CN103063721B - Solid nitrite ion electrode based on conductive polyaniline and preparing method thereof - Google Patents
Solid nitrite ion electrode based on conductive polyaniline and preparing method thereof Download PDFInfo
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- CN103063721B CN103063721B CN201210537816.9A CN201210537816A CN103063721B CN 103063721 B CN103063721 B CN 103063721B CN 201210537816 A CN201210537816 A CN 201210537816A CN 103063721 B CN103063721 B CN 103063721B
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- nitrite ion
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- aniline
- tinsel
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 72
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 71
- 229940005654 nitrite ion Drugs 0.000 title claims abstract description 71
- 239000007787 solid Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000035945 sensitivity Effects 0.000 claims abstract description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000012528 membrane Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 22
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000012047 saturated solution Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 6
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 5
- DBSSKVANIRDWJE-UHFFFAOYSA-N B(O)(O)O.FC(C=1C=C(C=C(C1)C(F)(F)F)[K])(F)F Chemical compound B(O)(O)O.FC(C=1C=C(C=C(C1)C(F)(F)F)[K])(F)F DBSSKVANIRDWJE-UHFFFAOYSA-N 0.000 claims description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 5
- 230000004087 circulation Effects 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 238000009360 aquaculture Methods 0.000 abstract 1
- 244000144974 aquaculture Species 0.000 abstract 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 14
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 9
- -1 Poly(vinyl chloride) Polymers 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UONHCVYLDTWLAR-JXHUONGFSA-M nitrite ionophore i Chemical compound O.[Co+2].N#[C-].[O-]Cl(=O)(=O)=O.C([C@@H]1\C=2\N=C(C1(C)C)\C=C1/N/C([C@@]([C@@H]1CCC(=O)OCCC=1C=CC=CC=1)(C)CC(=O)OCCC=1C=CC=CC=1)=C(C1=N[C@@]([C@@]([C@@H]1CCC(=O)OCCC=1C=CC=CC=1)(C)CC(=O)OCCC=1C=CC=CC=1)(C)C1N=C([C@]([C@H]1CC(=O)OCCC=1C=CC=CC=1)(C)CCC(=O)OCCC=1C=CC=CC=1)/C=2C)/C)CC(=O)OCCC1=CC=CC=C1 UONHCVYLDTWLAR-JXHUONGFSA-M 0.000 description 3
- CXVOIIMJZFREMM-UHFFFAOYSA-N 1-(2-nitrophenoxy)octane Chemical compound CCCCCCCCOC1=CC=CC=C1[N+]([O-])=O CXVOIIMJZFREMM-UHFFFAOYSA-N 0.000 description 2
- GAYXVMROHDLBTC-UHFFFAOYSA-N 2,2-bis(2-ethylhexyl)decanedioic acid dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC.CCCCC(CC)CC(C(O)=O)(CC(CC)CCCC)CCCCCCCC(O)=O GAYXVMROHDLBTC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000001488 breeding effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- WMGFZOGMMFWUJM-GRQAXCPQSA-N cobalt(3+);propyl 3-[(1r,2s,3s,5z,7s,8s,9z,13s,14z,17r,18r)-1,2,5,7,12,12,15,17-octamethyl-2,7,18-tris(2-oxo-2-propoxyethyl)-3,13,17-tris(3-oxo-3-propoxypropyl)-8,13,18,19-tetrahydro-3h-corrin-22-id-8-yl]propanoate;dicyanide Chemical compound [Co+3].N#[C-].N#[C-].N1=C(\C(C)=C2/[N-]C(/[C@H]([C@]2(C)CC(=O)OCCC)CCC(=O)OCCC)=C\C=2C([C@H](CCC(=O)OCCC)/C(/N=2)=C/2C)(C)C)[C@@H](CCC(=O)OCCC)[C@@](CC(=O)OCCC)(C)[C@]1(C)C1[C@H](CC(=O)OCCC)[C@](CCC(=O)OCCC)(C)C\2=N1 WMGFZOGMMFWUJM-GRQAXCPQSA-N 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a solid nitrite ion electrode based on conductive polyaniline and a preparing method thereof. The solid nitrite ion electrode comprises a metal wire, the conductive polyaniline, soluble conductive polyaniline, nitrite ion sensitive film and a heat shrink tube, wherein a layer of the conductive polyaniline is electroplated on the surface of the lower portion of the metal wire, a layer of the soluble conductive polyaniline is wrapped on the outer surface of the conductive polyaniline, the nitrite ion sensitive film is wrapped on the outer surface of the soluble conductive polyaniline, and the heat shrink tube is wrapped on a portion located in the middle of the metal wire and with a distance greater than 0.5-1cm from the end portion of the nitrite ion sensitive film. The solid nitrite ion electrode based on the conductive polyaniline has the advantages of being high in mechanical strength, large in toughness, high in sensitivity, small in size, quick in detection response, low in detection limit, long in service life and the like. When matched with a solid reference electrode for use, the solid nitrite ion electrode based on the conductive polyaniline is applicable to on line detection and long-term in situ monitoring of nitrite ion content in seawater, aquaculture water, and chemistry or chemical industry water mediums.
Description
Technical field
The present invention relates to electrochemical detection technology, relate in particular to a kind of solid nitrite ion electrode based on electrically conductive polyaniline and preparation method thereof.
Background technology
Water body Nitrite Ion Content is the important parameter that carries out environmental evaluation, and for the activity of understanding organism in water, microorganism, and environmental pollution monitoring is significant.At present all belong to liquid membrane electrode for the business nitrite ion electrode of this type of object, electrode interior need to fill electrolyte solution, i.e. so-called " salt bridge ", and its effect is the response signal that conduction detects between ion sensitive membrane and plain conductor.The major defect of liquid film type electrode comprises: volume more greatly, more fragile, easily there is signal drift, serviceable life is short.
Compare with traditional liquid film type electrode, solid electrode has that volume is little, intensity is high, and the comprehensive advantages such as long service life, are suitable for natural water body, especially the long term monitoring of marine environment and online observation.The present invention is directed to this demand and proposed a kind of solid nitrite ion electrode based on electrically conductive polyaniline and preparation method thereof.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of solid nitrite ion electrode based on electrically conductive polyaniline and preparation method thereof is provided.
The object of the invention is to be achieved through the following technical solutions:
Solid nitrite ion electrode based on electrically conductive polyaniline comprises tinsel, electrically conductive polyaniline, fusible conductive polyaniline, nitrite ion sensitive membrane, heat-shrink tube, tinsel lower surface is electroplated one deck electrically conductive polyaniline, at the coated one deck fusible conductive polyaniline of outside surface of electrically conductive polyaniline, outside surface at fusible conductive polyaniline is coated with again nitrite ion sensitive membrane, in the middle part of tinsel and from more than nitrite ion sensitive membrane end 0.5-1 centimetre part outside, is coated with heat-shrink tube.
Described tinsel is Ag, Au, Pt, or surface is coated with copper wire or the nickel wire of Ag, Au, Pt metal film.Described fusible conductive polyaniline be tinsel in the hydrochloric acid solution of aniline monomer, electroplate form.Described fusible conductive polyaniline is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.
The preparation method's of the solid nitrite ion electrode based on electrically conductive polyaniline step is as follows:
1) by length be the tinsel of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline by cyclic voltammetry on top layer wiry by CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline, dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 DEG C of baking ovens, dries 4～6 hours;
4) the nitrite ion carrier of company of Sigma and film forming agent, plastifier, kation impedance agent are dissolved in DMF, are mixed with mixed solution, it consists of by percentage to the quality:
Composition A:
Nitrite ion carrier I 1.0%;
Four [3,5-bis-(trifluoromethyl) phenyl] potassium borate 0.3%;
2-nitrobenzene octyl ether 65.7%;
PVC 33.0% ；
Composition B:
Nitrite ion carrier I 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
Composition C:
Nitrite ion carrier II 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
5) dip mixed solution 1～3 time with the surperficial electrode that is coated with soluble polyaniline, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane after volatilizing completely;
6) heat-shrink tube is coated in the middle part of tinsel and from more than nitrite ion sensitive membrane end 0.5-1 centimetre part.
Exploring electrode volume of the present invention is little, highly sensitive, and probe response is fast, has very high physical strength and toughness, has good serviceability under condition of high voltage.Therefore be applicable to the nitrite ion content in seawater, breeding water and chemistry, chemical industry aqueous medium to survey online and long-term in-situ monitoring, compared with traditional sampling analysis, both alleviated working strength, avoid the secondary pollution in sampling process, improve again the real-time of data, reliability.
brief description of the drawings:
Fig. 1 is the structural representation of the solid nitrite ion electrode based on electrically conductive polyaniline;
In figure: tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, nitrite ion sensitive membrane 4, heat-shrink tube 5.
Embodiment
Solid nitrite ion electrode based on electrically conductive polyaniline comprises tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, nitrite ion sensitive membrane 4, heat-shrink tube 5, tinsel 1 lower surface is electroplated one deck electrically conductive polyaniline 2, at the coated one deck fusible conductive polyaniline 3 of outside surface of electrically conductive polyaniline 2, outside surface at fusible conductive polyaniline 3 is coated with again nitrite ion sensitive membrane 4, tinsel 1 middle part and more than 0.5～1 centimetre away from nitrite ion sensitive membrane 4 ends part outside is coated with heat-shrink tube 5 be.
Described tinsel 1 is Ag, Au, Pt, and its effect is that the response signal that electrode surface is formed by nitrite ion carrier passes to detection circuit.Recommendation noble metal, the undesired signal that can avoid the dissolved constituent in tinsel self and water body to form because of electrochemical reaction.For reducing costs, can use copper wire, nickel wire that surface is coated with Ag, Au, Pt as electrode base material.
Described electrically conductive polyaniline 2 be tinsel 1 in the hydrochloric acid solution of aniline monomer, electroplate form.Conductive polyaniline film 2 has good electric conductivity, and the electric current conduction between the two does not exist obvious interlayer barrier; In addition, conductive polyaniline film has changed surface nature wiry, has increased the affinity between the organic coating layer of it and follow-up formation.
Described fusible conductive polyaniline 3 is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.The doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline can use commercial product, also can oneself be synthetic, and its chemical synthesis process is consistent with polyaniline, is the mixture replacing aniline of aniline and 2,5-dimethoxyaniline being pressed to 5:1 to 1:5.
Use the doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline to there are triple effects:
it has electric conductivity as electrically conductive polyaniline;
the plated conductive polyaniline composition of it and internal layer approaches, and chemical affinity is strong;
it and outermost layer nitrite ion carrier can be dissolved in N, dinethylformamide, thereby in the process of coated nitrite ion carrier, can be partly dissolved, be made nitrite ion sensitive membrane and soluble polyaniline close contact, conductive impairment between eliminating layer.
The preparation method's of the solid nitrite ion electrode based on electrically conductive polyaniline step is as follows:
1) by length be the tinsel 1 of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline 2 by cyclic voltammetry on the top layer of tinsel 1 by CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline 2, dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 DEG C of baking ovens, dries 4～6 hours;
4) the nitrite ion carrier of company of Sigma and film forming agent, plastifier, kation impedance agent are dissolved in DMF, are mixed with mixed solution, it consists of by percentage to the quality:
Composition A:
Nitrite ion carrier I 1.0%;
Four [3,5-bis-(trifluoromethyl) phenyl] potassium borate 0.3%;
2-nitrobenzene octyl ether 65.7%;
PVC 33.0% ；
Composition B:
Nitrite ion carrier I 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
Composition C:
Nitrite ion carrier II 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
5) dip mixed solution 1～3 time with the surperficial electrode that is coated with soluble polyaniline 3, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane 4 after volatilizing completely; Vacuum drying under recommendation normal temperature, avoids using hyperthermia drying, is the activity in order better to protect nitrite ion sensitive membrane;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and from more than 0.5～1 centimetre part in nitrite ion sensitive membrane 4 ends.
Embodiment 1
1) by length be the tinsel 1 of 10 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) take 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 1M; Electroplate one deck electrically conductive polyaniline 2 by cyclic voltammetry on the top layer of tinsel 1 by CHI760D electrochemical workstation.
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulates, and has electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer (mol ratio of the two is 5:1) of 5-dimethoxyaniline, be dissolved in and in 10mlDMF, be mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that surface is coated with electrically conductive polyaniline 2, dinethylformamide (DMF) saturated solution, be inserted in the crucible that fills sand, in 80 DEG C of baking ovens, dry 6 hours;
4) nitrite ion carrier and attached component thereof are dissolved in DMF according to composition A, are mixed with mixed solution, its composition A is by percentage to the quality:
Nitrite ion carrier (Nitrite ionophore I) 1.0%,
Four [3,5-bis-(trifluoromethyl) phenyl] potassium borate,
（Potassium tetrakis [3,5- bis (trifluoromethyl) phenyl ]）0.3% ，
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 65.7%,
PVC(Poly(vinyl chloride) high molecular weight)33.0% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and from the more than 0.5 centimetre part in nitrite ion sensitive membrane 4 ends.
Embodiment 2
1) by length be the tinsel 1 of 8 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 2M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) take respectively 10.1388g hydrochloric acid, 9.313g aniline, in 100ml volumetric flask, add water to scale and obtain the solution of hydrochloric acid: aniline=1M:1M; Electroplate one deck electrically conductive polyaniline 2 by cyclic voltammetry on the top layer of tinsel 1 by CHI760D electrochemical workstation.
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulates, and has electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer (mol ratio of the two is 1:1) of 5-dimethoxyaniline, be dissolved in and in 10mlDMF, be mixed with saturated solution, dip rapidly the DMF saturated solution of soluble polyaniline with the electrode that surface is coated with electrically conductive polyaniline 2, be inserted in the crucible that fills sand, in 100 DEG C of baking ovens, dry 5 hours;
4) nitrite ion carrier and attached component thereof are dissolved in DMF according to composition A, are mixed with mixed solution, its composition A is by percentage to the quality:
Nitrite ion carrier (Nitrite ionophore I) 1.0%,
Four [3,5-bis-(trifluoromethyl) phenyl] potassium borate,
（Potassium tetrakis [3,5- bis (trifluoromethyl) phenyl ]）0.3% ，
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 65.7%,
PVC(Poly(vinyl chloride) high molecular weight)33.0% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat once, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and from the more than 0.8 centimetre part in nitrite ion sensitive membrane 4 ends.
Embodiment 3
1) by length be the tinsel 1 of 10 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) take 0.9720g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 0.5M; Electroplate one deck electrically conductive polyaniline 2 by cyclic voltammetry on the top layer of tinsel 1 by CHI760D electrochemical workstation;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulates, and has electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer (mol ratio of the two is 5:1) of 5-dimethoxyaniline, be dissolved in and in 10mlDMF, be mixed with saturated solution, dip rapidly the DMF saturated solution of soluble polyaniline with the electrode that surface is coated with electrically conductive polyaniline 2, be inserted in the crucible that fills sand, in 150 DEG C of baking ovens, dry 4 hours;
4) nitrite ion carrier and attached component thereof are dissolved in DMF according to composition B, are mixed with mixed solution, its composition B is by percentage to the quality:
Nitrite ion carrier (Nitrite ionophore I) 1.0%,
Di-n-octyl sebacate (Bis (2-ethylhexyl) sebacate) 66.0%,
PVC(Poly(vinyl chloride) high molecular weight)33.0% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat twice, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and from the more than 1 centimetre part in nitrite ion sensitive membrane 4 ends.
Embodiment 4
1) by length be the tinsel 1 of 15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) take 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 1M; Electroplate one deck electrically conductive polyaniline 2 by cyclic voltammetry on the top layer of tinsel 1 by CHI760D electrochemical workstation;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulates, and has electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer (mol ratio of the two is 1:5) of 5-dimethoxyaniline, be dissolved in and in 10mlDMF, be mixed with saturated solution, dip rapidly the DMF saturated solution of soluble polyaniline with the electrode that surface is coated with electrically conductive polyaniline 2, be inserted in the crucible that fills sand, in 150 DEG C of baking ovens, dry 4 hours;
4) nitrite ion carrier and attached component thereof are dissolved in DMF according to composition C, are mixed with mixed solution, its composition C is by percentage to the quality:
Nitrite ion carrier (Nitrite ionophore II) 1.0%,
Di-n-octyl sebacate (Bis (2-ethylhexyl) sebacate) 66.0%,
PVC(Poly(vinyl chloride) high molecular weight)33.0% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat once, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and from the more than 0.5 centimetre part in nitrite ion sensitive membrane 4 ends.
Embodiment 5
Solid nitrite ion is selected the demarcation of electrode,
Preparation nitrite ion standard solution mother liquor used is the sodium nitrite solution of the 0.1M of company of Sigma production, and thinning agent used is deionized water.
Pipette 10ml10
-1the sodium nitrite solution of M, is diluted to 100ml with deionized water, makes 10
-2the sodium nitrite solution of M, successively dilution preparation 10
-3m, 10
-4m, 10
-5m, 10
-6the sodium nitrite solution of M.
Select electrode as working electrode taking self-control nitrite ion, commodity Ag/AgCl electrode is contrast electrode, respectively working electrode and contrast electrode are connected to CHI760D electrochemical workstation, the response electric signal from high concentration toward low concentration sequentially determining, according to response signal intensity and concentration relationship mapping, the two linear relationship slope is between 57.2 ~ 60.4, and meeting can Si Tedinglv.
Claims (1)
1. a preparation method for the solid nitrite ion electrode based on electrically conductive polyaniline, is characterized in that its step is as follows:
1) by length be the tinsel (1) of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with being dried after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline (2) by cyclic voltammetry on the top layer of tinsel (1) by CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel (1) does anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, wherein aniline and 2, the mol ratio of the doped hydrochloride multipolymer of 5-dimethoxyaniline is 1:5～5:1, is mixed with saturated solution taking DMF as solvent, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline (2), dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 DEG C of baking ovens, dries 4～6 hours;
4) the nitrite ion carrier of company of Sigma and film forming agent, plastifier, kation impedance agent are dissolved in DMF, are mixed with mixed solution, it consists of by percentage to the quality:
Composition A:
Nitrite ion carrier I 1.0%;
Four [3,5-bis-(trifluoromethyl) phenyl] potassium borate 0.3%;
2-nitrobenzene octyl ether 65.7%;
PVC 33.0% ；
Composition B:
Nitrite ion carrier I 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
Composition C:
Nitrite ion carrier II 1.0%;
Di-n-octyl sebacate 66.0%;
PVC 33.0% ；
5) dip mixed solution 1～3 time with the electrode that surface is coated with soluble polyaniline (3), be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains nitrite ion sensitive membrane (4) after volatilizing completely;
6) heat-shrink tube (5) is coated in the middle part of tinsel (1) and from more than 0.5～1 centimetre part in nitrite ion sensitive membrane (4) end.
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