CN106770470B - CuPc-cuprous oxide composite gas sensor and preparation method thereof - Google Patents
CuPc-cuprous oxide composite gas sensor and preparation method thereof Download PDFInfo
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- CN106770470B CN106770470B CN201710006271.1A CN201710006271A CN106770470B CN 106770470 B CN106770470 B CN 106770470B CN 201710006271 A CN201710006271 A CN 201710006271A CN 106770470 B CN106770470 B CN 106770470B
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Abstract
The invention discloses a kind of CuPc-cuprous oxide composite gas sensors and preparation method thereof.Gas sensor is to be covered with film-form CuPc-cuprous oxide on substrate with electrode, wherein CuPc be it is rodlike, cuprous oxide is graininess；Method is first to prepare CuPc sulfuric acid solution, it is added into after being stirred in deionized water and filters again, obtain filter cake, then, first filter cake is respectively placed in after dispersing in bronsted lowry acids and bases bronsted lowry solution and is filtered, the CuPc of purifying is made to be washed with deionized and be dried again, obtain CuPc nanometer rods, later, it is scattered in n-butanol after first mixing CuPc nanometer rods and cuprous oxide nano particle, method is filled by autonomous interface again, obtained mixed solution is formed into CuPc-cuprous oxide film in deionized water surface, finally, first film is fished for using the substrate with electrode, the film drying that will be overlying on substrate again, purpose product is made.It can be extremely easy to commercially be widely used in the high sensitivity detection to front three amine gas.
Description
Technical field
The present invention relates to a kind of gas sensor and preparation method, especially a kind of CuPc-cuprous oxide (CuPc-Cu2O)
Composite gas sensor and preparation method thereof.
Background technique
As the mankind deepen continuously to strategy of sustainable development understanding, environmental pollution and weather variation issue cause generation
The great attention of various countries, boundary.Trimethylamine is one of the main object of national foul gas contamination control, while being also in Fish
The predominant gas generated when breaks down proteins, content have become the important indicator of current aquatic products freshness.Therefore, to front three
The research and development of amine gas high sensitivity detection material have become important research topic, such as Chinese invention patent application CN
A kind of trimethylamine gas sensor and preparation method thereof that 103063705 A were announced on April 24th, 2013.The patent of invention Shen
Please in the gas sensor that refers to be Al with electrode2O3Air-sensitive film is covered on ceramic tube, air-sensitive film therein is by SnO2With account for
SnO2The Eu of molal weight 0.5~5%5+Or La5+Composition；Preparation method is first to obtain nano SnO using hydro-thermal method2, then adulterate
A certain amount of rare earth element prepares gas sensitive, later, gas sensitive is first coated in Al2O3Air-sensitive is made in the surface of ceramic tube
Electrode tube, then place it at 400~500 DEG C and anneal 2~4 hours, obtain product.Though this product can be used for trimethylamine
Detection, but all there is shortcomings with preparation method, firstly, the detection sensitivity of product is not high, only 8~10ppm；Its
Secondary, operating temperature when product detection front three amine gas is up to 150~250 DEG C；Finally, preparation method can not both accurately control
The film thickness of gas sensitive, and high annealing is needed, the product of higher trimethylamine detection sensitivity can't be obtained.
Summary of the invention
The technical problem to be solved in the present invention place in order to overcome the shortcomings in the prior art, providing a kind of has higher front three
The CuPc of amine gas detection sensitivity-cuprous oxide composite gas sensor.
The invention solves another technical problem be a kind of above-mentioned CuPc-cuprous oxide composite gas sensor is provided
Preparation method.
To solve technical problem of the invention, used technical solution are as follows: CuPc-cuprous oxide composite gas sensor
Including having the substrate of electrode, in particular,
Film-form CuPc-cuprous oxide is covered on the substrate with electrode, the film-form CuPc-oxidation is sub-
The film thickness of copper is 200~300nm, is made of CuPc and cuprous oxide that weight ratio is 1:3~7；
The CuPc be it is rodlike, a length of 10~15um of stick, stick diameter be 200~300nm；
The cuprous oxide is graininess, and partial size is 80~120nm.
As the further improvement of CuPc-cuprous oxide composite gas sensor:
Preferably, CuPc-cuprous oxide film resistivity is 120~160 Ω m.
Preferably, the shape of the substrate with electrode is plane or curved surface or tubulose.
To solve another technical problem of the invention, another used technical solution are as follows: above-mentioned CuPc-oxidation
The preparation method of cuprous composite gas sensor includes that autonomous interface dress method, especially key step are as follows:
Step 1, it is complete to it that CuPc is first placed in stirring in the sulfuric acid solution of 30~70 DEG C of mass fraction >=95%
Dissolution, obtains CuPc sulfuric acid solution, is the ratio of 1:8~12 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water
CuPc sulfuric acid solution is added in 90~100 DEG C of deionized water after stirring at least 3h and filters, obtains filter cake by example；
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.08~0.12mol/L and is filtered, obtained
To the CuPc of purifying, then after making to be washed with deionized to its filtrate to the CuPc of purifying and being in neutrality, it is placed in 60~100 DEG C
Lower drying, obtains CuPc nanometer rods；
It step 3, is first the ratio of 1:3~7 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by two
It is scattered in n-butanol after person's mixing, obtains the mixed solution of 0.005~0.015g/mL, then fill method by autonomous interface to mix
It closes solution and forms CuPc-cuprous oxide film in deionized water surface；
Step 4, at least 5min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode, is obtained
CuPc-the cuprous oxide film being overlying on substrate, then the CuPc-cuprous oxide film being overlying on substrate is placed in 100~
Dry at least 5min, is made CuPc-cuprous oxide composite gas sensor at 140 DEG C.
Further improvement as CuPc-cuprous oxide composite gas sensor preparation method:
Preferably, before being mixed with CuPc nanometer rods, cuprous oxide nano particle is placed at 100~150 DEG C at least
10h。
Preferably, acid solution is hydrochloric acid solution or sulfuric acid solution or nitric acid solution.
Preferably, aqueous slkali is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
Preferably, the shape of the substrate with electrode is plane or curved surface or tubulose.
Beneficial effect compared with the existing technology is:
First, using scanning electron microscope, powder x-ray diffraction and resistance meter to carry out respectively purpose product obtained
Characterization, as a result, it can be seen that, purpose product is the film being overlying on the substrate with electrode；Wherein, film with a thickness of 200~
300nm is made of nanometer rods and nano particle, a length of 10~15um of the stick of nanometer rods therein, stick diameter be 200~
300nm, the partial size of nano particle are 80~120nm.Film is made of the CuPc that weight ratio is 1:3~7 and cuprous oxide；Its
In CuPc be it is rodlike, cuprous oxide is graininess.The resistivity of film is 120~160 Ω m.It is this by CuPc and
Cuprous oxide is assembled into the purpose product of film-form, not only since the stability of CuPc is good, operating temperature is low, but also because of cuprous oxide
Higher sensitivity and fast response characteristic, due also to CuPc and cuprous oxide are to trimethylamine gas sensitization and the two
Combination and complement each other, more because CuPc and cuprous oxide are nanoscale, and be highly advantageous to and improve purpose product
Sensitivity to gas detection.
Second, being carried out to front three amine gas multiple under various concentration using purpose product obtained as gas sensor
The test of more batches remains to be effectively detected out when the concentration of tested gas trimethylamine is down to 50ppb.Purpose produces
Response speed≤4s of the object to front three amine gas, recovery time≤20s, operating temperature are 100~130 DEG C, the stabilization of detection
Property, invertibity and repeatability all very it is good.
Third, preparation method is simple, scientific, efficient.It has not only been made with higher trimethylamine gas detection sensitivity
Purpose product --- CuPc-cuprous oxide composite gas sensor, also makes it have faster response speed and recovery time,
And lower operating temperature, more have the characteristics that film thickness accurately controls, is not required to high annealing --- it is energy saving；To make
Purpose product is extremely easy to commercially be widely used in the high sensitivity detection to front three amine gas.
Detailed description of the invention
Fig. 1 is one of the result for using scanning electron microscope (SEM) to be characterized purpose product made from preparation method.SEM
Image shows that purpose product is made of nanometer rods and nano particle.
Fig. 2 is one of the result for using powder x-ray diffraction (XRD) instrument to be characterized purpose product obtained.XRD spectrum
Figure confirms that purpose product is made of CuPc and cuprous oxide.
Fig. 3 is by the response measured in front three amine gas that purpose product shown in FIG. 1 is placed under various concentration and front three
Amine concentration graph of relation.The condition of test are as follows: the test voltage at purpose product both ends it is constant be 10V, operating temperature be 100~
130℃.As seen from Figure 3, purpose product has response well to the trimethylamine in 0.05~50ppm of concentration range.
Fig. 4 is that purpose product shown in FIG. 1 is placed in the purpose measured in the front three amine gas that concentration is 1~50ppb to produce
Concentration gradient figure of the object to front three amine gas.The same Fig. 3 of the condition of test.As seen from Figure 4, purpose product is to front three amine gas
Detection sensitivity is up to 50ppb.
Fig. 5 is to be placed in purpose product shown in FIG. 1 in the front three amine gas that concentration is 2ppm to carry out circularity test
Result figure.The same Fig. 3 of the condition of test.As seen from Figure 5, stability, invertibity and the repetition that purpose product tests trimethylamine
Property very it is good.
Specific embodiment
Preferred embodiment of the invention is described in further detail with reference to the accompanying drawing.
It buys from market or is voluntarily made first:
CuPc；
The sulfuric acid solution of mass fraction >=95%；
Deionized water；
Hydrochloric acid solution, sulfuric acid solution and nitric acid solution as acid solution；
Sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as aqueous slkali；
Cuprous oxide nano particle；
N-butanol；
Substrate with electrode, shape are plane or curved surface or tubulose.
Wherein, before mixing cuprous oxide nano particle with CuPc nanometer rods, cuprous oxide nano particle is placed in
At least 10h at 100~150 DEG C.
Then,
Embodiment 1
The specific steps of preparation are as follows:
Step 1, CuPc is first placed in 30 DEG C of mass fraction to be completely dissolved to stir in 99% sulfuric acid solution to it,
Obtain CuPc sulfuric acid solution.The ratio for being 1:8 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by CuPc
Sulfuric acid solution is added in 90 DEG C of deionized water and filters after stirring 5h, obtains filter cake.
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.08mol/L and is filtered；Wherein, acid is molten
Liquid is hydrochloric acid solution, and aqueous slkali is sodium hydroxide solution, the CuPc purified.Deionization is used to the CuPc of purifying again
After water washing is in neutrality to its filtrate, it is placed in drying at 60 DEG C, obtains CuPc nanometer rods.
Step 3, the ratio for being first 1:3 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by the two
It is scattered in n-butanol after mixing, obtains the mixed solution of 0.005g/mL.Method is filled for mixed solution in going by autonomous interface again
Ion water surface forms CuPc-cuprous oxide film.
Step 4,5min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode；Wherein, have
The shape of the substrate of electrode is plane, obtains being overlying on CuPc-cuprous oxide film on substrate.The phthalein that will be overlying on substrate again
Cyanines copper-cuprous oxide film is placed at 100 DEG C dry 9min, is made and is similar to shown in Fig. 1, and such as Fig. 2, Fig. 3, Fig. 4 and Fig. 5
In curve shown in CuPc-cuprous oxide composite gas sensor.
Embodiment 2
The specific steps of preparation are as follows:
Step 1, CuPc is first placed in 40 DEG C of mass fraction to be completely dissolved to stir in 98% sulfuric acid solution to it,
Obtain CuPc sulfuric acid solution.The ratio for being 1:9 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by CuPc
Sulfuric acid solution is added in 93 DEG C of deionized water and filters after stirring 4.5h, obtains filter cake.
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.09mol/L and is filtered；Wherein, acid is molten
Liquid is hydrochloric acid solution, and aqueous slkali is sodium hydroxide solution, the CuPc purified.Deionization is used to the CuPc of purifying again
After water washing is in neutrality to its filtrate, it is placed in drying at 70 DEG C, obtains CuPc nanometer rods.
Step 3, the ratio for being first 1:4 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by the two
It is scattered in n-butanol after mixing, obtains the mixed solution of 0.008g/mL.Method is filled for mixed solution in going by autonomous interface again
Ion water surface forms CuPc-cuprous oxide film.
Step 4,6min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode；Wherein, have
The shape of the substrate of electrode is plane, obtains being overlying on CuPc-cuprous oxide film on substrate.The phthalein that will be overlying on substrate again
Cyanines copper-cuprous oxide film is placed at 110 DEG C dry 8min, is made and is similar to shown in Fig. 1, and such as Fig. 2, Fig. 3, Fig. 4 and Fig. 5
In curve shown in CuPc-cuprous oxide composite gas sensor.
Embodiment 3
The specific steps of preparation are as follows:
Step 1, CuPc is first placed in 50 DEG C of mass fraction to be completely dissolved to stir in 97% sulfuric acid solution to it,
Obtain CuPc sulfuric acid solution.The ratio for being 1:10 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by phthalocyanine
Copper sulfuric acid solution is added in 95 DEG C of deionized water and filters after stirring 4h, obtains filter cake.
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.1mol/L and is filtered；Wherein, acid is molten
Liquid is hydrochloric acid solution, and aqueous slkali is sodium hydroxide solution, the CuPc purified.Deionization is used to the CuPc of purifying again
After water washing is in neutrality to its filtrate, it is placed in drying at 80 DEG C, obtains CuPc nanometer rods.
Step 3, the ratio for being first 1:5 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by the two
It is scattered in n-butanol after mixing, obtains the mixed solution of 0.01g/mL.Method is filled for mixed solution in going by autonomous interface again
Ion water surface forms CuPc-cuprous oxide film.
Step 4,7min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode；Wherein, have
The shape of the substrate of electrode is plane, obtains being overlying on CuPc-cuprous oxide film on substrate.The phthalein that will be overlying on substrate again
Cyanines copper-cuprous oxide film is placed at 120 DEG C dry 7min, is made as shown in Figure 1, and as in Fig. 2, Fig. 3, Fig. 4 and Fig. 5
CuPc shown in curve-cuprous oxide composite gas sensor.
Embodiment 4
The specific steps of preparation are as follows:
Step 1, CuPc is first placed in 60 DEG C of mass fraction to be completely dissolved to stir in 96% sulfuric acid solution to it,
Obtain CuPc sulfuric acid solution.The ratio for being 1:11 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by phthalocyanine
Copper sulfuric acid solution is added in 98 DEG C of deionized water and filters after stirring 3.5h, obtains filter cake.
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.11mol/L and is filtered；Wherein, acid is molten
Liquid is hydrochloric acid solution, and aqueous slkali is sodium hydroxide solution, the CuPc purified.Deionization is used to the CuPc of purifying again
After water washing is in neutrality to its filtrate, it is placed in drying at 90 DEG C, obtains CuPc nanometer rods.
Step 3, the ratio for being first 1:6 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by the two
It is scattered in n-butanol after mixing, obtains the mixed solution of 0.013g/mL.Method is filled for mixed solution in going by autonomous interface again
Ion water surface forms CuPc-cuprous oxide film.
Step 4,8min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode；Wherein, have
The shape of the substrate of electrode is plane, obtains being overlying on CuPc-cuprous oxide film on substrate.The phthalein that will be overlying on substrate again
Cyanines copper-cuprous oxide film is placed at 130 DEG C dry 6min, is made and is similar to shown in Fig. 1, and such as Fig. 2, Fig. 3, Fig. 4 and Fig. 5
In curve shown in CuPc-cuprous oxide composite gas sensor.
Embodiment 5
The specific steps of preparation are as follows:
Step 1, CuPc is first placed in 70 DEG C of mass fraction to be completely dissolved to stir in 95% sulfuric acid solution to it,
Obtain CuPc sulfuric acid solution.The ratio for being 1:12 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by phthalocyanine
Copper sulfuric acid solution is added in 100 DEG C of deionized water and filters after stirring 3h, obtains filter cake.
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.12mol/L and is filtered；Wherein, acid is molten
Liquid is hydrochloric acid solution, and aqueous slkali is sodium hydroxide solution, the CuPc purified.Deionization is used to the CuPc of purifying again
After water washing is in neutrality to its filtrate, it is placed in drying at 100 DEG C, obtains CuPc nanometer rods.
Step 3, the ratio for being first 1:7 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, by the two
It is scattered in n-butanol after mixing, obtains the mixed solution of 0.015g/mL.Method is filled for mixed solution in going by autonomous interface again
Ion water surface forms CuPc-cuprous oxide film.
Step 4,9min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode；Wherein, have
The shape of the substrate of electrode is plane, obtains being overlying on CuPc-cuprous oxide film on substrate.The phthalein that will be overlying on substrate again
Cyanines copper-cuprous oxide film is placed at 140 DEG C dry 5min, is made and is similar to shown in Fig. 1, and such as Fig. 2, Fig. 3, Fig. 4 and Fig. 5
In curve shown in CuPc-cuprous oxide composite gas sensor.
Select the hydrochloric acid solution or sulfuric acid solution or nitric acid solution as acid solution, the hydroxide as aqueous slkali respectively again
Sodium solution or potassium hydroxide solution or lithium hydroxide solution and shape are the lining with electrode of plane or curved surface or tubulose
Bottom repeats above-described embodiment 1~5, has equally been made as or has been similar to shown in Fig. 1, and as in Fig. 2, Fig. 3, Fig. 4 and Fig. 5
CuPc shown in curve-cuprous oxide composite gas sensor.
Obviously, those skilled in the art can be to CuPc of the invention-cuprous oxide composite gas sensor and its system
Preparation Method carries out various modification and variations without departing from the spirit and scope of the present invention.If in this way, being repaired to of the invention these
Change with modification within the scope of the claims of the present invention and its equivalent technology, then the present invention be also intended to encompass these change and
Including modification.
Claims (5)
1. a kind of CuPc-cuprous oxide composite gas sensor preparation method, including interface self-assembly method, it is characterised in that main
Want that steps are as follows:
Step 1, first CuPc is placed in stir in the sulfuric acid solution of 30~70 DEG C of mass fraction >=95% to it and is completely dissolved,
CuPc sulfuric acid solution is obtained, is the ratio of 1:8~12 according still further to the volume ratio of CuPc sulfuric acid solution and deionized water, by phthalein
It is filtered after stirring at least 3h in the deionized water of 90~100 DEG C of cyanines copper sulfuric acid solution addition, obtains filter cake；
Step 2, first filter cake is respectively placed in after dispersing in the acid solution and aqueous slkali of 0.08~0.12mol/L and is filtered, obtained pure
The CuPc of change, then after making to be washed with deionized to its filtrate to the CuPc of purifying and being in neutrality, be placed at 60~100 DEG C and do
It is dry, obtain CuPc nanometer rods；
Step 3, first it is the ratio of 1:3~7 according to CuPc nanometer rods and the weight ratio of cuprous oxide nano particle, the two is mixed
It is scattered in n-butanol after conjunction, obtains the mixed solution of 0.005~0.015g/mL, then will mixed by interface self-assembly method molten
Liquid forms CuPc-cuprous oxide film in deionized water surface；
Step 4, at least 5min is stood after first fishing for CuPc-cuprous oxide film using the substrate with electrode, is overlying on
CuPc-cuprous oxide film on substrate, then the CuPc-cuprous oxide film being overlying on substrate is placed in 100~140 DEG C
CuPc-cuprous oxide composite gas sensor is made in lower drying at least 5min；
The CuPc-cuprous oxide composite gas sensor is sub- to be covered with film-form CuPc-oxidation on the substrate with electrode
Copper, wherein film-form CuPc-cuprous oxide film thickness be 200~300nm, by weight ratio be 1:3~7 CuPc and
Cuprous oxide composition, CuPc therein be it is rodlike, a length of 10~15um of stick, stick diameter be 200~300nm, cuprous oxide
For graininess, partial size is 80~120nm.
2. CuPc according to claim 1-cuprous oxide composite gas sensor preparation method, it is characterized in that with phthalein
Before the mixing of cyanines copper nanometer rods, cuprous oxide nano particle is placed at least 10h at 100~150 DEG C.
3. CuPc according to claim 1-cuprous oxide composite gas sensor preparation method, it is characterized in that acid solution
For hydrochloric acid solution or sulfuric acid solution or nitric acid solution.
4. CuPc according to claim 1-cuprous oxide composite gas sensor preparation method, it is characterized in that aqueous slkali
For sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
5. CuPc according to claim 1-cuprous oxide composite gas sensor preparation method, it is characterized in that with electricity
The shape of the substrate of pole is plane or curved surface or tubulose.
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| CN109828003B (en) * | 2019-02-18 | 2021-07-23 | 中国石油大学(华东) | Inorganic doping modification method for phthalocyanine molecular semiconductor material containing crown ether based on cadmium sulfide |
| CN113683115A (en) * | 2021-09-01 | 2021-11-23 | 深圳市动盈先进材料有限公司 | Preparation method of semiconductor material for 5G signal transmission |
| CN114100687B (en) * | 2021-11-19 | 2023-06-20 | 陕西科技大学 | Lithium/thionyl chloride battery anode catalytic material CoPc/CuPc and preparation method thereof |
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| US4350660A (en) * | 1980-06-07 | 1982-09-21 | Emi Limited | Ammonia gas sensors |
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| KR101645176B1 (en) * | 2015-02-26 | 2016-08-04 | 재단법인 나노기반소프트일렉트로닉스연구단 | Laminate having porous organic semicoductor thin film and chemical sensor comprising the same |
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| US4350660A (en) * | 1980-06-07 | 1982-09-21 | Emi Limited | Ammonia gas sensors |
| CN101819176A (en) * | 2009-12-31 | 2010-09-01 | 张洪延 | Gas sensor taking cuprous oxide microcrystalline film as sensing material |
| CN101881745A (en) * | 2010-07-12 | 2010-11-10 | 黑龙江大学 | Alcohol gas sensor of oxide phthalocyanine hybrid film in room temperature and preparation method thereof |
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