CN101059475A - Ampere type humidity sensing device - Google Patents
Ampere type humidity sensing device Download PDFInfo
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- CN101059475A CN101059475A CN 200710041408 CN200710041408A CN101059475A CN 101059475 A CN101059475 A CN 101059475A CN 200710041408 CN200710041408 CN 200710041408 CN 200710041408 A CN200710041408 A CN 200710041408A CN 101059475 A CN101059475 A CN 101059475A
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Abstract
The invention relates to an ampere humidity sensor and a relative check method, based on room temperature ion liquid, which comprises a humidity sensitive element with room temperature ion liquid and electrochemical probe, a signal amplifier circuit, a check circuit, a reference circuit, a gas system, and a display control system, to use the charge current of the humidity sensitive element and the reaction current of the electrochemical probe to detect the humidity. The invention is characterized in that using the room temperature ion liquid as the sensitive part of humidity, using the change of reversal electrochemical property of oxidization reduction couple to detect the humidity of current type. The invention can overcome the defects of prior humidity sensor as bad exchangeable property, high cost, complex device, bad interference resistance, and small response signal linear range, caused by using alternative-current signal, to obtain the advantages as simple structure, low cost, stable property and high sensitivity.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly relate to a kind of ampere type humidity sensing device and application process thereof.
Background technology
Humidity sensing device can be divided into capacitor type humidity sensing device (CN1220393A), resistance type humidity sensing device (CN1431489A), weight mode of resonance humidity sensing device and optical-fiber type humidity sensing device (CN1036635A) etc. by the difference of the signal that detects.Wherein the measurement of electrical signal is because its working method is simple, response sensitivity advantages of higher and especially receiving publicity.Yet common resistor-type or capacitor type humidity sensing device need use AC signal to measure, thereby make the cost of instrument higher relatively.The current-mode sense device has that equipment is simple, strong interference immunity, response signal are advantages such as linearity.And, conventional current-mode sense device is usually with the electrochemical reaction response signal of detected object, yet the electrochemical decomposition voltage of hydrone is higher and be subjected to characteristics such as the influence of electrode surface character is bigger, directly carries out amperometric determination and certainly will have a lot of electric active matters and verify to measure to produce and disturb.Literature search still finds no by adding the reversible redox electricity to (as: tetracyano-p-quinodimethane, N, N, N ', organic electroactive material or its derivants such as N '-tetramethyl-para-phenylene diamine or benzoquinones; Electroactive metal complex or its derivants such as ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin, metal phthalocyanine) as electrochemical probe, utilize the influence of hydrone to ionic liquid character, thereby and then the kinetic current that influences the charging current of humidity-sensitive element and electrochemical probe realize report to the detection of humidity.
Summary of the invention
Technical matters to be solved
Technical matters to be solved by this invention provides ampere type humidity sensing device and application process thereof, thereby existing needs to use that AC signal measures that the cost that makes instrument is higher relatively, equipment is complicated, anti-interference is poor to overcome, the defective of response signal non-linear domain etc.
Technical scheme
One of technical scheme of the present invention provides a kind of ampere type humidity sensing device, it consists of humidity-sensitive element, signal amplification circuit, detection loop, reference loop, gas system and the display control program that contains ionic liquid at room temperature and electrochemical probe, thereby the kinetic current of charging current by humidity-sensitive element and electrochemical probe is realized the detection to humidity.
One of preferred version of above-mentioned ampere type humidity sensing device is that described ionic liquid at room temperature is selected from one or more in alkyl imidazole, alkyl pyridine class, quaternary ammonium salt, quaternary phosphonium salt or the benzimidazole ionic liquid.Preferred described ionic liquid at room temperature is selected from [1-ethyl-3 methylimidazole] [tetrafluoro boric acid], [1-butyl-3 methylimidazole] [hexafluorophosphoric acid], [1-Kui Ji-3-methyl] [tetrafluoro boric acid], [N-butyl-pyridinium] [hexafluorophosphoric acid], [N-butyl-pyridinium] [tetrafluoro boric acid], [N-heptyl pyridine] [hexafluorophosphoric acid], [dimethyl ethanol base 3-sulfonic acid propyl ammonium] [p-methyl benzenesulfonic acid], [three ethanol based 3-sulfonic acid propyl ammoniums] [p-toluenesulfonic acid], [diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate], [tetrabutyl phosphorus] [two-(trifluoromethyl) sulfimides], [tributyl-methyl phosphonium phosphorus] [methane-sulforic acid], [tributyl myristyl phosphorus] [two-(trifluoromethyl) sulfimides], [1-ethyl-3-butyl benzimidazole] [tetrafluoro boric acid], [1-ethyl-3-butyl benzimidazole] [[hexafluorophosphoric acid], in [1-ethyl-3-butyl benzimidazole] [p-methyl benzenesulfonic acid] one or more.
Two of the preferred version of above-mentioned ampere type humidity sensing device is that described electrochemical probe is the oxidation-reduction pair that is dissolved in ionic liquid at room temperature.Preferred described oxidation-reduction pair is selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine, ferrocene, benzoquinones, ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin, metal phthalocyanine, perhaps its derivant.
Two of technical scheme of the present invention provides a kind of detection method of air humidity, comprise and utilize the humidity sensing device consist of humidity-sensitive element, signal amplification circuit, detection loop and the reference loop of containing ionic liquid at room temperature and electrochemical probe, thereby realize detection humidity by mensuration to the kinetic current of the charging current of humidity-sensitive element and electrochemical probe.
One of preferred version of the detection method of above-mentioned air humidity is that described ionic liquid at room temperature is selected from one or more in alkyl imidazole, alkyl pyridine class, quaternary ammonium salt, quaternary phosphonium salt or the benzimidazole ionic liquid.Preferred described ionic liquid at room temperature is selected from [1-ethyl-3 methylimidazole] [tetrafluoro boric acid], [1-butyl-3 methylimidazole] [hexafluorophosphoric acid], [1-Kui Ji-3-methyl] [tetrafluoro boric acid], [N-butyl-pyridinium] [hexafluorophosphoric acid], [N-butyl-pyridinium] [tetrafluoro boric acid], [N-heptyl pyridine] [hexafluorophosphoric acid], [sulfonic acid propyl group ethanol based Dimethyl Ammonium] [p-methyl benzenesulfonic acid], [sulfonic acid propyl group three ethanol based ammoniums] [p-toluenesulfonic acid], [diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate], [tetrabutyl phosphorus] [two-(trifluoromethyl) sulfimides], [tributyl-methyl phosphonium phosphorus] [two-(trifluoromethyl) sulfimides], [tributyl myristyl phosphorus] [two-(trifluoromethyl) sulfimides], [1-ethyl-3-butyl benzimidazole] [tetrafluoro boric acid], [1-ethyl-3-butyl benzimidazole] [[hexafluorophosphoric acid], in [1-ethyl-3-butyl benzimidazole] [p-methyl benzenesulfonic acid] one or more.
Technique scheme in force, the redox probe of selecting for use can be not limited to tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine, benzoquinones and etc. its derivant of organic electroactive material; Electroactive metal complex and derivants thereof such as ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin, metal phthalocyanine.Usually requiring this electrochemical probe is that electrochemical reversibility is good, dissolubility is higher in ionic liquid, and all stable oxidation-reduction pair of redox state.
Technique scheme in force, add reversible oxidation-reduction pair (as: tetracyano-p-quinodimethane) in the ionic liquid at room temperature as electrochemical probe, and the ionic liquid solution of functional composite material such as tetracyano-p-quinodimethane is adsorbed in the porous polyethylene film, realize the immobilization of ionic liquid at room temperature.Variation because of humidity in the air, make the water yield that is dissolved in the ionic liquid change, and cause physicochemical properties such as ion liquid viscosity, electric conductivity to change, changed the coefficient of diffusion of electroactive material and the electric double layer capacitance of electrode, thereby made the current signal that records become good linear relationship with relative humidity.
Technique scheme in force, adopting electric current is the detection signal of sensing device, described current detection signal can be the current signal of methods such as cyclic voltammetric, differentiated pulse, square wave volt-ampere.
Beneficial effect
The present invention is a kind of novel ampere type humidity sensing device.Be characterized in:
1) with the humidity sensitive material of ionic liquid at room temperature as sensing device.Wherein selected ionic liquid at room temperature can be ionic liquid at room temperature such as various common hydrophilic alkyl imidazoles, alkyl pyridine class, quaternary ammonium salt and quaternary phosphonium class.And but this ionic liquid can be fixed in the ionic liquid carrier that ion liquid container immobilized ionic liquid film, adsorbable ion liquid cotton-shaped carrier or silicon chip constituted.Because adoptable ion liquid diversity is so can prepare the sensitive membrane of diversified humidity sensitive characteristic; As the homogeneous phase sensitive material with definite molecular structure, the use ionic liquid at room temperature can improve the interchangeability between humidity-sensitive element effectively, and this performance has significant advantage to batch process.
2) with the electrochemical probe of reversible oxidation-reduction pair as sensing device.The redox probe of wherein selecting for use can be selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine, ferrocene or benzoquinones, perhaps its derivant, the electrochemical reversibility of these electrochemical probes is good, dissolubility is higher in ionic liquid, redox state is all relatively stable.Add above-mentioned reversible oxidation-reduction pair (as tetracyano-p-quinodimethane) in the ionic liquid at room temperature as electrochemical probe, can be because of the variation of humidity in the air, the water yield that is dissolved in the ionic liquid is changed, and cause physicochemical properties such as ion liquid viscosity, electric conductivity to change, changed the coefficient of diffusion of electroactive material (as tetracyano-p-quinodimethane) and the electric double layer capacitance of electrode, thereby made the current signal that records become good linear relationship with relative humidity.So that humidity sensing device of the present invention has is highly sensitive, good stability, easy to make, advantage such as cost is low.
3) adopting electric current is the detection signal of sensing device.Have that its working method is simple, response sensitivity is high, the characteristics of good stability; use direct current signal to measure; the cost of instrument is descended greatly; and advantages such as the current-mode sense device has, and equipment is simple, strong interference immunity, response signal are linearity and the range of linearity is wide, ampere type humidity sensing device of the present invention is easy to make, be easy to industrialization, large-scale production.
Description of drawings
Fig. 1 humidity sensing device system schematic.1: gas bomb; 2: the Drexel bottle that distilled water is housed; 3: gas mixer; 4: humidity sensor; 5: air chamber; 6: current return; 7: electrochemical workstation; 8: computing machine.
Fig. 2 is the multi-form synoptic diagram of humidity sensor parts.1: the immobilized room temperature ionic liquid film; 2 electrodes; 3 silicon chips.
Fig. 3 is the cyclic voltammetric response of TCNQ in ionic liquid under dry (a) and water saturation (b) condition in nitrogen (solid line) and oxygen (dotted line) atmosphere.
Fig. 4 humidity sensing device is under the nitrogen atmosphere, the cyclic voltammogram during different relative humidity.From a to f, relative humidity is respectively: 0%, 20%, 40%, 60%, 80%, 100%.
Fig. 5 is the reduction peak current in the response of humidity sensing device cyclic voltammetric and the graph of a relation of relative humidity.
Fig. 6 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable circulation voltammogram under water saturated atmosphere.
Fig. 7 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable circulation voltammogram under dry atmosphere.
Fig. 8 be humidity sensing device in nitrogen atmosphere, the differentiated pulse voltammogram under the different relative humidity.From a to f, relative humidity is respectively: 0%, 20%, 40%, 60%, 80%, 100%.
Fig. 9 be humidity sensing device in nitrogen atmosphere, oxidation and the difference of reduction current and the graph of a relation of relative humidity in the differentiated pulse response.
Figure 10 be humidity sensing device in oxygen atmosphere, the differentiated pulse voltammogram during different relative humidity.From a to f, relative humidity is respectively: 0%, 20%, 40%, 60%, 80%, 100%.
Figure 11 be humidity sensing device under oxygen atmosphere, the oxidation in the differentiated pulse response and the difference of reduction current are mapped to relative humidity content.
Continuous 10 circle differentiated pulse voltammograms when Figure 12 converts water saturated atmosphere for humidity sensing device to by dry atmosphere.
Continuous 10 circle differentiated pulse voltammograms when Figure 13 converts dry atmosphere for humidity sensing device to by water saturated atmosphere.
Figure 14 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable differentiated pulse voltammogram under water saturated atmosphere.
Figure 15 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable differentiated pulse voltammogram under dry atmosphere.
Figure 16 is in the humidity sensing device nitrogen atmosphere, the square wave voltammogram under the different relative humidity.From a to f, relative humidity is respectively: 0%, 20%, 40%, 60%, 80%, 100%.
Figure 17 be humidity sensing device under nitrogen atmosphere, the graph of a relation of the difference of oxidation and reduction current and relative humidity in the square wave voltammogram.
Figure 18 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable square wave voltammogram under water saturated atmosphere.
Figure 19 be humidity sensing device in continuous 8 dryings and water saturated atmosphere transfer process, the stable square wave voltammogram under dry atmosphere.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as operation manual, or the condition of advising according to manufacturer.The part preparation process of room temperature ionic liquid is according to Chinese patent application 200610025808.0 " a kind of double-functional group ionic liquid and preparation method ".
Embodiment 1
The preparation of 1-ethyl-3-methylimidazole bromine salt
Under room temperature, the stirring condition, the bromoethane (0.126mol) of 9.1ml slowly is added drop-wise in the N-methylimidazole of 10ml, behind the 24h, after ethyl acetate washing 3 times, filters vacuum drying.Reaction equation:
[1-ethyl-3-methylimidazole] [tetrafluoride boric acid] ion liquid preparation
Under room temperature, the quick stirring condition, with HBF
4Acid (15.2cm
30.116mol) add Ag slowly
2(13.49g 0.058molAg in the O mud
2O dissolves in 50cm
3In the water), stir fast.The container of reaction encases with aluminium foil, prevents that light from falling.Stir 1h again, until Ag
2The O complete reaction obtains colourless solution.Resulting 1-ethyl-3-methylimidazole inner salt adds wherein among the embodiment 1 with 22.24g0.116mol, stirs 2h under the room temperature, filters, and separates.Under 70 ℃, vacuum drying, product is a white liquid.Reaction equation is:
Embodiment 3
The preparation of 1-butyl-3-methylimidazole bromine salt
Under room temperature, the stirring condition, the positive n-butyl bromide of 6.46ml (0.06mol) is slowly splashed in the N-methylimidazole of 4.76ml, behind the 24h, with ethyl acetate washing 3 times.Filter vacuum drying.Reaction equation is:
Embodiment 4
[1-butyl-3 methylimidazole] [hexafluorophosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with KPF
6Slowly add in equimolar 1-butyl-3-methylimidazole bromine brine solution, again with ultrapure water 20ml washing 5 times, vacuum drying.Reaction equation is:
Embodiment 5
The preparation of 1-Kui Ji-3-methylimidazole bromine salt
Under room temperature, the stirring condition, the positive Kui n-butyl bromide of 1.32g (0.06mol) is slowly splashed in the N-methylimidazole of 4.76ml, behind the 24h, take off a layer solution, with ethyl acetate washing 3 times, again with ultrapure water 20ml washing 5 times, vacuum drying.Reaction equation is:
[1-Kui Ji-3-methylimidazole] [tetrafluoro boric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with NaBF
4Slowly add in equimolar 1-Kui Ji-3-methylimidazole bromine brine solution, after 12 hours, again with ultrapure water 20ml washing 5 times, vacuum drying.Reaction equation is:
Embodiment 7
The preparation of N-butyl-pyridinium bromine salt
The room temperature lower magnetic force stirs, and positive n-butyl bromide slowly is added drop-wise in the equimolar pyridine solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
Embodiment 8
[N-butyl-pyridinium] [tetrafluoro boric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with NaBF
4Slowly add in the aqueous solution of equimolar N-butyl-pyridinium bromine salt, after 12 hours, use dichloromethane extraction,, revolve and steam evaporation final vacuum drying again with ultrapure water 20ml washing 5 times.Reaction equation is:
Embodiment 9
[N-butyl-pyridinium] [hexafluorophosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with KPF
6Slowly add in the aqueous solution of equimolar N-butyl-pyridinium bromine salt, after 12 hours, take off a layer solution,, revolve and steam evaporation final vacuum drying at every turn with ultrapure water 20ml extraction 5 times.Reaction equation is:
Embodiment 10
The preparation of N-heptyl pyridinium tribromide salt
The room temperature lower magnetic force stirs, and positive bromine butane in heptan slowly is added drop-wise in the equimolar pyridine solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
Embodiment 11
[N-heptyl pyridine] [hexafluorophosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with KBF
6Slowly add in the aqueous solution of equimolar N-butyl-pyridinium bromine salt, after 12 hours, get organic phase, again with ultrapure water 20ml washing 5 times, vacuum drying.Reaction equation is:
The preparation of sulfonic acid propyl group ethanol based Dimethyl Ammonium inner salt
Under ice bath, the stirring condition, with 8.8mL 1,3-propane sultone (0.1mol) slowly is added drop-wise to and contains 10.1mL N, in the 30mL acetone mixed solution of N-dimethylethanolamine (0.1mol), promptly the mol ratio of reaction raw materials is 1: 1, and very fast adularescent solid is separated out, after 1 hour, white solid with acetone, ether washing 3 times, is filtered 50 ℃ of following vacuum drying.Reaction equation is:
Embodiment 13
[sulfonic acid propyl group ethanol based Dimethyl Ammonium] [p-methyl benzenesulfonic acid] ion liquid preparation
Under ice bath, the stirring condition,, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying with the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt and 1.81g p-toluenesulfonic acid (0.01mol) mixing of 1.95g (0.01mol) embodiment 12 gained.Product is a colourless transparent liquid, and reaction equation is:
Embodiment 14
[sulfonic acid propyl group ethanol based Dimethyl Ammonium] [trifluoromethane sulfonic acid] ion liquid preparation
N
2Under atmosphere, ice bath, the electronic stirring condition, the trifluoromethanesulfonic acid (0.02mol) of 1.80mL slowly is added drop-wise in the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt of 4.23g (0.02mol) embodiment 12 gained, after 12 hours, be heated to 50 ℃ to all becoming liquid, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 15
[sulfonic acid propyl group ethanol based Dimethyl Ammonium] [hydrogen sulfate] ion liquid preparation
Under ice bath, the stirring condition, the concentrated sulphuric acid (0.014mol) of 0.8mL slowly is added drop-wise in the dimethyl ethanol base 3-sulfonic acid propyl ammonium inner salt (0.014mol) of resultant embodiment 12 gained of 3.04g, be heated to 85 ℃ after 3 hours, all become liquid after 10 hours, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 16
The preparation of three ethanol based sulfonic acid propyl ammonium inner salts
Under ice bath, the stirring condition, with 13.2mL1,3-propane sultone (0.15mol) slowly is added drop-wise in toluene (30mL) mixed solution that contains 25.5mL triethanolamine (0.15mol), after 1 day, the adularescent solid generates, after usefulness toluene, ether wash 3 times, filter 50 ℃ of vacuum drying.Reaction equation is:
Embodiment 17
[sulfonic acid propyl group three ethanol based ammoniums] [p-toluenesulfonic acid] ion liquid preparation
Under ice bath, the stirring condition, will mix, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying by embodiment 16 resulting three ethanol based 3-sulfonic acid propyl ammonium inner salt 7.76g (0.028mol) and 5.16g p-toluenesulfonic acid (0.028mol).Product is a colourless transparent liquid, and reaction equation is:
Embodiment 18
[sulfonic acid propyl group three ethanol based ammoniums] [trifluoromethane sulfonic acid] ion liquid preparation
N
2Under atmosphere, ice bath, the stirring condition, the trifluoromethanesulfonic acid (0.029mol) of 2.6mL slowly is added drop-wise to by in embodiment 16 resulting 7.8g (0.029mol) the three ethanol based 3-sulfonic acid propyl ammonium inner salts, after 12 hours, be heated to 50 ℃ to all becoming liquid, cooling final vacuum drying.Product is a light yellow transparent liquid, and reaction equation is:
Embodiment 19
[sulfonic acid propyl group three ethanol based ammoniums] [pyrovinic acid] ion liquid preparation
Under ice bath, the stirring condition, the Loprazolam (0.03mol) of 2.0mL slowly is added drop-wise to 8.60g (0.03mol) by in the embodiment 16 resulting three ethanol based 3-sulfonic acid propyl ammonium inner salts, after 3 hours, be heated to 70 ℃ to all becoming liquid, cooling final vacuum drying.Product is a colourless transparent liquid, and reaction equation is:
The preparation of diethyl alcohol radical sulfonic acid butyl ammonium inner salt
Under room temperature, the stirring condition, the diethanolamine (0.1mol) of 9.6mL is scattered in the 20mL toluene solution, slowly drip 1 of 10.23mL again, behind the 4-sultones (0.1mol), be heated to 50 ℃, the adularescent solid generates after 15 hours, and white solid is washed 3 times with ethanol, filter 50 ℃ of following vacuum drying.Reaction equation is:
Embodiment 21
[diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate] ion liquid preparation
Under ice bath, the stirring condition, the concentrated sulphuric acid (0.012mol) of 0.65mL slowly is added drop-wise in the diethyl alcohol radical sulfonic acid butyl ammonium inner salt (0.012mol) that resulting 2.81g obtains by embodiment 20, be heated to 70 ℃ after 3 hours, all become liquid after 6 hours, cooling final vacuum drying.Product is a colourless transparent liquid, and reaction equation is:
Embodiment 22
The preparation of bromination tributyl myristyl microcosmic salt
The room temperature lower magnetic force stirs, and positive bromo-tetradecane slowly is added drop-wise in the equimolar tributyl phosphorus solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
Embodiment 23
The ion liquid preparation of [myristyl tributyl phosphorus] [two-(trifluoromethyl) sulfimides]
The ice bath lower magnetic force stirs, and two-(trifluoromethyl) sulfimide lithiums are slowly added in the aqueous solution of equimolar bromination tributyl myristyl microcosmic salt, after 12 hours, takes off a layer solution, at every turn with ultrapure water 20ml extraction 5 times, revolves and steams evaporation final vacuum drying.
Embodiment 24
The preparation of tributyl-methyl phosphonium iodide microcosmic salt
The room temperature lower magnetic force stirs, and iodomethane slowly is added drop-wise in the equimolar tributyl phosphorus solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
Embodiment 25
The ion liquid preparation of [tributyl-methyl phosphonium phosphorus] [two-(trifluoromethyl) sulfimides]
The ice bath lower magnetic force stirs, and two-(trifluoromethyl) sulfimide lithiums are slowly added in the aqueous solution of equimolar tributyl-methyl phosphonium iodide microcosmic salt, after 12 hours, takes off a layer solution, with ultrapure water 20ml washing 5 times, vacuum drying.
Embodiment 26
The preparation of bromination tetrabutyl microcosmic salt
The room temperature lower magnetic force stirs, and positive n-butyl bromide slowly is added drop-wise in the equimolar tributyl phosphorus solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
(CH
3CH
2CH
2CH
2)
3P+CH
3(CH
2)
13Br→(CH
3CH
2CH
2CH
2)
4P
+Br
-
Embodiment 27
The ion liquid preparation of [tetrabutyl phosphorus] [two-(trifluoromethyl) sulfimides]
The ice bath lower magnetic force stirs, and two-(trifluoromethyl) sulfimide lithiums are slowly added in the aqueous solution of equimolar bromination tetrabutyl microcosmic salt, after 12 hours, takes off a layer solution, at every turn with ultrapure water 20ml extraction 5 times, vacuum drying.
(CH
3CH
2CH
2CH
2)
4P
+Br
-+Li(CF
3SO
2)
2N→(CH
3CH
2CH
2CH
2)
4P
+(CF
3SO
2)
2N
-
Embodiment 28
The preparation of bromination 1-butyl-3-ethyl benzo imidazole salt
The room temperature lower magnetic force stirs, and positive n-butyl bromide slowly is added drop-wise in the equimolar 1-ethyl benzo imidazole solution, after 24 hours, with ethyl acetate washing 3 times, vacuum drying.Reaction equation is:
Embodiment 29
[1-butyl-3-ethyl benzo imidazole] [hexafluorophosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with KPF
6Slowly add in the aqueous solution of equimolar bromination 1-ethyl-3-butyl benzene benzimidazole salt, after 12 hours, get organic phase, at every turn with ultrapure water 20ml washing extraction 5 times, vacuum drying.
Embodiment 30
[1-butyl-3-ethyl benzo imidazole] [tetrafluoro phosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, with NaBF
4Slowly add in the aqueous solution of equimolar bromination 1-ethyl-3-butyl benzene benzimidazole salt, after 12 hours, get organic phase, at every turn with ultrapure water 20ml washing extraction 5 times, vacuum drying.
Embodiment 31
[1-butyl-3-ethyl benzo imidazole] [hexafluorophosphoric acid] ion liquid preparation
The ice bath lower magnetic force stirs, and paratoluenesulfonic acid sodium salt is slowly added in the aqueous solution of equimolar bromination 1-ethyl-3-butyl benzene benzimidazole salt, after 12 hours, gets organic phase, at every turn with ultrapure water 20ml washing extraction 5 times, vacuum drying.
Embodiment 32
Solid-state three electrode making
Glass carbon, silver and platinum are connected with copper wire as working electrode, contrast electrode with to electrode with silver conductive adhesive respectively.Be packaged into solid-state three electrodes shown in Fig. 2 A with AB glue.
Embodiment 33
The making of solid-state two electrodes
Glass carbon is connected as working electrode with to electrode with copper wire with silver conductive adhesive respectively with platinum.With solid-state two electrodes shown in AB glue Feng Chengru Fig. 2 B.
Embodiment 34
Polymer film absorbent-type humidity sensing device
Get the alkyl imidazole of the embodiment 1-31 preparation of certain volume, the alkyl pyridine class, quaternary ammonium salt, the quaternary phosphonium salt, benzimidazole room-temperature ion liquid liquid solution is as [1-ethyl-3 methylimidazole] [tetrafluoro boric acid], [1-butyl-3 methylimidazole] [hexafluorophosphoric acid], [1-Kui Ji-3-methyl] [tetrafluoro boric acid], [N-butyl-pyridinium] [hexafluorophosphoric acid], [N-butyl-pyridinium] [tetrafluoro boric acid], [N-heptyl pyridine] [hexafluorophosphoric acid], [dimethyl ethanol base 3-sulfonic acid propyl ammonium] [p-methyl benzenesulfonic acid], [three ethanol based 3-sulfonic acid propyl ammoniums] [p-toluenesulfonic acid], [diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate], [tetrabutyl phosphorus] [two-(trifluoromethyl) sulfimides], [tributyl-methyl phosphonium phosphorus] [methane-sulforic acid], [tributyl myristyl phosphorus] [two-(trifluoromethyl) sulfimides], [1-ethyl-3-butyl benzimidazole] [tetrafluoro boric acid], [1-ethyl-3-butyl benzimidazole] [[hexafluorophosphoric acid], [1-ethyl-3-butyl benzimidazole] [p-methyl benzenesulfonic acid].With tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine, ferrocene, benzoquinones, ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin or metal phthalocyanine add ionic liquid and dissolving.Respectively the above-mentioned oxidation-reduction pair ground ionic liquid that is dissolved with is adsorbed onto perforated membrane: in polyethylene film, Polyvinylchloride, teflon, poly-inclined to one side tetrafluoroethene, poly-cellulose acetate, again film is covered embodiment 32, the surface of 33 prepared electrodes or screen printing electrode, vapor deposited metal electrode, constitute wet quick part, with electrochemical probe, signal amplification circuit, detection loop, reference loop, gas system and display control program together, make humidity sensing device.
Embodiment 35
The making of silicon chip three electrode humidity sensing devices
On silicon chip or potsherd, metallic films such as gold evaporation or platinum are as working electrode, to electrode.With the method for laser-induced thermal etching or chemical etching, on silicon chip, etch a certain size hole.Silicon chip or potsherd thermocompression bonding that etching is crossed silicon chip and metal-coated films, thus as shown in the figure electrode structure formed.With embodiment 34, configuration contains the ionic liquid solution of electrochemical probe, and it is added dropwise in the silicon chip groove, constitutes wet quick part, with electrochemical probe, signal amplification circuit, detection loop, reference loop, gas system and display control program together, make the silicon chip humidity sensing device.
Embodiment 36
The making of polymer gel type humidity sensing device
The ionic liquid solution that contains electrochemical probe with embodiment 34 configurations, and with its same in proportion Kynoar, poly-N, the N-DMAA, polyoxyethylene, polymethylmethacrylate, or polyvinylpyrrolidone/acetate ethylene copolymer etc. is dissolved in carbonic allyl ester or the 4-methyl-2 pentanone together, form colloidal sol, colloidal sol is dripped in embodiment 32,33 prepared electrode or screen printing electrodes, the surface of vapor deposited metal electrode, constitute wet quick part after the vacuum drying, and electrochemical probe, signal amplification circuit, detect the loop, the reference loop, gas system and display control program are made polymer gel type humidity sensing device together.
Embodiment 37
The making of silicon gel-type humidity sensing device
The ionic liquid solution that contains electrochemical probe with embodiment 34 configurations, and with its in proportion with water, ethanol, and tetramethoxysilance or tetraethoxysilance mixes formation colloidal sol, with embodiment 36 this colloidal sol is dripped in embodiment 32 again, the surface of 33 prepared electrodes or screen printing electrode, vapor deposited metal electrode, constitute wet quick part after the vacuum drying, with electrochemical probe, signal amplification circuit, detection loop, reference loop, gas system and display control program together, make silicon polymer gel-type humidity sensing device.
Embodiment 38
The making of sandwich type humidity sensing device
Contain the ionic liquid solution of electrochemical probe with embodiment 34 configuration, and be impregnated among porous ceramics or apertured polymeric film such as polyethylene film, Polyvinylchloride, teflon, poly-inclined to one side tetrafluoroethene, the poly-cellulose acetate etc.As shown in the figure, it is sandwiched among carbon paper or the carbon cloth, and with stainless (steel) wire, copper mesh etc. as collector, constitute wet quick part, with electrochemical probe, signal amplification circuit, detection loop, reference loop, gas system and display control program together, the type that sandwiches humidity sensing device.
Embodiment 39
The test of ion liquid type humidity sensing device
The device of experiment as shown in Figure 1.
1. nitrogen (oxygen) is fed in the water, make water saturation N
2(water saturation O
2), and mixing, make the atmosphere of different humidity with the dry nitrogen gas phase, the air-flow velocity that feeds sensing device is 5L/min.
2. oxygen is to hygrometric interference
Measured the humidity sensing device that the 1-normal-butyl-3-methylimidazole hexafluorophosphoric acid ionic liquid the is made response of the cyclic voltammetric under nitrogen and oxygen atmosphere under dry and water saturation condition with the tetracyano-p-quinodimethane that contains 2mM respectively, the result as shown in Figure 3.No matter be as can be seen from the figure, illustrate that oxygen does not significantly disturb the mensuration of humidity almost consistent with the response under the oxygen atmosphere under drying or the water saturation condition at nitrogen.
3. adopt electrochemical method-cyclic voltammetry (CV) to measure the response of sensing device to humidity
Fig. 4 is under the nitrogen atmosphere, and the cyclic voltammogram of the TCNQ under the different liquid water contents, Fig. 5 are that reduction peak current and the mapping of relative humidity content are linear.Adopt identical experimental technique, promptly alternately use water saturation N continuously
2With dry N
2Feed sensing device, repeat 8 times, survey cyclic voltammetry simultaneously, continuous sweep 20 circles under the same case, the stability and the response time of investigation sensing device.By calculating water saturation N
2Under response time be 38-42.5s, dry N
2Under response time be 33.5-38s.
Fig. 6 and Fig. 7 are respectively water saturation N
2With dry N
2Down, the CV figure of the 20th of 8 times the circle.As can be seen from the figure, adopt cyclic voltammetry, sensing device stable fine.Can obtain water saturation N by calculating
2Down, the mean value of reduction current is-6.01 * 10
-7, standard deviation is 8.7535 * 10
-9, relative standard deviation is 1.4565%.Dry N
2Down, the mean value of reduction current is-4.089 * 10
-7, standard deviation is 1.8731 * 10
-9, relative standard deviation is 0.4581%.
4. adopt electrochemical method-differential pulse voltammetry (DPV) to measure the response of sensing device
Fig. 8 and 10 is respectively the differential pulse voltammogram under the different humidity under nitrogen and the oxygen atmosphere.The difference of oxidation current and reduction current is mapped to relative humidity, become good linear relationship (Fig. 9 and 11).Table 1 is under different humidity, reduction-oxidation current value and difference under oxygen, the nitrogen atmosphere.By table as seen: under the different atmosphere during same humidity, the reduction-oxidation current value basically identical of TCNQ, and nitrogen atmosphere lower linear pass is: Y=2.23443+0.01576X; The oxygen atmosphere lower linear is closed: Y=2.16181+0.01549X, both linear equations are basically identical also.Illustrate that oxygen is to the not influence of this sensing device.
Reduction-oxidation current value and the difference of table 1 TCNQ under oxygen, the nitrogen atmosphere under different humidity
| Water cut %/v/v | N 2Atmosphere/A | O 2Atmosphere/A | ||||
| Oxidation current | Reduction current | Difference | Oxidation current | Reduction | Difference | |
| 0 | 1.118 | -1.103 | 2.221 | 1.075 | -1.072 | 2.147 |
| 20 | 1.308 | -1.308 | 2.616 | 1.255 | -1.249 | 2.504 |
| 40 | 1.315 | -1.455 | 2.77 | 1.374 | -1.38 | 2.754 |
| 60 | 1.591 | -1.593 | 3.184 | 1.553 | -1.542 | 3.095 |
| 80 | 1.790 | -1.784 | 3.574 | 1.713 | -1.706 | 3.419 |
| 100 | 1.887 | -1.883 | 3.77 | 1.854 | -1.844 | 3.698 |
For response time and the stability of investigating sensing device, alternately use water saturation N continuously
2With dry N
2Feed sensing device, repeat 8 times, survey DPV simultaneously, continuous sweep 10 circles under the same case.Figure 12 and Figure 13 are respectively water saturation N
2With dry N
2Under the condition, the 6th time 10 circle situations of change, the situation of other number of times is similar.As can be seen from the figure, water saturation N
2Down, the reduction-oxidation electric current increases to gradually and reaches stable; Dry N
2Down, the reduction-oxidation electric current is decreased to gradually and reaches stable.By calculating, can obtain the response time of this sensing device, at water saturation N
2Be down 55.5-74s, at dry N
2Be down 92.5-111s.
Under the identical atmosphere, the DPV that repeats 8 times the 10th circle schemes as Figure 14 and shown in Figure 15.Can obtain water saturation N by calculating
2Down, the mean value of the difference of oxidation and reduction current is 3.5778 A, and standard deviation is 3.535 * 10
-8, relative standard deviation is 0.998%.Dry N
2Down, oxidation is 1.5556 * 10 with the mean value of the difference of reduction
-7, standard deviation is 4.312 * 10
-9, relative standard deviation is 2.7719%.
5. adopt electrochemical method-square wave voltammetry (SWV) to measure the response of sensing device
Figure 16 is under the nitrogen atmosphere, the cyclic voltammogram of TCNQ under the different liquid water contents.Figure 17 maps to relative humidity for the difference of oxidation peak current and reduction peak current, becomes good linear relationship.Adopt identical experimental technique, that is, alternately feed sensing device continuously, repeat 8 times, survey square wave voltammetry simultaneously, continuous sweep 10 circles under the same case with water saturation N2 and dry N2.By calculating, the response time under the water saturation N2 is 21-28s, and the response time under the dry N2 is 42-49s.
Figure 18 and Figure 19 are under water saturation N2 and the dry N2, and the SWV of 8 order, 10 circles schemes.Can obtain by calculating, under the water saturation N2, the mean value of the difference of oxidation peak current and reduction peak current is 4.184 * 10
-6, standard deviation is 4.6023 * 10
-8, relative standard deviation is 1.1000%.Under the dry N2, the mean value of the difference of oxidation peak current and reduction peak current is 1.7254 * 10
-6, standard deviation is 4.143 * 10
-8, relative standard deviation is 2.401%.
Claims (9)
1. ampere type humidity sensing device, it consists of humidity-sensitive element, signal amplification circuit, detection loop, reference loop, gas system and the display control program that contains ionic liquid at room temperature and electrochemical probe, thereby the kinetic current of charging current by humidity-sensitive element and electrochemical probe is realized the detection to humidity.
2. ampere type humidity sensing device according to claim 1 is characterized in that, described ionic liquid at room temperature is selected from one or more in alkyl imidazole, alkyl pyridine class, quaternary ammonium salt, quaternary phosphonium salt or the benzimidazole ionic liquid.
3. ampere type humidity sensing device according to claim 2, it is characterized in that described ionic liquid at room temperature is selected from [1-ethyl-3 methylimidazole] [tetrafluoro boric acid], [1-butyl-3 methylimidazole] [hexafluorophosphoric acid], [1-Kui Ji-3-methyl] [tetrafluoro boric acid], [N-butyl-pyridinium] [hexafluorophosphoric acid], [N-butyl-pyridinium] [tetrafluoro boric acid], [N-heptyl pyridine] [hexafluorophosphoric acid], [dimethyl ethanol base 3-sulfonic acid propyl ammonium] [p-methyl benzenesulfonic acid], [three ethanol based 3-sulfonic acid propyl ammoniums] [p-toluenesulfonic acid], [diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate], [tetrabutyl phosphorus] [two-(trifluoromethyl) sulfimides], [tributyl-methyl phosphonium phosphorus] [methane-sulforic acid], [tributyl myristyl phosphorus] [two-(trifluoromethyl) sulfimides], [1-ethyl-3-butyl benzimidazole] [tetrafluoro boric acid], [1-ethyl-3-butyl benzimidazole] [[hexafluorophosphoric acid], in [1-ethyl-3-butyl benzimidazole] [p-methyl benzenesulfonic acid] one or more.
4. ampere type humidity sensing device according to claim 1 is characterized in that, described electrochemical probe is the oxidation-reduction pair that is dissolved in ionic liquid at room temperature.
5. ampere type humidity sensing device according to claim 4, it is characterized in that, described oxidation-reduction pair is selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine, benzoquinones, ferrocene, the potassium ferricyanide, potassium ferrocyanide, four ammino rutheniums, metalloporphyrin, metal phthalocyanine, perhaps its derivant.
6. the detection method of an air humidity, comprise and utilize the humidity sensing device consist of humidity-sensitive element, signal amplification circuit, detection loop and the reference loop of containing ionic liquid at room temperature and electrochemical probe, thereby realize detection humidity by mensuration to the kinetic current of the charging current of humidity-sensitive element and electrochemical probe.
7. the detection method of air humidity according to claim 7 is characterized in that, described ionic liquid at room temperature is selected from one or more in alkyl imidazole, alkyl pyridine class, quaternary ammonium salt, quaternary phosphonium salt or the benzimidazole ionic liquid.
8. the detection method of air humidity according to claim 7, it is characterized in that described ionic liquid at room temperature is selected from [1-ethyl-3 methylimidazole] [tetrafluoro boric acid], [1-butyl-3 methylimidazole] [hexafluorophosphoric acid], [1-Kui Ji-3-methyl] [tetrafluoro boric acid], [N-butyl-pyridinium] [hexafluorophosphoric acid], [N-butyl-pyridinium] [tetrafluoro boric acid], [N-heptyl pyridine] [hexafluorophosphoric acid], [dimethyl ethanol base 3-sulfonic acid propyl ammonium] [p-methyl benzenesulfonic acid], [three ethanol based 3-sulfonic acid propyl ammoniums] [p-toluenesulfonic acid], [diethyl alcohol radical sulfonic acid butyl ammonium] [hydrogen sulfate], [tetrabutyl phosphorus] [two-(trifluoromethyl) acid imides], [tributyl-methyl phosphonium phosphorus] [methane-sulforic acid], [tributyl myristyl phosphorus] [two-(trifluoromethyl) acid imides], [1-ethyl-3-butyl benzimidazole] [tetrafluoro boric acid], [1-ethyl-3-butyl benzimidazole] [[hexafluorophosphoric acid], in [1-ethyl-3-butyl benzimidazole] [p-methyl benzenesulfonic acid] one or more.
9. the detection method of air humidity according to claim 7, it is characterized in that, described electrochemical probe is selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine or benzoquinones, ferrocene, the potassium ferricyanide, potassium ferrocyanide, four ammino rutheniums, metalloporphyrin, metal phthalocyanine, perhaps its derivant.
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| CN107805227A (en) * | 2016-09-09 | 2018-03-16 | 中国科学院化学研究所 | Supermolecule ionic material and preparation method thereof and the purposes in moisture sensor device is prepared |
| CN110105228A (en) * | 2019-06-05 | 2019-08-09 | 中国科学院兰州化学物理研究所 | A kind of proton type ionic liquid and preparation method thereof and application as Water-based Lubricating Additives |
| CN112014441A (en) * | 2020-09-04 | 2020-12-01 | 北京化工大学常州先进材料研究院 | Ionic gel humidity sensor, preparation method and application thereof |
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| CN1241720A (en) * | 1998-11-13 | 2000-01-19 | 康达（成都）电子有限公司 | Humidity sensor and its manufacture |
| US7060169B2 (en) * | 2002-08-14 | 2006-06-13 | Mst Technology Gmbh | Electrochemical cell for gas sensor |
| DE10245337B4 (en) * | 2002-09-27 | 2018-12-20 | Robert Bosch Gmbh | Electrochemical sensor with ionic liquids as electrolyte |
| CN1186624C (en) * | 2003-02-28 | 2005-01-26 | 北京青鸟元芯微系统科技有限责任公司 | Chip of miniature electric resistance type moisture sensor, sensor and their preparing method |
| CN1661043A (en) * | 2004-12-10 | 2005-08-31 | 中国科学院长春应用化学研究所 | Biosensor prepared from embedding enzyme of sol-gel composite membrane of ion liquid |
| JP2006250579A (en) * | 2005-03-08 | 2006-09-21 | Denso Corp | Inspection device and characteristic adjusting method of humidity sensor |
| CN2840031Y (en) * | 2005-09-05 | 2006-11-22 | 南京埃森环境技术有限公司 | The little water detector of online resistance-capacitance type sulfur hexafluoride |
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| CN107805227A (en) * | 2016-09-09 | 2018-03-16 | 中国科学院化学研究所 | Supermolecule ionic material and preparation method thereof and the purposes in moisture sensor device is prepared |
| CN107805227B (en) * | 2016-09-09 | 2020-02-18 | 中国科学院化学研究所 | Supermolecule ion material, preparation method thereof and application thereof in preparing humidity sensing device |
| CN110105228A (en) * | 2019-06-05 | 2019-08-09 | 中国科学院兰州化学物理研究所 | A kind of proton type ionic liquid and preparation method thereof and application as Water-based Lubricating Additives |
| CN112014441A (en) * | 2020-09-04 | 2020-12-01 | 北京化工大学常州先进材料研究院 | Ionic gel humidity sensor, preparation method and application thereof |
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