CN1306205A - Process for preparing ammonia cation free-radical modified single-layer membrane of carbon electrode - Google Patents
Process for preparing ammonia cation free-radical modified single-layer membrane of carbon electrode Download PDFInfo
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- CN1306205A CN1306205A CN 00121846 CN00121846A CN1306205A CN 1306205 A CN1306205 A CN 1306205A CN 00121846 CN00121846 CN 00121846 CN 00121846 A CN00121846 A CN 00121846A CN 1306205 A CN1306205 A CN 1306205A
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Abstract
A process for preparing ammonia cations and free radicals modified carbon electrode includes dissolving the amino compound and long-chain diamido compound containing 7,10, or 12 carbon atoms in absolute alcohol solution, anhydrous acetonitrile solution, or alkaline aqueous solution, adding the supporting electrolyte, putting electrode in the electrolytic liquid, and cyclic voltammetry scan. Its advantages include uniform single-layer film, and high repeatability and stability.
Description
The invention belongs to the preparation method of ammonia radical cation at carbon electrodes modified monolayer film.
Chemically modified electrode be nearly two during the last ten years in galvanochemistry and Electroanalytical Chemistry than the active research field.In used electrode material, carbon electrode is compared with electrodes such as other precious metals pd, Ag, Au, because wideer electrochemical window is arranged, and more negative hydrogen deposition potential, thereby its finishing becomes the emphasis of electrochemist's research.The modification of carbon electrode is adopted usually to drip and is coated with or physisorphtion [N.Oyama, K.B.Yap, F.C.Anson, J.Electroanal.Chem., 1979,100,233], must carry out strong oxidation before general the modification or the pre-service of reducing by force increases the carbon electrodes activity, for example, Palec ě k etc. is adsorbed onto graphite electrode surface with β-ferrocene diamines, but adsorbate firm inadequately [E.Palec ě k, F.Jelen, C.Teijeiro, V.Fucik, T.M.Jovin, Anal.Chim.Acta, 1993,273,175].As introducing the oxygen base, the carbon electrode that amino, halogen etc. are modified is more stable with the covalent bonding rule.But carry out that the pre-service to electrode surface requires harshness in the process of covalent bonding, follow-up surperficial organic synthesis complex steps is difficult to obtain the result [S.Mazur, T.Matusinovic, K.Camman, J.Am.Chem.Soc., 1977,99,3888] who estimates.
Recently, the free radical grafting method is to be used for the method preferably of modified graphite electrode.Allongne etc. adopt the electroreduction of diazo salt to form radical anion, thereby form and carbon electrodes covalence graft [P.Allongue with individual layer, M.Delamar, B.Desbat, O.Fagebarme, R.Hitmi, J.Pinson, J.-M.Sav é ant, J.Am.Chem.Soc.1997,119,201].But dressing agent only is confined to diazenium compound, and the dressing agent instability, and itself easily decomposes in electrochemical process.
The preparation method who the purpose of this invention is to provide a kind of ammonia cation free-radical modified single-layer membrane of carbon electrode, be about to have amino compound dissolution in ethanol solution, anhydrous acetonitrile or alkaline aqueous solution, add supporting electrolyte, electrode is put in carries out cyclic voltammetry scan in this electrolytic solution, promptly obtain amidized carbon electrode.
In electro-oxidation process, the amino of dressing agent at first loses an electronics and generates the ammonia radical cation, and the carbon atom generation electrophilic addition reaction of this living radical and electrode surface generates carbon nitrogen covalent bond.Because dressing agent and electrode surface are covalently bound, the chemical modification carbon electrode of preparing like this is stable, and chemical modifier is fixed on electrode surface with the form of individual layer.Selected dressing agent is extensive, is suitable for the various kinds of amine compounds.The preparation method is simple, and the current potential gentleness that applies can not destroyed electrode surface, and is applicable to multiple material with carbon element.And single-layer membrane structure is even, favorable reproducibility, and stability more is better than the gold electrode modified.
The present invention adopts following modification step:
With dressing agent 4-aminobenzoic acid, 4,4 '-two (n-aminopropyl) purpurine is dissolved in the ethanol solution of 0.1M lithium perchlorate respectively, with the dressing agent 4-aminopyridine, the amino butyl phosphoric acid of 4-is dissolved in the 0.1M sodium hydrate aqueous solution respectively, with dressing agent 3,4-dihydroxy benzyl ammonia, 1,7-diamino in heptan, 1,10-diamino in the last of the ten Heavenly stems, 1,12-diamido dodecane is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine respectively, and the concentration of dressing agent is 1～100mM; At room temperature clean carbon electrode: vitreous carbon, carbon fiber, graphite electrode, be immersed in the above-mentioned electrolyte solution, carbon paste electrode is immersed in the electrolyte aqueous solution as working electrode, platinized platinum is as to electrode, in absolute ethyl alcohol and the acetonitrile solution with Ag/Ag
+Being contrast electrode, is contrast electrode with Ag/AgCl in the aqueous solution, in 0～1.4V potential range, at 10～100mVs
-1The speed of sweeping carry out down cycle potentials scanning 2～70 minutes, take out and wash, with ethanol or water ultrasonic cleaning, promptly obtained carboxyl again, amino, phosphate, the unimolecular film carbon electrode of pyridine or purpurine functional group.
Ammonia radical cation method modified graphite electrode of the present invention, the preparation method is simple, quick.Electrode need not to carry out pre-activated processing under strong acid, highly basic or the noble potential before modifying, and a step finishes, and sweep time is short.Modify mild condition.Adopt ethanol, acetonitrile or alkaline aqueous solution to make solvent, the scanning current potential is moderate, and is harmless to electrode.Because the amino of purpose compound is covalently bound in electrode surface formation carbon nitrogen in the scan round process, therefore formed modified membrane is more stable.And modified membrane is smooth, a uniform unimolecular film on electrode.The favorable reproducibility of preparation.Owing to adopt carbon electrode, compare with noble metal electrode, the electrochemical window broad, the object that can study is more extensive.
Modified membrane on the carbon electrode that the present invention proposes, under certain acidity condition, the ionogen that is rich in electric charge can be provided, or other functional group, thereby for the galvanochemistry of charged species or biomolecule etc. and the research of other character provide a precursor basement membrane preferably, promote biology sensor, the research and development of material etc.
Embodiment provided by the invention is as follows:
Embodiment 1:
The 4-aminobenzoic acid is modified glassy carbon electrode.Clean glassy carbon electrode is put into the ethanol solution of 10mM 4-aminobenzoic acid+0.1M lithium perchlorate.Use Ag/Ag
+For contrast electrode 0～+ the 0.9V potential range in, with 10mVs
-1Sweep fast cycle potentials scanning 30 minutes.Take out electrode washing, with ethanol and water ultrasonic cleaning respectively, promptly make 4-aminobenzoic acid monofilm modified electrode again.
Embodiment 2:
The 4-aminopyridine decorating carbon paste electrode.Freshly prepd carbon paste electrode is put into 50mM 4-aminopyridine+0.1M sodium hydrate aqueous solution, with Ag/AgCl be contrast electrode 0～+ the 1.0V potential range in, with 50mVs
-1The speed of sweeping carried out cycle potentials scanning 7 minutes.Take out electrode, the water flushing promptly makes the 4-aminopyridine decorating carbon paste electrode.
Embodiment 3:
1,7-heptamethylene diamine modified glassy carbon electrode.Preparation 100mM 1, the anhydrous acetonitrile of 7-diamino in heptan+0.1M perchloric acid 4-butyl amine.Clean glassy carbon electrode is put into this electrolytic solution, use Ag/Ag
+As contrast electrode 0～+ the 1.2V potential range in, with 80mVs
-1The speed of sweeping carried out cycle potentials scanning 2 minutes.Take out electrode washing, with ethanol and water ultrasonic cleaning respectively, promptly make alkyl diamino individual layer and modify glassy carbon electrode again.
Embodiment 4:
1,10-decamethylene diamine modified glassy carbon electrode.Preparation 100mM 1, the anhydrous acetonitrile of 10-diamino in the last of the ten Heavenly stems+0.1M perchloric acid 4-butyl amine.As follows embodiment 3.
Embodiment 5:
1,12-diamido dodecane modified glassy carbon electrode.Preparation 100mM 1, the anhydrous acetonitrile of 12-diamido dodecane+0.1M perchloric acid 4-butyl amine.As follows embodiment 3.
Embodiment 6:
4,4 '-two (n-aminopropyl) purpurine is modified graphite electrode.Clean graphite electrode is put into 5mM4, in the ethanol solution of 4 '-two (n-aminopropyl) purpurine+lithium perchlorate, use Ag/Ag
+Be contrast electrode, in 0～1.0V potential range, with 20mVs
-1The speed of sweeping carried out cycle potentials scanning 60 minutes.Take out electrode washing, with ethanol and water ultrasonic cleaning respectively, promptly make purpurine and modify graphite electrode again.This purpurine modified electrode can be used as electron mediator and is used to study itself and dehydrogenasa and other protein interactions.
Embodiment 7:
The amino butyl phosphoric acid modifying carbon fibers of 4-electrode.The amino butyl phosphoric acid of preparation 1mM 4-+0.2MNaOH aqueous solution.Clean carbon fiber electrode is put into this electrolytic solution, use Ag/AgCl as contrast electrode, with 20mVs
-1Sweep speed 0～+ carry out cycle potentials scanning 70 minutes in the 1.4V potential range.Take out electrode, the water ultrasonic cleaning promptly makes the amino butyl phosphoric acid modifying carbon fibers of 4-electrode.
Embodiment 8:
3,4-dihydroxy benzyl ammonia is modified graphite electrode.Clean pyrolytic graphite electrode is put into 70mM 3, in the anhydrous acetonitrile of 4-dihydroxy benzyl ammonia+perchloric acid 4-butyl amine, use Ag/Ag
+Be contrast electrode, 0～+ the 1.4V potential range in, with 100mVs
-1The speed of sweeping carried out cycle potentials scanning 28 minutes.Take out electrode washing, with ethanol and water ultrasonic cleaning respectively, promptly make 3 again, 4-dihydroxy benzyl ammonia is modified graphite electrode.
Claims (9)
1. the preparation method of an ammonia cation free-radical modified single-layer membrane of carbon electrode, it is characterized in that aminobenzoic acid with dressing agent 4-, 4,4 '-two (n-aminopropyl) purpurine is dissolved in the ethanol solution of 0.1M lithium perchlorate respectively, with the dressing agent 4-aminopyridine, the amino butyl phosphoric acid of 4-is dissolved in the 0.1M sodium hydrate aqueous solution respectively, with dressing agent 3,4-dihydroxy benzyl ammonia, 1,7-diamino in heptan, 1,10-diamino in the last of the ten Heavenly stems, 1,12-diamido dodecane is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine respectively, and the concentration of dressing agent is 1～100mM; At room temperature clean carbon electrode: vitreous carbon, carbon fiber, graphite electrode, be immersed in the above-mentioned electrolyte solution, carbon paste electrode is immersed in the electrolyte aqueous solution as working electrode, platinized platinum is as to electrode, in absolute ethyl alcohol and the acetonitrile solution with Ag/Ag
+Being contrast electrode, is contrast electrode with Ag/AgCl in the aqueous solution, in 0～1.4V potential range, at 10～100mVs
-1The speed of sweeping carry out down cycle potentials scanning 2～70 minutes, take out and wash, with ethanol or water ultrasonic cleaning, promptly obtained carboxyl again, amino, phosphate, the unimolecular film carbon electrode of pyridine or purpurine functional group.
2. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 4-aminobenzoic acid is dissolved in the ethanol solution of 0.1M lithium perchlorate.
3. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 4, and 4 '-two (n-aminopropyl) purpurine is dissolved in the ethanol solution of 0.1M lithium perchlorate.
4. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that the dressing agent 4-aminopyridine is dissolved in the 0.1M sodium hydrate aqueous solution.
5. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that the amino butyl phosphoric acid of dressing agent 4-is dissolved in the 0.1M sodium hydrate aqueous solution.
6. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 4-dihydroxy benzyl ammonia is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine.
7. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 1, and 7-diamino in heptan is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine.
8. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 1, and 10-diamino in the last of the ten Heavenly stems is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine.
9. the preparation method of ammonia cation free-radical modified single-layer membrane of carbon electrode as claimed in claim 1 is characterized in that dressing agent 1, and 12-diamido dodecane is dissolved in the anhydrous acetonitrile of 0.1M perchloric acid 4-butyl amine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303710C (en) * | 2005-04-05 | 2007-03-07 | 中国科学院长春应用化学研究所 | Process for preparing nano structured super platinum film carbon electrodes |
| CN100570349C (en) * | 2007-06-21 | 2009-12-16 | 中国科学院长春应用化学研究所 | A kind of preparation method of carbon magma bismuth membrane electrode |
| CN105738451A (en) * | 2016-02-01 | 2016-07-06 | 大连理工大学 | Direct electron transfer type glucose biosensor and preparation method and application |
| CN113504284A (en) * | 2021-07-01 | 2021-10-15 | 北京师范大学 | Purple essence polymer film electrode, preparation method thereof, polymer contained in purple essence polymer film electrode and application of purple essence polymer film electrode |
-
2000
- 2000-07-26 CN CNB001218468A patent/CN1144041C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303710C (en) * | 2005-04-05 | 2007-03-07 | 中国科学院长春应用化学研究所 | Process for preparing nano structured super platinum film carbon electrodes |
| CN100570349C (en) * | 2007-06-21 | 2009-12-16 | 中国科学院长春应用化学研究所 | A kind of preparation method of carbon magma bismuth membrane electrode |
| CN105738451A (en) * | 2016-02-01 | 2016-07-06 | 大连理工大学 | Direct electron transfer type glucose biosensor and preparation method and application |
| CN113504284A (en) * | 2021-07-01 | 2021-10-15 | 北京师范大学 | Purple essence polymer film electrode, preparation method thereof, polymer contained in purple essence polymer film electrode and application of purple essence polymer film electrode |
| CN113504284B (en) * | 2021-07-01 | 2022-07-26 | 北京师范大学 | Viologen polymer film electrode, preparation method thereof, polymer contained in viologen polymer film electrode and application of polymer |
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