CN1229640C - Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method - Google Patents
Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method Download PDFInfo
- Publication number
- CN1229640C CN1229640C CN 03150682 CN03150682A CN1229640C CN 1229640 C CN1229640 C CN 1229640C CN 03150682 CN03150682 CN 03150682 CN 03150682 A CN03150682 A CN 03150682A CN 1229640 C CN1229640 C CN 1229640C
- Authority
- CN
- China
- Prior art keywords
- electrode
- sulfate radical
- water body
- epoxy resin
- radical content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention discloses a sulfate radical detecting electrode based on hydrotalcite, and a preparation method and a use method thereof. Base materials of the detecting electrode are gold wires or silver wires on which epoxy resin with ultra-fine silver powder is coated to be used as a middle layer; ionic selectivity membranes which are sensitive to sulfate radicals are coated on the middle layer and comprise the basic components of sulfate radical type hydrotalcite, surface active agents, solvent and membrane forming agents; and during use, the Ag/AgCl electrode is used as a reference electrode to form the detecting electrode pair. The sulfate radical detecting electrode has the advantages of small size, high mechanical strength and toughness, and good working performance in wide temperature and pressure conditions. Therefore, the sulfate radical detecting electrode can be used for on-line detection and long-term monitoring of the sulfate radical content in natural water, and chemical and chemical-industrial water media.
Description
Technical field
The present invention relates to a kind of electrode and preparation and using method of surveying dissolving sulfate radical content in the water body.
Background technology
Sulfate radical is one of modal negative ion of nature, also is chemistry, the most frequently used reagent and the raw material of chemical field.Sulfate radical content is significant for various geologic function of understanding and microbial activities in the natural water body, sulfate radical content also is important environmental evaluation parameter in the water body, therefore objectively need a kind of sensor that can carry out in-situ investigation, the present invention is directed to this demand and proposed required exploring electrode dissolving sulfate radical content in the aqueous medium.
Summary of the invention
The purpose of this invention is to provide a kind of electrode and preparation and using method of surveying dissolving sulfate radical content in the water body.
The electrode of surveying dissolving sulfate radical content in the water body is one section spun gold or filamentary silver, coated on it contain super fine silver powder epoxy resin as the middle layer, applied ion selective membrane on the middle layer to the sulfate radical sensitivity.
Ion selective membrane is characterised in that it contains sulfate radical type hydrotalcite, and its chemical structure of general formula is [Mg
1-xAl
x(OH)
2]
X+[SO
4]
X/2MH
2O, X is the electricity price of basic structure layer in the formula, m is a water molecule number.It is prepared from according to the following steps:
1) get an amount of aluminium salt and magnesium salts and mix, the molal quantity of magnesium salts is to four times of aluminium salt, and it is 1～3 mole solution that potpourri is mixed with concentration; Other gets 1.6～2.0 times of molal quantitys to the NaOH of aluminium salt and magnesium salts total amount, is mixed with concentration and is 2～4 moles solution;
2) NaOH solution is added in the there-necked flask, at N
2Protection slowly splashes into the magnalium mixed salt solution of being prepared in the alkali lye down, and strong agitation, with the NaOH lean solution pH of mixed value is adjusted to 9～11;
3) with gelatinous precipitate crystallization 20～40h in 50～80 ℃ baking oven of gained, suction filtration, washing then is no more than in 65 ℃ of baking ovens in temperature and dries, and is ground to less than 200～300 orders standby.
Said magnesium salts is magnesium sulphate or Magnesium sulfate heptahydrate, and said aluminium salt is aluminium sulphate or hydrazine aluminum sulfate.
The preparation process of surveying dissolving sulfate radical content electrode in the water body is:
1) take by weighing 100～500 milligrams of sulfate radical type hydrotalcites, in agate mortar, be milled to, add 0.2～1 milliliter of surfactant less than 300 orders, 1～5 milliliter of solvent, ultrasonic Treatment 3～5 minutes are used in the back that stirs;
2) add 0.02～0.1 milliliter of film forming agent in above-mentioned suspension, ultrasonic Treatment 3～5 minutes are used in the back that stirs, and the suspension that obtains mixing places closed container stand-by.
3) dip in the length of 0.5～2.0 centimetre at spun gold or filamentary silver one end and get a little and contain silver epoxy, under 100～150 ℃ of temperature, dry, be chilled to the position that epoxy resin will be arranged after the room temperature again and dip in and get above-mentioned suspension, under 60～80 ° of temperature, dry and get final product.
Said surfactant is a silane coupling agent, and its chemical structure of general formula is R (CH
2)
nSiX
3, R is the lipophilicity organic functional group, and X is halogen or organic acid, and n is a carbon number on the carbochain; Said solvent is a kind of in benzene, toluene or the dimethylbenzene or several; Said film forming agent is a dimethyl silicone polymer, and its chemical structure of general formula is-[(CH
3)
2SiO]
n-, n is the number of monomers in the condensate.
Using method is as working electrode with dissolve sulfur acid group content detection electrode, in addition with an Ag/AgCl electrode, or commercially available mercurous chloride electrode is as contrast electrode, working electrode and contrast electrode are connected on respectively on the both positive and negative polarity of millivoltmeter, with potential difference (PD) between the two and typical curve contrast, can draw the content of sulfate radical in the solution.
The Ag/AgCl contrast electrode is one section filamentary silver, or scribbles the spun gold that contains super fine silver powder epoxy resin, and the surface is coated with active A gCl film, and it can be the commercial goods, one of also can be by the following method makes:
The AgCl powder is placed platinum crucible, on spirit lamp, heat,,, be cooled to room temperature and get final product taking out after the several seconds in the end immersion melt of filamentary silver until its fusion;
Perhaps: get two filamentary silvers, be connected on respectively on the both positive and negative polarity of 1.2～3.0V direct supply, immerse concentration and be in 0.1～0.5 mole the hydrochloric acid solution and turn-on current, after 15～30 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product.
Perhaps: get a spun gold, length at 0.5～2 centimetre at one end is coated the epoxy resin that contains super fine silver powder, the oven dry back is not connected on the positive pole of 1.2～3.0V direct supply there being one of epoxy resin to terminate at, other gets a filamentary silver and is connected on the negative pole of same power supply, having the position of epoxy resin to immerse concentration spun gold is in 0.1～0.5 mole the hydrochloric acid solution, again filamentary silver is inserted, constitute loop and turn-on current, after 15～30 minutes, the epoxy resin surface that is connected on the positive pole has plated uniform AgCl film, use distilled water flushing, oven dry gets final product.
Advantage of the present invention is, the exploring electrode volume that is proposed is tiny, has very high physical strength and toughness, has good working performance under the temperature of broadness, pressure condition.Therefore be applicable to the sulfate radical content in natural water body and chemistry, the chemical industry aqueous medium is carried out online detection and long term monitoring.Compare with traditional sampling analysis, promptly alleviated working strength, improved the real-time of data.
Embodiment
The serviceability of exploring electrode of the present invention, as signal intensity, signal to noise ratio (S/N ratio) and sensitivity etc., all irrelevant with the size of electrode.Therefore, under the prerequisite that ensures required physical strength, should select for use thinner tinsel to make electrode as far as possible, help reducing cost, and dwindle the size of electrode.Diameter wiry generally should be between 0.1～0.3 millimeter.
The base material of exploring electrode can be selected a kind of in filamentary silver or the spun gold for use.Employing contains the epoxy resin of super fine silver powder as the middle layer, is because it and metal base and ion selective membrane have very high affinity and cohesiveness.Representational commercially available prod is the epoxy resin that Switzerland Polyscience company produces, and code name is Epo-tek415G.The PAD-54 type resin that similar homemade commodity are produced for the Shanghai synthetic resin plant, the two performance is more or less the same.
The present invention adopts sulfate radical type hydrotalcite as the negative ion carrier.The raw material of synthetic sulfate radical type hydrotalcite is aluminium sulphate, magnesium sulphate or its hydrate, and NaOH.Wherein the molal quantity of magnesium sulphate is 1～4 times of aluminium sulphate, and the consumption of NaOH is aluminium salt, magnesium salts molal quantity summation 1.6～2.0 times.Obtain solution need use deionized water, should boil, and uses after being chilled to room temperature, to remove dissolving CO
2Influence.Aluminium salt, magnesium salts mixed solution should slowly splash into alkali lye in the intensively stirred while.Should measure the pH value of mixed liquor after titration is finished, the pH value is lower than at 9 o'clock, can use the NaOH of 0.1～0.5M that the pH of mixed value is adjusted to 9～11.
When preparation dissolve sulfur acid group exploring electrode, earlier sulfate radical type hydrotalcite is milled in agate mortar less than 300 orders, add surfactant and solvent, fully stir and with ultrasonic Treatment 3～5 minutes, adding film forming agent, stir and with ultrasonic Treatment 3～5 minutes, the suspension that obtains mixing placed closed container stand-by.Dip in the length of 0.5～2.0 centimetre at spun gold or filamentary silver one end and to get a little and contain silver epoxy, under 100～150 ℃ of temperature, dry, be chilled to the position that epoxy resin will be arranged after the room temperature again and dip in and get above-mentioned suspension, under 60～80 ° of temperature, dry and get final product.Electrode should soak in distilled water 8～12 hours before use.The time spent is not answered kept dry for a long time.
Used surfactant is a silane coupling agent, and its chemical structure of general formula is R (CH
2)
nSiX
3, R is the lipophilicity organic functional group, and X is halogen or organic acid, and it can change the surface nature of hydrotalcite derivant, makes its hydrophilic surface be transformed into hydrophobicity.Film forming agent is a dimethyl silicone polymer, and its chemical structure of general formula is-[(CH
3)
2SiO]
n-.Solvent can be selected a kind of in benzene, toluene or the dimethylbenzene or several for use.For the negative ion carrier is uniformly dispersed in mother liquor, need it is carried out sonicated.The suspension for preparing is the outstanding liquid that mixes of milky, should use as early as possible, can not put for a long time.
The making of Ag/AgCl contrast electrode can be by the direct plating AgCl film on filamentary silver of fusion method or electrochemical process, makes simplyr, but that the AgCl film combines with metal base is firm inadequately, especially contains S in solution
2-, Br
-, I
-Electrode easily lost efficacy during Deng toxic component.Adopt spun gold to make base material, containing super fine silver powder epoxy resin is the middle layer, and the adhesion of AgCl film and electrode is obviously strengthened.The present invention recommends to use this scheme, and cost slightly increases, but electrode stability and serviceable life are doubled and redoubled.
Below in conjunction with embodiment the present invention is elaborated.
Example 1: the preparation of sulfate radical type hydrotalcite
1) gets 13.68g (0.06mol) MgSO
46H
2O and 15.12g (0.03mol) Al2 (SO
4)
39H
2O mixes, and is dissolved in 50mL and takes off CO
2Deionized water in; Other gets 7.20g NaOH (0.18mol) and is dissolved in 75mL and takes off CO
2Deionized water in.
2) NaOH solution is added in the there-necked flask, at N
2Protection slowly splashes into the magnalium mixed salt solution of being prepared in the alkali lye down, and strong agitation, with the NaOH solution of 0.1M the pH of mixed value is adjusted to 10;
3) with gelatinous precipitate crystallization 24h in 65 ℃ baking oven of gained, suction filtration, washing then is to dry in 60 ℃ of baking ovens in temperature, is ground to less than 300 orders standby.
Example 2: the preparation of ion selective membrane suspension
1) take by weighing 0.1 gram sulfate radical type hydrotalcite, in agate mortar, be milled to, add 0.2 milliliter of silane coupling agent less than 300 orders, 1 milliliter of dimethylbenzene, ultrasonic Treatment 5 minutes are used in the back that stirs;
2) add 0.02 milliliter of dimethyl silicone polymer in above-mentioned suspension, ultrasonic Treatment 5 minutes are used in the back that stirs, and the suspension that obtains mixing places closed container stand-by.
Example 3: the preparation of ion selective membrane suspension
1) take by weighing 0.2 gram sulfate radical type hydrotalcite, add 0.4 milliliter of silane coupling agent, 2 milliliters of toluene, ultrasonic Treatment 5 minutes are used in the back that stirs;
2) add 0.04 milliliter of dimethyl silicone polymer in above-mentioned suspension, ultrasonic Treatment 5 minutes are used in the back that stirs, and the suspension that obtains mixing places closed container stand-by.
Example 4: the preparation of ion selective membrane suspension
1) take by weighing 0.4 gram sulfate radical type hydrotalcite, add 0.8 milliliter of silane coupling agent, 4 milliliters of benzene, ultrasonic Treatment 5 minutes are used in the back that stirs;
2) add 0.08 milliliter of dimethyl silicone polymer in above-mentioned suspension, ultrasonic Treatment 5 minutes are used in the back that stirs, and the suspension that obtains mixing places closed container stand-by.
Example 5: the making of dissolve sulfur acid group exploring electrode
Get the spun gold of suitable length, the length that the one end is about 1 centimetre is dipped in and is got a little and contain silver epoxy, dries under 120 ℃ of temperature, is chilled to the position that epoxy resin will be arranged after the room temperature again and dips in and get the suspension for preparing, and dries to get final product under 60 ° of temperature.
Example 6: the making of dissolve sulfur acid group exploring electrode
Get the filamentary silver of suitable length, the length that an end is about 1 centimetre is dipped in and is got a little and contain silver epoxy, dries under 100 ℃ of temperature, is chilled to the position that epoxy resin will be arranged after the room temperature again and dips in and get the suspension for preparing, and dries to get final product under 80 ° of temperature.
The making of example 7:Ag/AgCl contrast electrode
Get the filamentary silver of suitable length, 3 gram AgCl powder are placed the platinum crucible of 5mL, heat on spirit lamp, until its fusion, a end that will filamentary silver immerses in the melt and takes out after the several seconds, and cooling is put room temperature and got final product.
The making of example 8:Ag/AgCl contrast electrode
1) adding 100mL concentration in the beaker of 200mL is 0.1 mole HCl;
2) get two filamentary silvers, be connected on respectively on the both positive and negative polarity of 2.4V direct supply, immerse in the hydrochloric acid solution and turn-on current the one end for about 1 centimetre, take out after 20 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product.
The making of example 9:Ag/AgCl contrast electrode
1) adding 100mL concentration in the beaker of 200mL is 0.1 mole HCl;
2) get a spun gold, coat the epoxy resin that contains super fine silver powder in the length of 1 centimetre at one end, the oven dry back is not there being one of epoxy resin to terminate on the positive pole of 2.4V direct supply, and other gets a filamentary silver and is connected on the negative pole of same power supply;
3) spun gold is had the position of epoxy resin immerse in the hydrochloric acid solution, filamentary silver is inserted again, constitute loop and turn-on current, take out after 20 minutes, the argentiferous epoxy resin surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product.
Example 10: the using method of dissolve sulfur acid group content detection electrode in the water body
To dissolve the sulfate radical content electrode as working electrode, in addition with an Ag/AgCl electrode as contrast electrode, working electrode and contrast electrode are connected on respectively on the both positive and negative polarity of millivoltmeter,, can draw the total content of sulfate radical in the solution potential difference (PD) between the two and typical curve contrast.
Example 11: the using method of surveying dissolving sulfate radical content electrode in the water body
To dissolve the sulfate radical content electrode as working electrode, in addition with a commercially available mercurous chloride electrode as contrast electrode, working electrode and contrast electrode are connected on respectively on the both positive and negative polarity of millivoltmeter,, can draw the total content of sulfate radical in the solution potential difference (PD) between the two and typical curve contrast.
Claims (10)
1. survey the electrode that dissolves sulfate radical content in the water body for one kind, it is characterized in that it is one section spun gold or filamentary silver, coated on it contain super fine silver powder epoxy resin as the middle layer, applied ion selective membrane on the middle layer to the sulfate radical sensitivity, ion selective membrane is to contain sulfate radical type hydrotalcite, and its chemical structure of general formula is [Mg
1-xAl
x(OH)
2]
X+[SO
4]
X/2MH
2O, X is the electricity price of basic structure layer in the formula, m is a water molecule number.
2. according to the said a kind of electrode of surveying in the water body dissolving sulfate radical content of claim 1, it is characterized in that the said preparation method's step that contains sulfate radical type hydrotalcite is as follows:
1) get an amount of aluminium salt and magnesium salts and mix, the molal quantity of magnesium salts is to four times of aluminium salt, and it is 1～3 mole solution that potpourri is mixed with concentration; Other gets 1.6～2.0 times of molal quantitys to the NaOH of aluminium salt and magnesium salts total amount, is mixed with concentration and is 2～4 moles solution;
2) NaOH solution is added in the there-necked flask, at N
2Protection slowly splashes into the magnalium mixed salt solution of being prepared in the alkali lye down, and strong agitation, with the NaOH lean solution pH of mixed value is adjusted to 9～11;
3) with gelatinous precipitate crystallization 20～40h in 50～80 ℃ baking oven of gained, suction filtration, washing then is no more than in 65 ℃ of baking ovens in temperature and dries, and is ground to less than 200～300 orders standby.
3. a kind of electrode of surveying dissolving sulfate radical content in the water body according to claim 2 is characterized in that said magnesium salts is magnesium sulphate or Magnesium sulfate heptahydrate, and said aluminium salt is aluminium sulphate or hydrazine aluminum sulfate.
4. the preparation method of dissolving sulfate radical content electrode in the detection water body as claimed in claim 1 is characterized in that its step is:
1) take by weighing 100～500 milligrams of sulfate radical type hydrotalcites, in agate mortar, be milled to, add 0.2～1 milliliter of surfactant less than 300 orders, 1～5 milliliter of solvent, ultrasonic Treatment 3～5 minutes are used in the back that stirs;
2) add 0.02～0.1 milliliter of film forming agent, ultrasonic Treatment 3～5 minutes are used in the back that stirs, and the suspension that obtains mixing places closed container stand-by;
3) dip in the length of 0.5～2.0 centimetre at spun gold or filamentary silver one end and get the epoxy resin that a little contains super fine silver powder, under 100～150 ℃ of temperature, dry, be chilled to the position that epoxy resin will be arranged after the room temperature again and dip in and get above-mentioned suspension, under 60～80 ° of temperature, dry and get final product.
5. according to the said a kind of preparation method who surveys dissolving sulfate radical content electrode in the water body of claim 4, it is characterized in that said surfactant is a silane coupling agent, its chemical structure of general formula is R (CH
2)
nSiX
3, R is the lipophilicity organic functional group, and X is halogen or organic acid, and n is the carbon number on the carbochain.
6. according to the said a kind of preparation method who surveys in the water body dissolving sulfate radical content electrode of claim 4, it is characterized in that said solvent is a kind of in benzene, toluene or the dimethylbenzene or several.
7. according to the said a kind of preparation method who surveys dissolving sulfate radical content electrode in the water body of claim 4, it is characterized in that said film forming agent is a dimethyl silicone polymer, its chemical structure of general formula is-[(CH
3)
2SiO]
n-, n is the number of monomers in the condensate.
8. the using method of dissolving sulfate radical content electrode in the detection water body as claimed in claim 1, it is characterized in that, to dissolve the sulfate radical content electrode in the water body as working electrode, in addition with an Ag/AgCl electrode, perhaps mercurous chloride electrode is as contrast electrode, working electrode and contrast electrode are connected on respectively on the both positive and negative polarity of millivoltmeter,, can draw the total content of sulfate radical in the solution potential difference (PD) between the two and typical curve contrast.
9. a kind of using method of surveying dissolving sulfate radical content electrode in the water body according to claim 8 is characterized in that said Ag/AgCl contrast electrode is one section filamentary silver, or scribbles the spun gold that contains super fine silver powder epoxy resin that the surface is coated with active A gCl film.
10. a kind of using method of surveying dissolving sulfate radical content electrode in the water body according to claim 8 is characterized in that the making point-score of said Ag/AgCl contrast electrode is as follows:
The AgCl powder is placed platinum crucible, on spirit lamp, heat,,, be cooled to room temperature and get final product taking out after the several seconds in the end immersion melt of filamentary silver until its fusion;
Perhaps: get two filamentary silvers, be connected on respectively on the both positive and negative polarity of 1.2～3.0V direct supply, immerse concentration and be in 0.1～0.5 mole the hydrochloric acid solution and turn-on current, after 15～30 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product;
Perhaps: get a spun gold, length at 0.5～2 centimetre at one end is coated the epoxy resin that contains super fine silver powder, the oven dry back is not connected on the positive pole of 1.2～3.0V direct supply there being one of epoxy resin to terminate at, other gets a filamentary silver and is connected on the negative pole of same power supply, having the position of epoxy resin to immerse concentration spun gold is in 0.1～0.5 mole the hydrochloric acid solution, again filamentary silver is inserted, constitute loop and turn-on current, after 15～30 minutes, the epoxy resin surface that is connected on the positive pole has plated uniform AgCl film, use distilled water flushing, oven dry gets final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150682 CN1229640C (en) | 2003-08-25 | 2003-08-25 | Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150682 CN1229640C (en) | 2003-08-25 | 2003-08-25 | Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1515899A CN1515899A (en) | 2004-07-28 |
| CN1229640C true CN1229640C (en) | 2005-11-30 |
Family
ID=34240596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03150682 Expired - Fee Related CN1229640C (en) | 2003-08-25 | 2003-08-25 | Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1229640C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706941B (en) * | 2012-02-08 | 2014-11-12 | 国网浙江杭州市萧山区供电公司 | Preparation method of ion-selective membrane electrode |
| CN103196971A (en) * | 2013-03-28 | 2013-07-10 | 浙江大学 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| CN110006978A (en) * | 2018-01-05 | 2019-07-12 | 张家港万众一芯生物科技有限公司 | A kind of arrays of interdigitated electrodes sensor applied to chlorine residue in quantitative detection water |
-
2003
- 2003-08-25 CN CN 03150682 patent/CN1229640C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1515899A (en) | 2004-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kocak et al. | Synthesis and characterization of novel nano-chitosan Schiff base and use of lead (II) sensor | |
| CN110514603B (en) | Photoelectrochemical sensor for detecting kanamycin and preparation method and application thereof | |
| Abollino et al. | Determination of copper, cadmium, iron, manganese, nickel and zinc in Antarctic sea water. Comparison of electrochemical and spectroscopic procedures | |
| CN109265698A (en) | A kind of MOF/ carbon dots chiral hybrid material and its preparation method and application | |
| Zhiqiang et al. | Preconcentration and differential-pulse voltammetric determination of iron (II) with Nafion—1, 10-phenanthroline-modified carbon paste electrodes | |
| CN1229640C (en) | Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method | |
| Galai et al. | Elaboration of an imprinted polymer film based on chitosan electrodeposition for the voltammetric detection of BPA | |
| Gao et al. | Differential pulse voltammetric determination of cobalt with a perfluorinated sulfonated polymer-2, 2-bipyridyl modified carbon paste electrode | |
| Hassanvand et al. | Electrocatalytic determination of glutathione using transition metal hexacyanoferrates (MHCFs) of copper and cobalt electrode posited on graphene oxide nanosheets | |
| CN1222769C (en) | Electrode for detecting dissolved carbon dioxide content in water and its preparation and use method | |
| CN104237361B (en) | Detect Cd based on Cys/graphene modified electrode simultaneously2+、Pb2+Electrochemical method | |
| Gao et al. | Voltammetric determination of trace amounts of gold (III) with a carbon paste electrode modified with chelating resin | |
| CN103616420B (en) | The Optical Electro-Chemistry assay method of glucose in serum | |
| CN110980688B (en) | Based on carbon quantum dots-TiO2Preparation method and application of nanorod electrode | |
| CN107434850B (en) | Metal-organic framework material for tryptophan detection and preparation method thereof | |
| CN110596220A (en) | Preparation method of quantum dot electrode for simultaneously carrying out fluorescence and electrochemical detection on metal ions | |
| Okajima et al. | Chemiluminescence of lucigenin by electrogenerated superoxide ions in aqueous solutions | |
| CN115182012A (en) | Preparation method and sensing application of bismuth nanoflower modified electrode | |
| CN102213688B (en) | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode | |
| Wu et al. | An All-Solid-State Phosphate Ion-Selective Electrode Using BiPO4 as a Sensitive Membrane | |
| Zeng et al. | An electrochemical sensor based on copper nanowires-PDDA modified glassy carbon electrode for amperometric detection of cysteine in alkaline medium | |
| Yu et al. | Liquid-membrane dicyanoargentate-sensitive electrodes based on quaternary ammonium salts | |
| Shan et al. | Simply amplificated signal in electrochemiluminescence sensor using nano-gold film as a bridge | |
| CN1007839B (en) | Liquid ion-exchanger composite used as acetylcholine ion-selective microelectrode | |
| Wang et al. | The enhanced electrochemiluminescence of luminol on the nickel phthalocyanine modified electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |