CN113219010A - Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation - Google Patents
Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation Download PDFInfo
- Publication number
- CN113219010A CN113219010A CN202110543850.6A CN202110543850A CN113219010A CN 113219010 A CN113219010 A CN 113219010A CN 202110543850 A CN202110543850 A CN 202110543850A CN 113219010 A CN113219010 A CN 113219010A
- Authority
- CN
- China
- Prior art keywords
- sensitive material
- ethanol
- ceramic tube
- shell hollow
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000004005 microsphere Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- 239000010931 gold Substances 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000975 co-precipitation Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 229910001120 nichrome Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- PJAHUDTUZRZBKM-UHFFFAOYSA-K potassium citrate monohydrate Chemical compound O.[K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PJAHUDTUZRZBKM-UHFFFAOYSA-K 0.000 claims description 5
- 229940050931 potassium citrate monohydrate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 abstract 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 30
- 239000007789 gas Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 6
- 206010006326 Breath odour Diseases 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010002091 Anaesthesia Diseases 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Images
Classifications
-
- 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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
An ethanol sensor based on a ZnO double-shell hollow-structure microsphere sensitive material, a preparation method and application thereof in detecting ethanol steam belong to the technical field of semiconductor oxide gas sensors. Al with two parallel, annular and mutually separated gold electrodes on the outer surface2O3Ceramic tube substrate coated with Al2O3ZnO double-shell hollow structure microsphere sensitive material arranged on outer surface of ceramic tube and gold electrode and Al2O3A nickel-chromium heating coil in the ceramic tube. The invention develops the high-performance ethanol gas sensor by utilizing the ZnO double-shell hollow structure microspheres with hollow interiors, loose structures and uniform sizes. The lower detection limit of the sensor can reach 1 ppm. In addition, the device has simple process, small volume and low cost, and is suitable for mass production, thereby having wide application prospect in the aspect of detecting the content of the ethanol gas.
Description
Technical Field
The invention belongs to the technical field of semiconductor oxide gas sensors, and particularly relates to an ethanol sensor based on a ZnO double-shell hollow-structure microsphere sensitive material, a preparation method and application of the ethanol sensor in detection of ethanol steam.
Background
The harm of ethanol to the human body is mainly manifested as an inhibitory effect on the central nervous system, first causing excitation and then inhibition. Acute poisoning can be divided into four stages of excitation, hypnosis, anesthesia and asphyxia. Prolonged exposure to high concentrations of ethanol can cause irritation symptoms in the nasal and ocular mucosae, as well as headache, dizziness, fatigue, nausea, and the like. In addition, the harmfulness of drunk driving is extremely high, according to the threshold values of the blood and breath alcohol content of vehicle drivers and the inspection standard (GB/T19522-2010) of the people's republic of China, the breath alcohol concentration is 20-80 mg/100mL (44-176 ppm), namely the drunk driving concentration, and the breath alcohol concentration is more than 80mg/100mL, and belongs to the drunk driving concentration. The sensor is widely concerned and applied as a means for acquiring information, so that the research and development of the ethanol gas sensor with high gas-sensitive response and low detection lower limit is of great significance.
In fact, research surrounding the improvement of the sensitivity of the oxide semiconductor sensor is continuously deepened, and especially the development of the nano scientific technology provides good opportunities for improving the performance of the sensor. Research shows that the recognition function, the conversion function and the utilization rate of a sensitive body of the gas sensitive material determine the sensitivity degree of the oxide semiconductor sensor. Through research, the sensitivity and selectivity of the sensor can be remarkably improved by synthesizing the semiconductor oxide material with a hollow structure. This is mainly because the hollow structure material can improve the utilization rate of the sensitive body by promoting the diffusion of gas molecules into the sensitive layer. Based on this, the development of the design and preparation of the hollow-structure semiconductor oxide has important significance for improving the performance of the gas sensor and expanding the application of the gas sensor.
Disclosure of Invention
The invention aims to provide an ethanol sensor based on a ZnO double-shell hollow-structure microsphere sensitive material, a preparation method and application of the ethanol sensor in the aspect of detecting ethanol steam in the environment. The invention increases the sensitivity of the sensor and reduces the detection lower limit of the sensor by adjusting the microstructure of the semiconductor material, thereby promoting the practicability of the sensor in the field of gas detection.
The sensor obtained by the invention has higher sensitivity, better selectivity and lower detection lower limit. The lower detection limit of the sensor is 1ppm, and the sensor can be used for detecting the content of ethanol vapor in the environment. The sensor with the tubular structure is simple in manufacturing process, small in size, low in price and beneficial to industrial mass production, so that the sensor has important application value.
The ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material comprises Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3Ceramic tube substrate coated with Al2O3The nano sensitive material on the outer surface of the ceramic tube and the gold electrode is arranged on the Al2O3A nichrome heating coil in the ceramic tube; the method is characterized in that: the nano sensitive material is loose ZnO double-shell hollow structure microspheres and is prepared by the following steps:
(1) firstly, 0.50-0.65 g of Zn (NO)3)2·6H2Dissolving O, 0.4-0.6 g of urea and 0.1-0.2 g of potassium citrate monohydrate in 90-110 mL of deionized water, and fully stirring for 20-40 min;
(2) putting the uniform transparent solution obtained in the step (1) into a beaker, carrying out coprecipitation reaction for 3-5 h at 95-115 ℃, cooling to room temperature, and then carrying out coprecipitation reaction for 3-5 h at 105-125 ℃ on the beaker;
(3) and (3) after the reaction in the step (2) is finished and the temperature is reduced to room temperature, alternately centrifuging and washing the obtained white precipitate for 4-8 times by using deionized water and absolute ethyl alcohol, drying the washed white precipitate at 70-90 ℃ for 10-15 h, and calcining at 450-550 ℃ for 0.5-1.5 h to obtain white powder of the microsphere sensitive material with the ZnO double-shell hollow structure.
Al2O3The inner diameter of the ceramic tube is 0.7-0.9 mm, the outer diameter is 1.1-1.3 mm, and the length is 3.8-4.2 m; the width of the gold electrode is 0.35-0.45 mm, the distance between the two gold electrodes is 0.4-0.6 mm, 2 platinum wire leads are led out of each gold electrode, and the length of each gold electrode is 4-6 mm.
The invention relates to a preparation method of an ethanol sensor based on a ZnO double-shell hollow structure microsphere sensitive material, which comprises the following steps:
(1) uniformly mixing 5-15 mg of calcined white ZnO double-shell hollow-structure microsphere sensitive material powder with 0.1mL of a mixed solvent of absolute ethyl alcohol (absolute ethyl alcohol being more than or equal to 99.7%) and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1) to form slurry, dipping the slurry by using a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube substrate and the two parallel, annular and mutually-separated gold electrodes are provided, and the thickness of the sensitive material is 15-30 mu m;
(2) coated Al2O3Calcining the ceramic tube at 450-550 ℃ for 0.5-1.5 h, and then enabling a nichrome heating coil (with the number of turns of 50-60) with the resistance value of 30-40 omega to penetrate through Al2O3In the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally four platinum wire leads of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat;
(3) and (3) aging the sensor in the step (2) in an air environment at 180-220 ℃ for 6-8 days to obtain the ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material.
The working principle is as follows:
when the ethanol sensor based on the microsphere sensitive material with the ZnO double-shell hollow structure is placed in the air, oxygen molecules in the air can take electrons from ZnO and take O2 -、O-Or O2-In the method (2), a depletion layer is formed on the surface of the material, and the resistance increases. When the sensor contacts ethanol gas at a certain proper temperature, ethanol gas molecules and adsorbed oxygen molecules generate oxidation-reduction reaction, and electrons are released back to ZnO, so that ZnOThe resistance drops. Here we define the sensitivity of the sensor as S: r ═ Sa/RgWherein R isaIs the resistance in air between the gold electrodes of the sensor, RgThe resistance of the gold electrode of the sensor after contacting with ethanol is shown.
The ethanol sensor based on the ZnO double-shell hollow structure microsphere sensitive material prepared by the invention has the following advantages:
1. the ZnO double-shell hollow structure can be synthesized by a simple coprecipitation method, and the synthesis method is simple and low in cost;
2. by regulating the internal structure of ZnO, the sensitivity to ethanol is improved, the lower limit of detection of the material is low, and the method has a wide application prospect in the aspect of content detection;
3. the tube sensor is commercially available, and the device has simple process and small volume and is suitable for mass production.
Drawings
FIG. 1: a structural schematic diagram of the ZnO double-shell hollow structure microsphere ethanol sensor; FIG. 1(a) is a sectional view, and FIG. 1(b) is a schematic view showing a welded state
FIG. 2: scanning electron micrographs and transmission electron micrographs of the sensitive materials prepared in comparative example, example 1 and example 2.
FIG. 3: comparative, example 1 and example 2 are graphs comparing sensitivity at 275 c to 100ppm of 5 different gases.
FIG. 4: sensitivity versus operating temperature for the comparative, example 1 and example 2 ethanol gas at 100 ppm.
FIG. 5: example 4 sensitivity curves for different concentrations of ethanol gas at the optimum operating temperature; FIG. 5(a) is a graph showing real-time sensitivity curves for ethanol gas at different concentrations; FIG. 5(b) is a graph showing the sensitivity of the gas sensor to ethanol gas of different concentrations.
As shown in fig. 1, the names of the respective components are: annular gold electrode 1, Al2O3An insulating ceramic tube 2, a ZnO double-shell hollow structure microsphere sensitive material 3, a nickel-chromium alloy heating coil 4, a platinum wire 5 and an indirectly heated hexagonal tube seat 6;
FIG. 2 is a scanning electron microscope (a, b, c, d, e, f, g, h, i) photograph and a transmission electron microscope (j, k) photograph of the sensitive materials prepared in comparative example, example 1 and example 2. As can be seen from the figure, the sensitive material of the comparative example corresponding to FIGS. 2a, b and c is a solid sphere structure, the size of the solid microspheres is about 1.5-2 μm, the sensitive material of the example 1 corresponding to FIGS. 2d, e and f is a core-shell sphere structure, the size of the microsphere structure is about 1.5-2 μm, and the sensitive material of the example 2 corresponding to FIGS. 2g, h and i is a double-shell hollow sphere structure, and the size of the microsphere structure is about 1.5-2 μm. In the experiment, three structures of a ZnO solid sphere, a ZnO core-shell sphere and a ZnO double-shell hollow sphere are synthesized by adjusting the temperature and the reaction time of the coprecipitation reaction. The specific reaction mechanism is that the Ostwald curing process is regulated and controlled by adjusting the coprecipitation reaction temperature and time, the longer the reaction time is, the higher the reaction temperature is, the more durable and violent the Ostwald curing process is in a certain reaction temperature and time range, and finally, the regulation and control of solid, core-shell and double-shell hollow structures of the ZnO internal structure are realized through the Ostwald curing process. Fig. 2j shows the lattice spacing as the (100) crystal plane of the pure phase ZnO, and the diffraction ring of fig. 2k shows the material as polycrystalline.
FIG. 3 is a graph comparing the sensitivity of comparative example, example 1 and example 2 at 275 deg.C to 100ppm of 5 different gases. As can be seen from the figure, the sensitivity of the sensor to ethanol is gradually improved along with the hollowing of the internal structure of the ZnO microsphere, and the highest sensitivity is achieved in the ZnO double-shell hollow structure.
FIG. 4 is a plot of sensitivity versus operating temperature for comparative example, example 1, and example 2, for 100ppm ethanol gas. It can be seen from the figure that the optimum working temperature for both sets of samples of the example is 275 ℃. At 275 deg.C, the sensitivity of the comparative example was 10.1, the sensitivity of example 1 was 31.1, the sensitivity of example 2 was 54.4, and the sensitivity of example 2 was the highest, approximately 5.4 times the sensitivity of the comparative example. Therefore, the ethanol sensor with high sensitivity can be constructed by regulating and controlling the inner cavity structure of ZnO.
FIG. 5(a) is a graph showing the real-time sensitivity of the test in example 2 at the optimum operating temperature for different concentrations of ethanol gas, and it can be seen that the concentration of ethanol decreasesThe sensitivity gradually decreased and 1ppm of ethanol gas could be detected. FIG. 5(b) is a graph showing the sensitivity of example 2 to different concentrations of ethanol gas at the optimum operating temperature. The sensitivity test method comprises the following steps: firstly, putting a sensor into an air bottle with the volume of 1L, testing real-time resistance through a resistance meter connected with the sensor, and obtaining the resistance value of the sensor in the air, namely R when the resistance value tends to be stablea(ii) a Then, a microsyringe is used for injecting 1-100 ppm of ethanol into a 1L gas cylinder, and after the resistance value is stable, the resistance value of the sensor in ethanol with different concentrations, namely R, is obtained through measurementgAccording to the definition of sensitivity S, formula S ═ Ra/RgAnd calculating the sensitivity of the sensor under different ethanol concentrations to finally obtain a standard working curve of ethanol concentration-sensitivity. As can be seen from the graph, the lower limit of detection of the sensor of example 2 is 1ppm, and the sensitivity at this time is about 1.5.
In actual measurement, R can be measured by the methoda、RgAnd comparing the obtained sensitivity value with a standard working curve of ethanol concentration-sensitivity to obtain the ethanol content in the atmosphere, wherein the ethanol sensor can be well applied to the detection of ethanol gas in the environment due to the characteristic.
Detailed Description
Comparative example:
a coprecipitation method is used for preparing a ZnO solid ball structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: 4h at 90 ℃;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h; obtaining white powder of the ZnO solid sphere structure microsphere sensitive material;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, and then a nichrome heating coil having a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And in the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally, four platinum wires of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO solid sphere structure nano material.
Example 1:
a coprecipitation method is used for preparing a ZnO core-shell sphere structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: 4h at 90 ℃; cooling to room temperature after the reaction is finished, and continuing heating, wherein the oven parameters are set as follows: at 100 ℃ for 4 h;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h; obtaining white powder of the ZnO core-shell sphere structure microsphere sensitive material;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, then a nichrome heating coil with a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And finally, welding four platinum wires of the sensor and two ends of the nickel-chromium alloy heating coil on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO core-shell structure nano material.
Example 2:
a coprecipitation method is used for preparing a ZnO double-shell sphere hollow structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: at 100 ℃ for 4 h; cooling to room temperature after the reaction is finished, and continuing heating, wherein the oven parameters are set as follows: 110 ℃ for 4 h; obtaining white powder of the ZnO double-shell sphere hollow structure microsphere sensitive material;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, then a nichrome heating coil with a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And in the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally, four platinum wires of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO double-shell hollow-structure nano material.
Claims (4)
1. An ethanol sensor based on ZnO double-shell hollow-structure microsphere sensitive material is composed of Al with two parallel, annular and mutually-separated gold electrodes on its external surface2O3Ceramic tube substrate coated with Al2O3The nano sensitive material on the outer surface of the ceramic tube and the gold electrode is arranged on the Al2O3A nichrome heating coil in the ceramic tube; the method is characterized in that: the nano sensitive material is loose ZnO double-shell hollow structure microspheres and is prepared by the following steps:
(1) firstly, 0.50-0.65 g of Zn (NO)3)2·6H2Dissolving O, 0.4-0.6 g of urea and 0.1-0.2 g of potassium citrate monohydrate in 90-110 mL of deionized water, and fully stirring for 20-40 min;
(2) putting the uniform transparent solution obtained in the step (1) into a beaker, carrying out coprecipitation reaction for 3-5 h at 95-115 ℃, cooling to room temperature, and then carrying out coprecipitation reaction for 3-5 h at 105-125 ℃ on the beaker;
(3) and (3) after the reaction in the step (2) is finished and the temperature is reduced to room temperature, alternately centrifuging and washing the obtained white precipitate for 4-8 times by using deionized water and absolute ethyl alcohol, drying the washed white precipitate at 70-90 ℃ for 10-15 h, and calcining at 450-550 ℃ for 0.5-1.5 h to obtain white powder of the microsphere sensitive material with the ZnO double-shell hollow structure.
2. The ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material of claim 1, which is characterized in that: al (Al)2O3The inner diameter of the ceramic tube is 0.7-0.9 mm, the outer diameter is 1.1-1.3 mm, and the length is 3.8-4.2 m; the width of the gold electrode is 0.35-0.45 mm, the distance between the two gold electrodes is 0.4-0.6 mm, 2 platinum wire leads are led out of each gold electrode, and the length of each gold electrode is 4-6 mm.
3. The preparation method of the ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material, which is disclosed by claim 2, comprises the following steps:
(1) uniformly mixing 5-15 mg of calcined white ZnO double-shell hollow-structure microsphere sensitive material powder in the claim 1 with 0.1mL of mixed solvent of absolute ethyl alcohol and deionized water to form slurry, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1; then dipping the slurry by a brush and coating the slurry on Al2O3The outer surface of the ceramic tube substrate and two parallel, annular and mutually-separated gold electrodes are provided, and the thickness of the nano sensitive material is 15-30 mu m;
(2) coated Al2O3Calcining the ceramic tube at 450-550 ℃ for 0.5-1.5 h, and then enabling a nichrome heating coil with the resistance value of 30-40 omega to penetrate through Al2O3In the ceramic tube, finally welding four platinum wire leads and two ends of a nichrome heating coil to an indirectly heated hexagonal tube seat;
(3) and (3) aging the sensor in the step (2) in an air environment at 180-220 ℃ for 6-8 days to obtain the ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material.
4. The application of the ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material in the detection of ethanol vapor in the claims 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110543850.6A CN113219010B (en) | 2021-05-19 | 2021-05-19 | Ethanol sensor of ZnO double-shell hollow-structure microsphere sensitive material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110543850.6A CN113219010B (en) | 2021-05-19 | 2021-05-19 | Ethanol sensor of ZnO double-shell hollow-structure microsphere sensitive material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113219010A true CN113219010A (en) | 2021-08-06 |
| CN113219010B CN113219010B (en) | 2024-08-16 |
Family
ID=77092878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110543850.6A Active CN113219010B (en) | 2021-05-19 | 2021-05-19 | Ethanol sensor of ZnO double-shell hollow-structure microsphere sensitive material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113219010B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113916946A (en) * | 2021-10-09 | 2022-01-11 | 吉林大学 | N-amyl alcohol gas sensor based on ZnO nano sensitive material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105551811A (en) * | 2016-01-18 | 2016-05-04 | 吉林大学 | SnO2 and TiO2 coated porous Ag@C nanosphere with hierarchical structure, and preparation method and application of nanosphere |
| CN106896142A (en) * | 2017-04-26 | 2017-06-27 | 吉林大学 | Acetone sensor, the preparation method and applications of the Ce doped In_2O_3 nano sensitive materials based on graded structure |
| CN108169291A (en) * | 2017-12-18 | 2018-06-15 | 吉林大学 | The ethanol sensor of Zn doping CdS nano sensitive materials based on graded structure, preparation method and applications |
| CN108918617A (en) * | 2018-07-31 | 2018-11-30 | 济南大学 | A kind of preparation method and application of the optical electro-chemistry beta-amyloid protein sensor based on multi-stage nano ZnO microsphere composite material |
| CN109709192A (en) * | 2018-12-14 | 2019-05-03 | 复旦大学 | It is a kind of based on tungsten oxide/tin oxide core-shell nano chip architecture air-sensitive nano material, preparation process and its application |
| CN110606504A (en) * | 2019-10-17 | 2019-12-24 | 武汉工程大学 | Hierarchical nuclear shell SnO2Microsphere and preparation method and application thereof |
| CN111812163A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
-
2021
- 2021-05-19 CN CN202110543850.6A patent/CN113219010B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105551811A (en) * | 2016-01-18 | 2016-05-04 | 吉林大学 | SnO2 and TiO2 coated porous Ag@C nanosphere with hierarchical structure, and preparation method and application of nanosphere |
| CN106896142A (en) * | 2017-04-26 | 2017-06-27 | 吉林大学 | Acetone sensor, the preparation method and applications of the Ce doped In_2O_3 nano sensitive materials based on graded structure |
| CN108169291A (en) * | 2017-12-18 | 2018-06-15 | 吉林大学 | The ethanol sensor of Zn doping CdS nano sensitive materials based on graded structure, preparation method and applications |
| CN108918617A (en) * | 2018-07-31 | 2018-11-30 | 济南大学 | A kind of preparation method and application of the optical electro-chemistry beta-amyloid protein sensor based on multi-stage nano ZnO microsphere composite material |
| CN109709192A (en) * | 2018-12-14 | 2019-05-03 | 复旦大学 | It is a kind of based on tungsten oxide/tin oxide core-shell nano chip architecture air-sensitive nano material, preparation process and its application |
| CN110606504A (en) * | 2019-10-17 | 2019-12-24 | 武汉工程大学 | Hierarchical nuclear shell SnO2Microsphere and preparation method and application thereof |
| CN111812163A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Semiconductor resistor type ethanol gas sensor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李雪伟: "ZｎＯ纳微分级结构的形貌调控及其气敏性能", 微纳电子技术, vol. 56, no. 12, 31 December 2019 (2019-12-31), pages 978 - 983 * |
| 梅超: "ZnO微纳结构的光电应用及界面研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), 15 January 2018 (2018-01-15), pages 21 - 22 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113916946A (en) * | 2021-10-09 | 2022-01-11 | 吉林大学 | N-amyl alcohol gas sensor based on ZnO nano sensitive material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113219010B (en) | 2024-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Enhanced performance of the tangerines-like CuO-based gas sensor using ZnO nanowire arrays | |
| CN113189153A (en) | Ethanol sensor based on ZnO porous nanosheet microsphere sensitive material, preparation method and application thereof | |
| CN106896142A (en) | Acetone sensor, the preparation method and applications of the Ce doped In_2O_3 nano sensitive materials based on graded structure | |
| CN108872325A (en) | One kind being based on SnSe2/SnO2Nitrogen dioxide gas sensor, preparation process and the application of hetero-junctions | |
| CN108254416A (en) | Meso-hole structure In is supported based on Au2O3The NO of nano sensitive material2Sensor, preparation method and applications | |
| CN109678214B (en) | Acetone-sensitive cobaltosic oxide/indium oxide nanotube composite film | |
| CN107364897A (en) | A kind of preparation method of ferrous acid zinc nano material | |
| CN107607591B (en) | SnO 2 -modified NiO nano-structure sensitive material-based ultra-sensitive toluene gas sensor and preparation method thereof | |
| CN104990961A (en) | Ethanol gas sensor based on Al-doped NiO nano rod-flower material and preparation method thereof | |
| Meng et al. | Synthesis of Au nanoparticle-modified spindle shaped α-Fe 2 O 3 nanorods and their gas sensing properties to N-butanol | |
| CN110455891B (en) | Based on CoWO4-Co3O4Dimethyl benzene gas sensor of heterojunction nano structure sensitive material and preparation method thereof | |
| CN111060560B (en) | Ru-WO3 nano material and preparation method and application thereof | |
| CN102012386A (en) | Preparation method of nitric oxide gas sensor element based on pseudodirected tungsten trioxide nano tape | |
| CN110398520A (en) | A kind of Pr doping In2O3The preparation method of gas-sensitive nano material | |
| CN108398464A (en) | A kind of H2S sensors and preparation method thereof based on hollow spherical structure La doped indium oxide nano sensitive materials | |
| CN111830089A (en) | Based on two shell shape Cu2N-propanol gas sensor of O-grade structure micron sphere sensitive material and preparation method thereof | |
| CN113219010A (en) | Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation | |
| CN113433174A (en) | Ethanol sensor based on ZnO porous structure microsphere sensitive material, preparation method and application thereof | |
| CN110068597A (en) | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof | |
| CN109470744B (en) | Acetone sensor based on composite sensitive material, preparation method and application thereof | |
| CN115015328B (en) | N-amyl alcohol gas sensor based on PtAu alloy nanocrystalline modified flower-shaped WO3 sensitive material and preparation method thereof | |
| CN113514506A (en) | Based on porous LaFeO3Acetone gas sensor of microsphere nano sensitive material and preparation method thereof | |
| CN110736770B (en) | N-GQDs modified 3DOM In2O3Composite material and preparation method and application thereof | |
| CN115856026A (en) | Gas sensor based on In2O3-ZnO porous hierarchical structure sensitive material, preparation method and application thereof | |
| He et al. | SnO2-doped α-Fe2O3 patulous microtubes for high performance formaldehyde sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |