CN107085027B - A kind of composite nano materials and its preparation method and application of room temperature detection hydrogen sulfide - Google Patents
A kind of composite nano materials and its preparation method and application of room temperature detection hydrogen sulfide Download PDFInfo
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- CN107085027B CN107085027B CN201710380001.7A CN201710380001A CN107085027B CN 107085027 B CN107085027 B CN 107085027B CN 201710380001 A CN201710380001 A CN 201710380001A CN 107085027 B CN107085027 B CN 107085027B
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- copper ion
- tin oxide
- composite nano
- room temperature
- doped tin
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
Abstract
The invention discloses a kind of inorganic/organic composite nano materials and its preparation method and application can to hydrogen sulfide gas at room temperature with sensitive response.Copper ion doped tin oxide is synthesized first, in-situ oxidizing-polymerizing pyrrole monomer in the presence of copper ion doped tin oxide, copper ion doped tin oxide polypyrrole compound is formed, the inorganic/organic composite material obtained is finally coated to interdigital electrode surface and forms gas sensing film.Raw material of the present invention is easy to get, and preparation process is simple, low in cost.Sensor has sensitive response to the hydrogen sulfide gas of trace at room temperature, and responds and restore rapidly, and stability is high.The present invention provides a kind of practicable method for the real-time monitoring of hydrogen sulfide gas at room temperature.
Description
Technical field
There can be the inorganic/organic multiple of sensitive response to hydrogen sulfide gas at room temperature the present invention relates to a kind of
Close nano material and preparation method thereof and and application, belong to semiconductor nano material and air-sensitive field of sensing technologies.
Background technique
Hydrogen sulfide (H2It S) is nature, a kind of hypertoxic gas being widely present in industrial production and daily life, research
Show H2S can not only cause device burn into catalyst poisoning, and (ppm grades) can be strong to human body under extremely low concentration
Kang Zaocheng extreme influence.Therefore, it realizes to H2S's is accurate, and quickly and highly sensitive detection is to environmental monitoring, industrial production and
Daily life is all particularly important.
At present for H2The monitoring means of S is broadly divided into two major classes, and compared to the instrument and equipment for relying on complex and expensive and
The conventional method (such as ICP-OES, HG-AFS, chromatography, colorimetric analysis etc.) of professional operation technology, gas sensing technology is due to letter
It is single, quickly, portable, characteristic of low cost and be considered as most effective detection mode.It is well known that the performance master of gas sensor
To depend on sensitive material used.Currently, about H2The research of S sensing material focuses mostly in metal-oxide semiconductor (MOS) (MOS),
Such material under certain condition can be to the H of low concentration2S gas is responded.And by adulterating to Material cladding,
The methods of surface modification and Morphological control, moreover it is possible to improve its sensing capabilities to a certain extent.However, being limited by its air-sensitive biography
Feel mechanism, MOS is in lower temperature (< 150oC common manifestation is that sensitivity is low under), poor selectivity, and resume speed is slow.Obviously,
High operating temperature not only reduces sensor service life, while but also device is complicated and high energy consumption.It is most important
Limit its application in some particular surroundings such as low temperature or inflammable and explosive environment.It is some organic poly- unlike MOS
Object semiconductor such as polyaniline is closed, polypyrrole (PPy) and polythiophene and their derivative etc. can be in lower temperature conditions
Under to gas molecule have quickly response and resume speed.Organic semiconducting materials are also commonly used for gas sensitive and pass in gas
Sense field is play an important role.But mechanical strength is insufficient, it is organic semiconductor that chemical stability is not high and sensitivity is relatively low
The common problem of nano material.Therefore development is at room temperature to H2There is S novel sensing material that is sensitive and responding rapidly to be still
H2One challenge of S sensory field and important research direction.
Summary of the invention
Based on background above, the purpose of the present invention is to provide a kind of at room temperature to H2S has sensitive response, fastly
Inorganic/organic composite nano material of quick-recovery ability and preparation method thereof, and corresponding room temperature sensing element realization pair is provided
H2S detection.Its technical principle is to first pass through metal ion mixing to increase inorganic semiconductor surface defect, improves its surface potential barrier,
Then compound with organic semiconductor again, inorganic organic heterojunction is formed, its response sensitivity is further increased.Meanwhile with it is organic
Surface area is increased after semiconductors coupling, more reaction sites are provided, enhances the diffusion and absorption of gas, and electronics is accelerated to turn
It moves, to greatly improve response and resume speed.
To achieve the above object, The technical solution adopted by the invention is as follows:
Inorganic/organic composite nano material of the present invention is copper ion doped tin oxide polypyrrole compound, at
Divide content characteristics as follows: Cu2+With Sn4+Molar ratio be 0.01-0.1, the mass ratio of polypyrrole and copper ion doped tin oxide
For 0.01-0.3.
It is further preferred that copper ion doped its component content feature of tin oxide polypyrrole compound is as follows: Cu2+With Sn4+
Molar ratio be 0.03-0.07, the mass ratio of polypyrrole and copper ion doped tin oxide is 0.05-0.2.
Preparation method provided by the invention is first to prepare copper ion doped tin oxide, and pyrrole monomer is in copper ion doped oxidation
In-situ oxidizing-polymerizing in the presence of tin forms copper ion doped tin oxide polypyrrole compound.Specific step is as follows:
1 prepares copper ion doped tin oxide: according to above-mentioned any Cu2+/Sn4+Under conditions of molar ratio, SnCl is weighed2·
2H2O and CuCl2·2H2O is dissolved in the in the mixed solvent of ethyl alcohol and water, is heated to 100oC is stirred at reflux 1-3 hours, cooling
It is centrifuged, washes after to room temperature, is dry, finally calcining 1-4 hours at a certain temperature.
2 prepare copper ion doped tin oxide polypyrrole compound: the copper ion doped tin oxide ultrasonic disperse of preparation is arrived
In the mixed solution of a certain amount of organic acid and surfactant, then under ice bath stirring, according to above-mentioned any polypyrrole and copper
Ion doping tin oxide mass ratio measures pyrrole monomer and is added in the lotion, three hours is stirred under the conditions of being protected from light, then fastly
A certain amount of ammonium persulfate (APS) is added in speed, and the reaction was continued half an hour, centrifuge washing, dry.
The volume ratio of the in the mixed solvent of ethyl alcohol described in step 1 and water, ethyl alcohol and water is 0.3-3.
Calcination temperature described in step 1 is 300-500 oC。
Organic acid described in step 2 includes oxalic acid, citric acid, any one in acetic acid and salicylic acid.
Surfactant described in step 2 includes neopelex (SDBS), cetab
(CTAB), any one in lauryl sodium sulfate (SDS).
A certain amount of organic acid described in step 2 and surfactant refer to organic acid and pyrrole monomer molar ratio is 0.5-
3.6 and surfactant and pyrrole monomer molar ratio be 0.5-3.6.
A certain amount of APS described in step 2 refers to APS and pyrrole monomer molar ratio is 1-3.
Composite nano materials are applied in H2On S room temperature sensing element, the H2S room temperature sensing element is by insulation base
Bottom, substrate surface interdigital electrode array and coated in above-mentioned inorganic/organic composite nanometer material on array with a thickness of 0.05-2 mm
Expect sensitive membrane composition.
Advantages of the present invention is as follows:
1 inorganic/organic composite nano material raw material provided by the present invention is easy to get, and preparation process is simple, low in cost.
Inorganic/organic composite nano material in 2 present invention is in specific Cu2+With Sn4+Molar ratio and polypyrrole and copper
Under the mass ratio of ion doping tin oxide, apply in H2In sensor, the vulcanization of extremely low concentration can be detected at room temperature
Hydrogen (0.3-50 ppm concentration), shows highly sensitive, response and restores rapidly, stability is high, the good feature of selectivity.
3 gas-sensitive sensor structures of the present invention and preparation process are very simple, low in cost, and versatility is good, and universality is strong,
It is with a wide range of applications.
4 provide a kind of new approaches for the exploitation of low temperature gas sensing materials.
Detailed description of the invention
The copper ion doped tin oxide polypyrrole compound scanning electron microscope (SEM) photograph of Fig. 1；
The copper ion doped tin oxide polypyrrole compound x-ray photoelectron spectroscopy figure of Fig. 2, illustration Cu2+The peak 2P；
Fig. 3 be based on copper ion doped tin oxide polypyrrole compound hydrogen sulfide sensing principle and schematic device (a) and
Based on Al2O3The Au interdigital electrode of substrate coats the photograph in kind before and after copper ion doped tin oxide polypyrrole compound gas sensitive
Piece (b) and corresponding electrode surface microphoto (c)；
The H of Fig. 4 preparation2VA characteristic curve of the S gas-sensitive sensing element in different atmosphere；
The H of Fig. 5 preparation2S gas-sensitive sensing element response and H2The linear relationship of S concentration, illustration ring for corresponding dynamic
Answer characteristic curve；
The H of Fig. 6 preparation2S gas-sensitive sensing element stability (a) and selectivity (b).
Specific embodiment
Below by specific implementation example, technical scheme is described further, but this cannot be limited with this
The range of invention.
Embodiment 1
1. the preparation of copper ion doped tin oxide
Weigh 1.6 g SnCl2·2H2O and 0.03 g CuCl2·2H2O is added to the in the mixed solvent (ethyl alcohol of 150 mL
It is 1:1 with water volume ratio), bluish white emulsion is heated to 100 under lasting stirringoC flows back after 3 hours are cooled to room temperature and is centrifuged
White solid product is collected, washing drying is ground into fine powder 400oC is calcined 1 hour.
2. the preparation of copper ion doped tin oxide polypyrrole compound
It weighs the copper ion doped tin oxide of 0.5 g and is distributed to the 70 ml water containing 0.15 g CTAB and 0.14 g citric acid
In solution, 30 min of ultrasonic disperse.The pyrroles of 40 uL is added after 10 min of ice bath stirring, is protected from light under condition of ice bath and continues stirring 3
Hour, then it is added at one time 2 mL of aqueous solution containing 0.2 g APS.Grey black solid is collected by centrifugation after the reaction was continued 30 min
Product, washing, vacuum drying.
3. H2The preparation of S gas-sensitive sensing element
Copper ion doped 0.1 g of tin oxide polypyrrole compound of above-mentioned preparation is weighed, is ground into homogenate with water, then
It is even to be applied to Al2O3On the Au interdigital electrode array of substrate, drying at room temperature forms sensitive membrane, and film thickness is 0.05 mm.
Fig. 1 is copper ion doped tin oxide polypyrrole compound scanning electron microscope (SEM) photograph prepared by embodiment 1, which is
Spheric granules, particle diameter distribution contain a large amount of copper ion doped tin oxide in 100-150 nm, surface irregularity.X-ray light
Electron spectrum shows that the material mainly forms (Fig. 2) by C, N, O, Sn and Cu element.A in Fig. 3 is H according to the present invention2S
Sensor operating principles and sensing element schematic diagram;B and c is in embodiment 1 respectively based on Al in Fig. 32O3The Au of substrate is interdigital
Electrode coats the photo in kind and corresponding electrode surface before and after copper ion doped tin oxide polypyrrole compound gas sensitive
Microphoto.The sensor is in air and H2VA characteristic curve in S atmosphere is as shown in figure 4, curve shows to deposit in " S " type
In Schottky behavior；In air and H2In S atmosphere, significant change occurs for electric current, illustrates the material to H2S has good response.Such as
Shown in Fig. 5, H of the sensor to 0.3-50 ppm concentration range2S has preferable linear response behavior, corresponding dynamic
Response characteristic curve is as shown in Fig. 5 illustration, responseRIt is defined asR = (I g - I a )/I a , whereinI g WithI a Respectively in H2S and
The sensor stabilization current value measured in air.In order to prove the composite material to H2The specificity of S, we have investigated a variety of normal
See the influence that Coexisting component responds sensor, a confirms H in Fig. 62S gas sensor is smaller to interfering component response, illustrates it
With preferable selectivity.Meanwhile passing through the H of the continuous one month high and low two kinds of concentration of monitoring2S, for same concentration, response
Value illustrates that sensing material has very high stability without significant changes (shown in the b in Fig. 6).
Embodiment 2
1. the preparation of copper ion doped tin oxide
Weigh 1.6 g SnCl2·2H2O and 0.05 g CuCl2·2H2O is added to the in the mixed solvent (ethyl alcohol of 150 mL
It is 1:3 with water volume ratio), bluish white emulsion is heated to 100 under lasting stirringoC flows back 2 hours, is centrifuged after being cooled to room temperature
White solid product is collected, washing drying is ground into fine powder 350oC is calcined 2 hours.
2. the preparation of copper ion doped tin oxide polypyrrole
It weighs the copper ion doped tin oxide of 0.3 g and is distributed to the 70 ml aqueous solutions containing 0.42 g SDS and 0.03 g oxalic acid
In, 30 min of ultrasonic disperse.The pyrroles of 30 uL is added after 10 min of ice bath stirring, is protected from light under condition of ice bath that continue stirring 3 small
When, then it is added at one time 2 mL of aqueous solution containing 0.3 g APS.The production of grey black solid is collected by centrifugation after the reaction was continued 30 min
Object, washing, vacuum drying.
3. H2The preparation of S gas-sensitive sensing element
Copper ion doped 0.2 g of tin oxide polypyrrole compound of above-mentioned preparation is weighed, is ground into homogenate with water, then
On the even ITO interdigital electrode array for being applied to substrate of glass, drying at room temperature forms sensitive membrane, and film thickness is 2 mm.
Copper ion doped tin oxide polypyrrole made from the copper ion doped tin oxide of table 1, polypyrrole and embodiment 1 is compound
The comparison of object BET surface area
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of composite nano materials of room temperature detection hydrogen sulfide, characterized in that the composite nano materials are copper ion doped
Tin oxide polypyrrole compound, specific component ratio are as follows: Cu2+With Sn4+Molar ratio be 0.01-0.1, polypyrrole and copper ion
The mass ratio of doped stannum oxide is 0.01-0.3.
2. composite nano materials according to claim 1, characterized in that copper ion doped tin oxide polypyrrole compound,
Specific component ratio are as follows: Cu2+With Sn4+Molar ratio be 0.03-0.07, the mass ratio of polypyrrole and copper ion doped tin oxide
For 0.05-0.2.
3. a kind of method for preparing composite nano materials as claimed in claim 1 or 2, which comprises the following steps:
(1) SnCl is weighed in proportion2·2H2O and CuCl2·2H2O is dissolved in the in the mixed solvent of ethyl alcohol and water, is heated to 100oC is stirred at reflux 1-3 hours, is cooled to centrifugation, washing, drying after room temperature, is finally calcined 1-4 hours, obtain at a certain temperature
To copper ion doped tin oxide；
(2) mixing of copper ion doped tin oxide ultrasonic disperse to a certain amount of organic acid and the surfactant of preparation is molten
In liquid, then under ice bath stirring, pyrrole monomer is added, three hours are stirred under the conditions of being protected from light, are then quickly added into a certain amount of
Ammonium persulfate, the reaction was continued half an hour, centrifuge washing, is drying to obtain the composite nano materials.
4. according to the method described in claim 3, it is characterized in that, the in the mixed solvent of the ethyl alcohol and water, ethyl alcohol and water
Volume ratio be 0.3-3.
5. according to the method described in claim 3, it is characterized in that, calcination temperature as described in step (1) is 300-500 oC。
6. according to the method described in claim 3, it is characterized in that, organic acid described in step (2) includes oxalic acid, lemon
Acid, any one in acetic acid and salicylic acid.
7. according to the method described in claim 3, it is characterized in that, the surfactant includes dodecyl benzene sulfonic acid
Sodium, cetab, any one in lauryl sodium sulfate.
8. according to the method described in claim 3, it is characterized in that, organic acid and pyrrole monomer molar ratio are 0.5-3.6 and table
Face activating agent and pyrrole monomer molar ratio are 0.5-3.6.
9. according to the method described in claim 3, it is characterized in that, a certain amount of ammonium persulfate refer to ammonium persulfate with
Pyrrole monomer molar ratio is 1-3.
10. a kind of application of composite nano materials as claimed in claim 1 or 2, which is characterized in that the composite Nano material
Material is in H2Application on S room temperature sensing element, the H2S room temperature sensing element includes dielectric base, substrate surface interdigital electrode battle array
Column and coated in the sensitive membrane on array, the sensitive membrane be composite nano materials coat to be formed it is quick with a thickness of 0.05-2 mm
Feel film.
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| CN110031514A (en) * | 2019-04-25 | 2019-07-19 | 吉林大学 | SnO is adulterated based on Pd2The H of nano sensitive material2S and NO2Sensor, preparation method and applications |
| CN114577864B (en) * | 2022-05-09 | 2022-07-12 | 成都晟铎传感技术有限公司 | MEMS hydrogen sulfide sensor for improving metal salt poisoning effect and preparation method thereof |
| CN115477323B (en) * | 2022-10-08 | 2023-06-27 | 吉林大学 | Mesoporous indium tin oxide microsphere gas-sensitive material, preparation method and application thereof in hydrogen detection |
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| CN103364453A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide composite hollow microsphere air-sensitive sensing device and preparation method thereof |
| CN104990959A (en) * | 2015-07-10 | 2015-10-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hydrogen sulfide gas sensitive material composited by copper and tin oxide |
| CN105067670A (en) * | 2015-07-07 | 2015-11-18 | 南京信息工程大学 | Ordered Cu-doped nano-porous tin oxide sensing device |
| CN106404847A (en) * | 2016-11-10 | 2017-02-15 | 合肥铭志环境技术有限责任公司 | Silicate mineral fiber/polypyrrole composite gas-sensitive material and preparation method thereof |
| CN106517315A (en) * | 2016-08-17 | 2017-03-22 | 安徽建筑大学 | One-dimensional nanometer complex metal oxide gas-sensitive material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364453A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide composite hollow microsphere air-sensitive sensing device and preparation method thereof |
| CN105067670A (en) * | 2015-07-07 | 2015-11-18 | 南京信息工程大学 | Ordered Cu-doped nano-porous tin oxide sensing device |
| CN104990959A (en) * | 2015-07-10 | 2015-10-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hydrogen sulfide gas sensitive material composited by copper and tin oxide |
| CN106517315A (en) * | 2016-08-17 | 2017-03-22 | 安徽建筑大学 | One-dimensional nanometer complex metal oxide gas-sensitive material and preparation method thereof |
| CN106404847A (en) * | 2016-11-10 | 2017-02-15 | 合肥铭志环境技术有限责任公司 | Silicate mineral fiber/polypyrrole composite gas-sensitive material and preparation method thereof |
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