CN105651844B - A kind of Bi2S3Base ammonia gas sensor and preparation method thereof - Google Patents

A kind of Bi2S3Base ammonia gas sensor and preparation method thereof Download PDF

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CN105651844B
CN105651844B CN201410633611.XA CN201410633611A CN105651844B CN 105651844 B CN105651844 B CN 105651844B CN 201410633611 A CN201410633611 A CN 201410633611A CN 105651844 B CN105651844 B CN 105651844B
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metal
ammonia gas
nanometer
gas sensor
substrate
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CN105651844A (en
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傅铁祥
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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Abstract

The invention discloses a kind of Bi2S3Base ammonia gas sensor and preparation method thereof.The sensor forms:Insulating substrate, a pair of metal electrodes and metal extraction wire on insulating substrate and is sprayed at gas sensitive layer on metal electrode.Gas sensitive layer is by Bi2S3Nano-particle and binder polyvinyl alcohol composition, nanometer Bi2S3By aqueous bismuth nitrate solution with hydrogen sulfide gas or sodium sulfide solution existing for ultrasonic wave under the conditions of react preparation.The sensor has good selectivity to ammonia, non-sintered, can work at room temperature.The ammonia of concentration range can be used for measuring and relate to automatically controlling for ammonia production process.

Description

A kind of Bi2S3Base ammonia gas sensor and preparation method thereof
Technical field
Bi provided by the invention2S3 Base ammonia gas sensor, is related to sensor field, and in particular, to one kind being based on nanometer Bi2S3 Ammonia gas sensor and preparation method thereof.
Background technology
Gas sensor is widely used in the alarm of toxic and Combustible Gas Leak, environment protection and monitoring etc.. Various gas sensors used at present are broadly divided by gas-sensitive property:Semi-conductor type, solid electrolyte type, connects electrochemistry type Touch five classes such as burning type, photochemistry type, wherein semiconductor gas sensor is aoxidized using metal oxide or metal semiconductor The element that object material is made generates adsorption or reacts, causes characterized by carrier moving when interacting with gas Conductivity or C-V characteristic or surface potential variation.Its changing value is related to the concentration of tested gas.To improve gas sensor Selectivity and sensitivity often add noble metal as catalyst in metal oxide.This kind of device fabrication is simple, at This is low.But operating temperature is high, and environment influences its measurement bigger.
Ammonia is a kind of unpleasant toxic gas, and the oral cavity and respiratory tract to humans and animals have stronger irritation and corruption Corrosion, high concentration ammonia even meeting causing death, can make the health of humans and animals the ammonia of low concentration even if in environment At serious harm.Therefore, how ammonia in environment is quickly detected, necessary data is provided according to having for the improvement of air environment Very important realistic meaning.
However, ammonia is also important industrial chemicals, intermediate and product, output occupies very in chemical industry Big ratio.As production and requirement of the scientific research to material and product purity are higher and higher, the change for producing high quality is needed Chemical product.This just needs to carry out very accurate automatically control to production process.It is automatically controlled to relating to the implementation of ammonia Chemical Manufacture Key is to develop the ammonia gas sensor for having high sensitivity, selectivity good ammonia in raw material or product.This sensor energy It is electric signal by ammonia concentration change transitions in raw material or product, is conveyed to control device, to is realized to relating to ammonia Chemical Manufacture It automatically controls.Since the ammonia concentration in Chemical Manufacture is higher, mostly in concentration range, therefore, it is necessary to it is a kind of can be to this One concentration range ammonia generates the gas sensor of response.Currently, this kind of ammonia gas sensor extremely lacks.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of based on nanometer Bi2S3 Ammonia gas sensor And preparation method thereof.
Nanometer Bi provided by the present invention2S3 Ammonia gas sensor is drawn by insulating substrate, a pair of metal electrodes, metal successively Conducting wire and nanometer Bi2S3Material layer forms, wherein nanometer Bi2S3Material layer includes polyvinyl alcohol adhesive.
The insulating substrate includes aluminum oxide ceramic substrate, SiO 2-ceramic substrate, glass substrate, phenoplasts Substrate/or bakelite substrate.
The metal electrode is that the interdigital electrode made by any one, the distance between two electrodes are by Pt metal and Au 1mm。
The metal lead-outs are made of any one of Pt metal and Au.
The nanometer Bi2S3The diameter of nano particles of material layer is 20-160 nm;Nanometer Bi2S3The thickness of material layer is 5 -50 μm。
The nanometer Bi2S3The detailed preparation method of ammonia gas sensor, including below step.
1)Prepare Bi2S3Nano-particle, under the ultrasonic wave of 40KHz, by Bi (NO3)3Aqueous solution and H2S gases or Na2S is molten Any one reaction of liquid, reaction temperature are room temperature to 50 DEG C of ranges, Bi (NO3)3Molar ratio with sulfide is 1:1, reaction End is centrifugally separating to obtain brownish black precipitation, is washed with distilled water, is dried to obtain Bi2S3Nano-particle.
2)By step 1)The Bi of preparation2S3Nano-particle and 0.1% polyvinyl alcohol, grind 2 hours, be made after dilution Slurry.
3) Au slurries or Pt slurries are coated on insulating substrate and interdigital electrode is made, welding metal lead-out wire after drying.
4)By step 2)The slurry of preparation is with being prepared into a nanometer Bi on electronic spray gun spraying to metal electrode and substrate2S3Material The bed of material, then drying obtain sensor element.
Advantageous effect:Nanometer Bi provided by the invention2S3Ammonia gas sensor has responsiveness high, and selectivity is good, responds and extensive It is multiple fast, it makes simply, need not be sintered, work under room temperature, the low and at low cost advantage of energy consumption.
Description of the drawings
Fig. 1 is Bi prepared by embodiment 12S3Nano-particle stereoscan photograph.
Fig. 2 is nanometer Bi prepared by embodiment 12S3The responsiveness of ammonia gas sensor is with ammonia concentration change curve.
Specific implementation mode
The present invention is described in further detail below by specific embodiment, but the present invention is not limited thereto.
Embodiment one.
1)Weigh the Bi (NO of 9.7 grams (0.02 mole)3)3•5H2O is put into 300mL beakers, and 20 milliliters of dilute nitre are added Acid dissolving, is then diluted to 100 milliliters.Bi (the NO that will have been dissolved3)3Solution is heated to 50 in ultrasonic thermostatic water bath pot DEG C, ultrasonic frequency is adjusted to 40 kHz, by the Na of 0.3 mol/L of concentration under stirring2100 milliliters of S solution is added dropwise to Bi (NO3)3In solution, Bi (NO3)3With Na2The molar ratio of S is 2:3.At this point, there is a large amount of brownish black Bi2S3Precipitation generates, and waits reacting After, it is cooled to room temperature, filters, be washed with distilled water three times, the Bi that will be obtained2S3Solid is put into baking oven, is dried at 150 DEG C Four hours.
2)By step 1)The Bi of preparation2S3Nano-particle and 0.1% polyvinyl alcohol, grind 2 hours, be made after dilution Slurry.
3) aluminum oxide ceramic substrate is taken, the sodium hydroxide solution for being put into a concentration of 6 mol/L boils 20 minutes, cold But it takes out afterwards, with distilled water flushing three times, is placed in baking oven and dries.Au slurries are coated on the Al 2 O ceramic substrate cleaned On interdigital electrode is made, dry, then by the Pt wire bonds of diameter 0.1mm be connected on electrode be used as lead-out wire.
4)By step 2)The slurry of preparation is prepared on electronic spray gun spraying to Au electrodes and aluminum oxide ceramic substrate The nanometer Bi for being 5 μm at thickness2S3Then material layer obtains sensor element in 120 DEG C of drying.
Embodiment two.
1)Weigh the Bi (NO of 9.7 grams (0.02 mole)3)3•5H2O is put into 300mL beakers, and 20 milliliters of dilute nitre are added Acid dissolving, is then diluted to 100 milliliters.Bi (the NO that will have been dissolved3)3Solution is placed in ultrasonic thermostatic water bath pot, will be ultrasonic Wave frequency rate is adjusted to 40 kHz, under room temperature by the Na of 0.3 mol/L of concentration2100 milliliters of S solution is added dropwise to Bi (NO3)3 In solution, Bi (NO3)3With Na2The molar ratio of S is 2:3.At this point, there is a large amount of brownish black Bi2S3Precipitation generates, and waits for after completion of the reaction, It is cooled to room temperature, filters, be washed with distilled water three times, the Bi that will be obtained2S3Solid is put into baking oven, is dried four hours at 150 DEG C.
2)By step 1)The Bi of preparation2S3Nano-particle and 0.1% polyvinyl alcohol, grind 2 hours, be made after dilution Slurry.
3) glass substrate is taken, the sodium hydroxide solution for being put into a concentration of 6 mol/L boils 20 minutes, is taken out after cooling, With distilled water flushing three times, it is placed in baking oven and dries.Pt slurries are coated on the glass substrate cleaned, interdigital electrode is made, dried It is dry, then the Pt wire bonds of diameter 0.1mm are connected on electrode and are used as lead-out wire.
4)By step 2)The slurry of preparation is 20 with thickness is prepared on electronic spray gun spraying to Pt electrodes and glass substrate The Bi of μm nanometer2S3Then material layer obtains sensor element in 120 DEG C of drying.
Embodiment three.
1)Weigh the Bi (NO of 9.7 grams (0.02 mole)3)3•5H2O is put into 300mL ground flasks, is added 20 milliliters Then dilute nitric acid dissolution is diluted to 100 milliliters.After covering the ground glass stopper with double duct, Bi (NO will be housed3)3Solution Flask moves into ultrasonic thermostatic water bath pot and is heated to 50 DEG C, and ultrasonic frequency is adjusted to 40 kHz.By flask conduit be equipped with H2The steel cylinder of S gases connects, by 0.03 mole of H2S gas slowlies are passed into Bi (NO3)3In solution, Bi (NO3)3With H2S's Molar ratio is 2:3, tail gas imports the sodium hydroxide solution mounted in another container(A concentration of 6 mol/L)In, so that it is absorbed Fall.There are a large amount of brownish black Bi in reaction process2S3Precipitation generates, and waits for after completion of the reaction, being cooled to room temperature, and filters, and is washed with distillation It washs three times, the Bi that will be obtained2S3Solid is put into baking oven, is dried four hours at 150 DEG C.
2)By step 1)The Bi of preparation2S3Nano-particle and 0.1% polyvinyl alcohol, grind 2 hours, be made after dilution Slurry.
3) silicon dioxide substrates are taken, the sodium hydroxide solution for being put into a concentration of 6 mol/L boils 20 minutes, is taken after cooling Go out, with distilled water flushing three times, is placed in baking oven and dries.Au slurries are coated on the glass substrate cleaned, interdigital electricity is made Then the Au wire bonds of diameter 0.1mm are connected on electrode and are used as lead-out wire by pole, drying.
4)By step 2)The slurry of preparation is prepared into thickness in electronic spray gun spraying to Au electrodes and silicon dioxide substrates For 35 μm of nanometer Bi2S3Then material layer obtains sensor element in 120 DEG C of drying.
Example IV.
1)Weigh the Bi (NO of 9.7 grams (0.02 mole)3)3•5H2O is put into 300mL ground flasks, is added 20 milliliters Then dilute nitric acid dissolution is diluted to 100 milliliters.After covering the ground glass stopper with double duct, Bi (NO will be housed3)3Solution Flask moves into ultrasonic thermostatic water bath pot, and ultrasonic frequency is adjusted to 40 kHz.By flask conduit and H is housed2S gases Steel cylinder connects, by 0.03 mole of H under room temperature2S gas slowlies are passed into Bi (NO3)3In solution, Bi (NO3)3With H2Mole of S Than being 2:3.Tail gas imports the sodium hydroxide solution mounted in another container(A concentration of 6 mol/L)In, so that it is predominantly absorbed.Instead The a large amount of brownish black Bi of Ying Zhongyou2S3Precipitation generates, and waits for after completion of the reaction, being cooled to room temperature, and filters, and is washed with distilled water three times, will Obtained Bi2S3Solid is put into baking oven, is dried four hours at 150 DEG C.
2)By step 1)The Bi of preparation2S3Nano-particle and 0.1% polyvinyl alcohol, grind 2 hours, be made after dilution Slurry.
3) aluminum oxide ceramic substrate is taken, the sodium hydroxide solution for being put into a concentration of 6 mol/L boils 20 minutes, cold But it takes out afterwards, with distilled water flushing three times, is placed in baking oven and dries.Au slurries are coated on the aluminum oxide ceramic base cleaned Interdigital electrode is made on piece, drying, and then the Pt wire bonds of diameter 0.1mm are connected on electrode and are used as lead-out wire.
4)By step 2)The slurry of preparation is received with thickness is prepared on electronic spray gun spraying to Au electrodes and substrate for 50 μm The Bi of rice2S3Then material layer obtains sensor element in 120 DEG C of drying.

Claims (6)

1. a kind of ammonia gas sensor, it is characterised in that:Successively by insulating substrate, a pair of metal electrodes, metal extraction wire and Nanometer Bi2S3Material layer forms, wherein nanometer Bi2S3Material layer includes a kind of polyvinyl alcohol adhesive.
2. by ammonia gas sensor described in claim 1, it is characterised in that:The insulating substrate includes aluminum oxide ceramic Substrate, SiO 2-ceramic substrate, glass substrate, phenoplasts substrate or bakelite substrate.
3. by ammonia gas sensor described in claim 1, it is characterised in that:The metal electrode is arbitrary by Pt metal and Au Interdigital electrode made of a kind of, the distance between two electrodes are 1mm.
4. by ammonia gas sensor described in claim 1, it is characterised in that:The metal extraction wire is by Pt metal and Au Any one is made.
5. by ammonia gas sensor described in claim 1, it is characterised in that:The nanometer Bi2S3The diameter of nano particles of material layer For 20-160nm;The nanometer Bi2S3The thickness of material layer is 5-50 μm.
6. the method for preparing any one of the claim 1-5 ammonia gas sensors, including below step:
1) Bi is prepared2S3Nano-particle, under the ultrasonic wave of 40KHz, by Bi (NO3)3Aqueous solution is reacted with sulfide, the vulcanization Object is H2S gases and Na2Any one of S solution, reaction temperature are room temperature to 50 DEG C of ranges, Bi (NO3)3With rubbing for sulfide You are than being 2:3, reaction terminates, and filters, and obtains brownish black precipitation, is washed with distilled water, is dried to obtain Bi2S3Nano-particle;
2) Bi for preparing step 1)2S3Nano-particle is mixed with binder, grinds 2 hours, slurry is made after dilution;
3) Au slurries or Pt slurries are coated on insulating substrate, welding metal extraction wire after drying;
4) slurry for preparing step 2) is with being prepared into a nanometer Bi on electronic spray gun spraying to metal electrode and substrate2S3Material layer, Then drying obtains sensor element.
CN201410633611.XA 2014-11-12 2014-11-12 A kind of Bi2S3Base ammonia gas sensor and preparation method thereof Expired - Fee Related CN105651844B (en)

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EP0398286A2 (en) * 1989-05-18 1990-11-22 Nisshinbo Industries, Inc. Ammonia sensor
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JP2010038806A (en) * 2008-08-07 2010-02-18 Ngk Spark Plug Co Ltd Multi-gas sensor and gas sensor controller
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EP0398286A2 (en) * 1989-05-18 1990-11-22 Nisshinbo Industries, Inc. Ammonia sensor
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JP2010038806A (en) * 2008-08-07 2010-02-18 Ngk Spark Plug Co Ltd Multi-gas sensor and gas sensor controller
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CN102636522A (en) * 2012-03-29 2012-08-15 浙江大学 Graphene/ stannic oxide nanometer compounding resistance type film gas sensor and manufacturing method thereof
CN102978578A (en) * 2012-08-28 2013-03-20 河北工业大学 Copper oxide doped tin dioxide base ammonia gas sensitive sensor manufacturing method
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