CN108445060A - A kind of preparation method of the sensor electrode of detection formaldehyde in air content - Google Patents
A kind of preparation method of the sensor electrode of detection formaldehyde in air content Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the sensor electrode of detection formaldehyde in air content, it is characterized in that, catalyst used in electrode is superconduction carbon carrying tin oxide copper oxide zinc oxide Co catalysts, base material is sulfonated polyether sulfone compound ions exchange membrane, electrode of the present invention has high sensitivity for measuring formaldehyde on sensor, and detection range is wide, and accuracy is high, it is linear good, selectivity and the good feature of stability.
Description
Technical field
The present invention relates to sensor field more particularly to a kind of electrochemistry formaldehyde sensings of the content of detection formaldehyde in air
The preparation method of device electrode.
Background technology
Under room temperature, formaldehyde is a kind of colourless readily soluble irritative gas, can be absorbed through respiratory tract, can be with biological cell albumen
Matter combines, and is a kind of very strong protoplasm material of toxicity, by international cancer, research institute is classified as one of carcinogen, occupies hypertoxicity
The second of substance control.Formaldehyde is a kind of plasm poisonous substance destroying biological cell protein, at typical condition, pure formaldehyde
Be a kind of colourless gas with stinkpot, the skin, respiratory tract and internal organ of people can be damaged, the extent of injury with
Its aerial concentration and the length of time of contact are closely related.Formaldehyde also has teratogenesis, carcinogenesis, Long Term Contact formaldehyde
People, the probability for suffering from nasal cavity, oral cavity, nasopharynx, throat, skin and alimentary tract cancer are higher than common people, mankind's Long Term Contact low amounts
Formaldehyde can cause chronic respiratory disease, feminine menstrual disorder, pregnancy syndrome, cause the reduction of newborn's constitution, chromosome
It is abnormal, or even cause nasopharyngeal carcinoma, the formaldehyde of high concentration is all toxic to nervous system, immune system, liver etc..
It causes to have a headache when 0.01 ~ 3.1 mg/m3, i.e. 0.008 ~ 2ppm, dizzy, insomnia；
When 0.06 ~ 0.07 mg/m3, i.e. 0.05 ~ 0.06ppm, asthma occurs for children；
It can cause liver function, abnormal pulmonary function, immune system abnormality when 0.12 ~ 1.2 mglm3, i.e. 0.1 ~ 1ppm.China is public
Place sanitary standard provides that the maximum concentration acceptable concentration of formaldehyde in air is the sanitary standard of formaldehyde in 0.1 ppm indoor airs
0.08ppm。
The main source of formaldehyde is:
The source of formaldehyde is mainly oil, coal, the burning of natural gas etc., oil ageing decomposition, automobile row in outdoor air
It puts, atmospheric photochemical reaction and some production formaldehyde, arteries and veins urea formaldehyde, chemical fibre, dyestuff, rubber product, plastics, ink,
Spray painting, the factory of coating etc..
Indoor formaldehyde is mainly derived from some construction materials, furniture, various adhesive coatings, synthesis fabric etc..Such as
Various wood-based plates, carpet synthetic, cleaning agent and cosmetics etc..
Studies have shown that the formaldehyde contained in finishing and furniture, acquisition time is up to 3 ~ 15 years, is created into China and is not fitted up
And in the house of finishing soon, the recall rate of formaldehyde is 100%, and formaldehyde is caused to become generally acknowledged " house ornamentation leading killer ".
Concentration of formaldehyde test mostly uses impingement in indoor environment and air of workplace, that is, utilizes sampling pump to extract
The air sample of certain volume passes through formaldehyde absorption bottle, carries out quantitative analysis with chemical colorimetric after going back to laboratory or uses gas-chromatography
It is analyzed, can also be directly detected at the scene.This method needs professional, professional equipment to carry out analysis test, and
It takes relatively long, it is costly, be not suitable for ordinary people family and use.
Existing methylene oxide detecting instrument, lowest detection 10ppm, and SO in by air2、H2S、NH3, NO etc. examines its content
Survey has a great impact, and is influenced by temperature and humidity also larger, and sensor activation substance used is mainly platinum, Jin Denggui
Heavy metal, cost are very high.
Therefore, exploitation is a kind of having high accuracy, highly sensitive, highly selective and low-cost for detecting formaldehyde
Sensor it is urgently to be resolved hurrily.
Invention content
To solve accuracy present in existing formaldehyde examination technology, sensitivity, low, the high technology of cost of manufacture of selectivity
Problem provides a kind of production method for detecting the sensor of content of formaldehyde, and prepared sensor can be sensitive, accurate
Measure the content of formaldehyde, and low manufacture cost.
To reach above-mentioned technical purpose, it is achieved by following technical solution：
A kind of preparation method of the sensor electrode of the content of detection formaldehyde in air, catalyst used in electrode is superconduction carbon
Carrying tin oxide-copper oxide-zinc oxide-cobalt oxide catalyst, base material are sulfonated polyether sulfone compound ions exchange membrane, are prepared
Process includes step in detail below：
Step 1, it weighs in putty powder, copper nitrate, zinc nitrate, cobalt oxide powder to unified beaker, then weighs excessive oxalic acid
It is added in beaker；It is then transferred to ball milling in ball mill, it is dry at 100 ~ 130 DEG C after taking-up, 10 ~ 12h is ground, for use；
Step 2, the superconduction carbon of the product and phase homogenous quantities in step 1 is weighed in beaker, the Strong oxdiative sodium instilled into beaker
Solution stirs evenly, and is put into water-bath, is taken out after colloid in beaker is dried；
Step 3, the catalyst powder that step 2 is taken out is moved in pottery, middle heat preservation under the conditions of 700 ~ 800 DEG C of Muffle furnace
4 ~ 6h takes out after cooling, is transferred to ball milling in ball mill, and taking-up is put in crucible, and the Nafion of addition 1 ~ 5% is molten thereto
Liquid is stirred until homogeneous, and catalyst material has just been made, and the catalyst is uniformly then applied to waterproof ventilated membrane with weighing scoop
On；
Step 4, processed sulfonated polyether sulfone compound ions exchange membrane is put into the beaker of deionized water, is put into water-bath
Middle heat preservation, is then pulled out, for use；
Step 5, the reference electrode of the waterproof ventilated membrane for being coated with catalyst and use same procedure making in step 3 and to electricity
Pole is attached to hot pressing on the sulfonated polyether sulfone compound ions exchange membrane formed after step 3, and the waterproof for being sprayed with catalyst is saturating
Air film is attached to the both sides of sulfonated polyether sulfone compound ions exchange membrane respectively, and side pastes one, and the other side pastes two, hot pressing rear chamber
Temperature is lower to place, and electrochemistry formaldehyde gas sensor electrode has just been made in this way.
Preferably, the putty powder in step 1, copper nitrate, zinc nitrate, cobalt oxide powder mass ratio be 1 ~ 3:4~6:8~9:
0.1~0.8。
Preferably, a concentration of 1 ~ 5g/ml of the sodium hydroxide solution in step 2, addition are 50 ~ 60ml/g catalyst；
The temperature of water-bath is 90 ~ 100 DEG C.
Preferably, the processed sulfonated polyether sulfone compound ions exchange membrane of step 4, described processing are to sulfonated polyether
Sulphones amberplex is pre-processed, and sulfonated polyether sulfone compound ions exchange membrane is first placed into the 3 ~ 5% of boiling
H2O20.5 ~ 1h is handled in solution under the conditions of 80 DEG C；Then it is small in 80 DEG C of 0.5 ~ 1M sulfuric acid 0.5 ~ 1 that it is dipped in temperature again
When, it is put into deionized water after the remaining acid solution of film surface is rinsed out with deionized water, then for use.
Preferably, the sulfonated polyether sulfone compound ions exchange membrane, includes the raw material of following parts by weight:Sulfonated polyether sulfone
60 ~ 80 parts of compound；1 ~ 10 part of thiophene-based ionic liquid；10 ~ 30 parts of casting solution；
Preferably, the sulfonated polyether sulphones are prepared by the following method：3,3 '-sodium disulfonates -4,4 '-dichloro two
18 ~ 20g of benzene sulfone, 4,4,5 ~ 15g of-dichloro disulfide, 3,3 ' -10 ~ 15g of diamino -4,4'- dichloro diphenyl sulfone, 3,3'
10 ~ 15g of 5,5' tetramethyl biphenyl diphenol, 16 ~ 20g of natrium carbonicum calcinatum, 200 ~ 250mL N,N-dimethylformamides, 150 ~
200mL dichlorotoleune mixes, and is heated to 200 ~ 210 DEG C of reflux water-dividings 2 ~ 3 hours.Dichlorotoleune is distilled off, by reaction temperature
It is kept for 200 ~ 210 DEG C, reacted 30 ~ 40 hours.Stop heating and stirring, cooled to room temperature.Reaction solution is slowly poured into 2 ~ 3L
In deionized water, white fibrous polymer is obtained, 4 ~ 6L deionized waters impregnate 6 ~ 8 hours under the conditions of 80 DEG C, in triplicate,
Filtering, drying, then be dried in vacuo 20 ~ 30 hours at 110 ~ 120 DEG C, obtain light yellow fibrous shaped polymer.
Preferably, the preparation method of the sulfonated polyether sulfone compound ions exchange membrane, including following preparation process：
A. sulfonated polyether sulphones are dissolved in casting solution, are configured to the system that mass percent concentration is 5.0%-35.0%
Film liquid；
B. thiophene-based ionic liquid is added in the preparation liquid obtained by step A, at 85 DEG C ~ 95 DEG C, is stirred under inert atmosphere protection
The h of 10h ~ 24, are cooled to room temperature, and filter and remove insoluble matter, dry to get to thiophene-based ionic liquid doped sulfonated polyether sulfone
Close object ion exchange membrane material；
C. by step B gained ion exchange membrane materials through being cast or suppressing film forming, then the solvent flashing at 40 DEG C ~ 90 DEG C, obtains
To wet film；Again by gained wet film at 50 DEG C ~ 100 DEG C 2 ~ 24 h of freeze-day with constant temperature；Or first 10h ~ 12 dry at 50 DEG C ~ 70 DEG C
H, then 70 DEG C ~ 120 DEG C dry 4h ~ 10h are warming up to, obtain thiophene-based ionic liquid doped sulfonated polyethers sulphones proton exchange
Film.
Preferably, the thiophene-based ionic liquid is entitled：Thiophane class ionic liquid or S- alkylthrophene class ionic liquids
Body.
Preferably, casting solution used is：Amyl formate, amyl acetate, dimethylbenzene, one kind of trichloro ethylene benzene or one
Kind or more.
Preferably, casting solution used is：Dimethylbenzene.
Advantageous effect：
Electrode of the present invention has high sensitivity for measuring formaldehyde on sensor, and detection range is wide, and accuracy is high, linear good,
Selectivity and stability are good.
Description of the drawings
The linear graph of the electrode detection formaldehyde gas concentration of Fig. 1 embodiments 2.
Specific embodiment
A kind of preparation method of the sensor electrode of the content of detection formaldehyde in air of embodiment 1
A kind of preparation method of the sensor electrode of the content of detection formaldehyde in air, catalyst used in electrode is superconduction carbon
Carrying tin oxide-copper oxide-zinc oxide-cobalt oxide catalyst, base material are sulfonated polyether sulfone compound ions exchange membrane, are prepared
Process includes step in detail below：
Step 1, it weighs in putty powder, copper nitrate, zinc nitrate, cobalt oxide powder to unified beaker, then weighs excessive oxalic acid
It is added in beaker；It is then transferred to ball milling in ball mill, it is dry at 100 DEG C after taking-up, 10 ~ 12h is ground, for use；
Step 2, the superconduction carbon of the product and phase homogenous quantities in step 1 is weighed in beaker, the Strong oxdiative sodium instilled into beaker
Solution stirs evenly, and is put into water-bath, is taken out after colloid in beaker is dried；
Step 3, the catalyst powder that step 2 is taken out is moved in pottery, middle heat preservation 4h under the conditions of 700 DEG C of Muffle furnace,
It takes out after cooling, is transferred to ball milling in ball mill, taking-up is put in crucible, and 1% Nafion solution, stirring are added thereto
To uniform, catalyst material is just made, then the catalyst has uniformly been applied on waterproof ventilated membrane with weighing scoop；
Step 4, processed sulfonated polyether sulfone compound ions exchange membrane is put into the beaker of deionized water, is put into water-bath
Middle heat preservation, is then pulled out, for use；
Step 5, the reference electrode of the waterproof ventilated membrane for being coated with catalyst and use same procedure making in step 3 and to electricity
Pole is attached to hot pressing on the sulfonated polyether sulfone compound ions exchange membrane formed after step 3, and the waterproof for being sprayed with catalyst is saturating
Air film is attached to the both sides of sulfonated polyether sulfone compound ions exchange membrane respectively, and side pastes one, and the other side pastes two, hot pressing rear chamber
Temperature is lower to place, and electrochemistry formaldehyde gas sensor electrode has just been made in this way.
The mass ratio of putty powder, copper nitrate, zinc nitrate, cobalt oxide powder in step 1 is 1:4:8:0.1.
A concentration of 1g/ml of sodium hydroxide solution in step 2, addition are 50ml/g catalyst；The temperature of water-bath
It is 90 DEG C.
The processed sulfonated polyether sulfone compound ions exchange membrane of step 4, described processing are to sulfonated polyether sulfone chemical combination
Object amberplex is pre-processed, and sulfonated polyether sulfone compound ions exchange membrane is first placed into 3% H of boiling2O2Solution
In handle 0.5h under the conditions of 80 DEG C；Then it is dipped in the 0.5M sulfuric acid that temperature is 80 DEG C 0.5 hour, is rushed with deionized water again
It is put into deionized water after washing off the remaining acid solution of film surface, then for use.
The sulfonated polyether sulfone compound ions exchange membrane, includes the raw material of following parts by weight:Sulfonated polyether sulphones
60 parts；1 part of thiophene-based ionic liquid；10 parts of casting solution；
The sulfonated polyether sulphones are prepared by the following method：3,3 '-sodium disulfonates -4,4 '-dichloro diphenyl sulfone
18g, 4,4,-dichloro disulfide 5g, 3,3 '-diamino -4,4'- dichloro diphenyl sulfone 10g, 3,3'5,5' tetramethyl biphenyls
Diphenol 10g, natrium carbonicum calcinatum 16g, 200mL n,N-Dimethylformamide, the mixing of 150mL dichlorotoleune, are heated to 200 DEG C and return
Flow point water 2 hours.Dichlorotoleune is distilled off, reaction temperature is kept for 200 DEG C, is reacted 30 hours.Stop heating and stirring, from
So it is cooled to room temperature.Reaction solution is slowly poured into 2L deionized waters, obtains white fibrous polymer, 4L deionized waters are at 80 DEG C
Under the conditions of impregnate 6 hours, in triplicate, filter, drying, then be dried in vacuo 20 hours at 110 DEG C, obtain light yellow fibrous shape
Polymer.
The preparation method of the sulfonated polyether sulfone compound ions exchange membrane, including following preparation process：
A. sulfonated polyether sulphones are dissolved in casting solution, are configured to the preparation liquid that mass percent concentration is 5.0%；
B. thiophene-based ionic liquid is added in the preparation liquid obtained by step A, at 85 DEG C, 10h is stirred under inert atmosphere protection, it is cold
But it to room temperature, filters and removes insoluble matter, it is dry to be exchanged to get to thiophene-based ionic liquid doped sulfonated polyether sulfone compound ions
Membrane material；
C. by step B gained ion exchange membrane materials through being cast or suppressing film forming, then the solvent flashing at 40 DEG C, obtains wet
Film；Again by gained wet film at 50 DEG C 2 h of freeze-day with constant temperature；Or first 10h dry at 50 DEG C, then 70 DEG C of dry 4h are warming up to,
Obtain trimetaphan class ionic liquid doped sulfonated polyethers sulphones proton exchange membrane.
The thiophene-based ionic liquid is entitled：Thiophane class ionic liquid.
Casting solution used is：Amyl formate.
With the sensor of the preparation-obtained electrode fabrication of the present embodiment, PARA FORMALDEHYDE PRILLS(91,95) is detected, 0.0001ppm ~
Within the scope of 20ppm, electric current（I, uA）With content of formaldehyde（C, ppm）Linear relationship be：I=65C+7.8（R=0.9997, n=6）.
Selectivity：SO2、H2S, noiseless to detecting.
The sensor prepared using electrode of the present invention is used for the test of formaldehyde gas response performance.Experimental condition is in room
Under the conditions of temperature, operating procedure：Cleaned air is first imported, then is directed respectively into 20ppm SO successively2Gas, 20ppmH2S gases, sensing
The response signal changing value of device is substantially zeroed, and the changing value that sensor responds when importing 2ppm formaldehyde gas is 137.8uA.
When carrying out formaldehyde examination with commercially available formaldehyde electrode sensor：Cleaned air is first imported, then is directed respectively into successively
20ppm SO2Gas and 20ppmH2S gases, response signal changing value substantially more 120 uA of sensor, when importing 2ppm first
The changing value that sensor responds when aldehyde gas is 257.8uA.
As can be seen that using commercially available formaldehyde sensor, SO2、H2S can seriously affect the detection of formaldehyde gas.
A kind of preparation method of the sensor electrode of the content of detection formaldehyde in air of embodiment 2
A kind of preparation method of the sensor electrode of the content of detection formaldehyde in air, catalyst used in electrode is superconduction carbon
Carrying tin oxide-copper oxide-zinc oxide-cobalt oxide catalyst, base material are sulfonated polyether sulfone compound ions exchange membrane, are prepared
Process includes step in detail below：
Step 1, it weighs in putty powder, copper nitrate, zinc nitrate, cobalt oxide powder to unified beaker, then weighs excessive oxalic acid
It is added in beaker；It is then transferred to ball milling in ball mill, it is dry at 120 DEG C after taking-up, 11h is ground, for use；
Step 2, the superconduction carbon of the product and phase homogenous quantities in step 1 is weighed in beaker, the Strong oxdiative sodium instilled into beaker
Solution stirs evenly, and is put into water-bath, is taken out after colloid in beaker is dried；
Step 3, the catalyst powder that step 2 is taken out is moved in pottery, middle heat preservation 5h under the conditions of 750 DEG C of Muffle furnace,
It takes out after cooling, is transferred to ball milling in ball mill, taking-up is put in crucible, and 4% Nafion solution, stirring are added thereto
To uniform, catalyst material is just made, then the catalyst has uniformly been applied on waterproof ventilated membrane with weighing scoop；
Step 4, processed sulfonated polyether sulfone compound ions exchange membrane is put into the beaker of deionized water, is put into water-bath
Middle heat preservation, is then pulled out, for use；
Step 5, the reference electrode of the waterproof ventilated membrane for being coated with catalyst and use same procedure making in step 3 and to electricity
Pole is attached to hot pressing on the sulfonated polyether sulfone compound ions exchange membrane formed after step 3, and the waterproof for being sprayed with catalyst is saturating
Air film is attached to the both sides of sulfonated polyether sulfone compound ions exchange membrane respectively, and side pastes one, and the other side pastes two, hot pressing rear chamber
Temperature is lower to place, and electrochemistry formaldehyde gas sensor electrode has just been made in this way.
Preferably, the putty powder in step 1, copper nitrate, zinc nitrate, cobalt oxide powder mass ratio be 2:5:8.5:0.5.
Preferably, a concentration of 1 ~ 5g/ml of the sodium hydroxide solution in step 2, addition are 50 ~ 60ml/g catalyst；
The temperature of water-bath is 95 DEG C.
The processed sulfonated polyether sulfone compound ions exchange membrane of step 4, described processing are to sulfonated polyether sulfone
Compound ions exchange membrane is pre-processed, and sulfonated polyether sulfone compound ions exchange membrane is first placed into 4% H of boiling2O2
In solution 0.8h is handled under the conditions of 80 DEG C；Then it is dipped in again in the 0.5M sulfuric acid that temperature is 80 DEG C 0.5 hour, uses deionization
Water is put into after rinsing out the remaining acid solution of film surface in deionized water, then for use.
The sulfonated polyether sulfone compound ions exchange membrane, includes the raw material of following parts by weight:Sulfonated polyether sulphones
70 parts；1 part of thiophene-based ionic liquid；10 parts of casting solution；
The sulfonated polyether sulphones are prepared by the following method：3,3 '-sodium disulfonates -4,4 '-dichloro diphenyl sulfone
19g, 4,4,-dichloro disulfide 10g, 3,3 '-diamino -4,4'- dichloro diphenyl sulfone 12g, 3,3'5,5' tetramethyls connection
Benzenediol 13g, natrium carbonicum calcinatum 18g, 230mL n,N-Dimethylformamide, the mixing of 180mL dichlorotoleune, are heated to 205 DEG C
Reflux water-dividing 2 ~ 3 hours.Dichlorotoleune is distilled off, reaction temperature is kept for 205 DEG C, is reacted 35 hours.Stop heating and stirs
It mixes, cooled to room temperature.Reaction solution is slowly poured into 2.5L deionized waters, obtains white fibrous polymer, 5L deionizations
Water impregnates 7 hours under the conditions of 80 DEG C, in triplicate, filters, drying, then be dried in vacuo 25 hours at 115 DEG C, obtains pale yellow
Color fibre shaped polymer.
The preparation method of the sulfonated polyether sulfone compound ions exchange membrane, including following preparation process：
A. sulfonated polyether sulphones are dissolved in casting solution, are configured to the preparation liquid that mass percent concentration is 25%；
B. thiophene-based ionic liquid is added in the preparation liquid obtained by step A, at 90 DEG C, 15 h are stirred under inert atmosphere protection,
It is cooled to room temperature, filters and remove insoluble matter, it is dry to be handed over to get to thiophene-based ionic liquid doped sulfonated polyether sulfone compound ions
Change membrane material；
C. by step B gained ion exchange membrane materials through being cast or suppressing film forming, then the solvent flashing at 80 DEG C, obtains wet
Film；Again by gained wet film at 80 DEG C 10 h of freeze-day with constant temperature；Or first 11 h dry at 55 DEG C, then it is warming up to 100 DEG C of dryings
6h obtains thiophene-based ionic liquid doped sulfonated polyethers sulphones proton exchange membrane.
Thiophene-based ionic liquid used is entitled：Thiophane class ionic liquid or S- alkylthrophene class ionic liquids.
Casting solution used is：Dimethylbenzene.
With the sensor of the preparation-obtained electrode fabrication of the present embodiment, PARA FORMALDEHYDE PRILLS(91,95) is detected, 0.0001ppm ~
Within the scope of 30ppm, electric current（I, uA）With content of formaldehyde（C, ppm）Linear relationship be：I=75C+8.9（R=0.9999, n=6）.
Selectivity：SO2、H2S 、NH3, NO to detect it is noiseless.
The sensor prepared using electrode of the present invention is used for the test of formaldehyde gas response performance.Experimental condition
For at ambient temperature, operating procedure：Cleaned air is first imported, then is directed respectively into 40ppm SO successively2、40ppmH2S、
40ppm NH3, 40ppm NO, the response signal changing value of sensor is substantially zeroed, the sensor when importing 3ppm formaldehyde gas
The changing value of response is 233.9uA.
When carrying out formaldehyde examination with commercially available formaldehyde electrode sensor：Cleaned air is first imported, then is directed respectively into successively
40ppm SO2、40ppmH2S、40ppm NH3, 40ppm NO, the response signal changing value substantially more 250uA of sensor, when leading
The changing value that sensor responds when entering 3ppm formaldehyde gas is 483.9uA.
As can be seen that using commercially available formaldehyde sensor, SO2、H2S 、NH3, NO can seriously affect the detection of formaldehyde gas.
A kind of preparation method of the sensor of the content of detection formaldehyde in air of embodiment 3
A kind of preparation method of the sensor of the content of detection formaldehyde in air, catalyst used in electrode is the load of superconduction carbon
Tin oxide-copper oxide-zinc oxide-cobalt oxide catalyst, base material are sulfonated polyether sulfone compound ions exchange membrane, preparation process
Including step in detail below：
Step 1, it weighs in putty powder, copper nitrate, zinc nitrate, cobalt oxide powder to unified beaker, then weighs excessive oxalic acid
It is added in beaker；It is then transferred to ball milling in ball mill, it is dry at 130 DEG C after taking-up, 12h is ground, for use；
Step 2, the superconduction carbon of the product and phase homogenous quantities in step 1 is weighed in beaker, the Strong oxdiative sodium instilled into beaker
Solution stirs evenly, and is put into water-bath, is taken out after colloid in beaker is dried；
Step 3, the catalyst powder that step 2 is taken out is moved in pottery, middle heat preservation 6h under the conditions of 800 DEG C of Muffle furnace,
It takes out after cooling, is transferred to ball milling in ball mill, taking-up is put in crucible, and 5% Nafion solution, stirring are added thereto
To uniform, catalyst material is just made, then the catalyst has uniformly been applied on waterproof ventilated membrane with weighing scoop；
Step 4, processed sulfonated polyether sulfone compound ions exchange membrane is put into the beaker of deionized water, is put into water-bath
Middle heat preservation, is then pulled out, for use；
Step 5, the reference electrode of the waterproof ventilated membrane for being coated with catalyst and use same procedure making in step 3 and to electricity
Pole is attached to hot pressing on the sulfonated polyether sulfone compound ions exchange membrane formed after step 3, and the waterproof for being sprayed with catalyst is saturating
Air film is attached to the both sides of sulfonated polyether sulfone compound ions exchange membrane respectively, and side pastes one, and the other side pastes two, hot pressing rear chamber
Temperature is lower to place, and electrochemistry formaldehyde gas sensor electrode has just been made in this way.
The mass ratio of putty powder, copper nitrate, zinc nitrate, cobalt oxide powder in step 1 is 3: 6: 9: 0.8.
A concentration of 5g/ml of sodium hydroxide solution in step 2, addition are 60ml/g catalyst；The temperature of water-bath
It is 100 DEG C.
The processed sulfonated polyether sulfone compound ions exchange membrane of step 4, described processing are to sulfonated polyether sulfone chemical combination
Object amberplex is pre-processed, and sulfonated polyether sulfone compound ions exchange membrane is first placed into 5% H of boiling2O2Solution
In handle 1h under the conditions of 80 DEG C；Then it is dipped in again in the 1M sulfuric acid that temperature is 80 DEG C 1 hour, film is rinsed out with deionized water
It is put into deionized water after the remaining acid solution on surface, then for use.
The sulfonated polyether sulfone compound ions exchange membrane, includes the raw material of following parts by weight:Sulfonated polyether sulphones
80 parts；10 parts of thiophene-based ionic liquid；30 parts of casting solution；
The sulfonated polyether sulphones are prepared by the following method：3,3 '-sodium disulfonates -4,4 '-dichloro diphenyl sulfone
20g, 4,4,-dichloro disulfide 15g, 3,3 '-diamino -4,4'- dichloro diphenyl sulfone 15g, 200mL dichlorotoleune are mixed
It closes, is heated to 210 DEG C of reflux water-dividings 3 hours.Dichlorotoleune is distilled off, reaction temperature is kept for 210 DEG C, is reacted 40 hours.
Stop heating and stirring, cooled to room temperature.Reaction solution is slowly poured into 3L deionized waters, obtains white fibrous polymerization
Object, 6L deionized waters are impregnated 8 hours under the conditions of 80 DEG C, in triplicate, are filtered, drying, then be dried in vacuo 30 at 120 DEG C
Hour, obtain light yellow fibrous shaped polymer.
The preparation method of the sulfonated polyether sulfone compound ions exchange membrane, including following preparation process：
A. sulfonated polyether sulphones are dissolved in casting solution, are configured to the preparation liquid that mass percent concentration is 35.0%；
B. thiophene-based ionic liquid is added in the preparation liquid obtained by step A, at 95 DEG C, 24 h are stirred under inert atmosphere protection,
It is cooled to room temperature, filters and remove insoluble matter, it is dry to be handed over to get to thiophene-based ionic liquid doped sulfonated polyether sulfone compound ions
Change membrane material.
C. by step B gained ion exchange membrane materials through being cast or suppressing film forming, then the solvent flashing at 90 DEG C, obtains
Wet film；Again by gained wet film at 100 DEG C 24 h of freeze-day with constant temperature；Or first 12 h dry at 70 DEG C, then be warming up to 120 DEG C and do
Dry 10h obtains thiophene-based ionic liquid doped sulfonated polyethers sulphones proton exchange membrane.
The thiophene-based ionic liquid is entitled：S- alkylthrophene class ionic liquids.
Casting solution used is：Amyl acetate, trichloro ethylene benzene.
With the sensor of the preparation-obtained electrode fabrication of the present embodiment, PARA FORMALDEHYDE PRILLS(91,95) is detected, 0.0001ppm ~
Within the scope of 25ppm, electric current（I, uA）With content of formaldehyde（C, ppm）Linear relationship be：I=68C+7.3（R=0.9996, n=6）.
Selectivity：SO2、H2S 、NH3, NO to detect it is noiseless.
The sensor prepared using electrode of the present invention is used for the test of formaldehyde gas response performance.Experimental condition
For at ambient temperature, operating procedure：Cleaned air is first imported, then is directed respectively into 30ppm SO successively2、30ppmH2S、
30ppm NH3, 30ppm NO, the response signal changing value of sensor is substantially zeroed, the sensor when importing 3ppm formaldehyde gas
The changing value of response is 211.3uA.
When carrying out formaldehyde examination with commercially available formaldehyde electrode sensor：Cleaned air is first imported, then is directed respectively into successively
40ppm SO2、40ppmH2S、40ppm NH3, 40ppm NO, the response signal changing value of sensor is about 250uA substantially, when leading
The changing value that sensor responds when entering 3ppm formaldehyde gas is 461.3uA.
As can be seen that using commercially available formaldehyde sensor, SO2、H2S 、NH3, NO can seriously affect the detection of formaldehyde gas.
Claims (10)
1. a kind of preparation method of the sensor electrode of detection formaldehyde in air content, which is characterized in that urged used in electrode
Agent is superconduction carbon carrying tin oxide-copper oxide-zinc oxide-cobalt oxide catalyst, and base material is sulfonated polyether sulfone compound ions
Exchange membrane, preparation process include step in detail below：
Step 1, it weighs in putty powder, copper nitrate, zinc nitrate, cobalt oxide powder to unified beaker, then weighs excessive oxalic acid
It is added in beaker；It is then transferred to ball milling in ball mill, it is dry at 100 ~ 130 DEG C after taking-up, 10 ~ 12h is ground, for use；
Step 2, the superconduction carbon of the product and phase homogenous quantities in step 1 is weighed in beaker, the Strong oxdiative sodium instilled into beaker
Solution stirs evenly, and is put into water-bath, is taken out after colloid in beaker is dried；
Step 3, the catalyst powder that step 2 is taken out is moved in pottery, middle heat preservation under the conditions of 700 ~ 800 DEG C of Muffle furnace
4 ~ 6h takes out after cooling, is transferred to ball milling in ball mill, and taking-up is put in crucible, and the Nafion of addition 1 ~ 5% is molten thereto
Liquid is stirred until homogeneous, and catalyst material has just been made, and the catalyst is uniformly then applied to waterproof ventilated membrane with weighing scoop
On；
Step 4, processed sulfonated polyether sulfone compound ions exchange membrane is put into the beaker of deionized water, is put into water-bath
Middle heat preservation, is then pulled out, for use；
Step 5, the reference electrode of the waterproof ventilated membrane for being coated with catalyst and use same procedure making in step 3 and to electricity
Pole is attached to hot pressing on the sulfonated polyether sulfone compound ions exchange membrane formed after step 3, and the waterproof for being sprayed with catalyst is saturating
Air film is attached to the both sides of sulfonated polyether sulfone compound ions exchange membrane respectively, and side pastes one, and the other side pastes two, hot pressing rear chamber
Temperature is lower to place, and electrochemistry formaldehyde gas sensor electrode has just been made in this way.
2. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 1, which is characterized in that step 1
In putty powder, copper nitrate, zinc nitrate, cobalt oxide powder mass ratio be 1 ~ 3:4~6:8~9:0.1~0.8.
3. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 1, which is characterized in that step 2
In sodium hydroxide solution a concentration of 1 ~ 5g/ml, addition be 50 ~ 60ml/g catalyst；The temperature of water-bath is 90 ~ 100
℃。
4. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 1, which is characterized in that step 4
Processed sulfonated polyether sulfone compound ions exchange membrane, described processing be to sulfonated polyether sulfone compound ions exchange membrane into
Row pretreatment, is first placed into sulfonated polyether sulfone compound ions exchange membrane 3 ~ 5% H of boiling2O2In solution under the conditions of 80 DEG C
Handle 0.5 ~ 1h；Then it is dipped in again in 0.5 ~ 1M sulfuric acid that temperature is 80 DEG C 0.5 ~ 1 hour, film is rinsed out with deionized water
It is put into deionized water after the remaining acid solution on surface, then for use.
5. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 1, which is characterized in that the sulphur
Change polyether sulfone compound ions exchange membrane, includes the raw material of following parts by weight:60 ~ 80 parts of sulfonated polyether sulphones；Thiophene-based
1 ~ 10 part of ionic liquid；10 ~ 30 parts of casting solution.
6. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 5, which is characterized in that the sulphur
Change polyethers sulphones to be prepared by the following method：3,3 '-sodium disulfonate -4,4 ' -18 ~ 20g of dichloro diphenyl sulfone, 4,4, -
5 ~ 15g of dichloro disulfide, 3,3 ' -10 ~ 15g of diamino -4,4'- dichloro diphenyl sulfones, 3,3'5,5' tetramethyl biphenyl diphenol
10 ~ 15g, 16 ~ 20g of natrium carbonicum calcinatum, 200 ~ 250mL n,N-Dimethylformamide, the mixing of 150 ~ 200mL dichlorotoleune, add
Dichlorotoleune was distilled off to 200 ~ 210 DEG C of reflux water-dividings 2 ~ 3 hours in heat, and reaction temperature is kept for 200 ~ 210 DEG C, and reaction 30 ~
40 hours, stop heating and stirring, cooled to room temperature, reaction solution is slowly poured into 2 ~ 3L deionized waters, obtains white fibre
Shaped polymer is tieed up, 4 ~ 6L deionized waters are impregnated 6 ~ 8 hours under the conditions of 80 DEG C, in triplicate, filtered, drying, then 110 ~ 120
It is dried in vacuo 20 ~ 30 hours at DEG C, obtains light yellow fibrous shaped polymer.
7. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 5, which is characterized in that the sulphur
The preparation method for changing polyether sulfone compound ions exchange membrane, including following preparation process：
A. sulfonated polyether sulphones are dissolved in casting solution, are configured to the system that mass percent concentration is 5.0% ~ 35.0%
Film liquid；
B. thiophene-based ionic liquid is added in the preparation liquid obtained by step A, at 85 DEG C ~ 95 DEG C, is stirred under inert atmosphere protection
The h of 10h ~ 24, are cooled to room temperature, and filter and remove insoluble matter, dry to get to thiophene-based ionic liquid doped sulfonated polyether sulfone
Close object ion exchange membrane material；
C. by step B gained ion exchange membrane materials through being cast or suppressing film forming, then the solvent flashing at 40 DEG C ~ 90 DEG C, obtains
To wet film；Again by gained wet film at 50 DEG C ~ 100 DEG C 2 ~ 24 h of freeze-day with constant temperature；Or first 10h ~ 12 dry at 50 DEG C ~ 70 DEG C
H, then 70 DEG C ~ 120 DEG C dry 4h ~ 10h are warming up to, obtain thiophene-based ionic liquid doped sulfonated polyethers sulphones proton exchange
Film.
8. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 6, which is characterized in that the thiophene
Class ionic liquid is entitled：Thiophane class ionic liquid or S- alkylthrophene class ionic liquids.
9. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 6, which is characterized in that used
Casting solution is：The one or more of amyl formate, amyl acetate, dimethylbenzene, trichloro ethylene benzene.
10. the preparation method of electrochemistry formaldehyde gas sensor electrode according to claim 6, which is characterized in that used
Casting solution be：Dimethylbenzene.
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| CN113504285A (en) * | 2021-07-09 | 2021-10-15 | 杭州麦乐克科技股份有限公司 | Preparation method of formaldehyde electrochemical sensor membrane electrode |
| CN113588738A (en) * | 2021-07-29 | 2021-11-02 | 深圳宇问加壹传感系统有限公司 | Ultrathin all-solid-state formaldehyde electrochemical gas sensor |
| US11940436B1 (en) * | 2023-06-21 | 2024-03-26 | United Arab Emirates University | Electroanalytical sensor for meloxicam detection |
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