CN107085027A - A kind of composite nano materials of room temperature detection hydrogen sulfide and its preparation method and application - Google Patents
A kind of composite nano materials of room temperature detection hydrogen sulfide and its preparation method and application Download PDFInfo
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- CN107085027A CN107085027A CN201710380001.7A CN201710380001A CN107085027A CN 107085027 A CN107085027 A CN 107085027A CN 201710380001 A CN201710380001 A CN 201710380001A CN 107085027 A CN107085027 A CN 107085027A
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- copper ion
- tin oxide
- composite nano
- doped tin
- ion doped
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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 material can to hydrogen sulfide gas at ambient temperature with sensitive response and its preparation method and application.Copper ion doped tin oxide is synthesized first, the 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 obtained inorganic/organic composite material finally is coated into interdigital electrode surface forms gas sensing film.Raw material of the present invention is easy to get, and preparation technology is simple, with low cost.Sensor has sensitive response to the hydrogen sulfide gas of trace at ambient temperature, and response and recovery are rapid, 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 ambient 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 technology
Hydrogen sulfide（H2S）It is a kind of hypertoxic gas being widely present in nature, industrial production and daily life, research
Show H2S can not only cause device burn into catalyst poisoning, and under extremely low concentration（Ppm grades）Can be strong to human body
Kang Zaocheng extreme influences.Therefore, realize to H2S's is accurate, quick and highly sensitive detection to environmental monitoring, industrial production and
Daily life is all particularly important.
At present for H2S monitoring means is broadly divided into two major classes, and compared to the instrument and equipment for relying on complex and expensive and
The conventional method of professional operation technology（Such as ICP-OES, HG-AFS, chromatogram, colorimetric analysis etc.）, gas sensing technology is due to letter
It is single, quick, portable, characteristic of low cost and be considered as maximally effective detection mode.It is well known that the performance master of gas sensor
To depend on sensitive material used.At present, on H2The research of S sensing materials focuses mostly in metal-oxide semiconductor (MOS)（MOS）,
Such material under certain condition can be to the H of low concentration2S gases are responded.And by Material cladding, adulterating,
The method such as 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）Lower common manifestation is that sensitivity is low, and poor selectivity, resume speed is slow.Obviously,
High operating temperature not only reduces sensor service life, while also causing device 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.From unlike MOS, some are organic poly-
Compound semiconductor such as polyaniline, polypyrrole（PPy）Can be in relatively low temperature conditionss with polythiophene and their derivative etc.
Under have to gas molecule quickly response and resume speed.Organic semiconducting materials are also commonly used for gas sensitive and passed in gas
Sense field occupies critical role.But mechanical strength is not enough, chemical stability is not high and sensitivity it is relatively low be organic semiconductor
The common problem of nano material.Therefore development is at room temperature to H2There is S new sensing material that is sensitive and responding rapidly to be still
H2One challenge of S sensory fields and important research direction.
The content of the invention
Based on background above, it is an object of the invention to provide a kind of at ambient temperature to H2S has sensitive response, soon
Inorganic/organic composite nano material of quick-recovery ability and preparation method thereof, and corresponding room temperature sensing element realization pair is provided
H2S is detected.Its technical principle is to first pass through metal ion mixing increase inorganic semiconductor surface defect, improves its surface potential barrier,
Then it is compound with organic semiconductor again, inorganic organic heterojunction is formed, its response sensitivity is further improved.Meanwhile, it is and organic
Surface area is increased after semiconductors coupling there is provided more reaction sites, strengthens the diffusion and absorption of gas, accelerates electronics to turn
Move, so as to be greatly enhanced response and resume speed.
To achieve the above object, the technical solution adopted by the present invention is as follows：
Inorganic/organic composite nano material of the present invention is copper ion doped tin oxide polypyrrole compound, and its composition contains
Measure feature is as follows: Cu2+With Sn4+Mol ratio be 0.01-0.1, the mass ratio of polypyrrole and copper ion doped tin oxide is
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+
Mol ratio be 0.03-0.07, the mass ratio of polypyrrole and copper ion doped tin oxide is 0.05-0.2.
The preparation method that the present invention is provided 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.Comprise the following steps that：
1 prepares copper ion doped tin oxide：According to above-mentioned any Cu2+/Sn4+Under conditions of mol ratio, SnCl is weighed2·2H2O and
CuCl2·2H2O is dissolved in the in the mixed solvent of ethanol and water, is heated to 100oC, is stirred at reflux 1-3 hours, is cooled to after room temperature
Centrifuge, wash, dry, finally calcine 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 emulsion, three hours is stirred under the conditions of lucifuge, then soon
Speed adds a certain amount of ammonium persulfate（APS）, continue to react half an hour, centrifuge washing is dried.
The volume ratio of the in the mixed solvent of ethanol and water described in step 1, ethanol and water is 0.3-3.
Calcining heat described in step 1 is 300-500 oC。
Organic acid described in step 2 includes any one in oxalic acid, citric acid, acetic acid and salicylic acid.
Surfactant described in step 2 includes neopelex（SDBS）, cetab
（CTAB）, lauryl sodium sulfate（SDS）In any one.
A certain amount of organic acid described in step 2 refers to that organic acid is 0.5- with pyrrole monomer mol ratio with surfactant
3.6 and surfactant and pyrrole monomer mol ratio are 0.5-3.6.
A certain amount of APS described in step 2 refers to that APS is 1-3 with pyrrole monomer mol ratio.
Composite nano materials are applied in H2On S room temperature sensing elements, the H2S room temperature sensing elements, are by insulation base
Bottom, substrate surface interdigital electrode array and is coated in the above-mentioned inorganic/organic composite nanometer material of thickness on array for 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 technology is simple, with low cost.
Inorganic/organic composite nano material in 2 present invention is in specific Cu2+With Sn4+Mol 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 ambient temperature
Hydrogen（0.3-50 ppm concentration）, show highly sensitive, response and recover rapid, stability is high, the characteristics of selectivity is good.
3 gas-sensitive sensor structures of the present invention and preparation technology are very simple, with low 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.
Brief description of the drawings
The copper ion doped tin oxide polypyrrole compound scanning electron microscope (SEM) photographs of Fig. 1；
The copper ion doped tin oxide polypyrrole compound x-ray photoelectron energy spectrum diagrams of Fig. 2, illustration is Cu2+2P peaks；
Fig. 3 is based on copper ion doped tin oxide polypyrrole compound hydrogen sulfide sensing principle and schematic device（a）And be based on
Al2O3The Au interdigital electrodes of substrate coat the photo in kind before and after copper ion doped tin oxide polypyrrole compound gas sensitive（b）
With corresponding electrode surface microphoto（c）；
H prepared by Fig. 42VA characteristic curve of the S gas-sensitive sensing elements in different atmosphere；
H prepared by Fig. 52S gas-sensitive sensing elements response and H2The linear relationship of S concentration, illustration is that corresponding dynamic response is special
Linearity curve；
H prepared by Fig. 62S gas-sensitive sensing element stability（a）And selectivity（b）.
Embodiment
Technical scheme is described further below by specific implementation example, but this can not be limited with this
The scope 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 150 mL in the mixed solvent（Ethanol and water body
Product is than being 1:1）, bluish white emulsion is heated to 100 under lasting stirringoC flow back 3 hours be cooled to after room temperature be collected by centrifugation it is white
Color solid product, washing drying, grinds to form fine powder 400oC is calcined 1 hour.
2. the preparation of copper ion doped tin oxide polypyrrole compound
Weigh the copper ion doped tin oxide of 0.5 g and be distributed to the 70 ml aqueous solution containing 0.15 g CTAB and 0.14 g citric acids
In, the min of ultrasonic disperse 30.It is small that ice bath stirs continuation stirring 3 under the pyrroles that 40 uL are added after 10 min, lucifuge condition of ice bath
When, it is then disposable to add the mL of the aqueous solution 2 containing 0.2 g APS.Continue to react and the production of grey black solid is collected by centrifugation after 30 min
Thing, washing, vacuum drying.
3. H2The preparation of S gas-sensitive sensing elements
The copper ion doped g of tin oxide polypyrrole compound 0.1 of above-mentioned preparation is weighed, homogenate is ground to form with water, it is then uniform to apply
Cloth is to Al2O3On the Au interdigital electrode arrays of substrate, drying at room temperature formation sensitive membrane, thickness is 0.05 mm.
Fig. 1 is copper ion doped tin oxide polypyrrole compound scanning electron microscope (SEM) photograph prepared by embodiment 1, and the composite is
Spheric granules, particle diameter distribution contains substantial amounts of copper ion doped tin oxide in 100-150 nm, surface irregularity.X-ray light
Electron spectrum shows that the material is mainly made up of C, N, O, Sn and Cu element（Fig. 2）.A in Fig. 3 is H involved in the present invention2S
Sensor operating principles and sensing element schematic diagram;B and c are that Al is based in embodiment 1 respectively 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 ranges2S has preferable linear response behavior, its corresponding dynamic
Response characteristic curve is as shown in Fig. 5 illustrations, 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 to H2S specificity, we have investigated a variety of normal
See that a confirms H in the influence that Coexisting component is responded to sensor, Fig. 62S gas sensors are smaller to interfering component response, illustrate it
With preferable selectivity.Meanwhile, pass 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 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 150 mL in the mixed solvent（Ethanol and water body
Product is than being 1:3）, bluish white emulsion is heated to 100 under lasting stirringoC flow back 2 hours, be cooled to after room temperature be collected by centrifugation it is white
Color solid product, washing drying, grinds to form fine powder 350oC is calcined 2 hours.
2. the preparation of copper ion doped tin oxide polypyrrole
The copper ion doped tin oxide of 0.3 g is weighed to be distributed in the 70 ml aqueous solution containing 0.42 g SDS and 0.03 g oxalic acid,
The min of ultrasonic disperse 30.Ice bath, which is stirred, continues stirring 3 hours under the pyrroles that 30 uL are added after 10 min, lucifuge condition of ice bath, so
It is disposable afterwards to add the mL of the aqueous solution 2 containing 0.3 g APS.Continue that grey black solid product, water is collected by centrifugation after reacting 30 min
Wash, vacuum drying.
3. H2The preparation of S gas-sensitive sensing elements
The copper ion doped g of tin oxide polypyrrole compound 0.2 of above-mentioned preparation is weighed, homogenate is ground to form with water, it is then uniform to apply
Cloth is on the ITO interdigital electrode arrays of substrate of glass, drying at room temperature formation sensitive membrane, and thickness is 2 mm.
The copper ion doped tin oxide of table 1, polypyrrole and copper ion doped tin oxide polypyrrole made from embodiment 1 are compound
Thing BET surface area is contrasted
Presently preferred embodiments of the present invention is the foregoing is only, all equivalent changes done according to scope of the present invention patent are with repairing
Decorations, should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of room temperature detects the composite nano materials of hydrogen sulfide, it is characterized in that, the composite nano materials are copper ion doped
Tin oxide polypyrrole compound, specific component ratio is: Cu2+With Sn4+Mol 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, it is characterized in that, copper ion doped tin oxide polypyrrole compound,
Specifically component ratio is：Cu2+With Sn4+Mol 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, it is characterised in that comprise the following steps：
(1) SnCl is weighed in proportion2·2H2O and CuCl2·2H2O is dissolved in the in the mixed solvent of ethanol and water, is heated to 100oC,
It is stirred at reflux 1-3 hours, is cooled to after room temperature and centrifuges, wash, drying, finally calcine 1-4 hours at a certain temperature, obtain copper
Ion doping tin oxide；
(2) it is the 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 measured in proportion and is added in the emulsion, three hours are stirred under the conditions of lucifuge,
A certain amount of ammonium persulfate is then quickly added into, continues to react half an hour, centrifuge washing is drying to obtain the composite Nano material
Material.
4. method according to claim 3, it is characterised in that described ethanol and the in the mixed solvent of water, ethanol and water
Volume ratio be 0.3-3.
5. method according to claim 3, it is characterised in that step（1）Described in calcining heat be 300-500 oC。
6. method according to claim 3, it is characterised in that step（2）Described in organic acid include oxalic acid, lemon
Any one in acid, acetic acid and salicylic acid.
7. method according to claim 3, it is characterised in that described surfactant includes DBSA
Any one in sodium, cetab, lauryl sodium sulfate.
8. method according to claim 3, it is characterised in that described a certain amount of organic acid refers to surfactant
Organic acid is 0.5-3.6 with pyrrole monomer mol ratio and surfactant and pyrrole monomer mol ratio are 0.5-3.6.
9. method according to claim 3, it is characterised in that described a certain amount of ammonium persulfate refer to ammonium persulfate with
Pyrrole monomer mol ratio is 1-3.
10. a kind of application of composite nano materials as claimed in claim 1 or 2, it is characterised in that the composite nano materials
In H2Application on S room temperature sensing elements, the H2S room temperatures sensing element includes dielectric base, substrate surface interdigital electrode array
With the sensitive membrane being coated on array, the sensitive membrane is that to coat the thickness to be formed be 0.05-2 mm sensitive to composite nano materials
Film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN114577864A (en) * | 2022-05-09 | 2022-06-03 | 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 |
| CN115477323A (en) * | 2022-10-08 | 2022-12-16 | 吉林大学 | Mesoporous indium tin oxide microsphere gas-sensitive material, preparation method and application thereof in hydrogen detection |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114577864A (en) * | 2022-05-09 | 2022-06-03 | 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 |
| 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 |
| CN115477323A (en) * | 2022-10-08 | 2022-12-16 | 吉林大学 | Mesoporous indium tin oxide microsphere gas-sensitive material, preparation method and application thereof in hydrogen detection |
| 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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