C that Fig. 9, which is in operating temperature, under conditions of formaldehyde gas a concentration of 10ppm, 30ppm, 50ppm, 100ppm
The linear relationship simulation drawing of gas sensor PARA FORMALDEHYDE PRILLS(91,95) sensitivity in gas sensor used in the formaldehyde examination of measurement, from Fig. 9
In it can be seen that concentration of formaldehyde increase, the sensitivity of the gas sensor in gas sensor used in formaldehyde examination also increases therewith
Add and present linear relationship, is indicated above the sensitive of the gas sensor in the gas sensor used in the formaldehyde examination of the present invention
Degree is in positive linear relationships with formaldehyde gas concentration.
In conclusion the present invention formaldehyde examination used in gas sensor in gas sensor have operating temperature it is low,
The features such as high sensitivity, the gas sensor in gas sensor used in the formaldehyde examination of the present invention under the same terms it is sensitive
Degree is approximately 10 times of commercial instruments or more.
Using CGS-8 Testing system of gas-sensor built, according to static volumetric method, with reference to bibliography [1], to 1 institute of embodiment
The sensitivity of gas sensor PARA FORMALDEHYDE PRILLS(91,95) gas, PARA FORMALDEHYDE PRILLS(91,95), ethyl alcohol, methanol, acetone, ammonia used in the formaldehyde gas sensor obtained
The selecting property performance of the multiple gases such as gas, toluene and detectable limit etc., test condition is as follows：
1. detection range：Gas concentration 0.25ppm-100ppm；
2. element manipulation temperature：40-90℃；
Test result is as follows：
1. detection sensitivity (Ra/Rg)：100ppm formaldehyde sensitivity is about 2200；
2. selectivity：The sensitive of PARA FORMALDEHYDE PRILLS(91,95) is below to the sensitivity of 100ppm ethyl alcohol, methanol, acetone, ammonia, toluene
Degree；
3. the element responds time：Less than 70s；
4. element recovery time：Less than 90s.
Gas sensitive element from the gas sensor used in the formaldehyde examination that can be seen that the present invention in test result above
Part reaches 2200 to 100ppm formaldehyde sensitivity, and the response time is less than 70s, and recovery time is less than 90s, has been indicated above the present invention
Formaldehyde examination used in gas sensor in gas sensor PARA FORMALDEHYDE PRILLS(91,95) have high sensitivity, quick response resume speed, this
A little characteristics make it easy to integrate in fields such as household electrical appliance, mobile electronic equipment, automobiles, make the intelligent monitoring of formaldehyde nowhere
Do not exist.
Embodiment 2
A kind of sensitive material used in formaldehyde examination, is prepared by a method comprising the following steps:：
The different only step of preparation process 4. in, product of the step after 3. gained is dry is put into Muffle furnace, with 2
DEG C/rate of min is warming up to 500 DEG C of progress calcination processing 2h, other are identical as in embodiment 1.
Sensitive material used in the formaldehyde examination of above-mentioned gained is surface, and there is the redox graphene of meso-hole structure to mix
Miscellaneous tin oxide gas sensitive is tin oxide nano piece, and after measured, thickness 10-15nm, length is 5-10 μm, and width is 5-8 μ
M, surface have meso-hole structure, and mesoporous pore size 5-10nm, specific surface area is up to 72.9m2·g-1, the oxygen in tin oxide nano piece
Change tin is tetragonal crystal system tin oxide structure, and wherein the content of redox graphene is 0.5wt% count by weight percentage.
Sensitive material used in the formaldehyde examination of above-mentioned gained is for the air-sensitive in the gas sensor used in formaldehyde examination
The preparation of element finally obtains the gas sensor in the gas sensor used in formaldehyde examination with embodiment 1.
Embodiment 3
A kind of sensitive material used in formaldehyde examination, is prepared by a method comprising the following steps:：
The different only step of preparation process 4. in, product of the step after 3. gained is dry is put into Muffle furnace, with 1
DEG C/rate of min is warming up to 450 DEG C of progress calcination processing 2h, other are identical as in embodiment 1.
Sensitive material used in the formaldehyde examination of above-mentioned gained, which is surface, has the redox graphene of meso-hole structure negative
The tin oxide nano piece of load, thickness 5-10nm, length are 10-12 μm, and width is 5-10 μm, and surface has meso-hole structure, is situated between
Hole aperture is 5-10nm, and specific surface area is up to 105.7m2·g-1, the tin oxide in tin oxide nano piece is tetragonal crystal system tin oxide
Structure, the wherein content of redox graphene are 3.7wt% count by weight percentage.
Sensitive material used in the formaldehyde examination of above-mentioned gained is for the air-sensitive in the gas sensor used in formaldehyde examination
The preparation of element finally obtains the gas sensor in the gas sensor used in formaldehyde examination with embodiment 1.
In the case that corresponding embodiment 1-3 calcination temperatures are respectively 450 DEG C, 475 DEG C, 500 DEG C, the formaldehyde examination of gained
The gas sensor used in formaldehyde examination that sensitive material used is prepared (in addition to calcination temperature is different, other all sames)
In gas sensor concentration of formaldehyde be 10ppm, 30ppm, 50ppm, 100ppm under gained PARA FORMALDEHYDE PRILLS(91,95) sensitivity and formaldehyde
Graph of relation between concentration is as shown in Figure 10, it can be seen from fig. 10 that the formaldehyde of the gained of corresponding different calcination temperatures
Gas sensor in the gas sensor used in formaldehyde examination that detection sensitive material used is prepared is to various concentration
Formaldehyde all has good linear relationship, thus its easily facilitated when practical application in formaldehyde gas sensor data acquisition and
Processing.Also, the formaldehyde examination institute that the sensitive material used in the formaldehyde examination obtained by when calcination temperature is 475 DEG C is made
Gas sensor PARA FORMALDEHYDE PRILLS(91,95) in gas sensor has best response signal.
In conclusion the sensitive material used in the formaldehyde examination of the present invention is the oxygen reduction fossil that surface has meso-hole structure
The tin oxide nano piece of black alkene load, surface have a meso-hole structure, mesoporous pore size 3-10nm, the oxidation in tin oxide nano piece
Tin is tetragonal crystal system tin oxide structure, and wherein the content of redox graphene is 0.5-3.7wt% count by weight percentage,
Since surface has meso-hole structure, there is big specific surface area, specific surface area is up to 69.8m2·g-1-105.7m2·g-1,
Surface has more active sites, therefore has using the gas sensor in the gas sensor used in the formaldehyde examination of its preparation
Have that high sensitivity, response/recovery capability selectively good to interference gas be strong, detection limits low, steady performance.It utilizes
CGS-8 Testing system of gas-sensor built is tested, gas concentration 0.25ppm-100ppm, and operating temperature can be 40-90 DEG C, right
100ppm formaldehyde sensitivity reaches 2200, and the response time is less than 70s, and recovery time is less than 90s, therefore it is used in formaldehyde examination
Gas sensor in application, sensitivity and the selectivity of formaldehyde gas sensor can be improved effectively, it is existing to solve
There are detection sensitivity and the more low technical problem of selectivity in technology.
Although the present invention is disclosed as above with preferred embodiment, right embodiment is illustrated only for the purposes of explanation, and
It is non-to limit the present invention, those skilled in the art can make without departing from the spirit and scope of the present invention it is several more
Dynamic and retouching, the protection domain that the present invention is advocated should be subject to claims.
Claims (10)
1. the sensitive material used in a kind of formaldehyde examination, it is characterised in that the sensitive material used in the formaldehyde examination has for surface
There is the tin oxide nano piece of the load redox graphene of meso-hole structure.
2. the sensitive material used in formaldehyde examination as described in claim 1, it is characterised in that the surface has mesoporous knot
Structure load redox graphene tin oxide nano piece, thickness be 3~15nm, a length of 5~20 μm, width be 5~15 μm,
Specific surface area reaches 69.8m2·g-1-105.7m2·g-1, surface mesoporous to be evenly distributed, aperture 3-10nm.
3. the sensitive material used in formaldehyde examination as described in claim 1, it is characterised in that the surface has mesoporous knot
The content of the tin oxide nano piece of the load redox graphene of structure, redox graphene therein is 0.5-50wt%,
Tin oxide is tetragonal crystalline structure.
4. the sensitive material used in formaldehyde examination as claimed in claim 3, it is characterised in that the surface has mesoporous knot
The content of the tin oxide nano piece of the load redox graphene of structure, redox graphene therein is 0.5-3.7wt%,
Tin oxide is tetragonal crystalline structure.
5. the preparation method of the sensitive material used in formaldehyde examination as described in claim 1, it is characterised in that specifically include as
Lower step：
1., add graphene oxide into absolute ethyl alcohol, control power be 400W, frequency be 32KHz be ultrasonically treated
30min obtains graphene oxide dispersion so that graphene oxide is dispersed in absolute ethyl alcohol；
The dosage of above-mentioned graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 10-200mg：20-200mL's
Ratio calculates；
2., tin source is added to step 1. in the graphene oxide dispersion of gained, be controlled at 10~50 DEG C, rotating speed
1000r/min is stirred 12-18h, obtains mixed solution；
The tin source is four N-butyl of butter of tin, dibutyl tin laurate or stannic acid；The addition of tin source, by volume
It calculates, graphene oxide dispersion：Tin source is 1：4-16；
3., the mixed solution control rotating speed 10000r/min of step 2. gained is subjected to centrifugation 15min, the precipitation of gained is with anhydrous
Ethyl alcohol, which is washed, not to be had into efflux subject to tin source, and then control rotating speed 10000r/min carries out centrifugation 15min again, will
The precipitation of centrifugation gained is dried controlled at 60 DEG C again, collects the product after drying；
4., product of the step after 3. gained is dry be put into Muffle furnace, be warming up to 450~500 DEG C with the rate of 1-5 DEG C/min
Calcination processing 2-12h is carried out to get the sensitive material used in formaldehyde examination.
6. the preparation method of the sensitive material used in formaldehyde examination as claimed in claim 5, it is characterised in that specifically include as
Under：
Step 1. in：The dosage of graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 100mg:200mL's
Ratio calculates；
Step 2. in：It is that 1000r/min is stirred 16h controlled at 25 DEG C, rotating speed, obtains mixed solution；
The tin source is dibutyl tin laurate, is calculated by volume, graphene oxide dispersion：Tin source is 1：16；
Step 4. in：Product after step 3. gained drying is put into Muffle furnace, 475 DEG C are warming up to the rate of 2 DEG C/min
Carry out calcination processing 2h.
7. the sensitive material used in formaldehyde examination as described in claim 1 is in the gas sensor used in formaldehyde examination
The preparation of gas sensor, preparation process specifically comprise the following steps：
(1), deionized water or absolute ethyl alcohol are added in the sensitive material used in formaldehyde examination, obtains paste slurry after mixing
Material；
The dosage of sensitive material and deionized water or absolute ethyl alcohol used in formaldehyde examination, by the sensitive material used in formaldehyde examination
Material：Deionized water or absolute ethyl alcohol are 20mg:The ratio of 1ml calculates；
Sensitive material used in above-mentioned formaldehyde examination is prepared by a method comprising the following steps：
1., add graphene oxide into absolute ethyl alcohol, control power be 400W, frequency be 32KHz be ultrasonically treated
30min obtains graphene oxide dispersion so that graphene oxide is dispersed in absolute ethyl alcohol；
The dosage of above-mentioned graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 10-200mg：20-200mL's
Ratio calculates；
2., tin source is added to step 1. in the graphene oxide dispersion of gained, be controlled at 10~50 DEG C, rotating speed
1000r/min is stirred 12-18h, obtains mixed solution；
The tin source is four N-butyl of butter of tin, dibutyl tin laurate or stannic acid；The addition of tin source, by volume
It calculates, graphene oxide dispersion：Tin source is 1：4-16；
3., the mixed solution control rotating speed 10000r/min of step 2. gained is subjected to centrifugation 15min, the precipitation of gained is with anhydrous
Ethyl alcohol, which is washed, not to be had into efflux subject to tin source, and then control rotating speed 10000r/min carries out centrifugation 15min again, will
The precipitation of centrifugation gained is dried controlled at 60 DEG C again, collects the product after drying；
4., product of the step after 3. gained is dry be put into Muffle furnace, be warming up to 450~550 DEG C with the rate of 1-5 DEG C/min
Calcination processing 2-12h is carried out to get the sensitive material used in formaldehyde examination；
(2) pasty slurry obtained by step (1) is coated uniformly on to the surface of semiconductor element, control coating thickness is 0.5-
Then 1.5mm is dried controlled at 60 DEG C, then carry out heat treatment 2h again controlled at 400 DEG C, obtains having dry
The semiconductor element of dry coating；
The semiconductor element is alumina ceramic tube；
Then, above-mentioned gained is had the semiconductor for drying coating by heater-type semiconductor gas sensor manufacture craft routinely
Element and base material welded, aging and encapsulation, finally obtains the gas sensitive element in the gas sensor used in formaldehyde examination
Part；
The base material is plastic-metal electrode base.
8. the sensitive material used in formaldehyde examination as claimed in claim 7 is in the gas sensor used in formaldehyde examination
The preparation of gas sensor, it is characterised in that in its preparation process：
In step (1) 1.：The dosage of graphene oxide and absolute ethyl alcohol, by graphene oxide：Absolute ethyl alcohol is 100mg：
The ratio of 200mL calculates；
②：It is that 1000r/min is stirred 16h controlled at 25 DEG C of rotating speeds；The tin source is dibutyl tin laurate；
The addition of tin source, calculates by volume, graphene oxide dispersion：Tin source is 1：16；
3., be dried controlled at 60 DEG C；
4., be warming up to the rate of 2 DEG C/min 475 DEG C and carry out calcination processing 2h.
In step (2)：Control coating thickness is 1mm.
9. the sensitive material used in formaldehyde examination as claimed in claim 7 or 8 is for the gas sensor used in formaldehyde examination
In gas sensor a kind of formaldehyde examination being prepared used in gas sensor in gas sensor, utilize CGS-8 gas
Quick element test system is tested, gas concentration 0.25ppm-100ppm, under conditions of 40-90 DEG C of operating temperature, to 100ppm
Formaldehyde sensitivity is about 2200, response recovery time is respectively less than 90s.
10. the gas sensor in gas sensor used in a kind of formaldehyde examination as claimed in claim 9, utilizes CGS-8 gas
Quick element test system is tested, and is about 2200 to 100ppm formaldehyde sensitivity, the response time under conditions of 60 DEG C of operating temperature
It is less than 90s less than 70s, recovery time.
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