CN105651813A

CN105651813A - Novel aniline gas sensor and preparation method thereof

Info

Publication number: CN105651813A
Application number: CN201410633403.XA
Authority: CN
Inventors: 傅铁祥
Original assignee: Changsha University of Science and Technology
Current assignee: Changsha University of Science and Technology
Priority date: 2014-11-12
Filing date: 2014-11-12
Publication date: 2016-06-08
Anticipated expiration: 2034-11-12
Also published as: CN105651813B

Abstract

The present invention discloses a novel aniline gas sensor and a preparation method thereof. The sensor comprises an insulating ceramic substrate, a pair of metal electrodes arranged on the insulating ceramic substrate, metal leading-out conducting wires, and a nickel dimethylglyoxime nanometer material layer sprayed on the metal electrodes, wherein a NiCl2 aqueous solution and a dimethylglyoxime ethanol solution are subjected to a reaction at a temperature of from a room temperature to 50 DEG C in the presence of ultrasonic waves so as to prepare the nickel dimethylglyoxime nanometer material. According to the present invention, the sensor has advantages of good aniline response, rapid response, rapid recovery, being free of sintering, and stable performance, can work at a room temperature, and can be used for determination of aniline steam within a concentration range of 260-1300 ppm.

Description

A kind of novel aniline gas sensor and preparation method thereof

Technical field

The present invention relates to sensor field, in particular it relates to a kind of aniline gas sensor based on nickel chelate and preparation method thereof.

Background technology

The core of gas detecting system is gas sensor, and it is typically mounted in detecting head. The essence of gas sensor is a kind of certain gas concentration signal to convert the transducer becoming the electricity of certain relation to export with it to. Its operation principle is usually gas molecule and occurs adsorption and desorption, catalysis burning, oxidoreduction etc. to interact with gas sensitive surface, the electrochemical properties making material changes, under additional circuit, by the measurement of electric current, change in voltage in circuit, it is achieved gas detecting. Gas sensor is mainly used in poisonous, flammable, the Leak Detection of explosion hazard gases and warning, it is prevented that because the leakage of these gas causes fire, blast and intoxication accident. At present, what employ up to is metal-oxide semiconductor (MOS) gas sensor, and its advantage is that detection limit is low, and the Monitoring lower-cut concentration of some this kind of gas sensor reaches ppb level. The shortcoming of this kind of gas sensor is that operating temperature is high, and energy consumption is big and poor selectivity. Gas sensor based on metallo-chelate is few, mainly using metal phthalein mountain valley with clumps of trees and bamboo macrocyclic complex as sensitive material.

Aniline is important industrial chemicals, is mainly used in medicine and thiofide, is also the raw material manufacturing resin and coating. Aniline to blood and neural toxicity strongly, The book of Changes skin absorption. Mainly cause methemoglobinemia, hemolytic anemia regulating liver-QI, renal damage. Acute poisoning: patient's lip, finger tip, auricle cyanosis, has headache, dizziness, Nausea and vomiting, numb, the absentminded of finger etc.; During severe intoxication, skin, mucosa are seriously livid purple, dyspnea, twitch, even go into a coma, shock. Additionally, aniline is also inflammable, explosive with the mixture of air, explosion limit is 1.3% ~ 11.0%. Development can detect the gas sensor of aniline in the environment quickly and accurately, provides necessary data to have very important realistic meaning for administering air ambient. At present, it is possible to the gas sensor of detection aniline is little.

Ultrasound wave has the effect of uniqueness in preparing inorganic nano material, sonochemistry method has become preparation and has had a kind of useful technology of property new material, the specific physical that acoustic cavitation causes, chemical environment provides important approach for preparation nano material, preparation method mainly has, ultrasonic atomizatio decomposition method, metallorganic ultrasonic decomposition method, chemical precipitation method harmony electrochemical process etc., gradually formed new science-sonochemistry that goalkeeper's ultrasonic technology is combined closely with chemistry.

Summary of the invention

It is an object of the invention to provide a kind of method adopting ultrasonic technology to prepare nickel dimethylglyoximate nano material and a kind of novel aniline gas sensor based on nickel dimethylglyoximate nano material.

Aniline gas sensor provided by the present invention is made up of insulating substrate, pair of metal electrodes, metal extraction wire and nickel dimethylglyoximate layer of nanomaterial successively, and wherein nickel dimethylglyoximate layer of nanomaterial includes polyvinyl alcohol adhesive.

Described insulating substrate is aluminum oxide ceramic square substrate.

Described metal electrode is the interdigital electrode made by metal Au, and the distance between two electrodes is 1mm.

Described metal lead-outs is made up of Pt metal silk.

The diameter of nano particles of described nickel dimethylglyoximate layer of nanomaterial is 80-200nm; The thickness of described nickel dimethylglyoximate layer of nanomaterial is 50-120 ��m.

The described detailed preparation method of aniline gas sensor, including below step.

1) prepare diacetyldioxime nickel nano particle, under the ultrasound wave of 30KHz, diacetyldioxime alcoholic solution is added dropwise over NiCl₂In aqueous solution, reaction temperature is room temperature to 50 DEG C of scopes, NiCl₂It is 2:1 with the mol ratio of diacetyldioxime, treats that it reacts completely, sucking filtration, obtain cerise precipitation, precipitate 3 times with distilled water wash, the nickel dimethylglyoximate solid obtained is put into baking oven, dry 4 hours at 115 DEG C.

2) diacetyldioxime nickel nano particle step 1) prepared and polyvinyl alcohol, grind 1-2 hour, make slurry after dilution.

3) insulating substrate after Au slurry being coated on cleaning makes interdigital electrode, after drying, welds metal lead-outs.

4) by step 2) the slurry electronic spray gun spraying to metal electrode prepared prepares into nickel dimethylglyoximate layer of nanomaterial with on insulating substrate, and then dry and obtain sensor element.

Beneficial effect: aniline gas sensor provided by the invention has response and recovers fast, stable performance makes simple, it is not necessary to sintering, the advantage of room temperature operation.

Accompanying drawing explanation

Fig. 1 is the responsiveness that described aniline gas sensor is exposed to a series of inorganic gas and volatile organic compounds.

Fig. 2 is that the responsiveness of the aniline gas sensor of embodiment 1 preparation is with concentration of aniline change curve.

Detailed description of the invention

Below by specific embodiment, the present invention is described in further detail, but the invention is not limited in this.

Embodiment 1.

1) weigh 2.32 grams of (0.02 mole) diacetyldioximes, put in 250 ml beakers, add 100 milliliters of ethanol dissolvings and make diacetyldioxime alcoholic solution. Separately take 2.37 grams of (0.01 mole) NiCl₂��6H₂O, puts in 250 ml beakers, adds 100 ml distilled waters dissolving solutions and makes NiCl₂Aqueous solution, will fill NiCl₂The beaker of aqueous solution is put in ultrasonic thermostatic water bath pot, and heating, to 50 DEG C, is adjusted ultrasonic frequency to 30KHz, diacetyldioxime alcoholic solution is added dropwise over NiCl₂In aqueous solution, diacetyldioxime and NiCl₂Mol ratio be 2:1. Treat that it reacts completely, be cooled to room temperature, sucking filtration, obtain cerise precipitation. Precipitate 3 times with distilled water wash, the nickel dimethylglyoximate solid obtained is put into baking oven, dry 4 hours at 115 DEG C.

2) dry nickel dimethylglyoximate step 1) prepared and the polyvinyl alcohol of 0.05%, grind 2 hours, make slurry after dilution.

3) take aluminum oxide ceramic square substrate, put into the sodium hydroxide solution that concentration is 6 mol/L and boil 15 minutes, take out after cooling, with distilled water flushing three times, be placed in baking oven and dry.Au slurry is coated on cleaned Al 2 O ceramic substrate and makes interdigital electrode, dries, then the Pt wire bond of diameter 0.1mm is received on electrode as lead-out wire.

4) by step 2) the electronic spray gun spraying of slurry prepared prepares into, on Au electrode and aluminum oxide ceramic substrate, the nickel dimethylglyoximate layer of nanomaterial that thickness is 50 ��m, obtains sensor element 115 DEG C of drying.

Embodiment 2.

1) weigh 2.32 grams of (0.02 mole) diacetyldioximes, put in 250 ml beakers, add 100 milliliters of ethanol dissolvings and make diacetyldioxime alcoholic solution. Separately take 2.37 grams of (0.01 mole) NiCl₂��6H₂O, puts in 250 ml beakers, adds 100 ml distilled waters dissolving solutions and makes NiCl₂Aqueous solution, will fill NiCl₂The beaker of aqueous solution is put in ultrasonic thermostatic water bath pot, adjusts ultrasonic frequency to 30KHz, at room temperature diacetyldioxime alcoholic solution is added dropwise over NiCl₂In aqueous solution, diacetyldioxime and NiCl₂Mol ratio be 2:1. Treat that it reacts completely, sucking filtration, obtain cerise precipitation. Precipitate 3 times with distilled water wash, the nickel dimethylglyoximate solid obtained is put into baking oven, dry 4 hours at 115 DEG C.

2) diacetyldioxime nickel nano particle step 1) prepared and the polyvinyl alcohol of 0.1%, grind 1 hour, make slurry after dilution.

3) take aluminum oxide ceramic square substrate, put into the sodium hydroxide solution that concentration is 6 mol/L and boil 10 minutes, take out after cooling, with distilled water flushing three times, be placed in baking oven and dry. Au slurry is coated on cleaned aluminum oxide ceramic substrate and makes interdigital electrode, dries, then the Pt wire bond of diameter 0.1mm is received on electrode as lead-out wire.

4) by step 2) the electronic spray gun spraying of slurry prepared prepares into, on Pt electrode and aluminum oxide ceramic substrate, the nickel dimethylglyoximate layer of nanomaterial that thickness is 120 ��m, obtains sensor element 105 DEG C of drying.

Claims

1. a novel aniline gas sensor, it is characterised in that: being made up of insulating ceramics substrate, pair of metal electrodes, metal extraction wire and nickel chelate material layer successively, wherein nickel chelate material layer includes a kind of polyvinyl alcohol adhesive.

2. the aniline gas sensor described in claim 1, it is characterised in that: described nickel chelate material layer is nickel dimethylglyoximate nano material.

3. the aniline gas sensor described in claim 1, it is characterised in that: described insulating ceramics substrate is aluminium sesquioxide square insulating ceramic substrate.

4. the aniline gas sensor described in claim 1, it is characterised in that: the interdigital electrode that described metal electrode is made up of metal Au, the distance between two electrodes is 1mm.

5. the aniline gas sensor described in claim 1, it is characterised in that: described metal lead-outs is Pt metal silk.

6. the aniline gas sensor described in claim 1, it is characterised in that: the diameter of nano particles of described nickel dimethylglyoximate layer of nanomaterial is 80-200nm; The thickness of described nickel dimethylglyoximate layer of nanomaterial is 50-120 ��m.

7. the preparation method of aniline gas sensor according to any one of preparation claim 1-5, including below step:

1) prepare diacetyldioxime nickel nano particle, under the ultrasound wave of 30KHz, diacetyldioxime alcoholic solution is added dropwise over NiCl₂In aqueous solution, reaction temperature is room temperature to 50 DEG C of scopes, diacetyldioxime and NiCl₂Mol ratio be 2:1, treat that it reacts completely, sucking filtration, obtain cerise precipitation, with distilled water wash precipitate 3 times, the nickel dimethylglyoximate solid obtained is put into baking oven, 115 DEG C dry 4 hours;

2) diacetyldioxime nickel nano particle step 1) prepared mixes with binding agent, grinds 1-2 hour, makes slurry after dilution;

3) Au slurry is coated on the insulating ceramics substrate after cleaning, after drying, welds metal lead-outs;

4) by step 2) the electronic spray gun spraying of slurry prepared prepares into nickel dimethylglyoximate layer of nanomaterial on metal electrode with insulating ceramics substrate, and then 105-115 DEG C of drying obtains sensor element.