CN101059476A - Electrochemical probe type humidity sensor - Google Patents
Electrochemical probe type humidity sensor Download PDFInfo
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- CN101059476A CN101059476A CN 200710041409 CN200710041409A CN101059476A CN 101059476 A CN101059476 A CN 101059476A CN 200710041409 CN200710041409 CN 200710041409 CN 200710041409 A CN200710041409 A CN 200710041409A CN 101059476 A CN101059476 A CN 101059476A
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Abstract
The invention relates to an electrochemical probe humidity sensor and a relative production, which comprises a humidity sensitive material with room temperature ion liquid, at least two electrodes, an electrochemical probe containing an oxidization reduction couple, a power supply, a current meter and a signal circuit. The oxidization reduction couple is dissolved in ion liquid, with reversible process. The invention is characterized in that the invention uses room temperature ion liquid as the sensitive film of humidity, which has dissolved reversal oxidization reduction couple as the electrochemical probe. The invention uses the cooperation of water molecule and room temperature ion liquid film, to affect the electrochemical reaction current of the oxidization reduction couple to realize humidity detection. The inventive humidity sensor has stable property, high sensitivity, simple structure and low cost or the like.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly relate to a kind of electrochemical probe type humidity sensor and preparation method thereof.
Background technology
Humidity is not only playing an important role aspect commercial production, quality management, the environment control, and is and the closely-related physical quantity of we human lives.In the moisture measurement field, humidity sensor is based on to be made on the basis that physical influence relevant with humidity or chemical effect can take place its functional material, and it has the function that the humidity physical quantity can be converted to measurable electric signal.Comprise capacitance type humidity sensor (CN1220393A), resistance type humidity sensor (CN1431489A), light fibre humidity transducer (CN1036635A) and weight resonance method, microwave method, thermo-electric method etc. by sensing principle; Can be divided into again by the humidity sensitive principle: the humidity sensor of Electrolyte type humidity sensor, polymer-type (CN1423123A), Ceramic Humidity Sensor (CN2168250Y), porous metal oxide humidity sensor (CN1571184A) etc.Chen has summarized the wet sensory material and the sensor mechanism of different moisture levels sensor at " sensor letters " 2005 on the 3:274-295.
Ionic liquid at room temperature is meant the material that is in a liquid state and is made of ion under near temperature room temperature or the room temperature, be another class green solvent system behind water and supercritical carbon dioxide.In twentieth century nineties, the ionic liquid stable to water and air synthesized to come out successively.These ionic liquids are mostly by being made up of with fluo anion respectively alkyl pyridine kation, alkyl imidazole kation, quaternary ammonium alkyl salt cation and alkyl quaternary microcosmic salt kation.Because they have good physicochemical characteristicss such as low-steam pressure, high ionic conductivity, Heat stability is good, electrochemical window be wide and all are with a wide range of applications in fields such as galvanochemistry, chemosynthesis, detachment process, catalysis.The water wettability ionic liquid at room temperature can with water immiscible phase, even hydrophobic ionic liquid also can have a spot of water-soluble separating therein.After water is dissolved in ionic liquid, can exert an influence to physicochemical properties such as ion liquid viscosity, electric conductivity, in addition, the liquid water content in the ionic liquid also can make the coefficient of diffusion that is dissolved in the solute in the ionic liquid change.Utilizing liquid water content to the characteristic that ionic liquid character changes, just may be the mensuration that the sensitive membrane of sensor realizes humidity with the ionic liquid at room temperature.
At present, yet there are no, be applied to the galvanochemistry humidity sensor, adopt electrochemical means, make the similar report of electrochemical probe type humidity sensor based on ionic liquid and the physicochemical property that are dissolved in the uniqueness of oxidation-reduction pair wherein.
Summary of the invention
Technical matters to be solved
Technical matters to be solved by this invention provides a kind of ionic liquid humidity sensor, to overcome existing conventional amperometric sensor usually with the electrochemical reaction response signal of detected object, the electrochemical decomposition voltage of hydrone is higher and be subjected to the influence of electrode surface character bigger, directly carries out amperometric determination and has the defective that the generation interference is measured in a lot of electric active matters confrontations.
Technical scheme
One of technical scheme of the present invention provides a kind of electrochemical probe type humidity sensor, its composition comprises: contain the humidity sensitive material of ionic liquid at room temperature, at least two electrodes and be electrochemical probe, power supply, galvanometer and the signal circuit of composition with the oxidation-reduction pair, wherein, described oxidation-reduction pair is dissolved in the ionic liquid, and is reversible.
One of preferred version of above-mentioned electrochemical probe type humidity sensor is that described oxidation-reduction pair is selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine or benzoquinones, perhaps its derivant.
Two of the preferred version of above-mentioned electrochemical probe type humidity sensor is that described oxidation-reduction pair is selected from ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin or metal phthalocyanine, perhaps its derivant.
Three of the preferred version of above-mentioned electrochemical probe type humidity sensor 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.The scheme that is more preferably is 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.
Four of the preferred version of above-mentioned electrochemical probe type humidity sensor is, but its composition also comprises the ionic liquid carrier that ion liquid container immobilized ionic liquid film or gel, adsorbable ion liquid cotton-shaped carrier or silicon chip are constituted.
Described ionic liquid carrier can be porous polyethylene film or polymer gel, the ionic liquid solution of functional composite material-tetracyano-p-quinodimethane can be adsorbed in the film, realizes the immobilization of ionic liquid at room temperature.
Five of the preferred version of above-mentioned electrochemical probe type humidity sensor is that described electrode is metal electrode or nonmetal electrode.Further preferred, described nonmetal electrode is metal electrode, carbon electrode or semi-conducting electrode.
Six of the preferred version of above-mentioned electrochemical probe type humidity sensor is that when described electrode was three, one of them was a contrast electrode.They are by respectively as the anode and cathode of electrode loop when described electrode is two.
Two of technical scheme of the present invention provides a kind of preparation method of electrochemical probe type humidity sensor, and its step comprises: the preparation room temperature ionic liquid; Oxidation-reduction pair is dissolved in the ionic liquid; With ionic liquid at room temperature, oxidation-reduction pair, ionic liquid carrier are become humidity sensor with combination of electrodes.
The preparation method's of above-mentioned electrochemical probe type humidity sensor preferred version 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.
Beneficial effect
The invention provides a kind of novel electrochemical probe type humidity sensor.By adding the reversible redox electricity, utilize the influence of hydrone, thereby and then influence the detection of the current-responsive realization of electrochemical probe humidity to ionic liquid character to as electrochemical probe.Be characterized in:
1) with the humidity sensitive material of ionic liquid at room temperature as sensor.Wherein selected ionic liquid at room temperature can be ionic liquid at room temperature such as various common 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 sensor.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; Perhaps ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin or metal phthalocyanine, 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.Owing to used electrochemical probe as the electrochemical response semiochemicals, avoided using the needed high working voltage of direct brine electrolysis molecule, caused other electroactive substances are to measuring the interference that produces.And the low-power consumption that reduces sensor that operating voltage is brought.So that humidity sensor of the present invention has is highly sensitive, good stability, advantage such as easy to make, low in energy consumption.
Description of drawings
Fig. 1 is the structural representation of humidity sensor.1: the immobilized room temperature ionic liquid film; 2 electrodes; 3 silicon chips; 4 power supplys; 5 galvanometer; 6 signal circuits.
Fig. 2 is a humidity sensor performance examining system synoptic diagram.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. 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 sensor 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 sensor cyclic voltammetric and the graph of a relation of relative humidity.
Fig. 6 be humidity sensor in continuous 8 dryings and water saturated atmosphere transfer process, the stable circulation voltammogram under water saturated atmosphere.
Fig. 7 be humidity sensor in continuous 8 dryings and water saturated atmosphere transfer process, the stable circulation voltammogram under dry atmosphere.
Fig. 8 be humidity sensor 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 sensor 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 sensor 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 sensor 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 sensor to by dry atmosphere.
Continuous 10 circle differentiated pulse voltammograms when Figure 13 converts dry atmosphere for humidity sensor to by water saturated atmosphere.
Figure 14 be humidity sensor in continuous 8 dryings and water saturated atmosphere transfer process, the stable differentiated pulse voltammogram under water saturated atmosphere.
Figure 15 be humidity sensor in continuous 8 dryings and water saturated atmosphere transfer process, the stable differentiated pulse voltammogram under dry atmosphere.
Figure 16 is in the humidity sensor 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 sensor 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 sensor in continuous 8 dryings and water saturated atmosphere transfer process, the stable square wave voltammogram under water saturated atmosphere.
Figure 19 be humidity sensor 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 ".
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 0.058mol Ag 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 colourless 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:
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:
Embodiment 6
[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:
[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:
[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:
[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:
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.
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
-
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 Figure 1A 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 Figure 1B.
Embodiment 34
Polymer film absorbent-type humidity sensor
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, 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 the wet quick part of humidity sensor, make humidity sensor with parts such as power supply, galvanometer and signal circuits again, shown in Figure 1A and 1B.
Embodiment 35
The making of silicon chip three electrode moisture sensors
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 the wet quick part of humidity sensor, makes silicon chip moisture sensor shown in Fig. 1 C with parts such as power supply, galvanometer and signal circuits again.
Embodiment 36
The making of polymer gel type moisture sensor
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 the wet quick part of humidity sensor after the vacuum drying, again with power supply, parts such as galvanometer and signal circuit are made polymer gel type moisture sensor together, and structure is shown in Figure 1A and 1B.
Embodiment 37
The making of silicon gel-type moisture sensor
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 the wet quick part of humidity sensor after the vacuum drying, make silicon polymer gel-type moisture sensor with parts such as power supply, galvanometer and signal circuits again, structure is shown in Figure 1A and 1B.
Embodiment 38
The making of sandwich type moisture sensor
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 the wet quick part of humidity sensor, with parts such as power supply, galvanometer and the signal circuit type moisture sensor that sandwiches, structure is shown in Fig. 1 D again.
Embodiment 39
The test of ion liquid type moisture sensor
The device of experiment as shown in Figure 2.
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 sensor is 5L/min.
2. oxygen is to hygrometric interference
Measured the humidity sensor 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 of the response of electrochemical method-cyclic voltammetry (CV) survey sensor 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 sensor, repeat 8 times, survey cyclic voltammetry simultaneously, continuous sweep 20 circles under the same case, the stability and the response time of investigation sensor.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, sensor 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 the response of electrochemical method-differential pulse voltammetry (DPV) survey sensor
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 sensor.
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 sensor, alternately use water saturation N continuously
2With dry N
2Feed sensor, 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 sensor, 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 3.5778A, 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 the response of electrochemical method-square wave voltammetry (SWV) survey sensor
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 sensor 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 (10)
1. electrochemical probe type humidity sensor, its composition comprises: contain the humidity sensitive material of ionic liquid at room temperature, at least two electrodes and be electrochemical probe, power supply, galvanometer and the signal circuit of composition with the oxidation-reduction pair, wherein, described oxidation-reduction pair is dissolved in the ionic liquid, and is reversible.
2. electrochemical probe type humidity sensor according to claim 1 is characterized in that described oxidation-reduction pair is selected from tetracyano-p-quinodimethane, N, N, N ', N '-tetramethyl-para-phenylene diamine or benzoquinones, perhaps its derivant.
3. electrochemical probe type humidity sensor according to claim 1 is characterized in that, described oxidation-reduction pair is selected from ferrocene, the potassium ferricyanide, four ammino rutheniums, metalloporphyrin or metal phthalocyanine, perhaps its derivant.
4. electrochemical probe type humidity sensor 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.
5. electrochemical probe type humidity sensor according to claim 4, 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.
6. electrochemical probe type humidity sensor according to claim 1, it is characterized in that, but its composition also comprises the ionic liquid carrier that ion liquid container immobilized ionic liquid film or gel, adsorbable ion liquid cotton-shaped carrier or silicon chip are constituted.
7. electrochemical probe type humidity sensor according to claim 1 is characterized in that, described electrode is metal electrode, carbon electrode or semi-conducting electrode.
8. electrochemical probe type humidity sensor according to claim 1 is characterized in that, when described electrode was three, one of them was a contrast electrode.
9. the preparation method of an electrochemical probe type humidity sensor, its step comprises: the preparation room temperature ionic liquid; Oxidation-reduction pair is dissolved in the ionic liquid; Ionic liquid at room temperature, oxidation-reduction pair, ionic liquid carrier are become humidity sensor with combination of electrodes.
10. the preparation method of electrochemical probe type humidity sensor according to claim 9, it 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.
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