CN1222769C - Electrode for detecting dissolved carbon dioxide content in water and its preparation and use method - Google Patents
Electrode for detecting dissolved carbon dioxide content in water and its preparation and use method Download PDFInfo
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- CN1222769C CN1222769C CN 03150691 CN03150691A CN1222769C CN 1222769 C CN1222769 C CN 1222769C CN 03150691 CN03150691 CN 03150691 CN 03150691 A CN03150691 A CN 03150691A CN 1222769 C CN1222769 C CN 1222769C
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Abstract
The present invention discloses an electrode for detecting CO2 dissolution content in water and a preparation and application method thereof. The electrode takes gold wires or silver wires as a base material, epoxy resin containing superfine silver powder is coated on the base material as an intermediate layer, and an ionic selectivity film which is sensitive to carboxylic acid radical and bicarbonate radicals is coated on the intermediate layer. The basic components of the ionic selectivity film comprise bicarbonate radical type hydrotalcite, a surfactant, a solvent and a film forming agent. When the electrode is used, an Ag/AgCl electrode can be used as a reference electrode so as to form a detecting electrode pair. The electrode disclosed by the present invention has the advantages of small volume, high mechanical strength and toughness and good working performance under wide temperature and pressure conditions. Therefore, the electrode is suitable for the on-line detection and the long-term monitoring of the CO2 content in natural water, chemical water media and chemical industrial water media.
Description
Technical field
The present invention relates to dissolve CO in a kind of detection water body
2Electrode of content and preparation method thereof.
Background technology
Total dissolving CO in the water body
2Content is important environmental evaluation parameter, and for the activity of understanding organism in water and microorganism, and the carbon cycle between hydrosphere and the air sphere is significant.Dissolve CO in the seawater at present
2Content normally obtain according to calculation of parameter such as the pH value of water body and basicity change the CO that causes because the analytical approach in the laboratory mostly is difficult to overcome sampling process pressure
2Volatilization.Indirect calculation has remedied CO to a certain extent
2Therefore the problem brought of volatilization, but its influence still exists objectively needs a kind ofly can dissolve CO to natural water body
2Content carries out the sensor of in-situ investigation, the present invention is directed to this demand and has proposed required exploring electrode.
Summary of the invention
The purpose of this invention is to provide in a kind of detection water body and dissolve CO
2Electrode of content and preparation method thereof.
Be used for surveying water body and dissolve CO
2The electrode of content 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 bicarbonate radical sensitivity.
Ion selective membrane is characterised in that it contains bicarbonate radical type hydrotalcite, and its chemical structure of general formula is [Mg
1-xAl
x(OH)
2]
X+[HCO
3 -]
xMH
2O is prepared from according to the following steps:
1) hydrotalcite was calcined 1～4 hour in 450～600 ℃ of muffle furnaces, be chilled to room temperature after the taking-up;
2) get the above-mentioned calcined product of 1～2 gram and place large beaker, add sodium bicarbonate solution 300～500mL that pre-configured concentration is 0.5～2M, stir, and on oscillator, vibrated 2～6 hours;
3) with filtration, suction filtration or centrifugal method solid phase is separated from liquid phase, distilled water cleans 2～3 times, dries in temperature is no more than 80 ℃ baking oven, obtains bicarbonate radical type hydrotalcite, is ground to less than 200～300 orders standby.
Survey in the water body and dissolve CO
2The preparation process of content electrode is:
1) take by weighing 100～500 milligrams of bicarbonate radical type hydrotalcites, in agate mortar, be milled to, add 0.2～1 milliliter of silane coupling agent surfactant less than 300 orders, 1～5 milliliter of benzene solvent, ultrasonic Treatment 3～5 minutes are used in the back that stirs;
2) add 0.02～0.1 milliliter of dimethyl silicone polymer 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.
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 CO in natural water body and chemistry, the chemical industry aqueous medium
2Content carries out online detection and long term monitoring.Compare with traditional sampling analysis, promptly alleviated working strength, improved the real-time of data, avoided simultaneously in the sampling process because of CO
2The influence that volatilization causes.
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 bicarbonate radical type hydrotalcite as the negative ion carrier.Because commercially available hydrotalcite is the carbonate type, for improving it to different dissolved form CO
2Susceptibility, need before using the carbanion between its structural sheet is substituted by bicarbonate ion through pre-service.
At preparation dissolving CO
2During exploring electrode, earlier bicarbonate 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 mother liquor 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 bicarbonate radical type hydrotalcite
1) commercially available hydrotalcite was calcined 2 hours in 500 ℃ of muffle furnaces, be chilled to room temperature after the taking-up;
2) get the above-mentioned calcined product of 2 grams and place large beaker, add the sodium bicarbonate solution 500mL that pre-configured concentration is 1M, stir, and on oscillator, vibrated 4 hours;
3) with solid phase isolated by filtration from liquid phase, distilled water cleans 2～3 times, dries in 60 ℃ baking oven, is ground to less than 300 orders standby.
Example 2: the preparation of ion selective membrane suspension
1) take by weighing 0.1 gram bicarbonate radical type hydrotalcite, add 0.2 milliliter of silane coupling agent, 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 bicarbonate 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 bicarbonate 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: dissolving CO
2The making of 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: dissolving CO
2The making of 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 the HCl of 0.1N;
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 the HCl of 0.1N;
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: dissolve CO in the water body
2The using method of content detection electrode
To dissolve CO
2The content electrode is 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 carbonate in the solution, bicarbonate radical potential difference (PD) between the two and typical curve contrast.
Example 11: dissolve CO in the water body
2The using method of content detection electrode
To dissolve CO
2The content electrode is 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 carbonate in the solution, bicarbonate radical potential difference (PD) between the two and typical curve contrast.
Claims (3)
1. dissolve CO in a detection water body
2The electrode of content 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 the ion selective membrane that contains bicarbonate radical type hydrotalcite on the middle layer, its chemical structure of general formula is [Mg
1-xAl
x(OH)
2]
X+[HCO
3 -]
xMH
2O.
2. dissolve CO in a kind of detection water body according to claim 1
2The electrode of content is characterized in that preparation method's step of described bicarbonate radical type hydrotalcite is as follows:
1) hydrotalcite was calcined 1～4 hour in 450～600 ℃ of muffle furnaces, be chilled to room temperature after the taking-up;
2) get the above-mentioned calcined product of 1～2 gram and place large beaker, add sodium bicarbonate solution 300～500mL that pre-configured concentration is 0.5～2M, stir, and on oscillator, vibrated 2～6 hours;
3) with filtration, suction filtration or centrifugal method solid phase is separated from liquid phase, distilled water cleans 2～3 times, dries in temperature is no more than 80 ℃ baking oven, obtains bicarbonate radical type hydrotalcite, is ground to less than 200～300 orders standby.
3. dissolve CO in a detection water body
2The preparation method of content electrode is characterized in that its step is:
1) takes by weighing 100～500 milligrams of bicarbonate radical type hydrotalcites, in agate mortar, be milled to less than 300 orders, add 0.2～1 milliliter of silane coupling agent surfactant, 1～5 milliliter of benzene solvent, use ultrasonic Treatment 3～5 minutes after stirring, add 0.02～0.1 milliliter of dimethyl silicone polymer film forming agent, ultrasonic Treatment 3～5 minutes are used in the back that stirs, the suspension that obtains mixing places closed container stand-by.
2) 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.
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|---|---|---|---|
| CN 03150691 CN1222769C (en) | 2003-08-25 | 2003-08-25 | Electrode for detecting dissolved carbon dioxide content in water and its preparation and use method |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101536177B (en) * | 2006-10-24 | 2011-09-07 | 威世通用半导体公司 | Semiconductor wafer suitable for forming a semiconductor junction diode device and method of forming same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100454012C (en) * | 2006-08-21 | 2009-01-21 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method |
| CN102156157B (en) * | 2011-01-10 | 2013-06-05 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
| CN105738438B (en) * | 2016-02-19 | 2019-05-10 | 中国地质调查局水文地质环境地质调查中心 | A kind of bipolar electrode method realizes bicarbonate radical and carbonate rapid detection apparatus and its method in water |
| 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 |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101536177B (en) * | 2006-10-24 | 2011-09-07 | 威世通用半导体公司 | Semiconductor wafer suitable for forming a semiconductor junction diode device and method of forming same |
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