CN1731166A - Gold amalgam microelectrode and preparation method thereof - Google Patents
Gold amalgam microelectrode and preparation method thereof Download PDFInfo
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- CN1731166A CN1731166A CN 200510091889 CN200510091889A CN1731166A CN 1731166 A CN1731166 A CN 1731166A CN 200510091889 CN200510091889 CN 200510091889 CN 200510091889 A CN200510091889 A CN 200510091889A CN 1731166 A CN1731166 A CN 1731166A
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Abstract
The invention relates to a mercury micro electrode and its preparing method and its application which is suit for measuring the mercury micro electrode of seawater and deposition. It arranges a glass pipe, a golden wire with 25-100 mum diameter on the lower part of the glass pipe, a silver wire leading end on the upper end of the glass pipe, wherein the upper end of the golden wire is connected with the lower end of the silver wire leading end by grey silver conducting resin; the top of the glass pipe is sealed by peroxide-resin glue and fixes the silver wire leading end; the lower end surface has mercury film. It can directly insert into the seawater or deposition to measure the sea deposition and the biology dissolved oxygen, Mn2+, Fe2+ and S2- redox chemical constituent.
Description
Technical field
The present invention relates to a kind of gold amalgam microelectrode, especially relate to a kind of mainly being applicable to and measure seawater and sedimental gold amalgam microelectrode and preparation method and the application in environment measurement.
Background technology
In electrochemical analysis, the VA polarographic technology is generally used and is dripped mercury or hanging mercury electrode, this mercury electrode enters connection by liquid mercury by packoff usually under the driving of nitrogen glass capillary dangles and forms, use very inconvenient and dangerous, and mercury drip waste liquid may contaminated environment.Owing to come off easily, a liquid mercury or hanging mercury electrode are not suitable for measuring the mud dielectric sample as sediment and so on, and this has limited VA polarographic The Application of Technology scope.In order to break through this restriction, electrochemists attempt mercury is dripped plating on platinum electrode, gold electrode or iridium electrode, but because technical matters, resulting mercury electrode often can not be applied to the environment deposition medium.In China, the method for making of gold electrode has detailed document introduction, but gold amalgam microelectrode particularly be applicable to and measure seawater and sediment redox chemistry composition, diameter is the gold amalgam microelectrode of 25 μ m to 100 μ m, nobody studied so far.Dissolved oxygen DO length of penetration in the research oceanic sediment, the biogeochemical process of manganese and iron presses for a kind of gold amalgam microelectrode of stable performance.Publication number is that the application for a patent for invention of CN1257843 discloses a kind of process for preparing gold electrode by sealing gold metal with ordinary glass of using, adopt simple glass, melten glass in oxyhydrogen flame, the decompression of glass tube inner vacuum is because the atmospheric pressure effect makes glass closely wrap spun gold.After the spun gold sealing-in was good, the spun gold of reserving in the glass tube was connected with plain conductor with conducting resinl, and the plate-like gold electrode is exposed by grinding in bag wall glass tube termination.Publication number is the method for making that the application for a patent for invention of CN1306204 discloses a kind of gold electrode.This method is to be coated with the skim silicon rubber sealant on the surface of gold, and the gold copper-base alloy that then this is scribbled the skim silicon rubber sealant is fixed in the hole of electrode sleeve or in the cutting of housing, treats promptly to make gold electrode after the silicone rubber seal adhesive curing.
Summary of the invention
The objective of the invention is to be used for the problem of measurement environment deposition medium, a kind of gold amalgam microelectrode and the preparation method and application in environment measurement thereof of measuring sediment redox chemistry composition that mainly be applicable to is provided at existing mercury electrode.
The said gold amalgam microelectrode of the present invention is provided with glass tube, bottom in glass tube is provided with the spun gold that diameter is 25～100 μ m, top in glass tube is provided with silver-colored line exit, the upper end of spun gold is connected by grey silver conductive adhesive with the lower end of silver-colored line exit, by epoxide-resin glue sealing and fixing silver-colored line exit, be coated with the mercury film at the glass tube top at the rear surface of spun gold.
Said glass tube is selected the pyrex pipe for use.
The preparation method of the said gold amalgam microelectrode of the present invention the steps include:
1) adopting diameter is that high-purity (＞99.99%) spun gold of 25～100 μ m is made gold electrode in glass tube, and the gold electrode tip polishes and be polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive;
2) on gold electrode, electroplate one deck mercury film by electrochemical method, form the gold amalgam electrode.
The step of electroplating one deck mercury film with electrochemical method on gold electrode is:
1) gold electrode is placed on usefulness ultrasonic cleaning 10～20s in the pure water, cleans up with the rare nitric acid of 0.01～0.1M again;
2) gold electrode that will clean is placed on 0.1M Hg (NO
3)
2/ 0.03M HNO
3Electrolytic solution in, be to continue 2～5min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, electroplating current is 50～90nA;
3) in order to guarantee that the mercury film in gold surface absorption firmly, places 1M NaOH solution to electrode again, with respect to platinum electrode add-9.0～-DC voltage and galvanization 100～200 μ A of 12.0V, continue 20～50s, this activation polarization process is at reduction H
+And Na
+Impel the mercury gold to combine closely in the time of ion and become gold amalgam.Adopt optical microscope, can be observed on diameter is the golden disk of 100 μ m has the bright mercury film of a bed thickness at 30～50 μ m.
The present invention has studied gold amalgam microelectrode and preparation method thereof, and utilizes the VA polarographic method, and it is applied to Measuring Oceanic sediment and biomembranous dissolved oxygen DO, Mn
2+, Fe
2+And S
2-The redox chemistry composition.
The said gold amalgam microelectrode of the present invention can directly insert in seawater or the sediment and measure dissolved oxygen DO, Mn
2+, Fe
2-, S
2-Etc. chemical constitution.Adopt three-electrode electro Chemical work pool device during measurement, with gold amalgam microelectrode as working electrode, with platinum electrode as to electrode, with saturated calomel electrode as the reference electrode, utilize square wave voltammetry, with the scanning of the speed negative sense of 60mV/s with respect to saturated calomel-0.10～-potential range of 1.70V, can measure multiple redox chemistry composition simultaneously, wherein electrode reaction and lowest detectable limit concentration are as shown in table 1.
Table 1
| The electrode chemical equation | Peak voltage (V) relative saturation calomel | Lowest detectable limit (μ M) |
| ?O 2+2H ++2e→H 2O 2 | -0.28 | ?3 |
| ?HS -+Hg←→HgS+H ++2e | -0.62 | ?0.05 |
| ?H 2O 2+2H ++2e→2H 2O | -1.23 | ?3 |
| ?Fe 2++Hg+2e→Fe(Hg) | -1.43 | ?10 |
| ?Mn 2++Hg+2e←→Mn(Hg) | -1.55 | ?3 |
Description of drawings
Fig. 1 is the structural representation of the said gold amalgam microelectrode of the present invention.
Embodiment
As shown in Figure 1, gold amalgam microelectrode is provided with pyrex pipe 3, bottom in glass tube 3 is provided with spun gold 5, the diameter of spun gold 5 is 25～100 μ m, top in glass tube 3 is provided with silver-colored line exit 1, the upper end of spun gold 5 is connected by grey silver conductive adhesive 4 with the lower end of silver-colored line exit 1, by epoxide-resin glue 2 sealing and fixing silver-colored line exit 1, is coated with mercury film 6 at the rear surface of spun gold 5 at glass tube 3 tops.
During the preparation gold amalgam microelectrode, the employing diameter is that high-purity (＞99.99%) spun gold of 25 μ m is made gold electrode in glass tube, and the gold electrode tip polishes and be polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive; Electroplate one deck mercury film by electrochemical method on gold electrode, form the gold amalgam electrode, concrete steps are: gold electrode is placed on uses ultrasonic cleaning 15s in the pure water, clean up with the rare nitric acid of 0.05M; The gold electrode that cleaned is placed on 0.1MHg (NO
3)
2/ 0.03M HNO
3Electrolytic solution in, be to continue 3min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, last electroplating current is 50nA; In order to guarantee that the mercury film in gold surface absorption firmly, places 1M NaOH solution to electrode again, add-DC voltage and the galvanization 150 μ A of 10V with respect to platinum electrode, continue 20s, this activation polarization process is at reduction H
+And Na
+Impel the mercury gold to combine closely in the time of ion and become gold amalgam.Adopt optical microscope, can be observed on diameter is the golden disk of 100 μ m has a layer thickness to be about the bright mercury film of 30 μ m.
Utilize the VA polarographic method, can be applied to Measuring Oceanic sediment and biomembranous dissolved oxygen DO, Mn
2+, Fe
2+And S
2-The redox chemistry composition.
During the preparation gold amalgam microelectrode, similar to Example 1, it is that high-purity (＞99.99%) spun gold of 50 μ m is made gold electrode in glass tube that its difference is to adopt diameter, the gold electrode tip polishes and is polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive; Electroplate one deck mercury film by electrochemical method on gold electrode, form the gold amalgam electrode, concrete steps are: gold electrode is placed on uses ultrasonic cleaning 16s in the pure water, clean up with the rare nitric acid of 0.01M; The gold electrode that cleaned is placed on 0.1MHg (NO
3)
2/ 0.03MHNO
3Electrolytic solution in, be to continue 4min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, last electroplating current is 75nA; In order to guarantee that the mercury film in gold surface absorption firmly, places 1M NaOH solution to electrode again, add-DC voltage and the galvanization 170 μ A of 11V with respect to platinum electrode, continue 30s, this activation polarization process is at reduction H
+And Na
+Impel the mercury gold to combine closely in the time of ion and become gold amalgam.
During the preparation gold amalgam microelectrode, similar to Example 1, it is that high-purity (＞99.99%) spun gold of 75 μ m is made gold electrode in glass tube that its difference is to adopt diameter, the gold electrode tip polishes and is polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive; Electroplate one deck mercury film by electrochemical method on gold electrode, form the gold amalgam electrode, concrete steps are: gold electrode is placed on uses ultrasonic cleaning 10s in the pure water, clean up with the rare nitric acid of 0.08M; The gold electrode that cleaned is placed on 0.1M Hg (NO
3)
2/ 0.03M HNO
3Electrolytic solution in, be to continue 4min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, last electroplating current is 80nA; In order to guarantee that the mercury film in gold surface absorption firmly, places 1M NaOH solution to electrode again, add-DC voltage and the galvanization 100 μ A of 12V with respect to platinum electrode, continue 50s.
During the preparation gold amalgam microelectrode, similar to Example 1, it is that high-purity (＞99.99%) spun gold of 100 μ m is made gold electrode in glass tube that its difference is to adopt diameter, the gold electrode tip polishes and is polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive; Electroplate one deck mercury film by electrochemical method on gold electrode, form the gold amalgam electrode, concrete steps are: gold electrode is placed on uses ultrasonic cleaning 20s in the pure water, clean up with the rare nitric acid of 0.1M; The gold electrode that cleaned is placed on 0.1M Hg (NO
3)
2/ 0.03M HNO
3Electrolytic solution in, be to continue 5min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, last electroplating current is 90nA; In order to guarantee that the mercury film in gold surface absorption firmly, places 1MNaOH solution to electrode again, add-DC voltage and the galvanization 200 μ A of 9V with respect to platinum electrode, continue 40s.
Claims (4)
1, gold amalgam microelectrode, it is characterized in that being provided with glass tube, bottom in glass tube is provided with the spun gold that diameter is 25～100 μ m, top in glass tube is provided with silver-colored line exit, the upper end of spun gold is connected by grey silver conductive adhesive with the lower end of silver-colored line exit, by epoxide-resin glue sealing and fixing silver-colored line exit, be coated with the mercury film at the glass tube top at the rear surface of spun gold.
2, gold amalgam microelectrode as claimed in claim 1 is characterized in that glass tube is selected from the pyrex pipe.
3, the preparation method of gold amalgam microelectrode as claimed in claim 1 is characterized in that the steps include:
1) adopting diameter is 25～100 μ m, and the spun gold of purity＞99.99% is made gold electrode in glass tube, and the gold electrode tip polishes and be polished to a smooth circular plate, and the gold electrode other end connects silver-colored line as exit by grey silver conductive adhesive;
2) on gold electrode, electroplate one deck mercury film by electrochemical method, form the gold amalgam electrode.
4, gold amalgam microelectrode as claimed in claim 3 is characterized in that the step of electroplating one deck mercury film with electrochemical method on gold electrode is:
1) gold electrode is placed on usefulness ultrasonic cleaning 10～20s in the pure water, cleans up with the rare nitric acid of 0.01～0.1M again;
2) gold electrode that will clean is placed on 0.1M Hg (NO
3)
2/ 0.03M HNO
3Electrolytic solution in, be to continue 2～5min under with respect to the condition of saturated calomel electrode-0.10V at electromotive force, electroplating current is 50～90nA;
3) again electrode is placed 1M NaOH solution, with respect to platinum electrode add-9.0～-DC voltage and galvanization 100～200 μ A of 12.0V, continue 20～50s, the mercury gold is combined closely becomes gold amalgam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510091889XA CN100454011C (en) | 2005-08-15 | 2005-08-15 | Gold amalgam microelectrode and preparation method thereof |
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|---|---|---|---|
| CNB200510091889XA CN100454011C (en) | 2005-08-15 | 2005-08-15 | Gold amalgam microelectrode and preparation method thereof |
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| CN100454011C CN100454011C (en) | 2009-01-21 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102445468A (en) * | 2011-09-29 | 2012-05-09 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN104062336A (en) * | 2014-05-21 | 2014-09-24 | 中国科学院合肥物质科学研究院 | Golden wire electrochemical microelectrode, manufacturing method and application of golden wire electrochemical microelectrode |
| CN108398474A (en) * | 2018-02-13 | 2018-08-14 | 中国科学院烟台海岸带研究所 | It is a kind of to can be used for the electric potential type microelectrode sensors and its application that deposit intermediate ion detects |
| CN109541004A (en) * | 2017-09-21 | 2019-03-29 | 赛默飞世尔（上海）仪器有限公司 | A kind of method and its application making the mercury deposition in water body |
| CN110672683A (en) * | 2019-09-05 | 2020-01-10 | 苏州科技大学 | Preparation device of free chlorine microelectrode |
| US11326439B2 (en) * | 2020-05-15 | 2022-05-10 | Saudi Arabian Oil Company | Compositions, systems, and methods for iron sulfide scale identification, prevention, and reduction |
| TWI774257B (en) * | 2021-03-05 | 2022-08-11 | 國立陽明交通大學 | Flexible and thin gold microelectrode and method for manufacturing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5773628A (en) * | 1980-10-27 | 1982-05-08 | Showa Electric Wire & Cable Co Ltd | Oil level detector |
| CN1091431C (en) * | 1998-12-24 | 2002-09-25 | 中国科学院长春应用化学研究所 | Process for preparing gold electrode by sealing gold metal with ordinary glass |
| CN1226617C (en) * | 2003-11-27 | 2005-11-09 | 中国科学院长春应用化学研究所 | Preparing method for figure controllable nanometer grade gold micro-strip electrode |
-
2005
- 2005-08-15 CN CNB200510091889XA patent/CN100454011C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102445468A (en) * | 2011-09-29 | 2012-05-09 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN102445468B (en) * | 2011-09-29 | 2013-01-16 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN104062336A (en) * | 2014-05-21 | 2014-09-24 | 中国科学院合肥物质科学研究院 | Golden wire electrochemical microelectrode, manufacturing method and application of golden wire electrochemical microelectrode |
| CN109541004A (en) * | 2017-09-21 | 2019-03-29 | 赛默飞世尔（上海）仪器有限公司 | A kind of method and its application making the mercury deposition in water body |
| CN108398474A (en) * | 2018-02-13 | 2018-08-14 | 中国科学院烟台海岸带研究所 | It is a kind of to can be used for the electric potential type microelectrode sensors and its application that deposit intermediate ion detects |
| CN110672683A (en) * | 2019-09-05 | 2020-01-10 | 苏州科技大学 | Preparation device of free chlorine microelectrode |
| US11326439B2 (en) * | 2020-05-15 | 2022-05-10 | Saudi Arabian Oil Company | Compositions, systems, and methods for iron sulfide scale identification, prevention, and reduction |
| TWI774257B (en) * | 2021-03-05 | 2022-08-11 | 國立陽明交通大學 | Flexible and thin gold microelectrode and method for manufacturing the same |
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Granted publication date: 20090121 Termination date: 20110815 |