CN101539525B - Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium - Google Patents
Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium Download PDFInfo
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- CN101539525B CN101539525B CN2009100668553A CN200910066855A CN101539525B CN 101539525 B CN101539525 B CN 101539525B CN 2009100668553 A CN2009100668553 A CN 2009100668553A CN 200910066855 A CN200910066855 A CN 200910066855A CN 101539525 B CN101539525 B CN 101539525B
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Abstract
The invention relates to a method for measuring formaldehyde in aqueous solution by utilizing electrochemical luminescence of terpyridyl ruthenium. The aqueous solution sample containing the formaldehyde is mixed with terpyridyl ruthenium solution with the pH value of 8.6 and the concentration of 1mmol/L, wherein, the concentration of the formaldehyde aqueous solution before mixing with the terpyridyl ruthenium solution is 0.9-300mg/L. After that, cyclic voltammetry scan is carried out within the range of 0.2-1.5v, and the speed is 0.1v/s. A working electrode of electrochemical luminescence measurement is a glassy carbon electrode. Quantitative analysis is carried out on the formaldehyde in the aqueous solution according to a linear relation of the electrochemical illumination intensity and the concentration of the formaldehyde within a certain range. The method can be used for measuring the content of the formaldehyde within the concentration range of 0.9-300mg/L. The method for measuring formaldehyde by utilizing electrochemical luminescence has the advantages of simple operation, rapid measuring speed, lower price of an analytical instrument and the like, and can be expected to be used for daily analysis.
Description
Technical field
The present invention relates to utilize the tris (bipyridine) ruthenium electrochemiluminescence to measure the method for formaldehyde in aqueous solution, belong to the formaldehyde determination technical field.
Background technology
Formaldehyde is a kind of colourless, has pungency and gas soluble in water.Formaldehyde is gaseous state at normal temperatures, and the form with the WS occurs usually.Formaldehyde is the material than high toxicity, preferentially controls on the list formaldehyde at China's toxic chemical and is in second.The purposes of formaldehyde is very extensive, all will use formaldehyde in synthetic resin, surfactant, plastics, rubber, leather, papermaking, dyestuff, pharmacy, agricultural chemicals, photographic film, explosive, building materials and sterilization, the stifling and anticorrosion process.Yet formaldehyde uses the pollution that but inevitably brings water and air widely, so the content of measuring formaldehyde accurately has very important meaning to people's health.At present, the representative method of the formaldehyde in the detection WS mainly contains spectrophotometric, liquid chromatography and enzyme sensor method.AAS and liquid phase chromatography have adopted the toxic reagent and the operation relative complex that can cause new pollution, and also there is very big difficulty in the preparation of enzyme sensor method with long-term the use.So the method that develops the content of new detection formaldehyde in aqueous solution has important practical application.
The tris (bipyridine) ruthenium electrochemiluminescence is that a kind of development in recent years is highly sensitive rapidly, and the range of linearity is wide, and analysis speed is fast, and analytical approach simple to operate has been widely used in mensuration, immunoassay and the foranalysis of nucleic acids of oxalic acid, amino acid and fatty amine etc.Chang, Saji and Bard in 1977 time have reported that tris (bipyridine) ruthenium and oxalic acid electrochemical reaction take place can produce electrochemiluminescence in J.Am.Chem.Soc. the 99th volume the 5399th beginning of the page in organic solution; Rubinstein in 1981 and Bard time have reported that tris (bipyridine) ruthenium and oxalic acid electrochemical reaction take place can produce electrochemiluminescence in J.Am.Chem.Soc. the 99th volume the 5399th beginning of the page in organic solution; Rubinstein in 1981 and Bard have reported that the 512nd page of J.Am.Chem.Soc. the 103rd volume tris (bipyridine) ruthenium and oxalic acid galvanochemistry take place sends out and should produce electrochemiluminescence in the WS.
Summary of the invention
The committed step that tris (bipyridine) ruthenium and oxalic acid generation electrochemical reaction produce electrochemiluminescence is that oxalic acid has been generated living radical intermedium CO by electrochemical oxidation
2 -Formaldehyde also has CO in electrochemical oxidation process
2 -Generate, should produce electrochemiluminescence so also possibly send out with tris (bipyridine) ruthenium generation galvanochemistry.We through experiment confirm at formaldehyde on the glass-carbon electrode and tris (bipyridine) ruthenium galvanochemistry to take place in the WS send out and should produce electrochemiluminescence; It is maximum that electrochemiluminescence intensity reaches when pH value 8.6, and the concentration of electrochemiluminescence intensity and formaldehyde is linear within the specific limits.Given this, the invention provides the method that a kind of tris (bipyridine) ruthenium electrochemiluminescence is measured formaldehyde in aqueous solution.
The purpose of this invention is to provide a kind of tris (bipyridine) ruthenium electrochemiluminescence, to measure the step and the condition of method of formaldehyde in aqueous solution following:
Getting the aqueous sample that contains formaldehyde and pH value and be 8.6 concentration is that 1 mM/rising the terpyridyl ruthenium solution mixes, and wherein, the concentration of aqueous solution of formaldehyde is the 0.9-300 mg/litre before mixing with the terpyridyl ruthenium solution; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan afterwards, sweep 0.1 volt of speed/second, when carrying out cyclic voltammetry scan, measure electrochemiluminescence intensity; Linear within the specific limits according to the concentration of electrochemiluminescence intensity and formaldehyde then, formaldehyde in aqueous solution is carried out quantitative test; The working electrode that electrochemiluminescence is measured is a glass-carbon electrode.
Beneficial effect: electrochemical reaction generation electrochemiluminescence can directly take place in formaldehyde and tris (bipyridine) ruthenium among the present invention in weakly alkaline solution; Directly electrochemiluminescence intensity is analyzed the content that just can obtain formaldehyde; Simplify operation, and shortened analysis time.Because formaldehyde has been participated in the electrochemiluminescence reaction directly, electrochemiluminescence intensity and content of formaldehyde have good linear relationship, range of linearity broad, and also error is less.Utilize the present invention can detect the concentration of formaldehyde in the 0.9-300 mg/litre scope, be expected to be used for routine analysis.
Description of drawings
Fig. 1 is the measured electrochemiluminescence intensity of the formaldehyde sample solution of variable concentrations.Among the figure, horizontal ordinate is that (unit: mg/litre), ordinate is measured electrochemiluminescence intensity for the concentration of formaldehyde sample solution.
Embodiment
Embodiment 1
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 0.9 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 280, sees accompanying drawing 1.
Embodiment 2
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 3 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 320, sees accompanying drawing 1.
Embodiment 3
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 9 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 370, sees accompanying drawing 1.
Embodiment 4
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 30 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 620, sees accompanying drawing 1.
Embodiment 5
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 90 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 1260, sees accompanying drawing 1.
Embodiment 6
Get aqueous sample and 900 microlitre pH values that 100 microlitres contain 300 mg/litre formaldehyde and be 8.6 1 mM/rise the terpyridyl ruthenium solution to mix; The employing glass-carbon electrode is a working electrode; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan; Sweep 0.1 volt of speed/second, measured electrochemiluminescence intensity is 3010, sees accompanying drawing 1.
Claims (1)
1. a tris (bipyridine) ruthenium electrochemiluminescence is measured the method for formaldehyde in aqueous solution; It is characterized in that; Getting the aqueous sample that contains formaldehyde and pH value and be 8.6 concentration is that 1 mM/rising the terpyridyl ruthenium solution mixes; Wherein, mix with the terpyridyl ruthenium solution before the concentration of aqueous solution of formaldehyde be the 0.9-300 mg/litre; In 0.2-1.5 volt scope, carry out cyclic voltammetry scan afterwards, sweep 0.1 volt of speed/second, when carrying out cyclic voltammetry scan, measure electrochemiluminescence intensity; Linear within the specific limits according to the concentration of electrochemiluminescence intensity and formaldehyde then, formaldehyde in aqueous solution is carried out quantitative test; The working electrode that electrochemiluminescence is measured is a glass-carbon electrode.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100668553A CN101539525B (en) | 2009-04-21 | 2009-04-21 | Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium |
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| CN2009100668553A CN101539525B (en) | 2009-04-21 | 2009-04-21 | Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium |
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| CN101539525A CN101539525A (en) | 2009-09-23 |
| CN101539525B true CN101539525B (en) | 2012-03-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102042977B (en) * | 2010-10-19 | 2012-10-17 | 广西师范大学 | Method for indirectly measuring formaldehyde content of air or water by adopting capillary electrophoresis and Rucbpy electrochemiluminescence |
| CN102727213B (en) * | 2012-06-20 | 2014-06-04 | 浙江大学 | Method for manifesting latent fingerprints on basis of electrochemical luminescence marker |
| CN104261506B (en) * | 2014-09-19 | 2016-04-20 | 山东大学 | The method of the formaldehyde in a kind of terpyridyl base gelatinous material process trade effluent |
| CN105259166B (en) * | 2015-11-09 | 2017-12-15 | 山东省科学院海洋仪器仪表研究所 | Formaldehyde examination device and detection method |
| CN106596666B (en) * | 2016-11-18 | 2018-12-04 | 常州大学 | A kind of fixing tripyridyl ruthenium and electrochemical luminescence detection lure red method |
| CN106645337B (en) * | 2016-11-18 | 2019-02-12 | 常州大学 | A kind of method of fixing tripyridyl ruthenium and electrochemical luminescence detection brilliant blue |
| CN106645111A (en) * | 2017-03-01 | 2017-05-10 | 桂林理工大学 | Method for rapidly detecting concentration of antibiotic Zwittermicin A through electrochemical luminescence |
| CN114486756B (en) * | 2022-01-18 | 2024-07-23 | 河北先河环保科技股份有限公司 | Method for estimating formaldehyde concentration in atmosphere |
Citations (3)
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|---|---|---|---|---|
| US5801300A (en) * | 1996-04-19 | 1998-09-01 | Life Science Laboratories, Inc. | Method for determining glycol and formaldehyde contaminants in ground water samples |
| CN1661360A (en) * | 2004-02-27 | 2005-08-31 | 上海塞艾生物科技有限公司 | One-off simple rapid test kit for color matching formaldehyde and preparation method |
| CN101000310A (en) * | 2007-01-15 | 2007-07-18 | 浙江大学 | Method for investigating formol |
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- 2009-04-21 CN CN2009100668553A patent/CN101539525B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5801300A (en) * | 1996-04-19 | 1998-09-01 | Life Science Laboratories, Inc. | Method for determining glycol and formaldehyde contaminants in ground water samples |
| CN1661360A (en) * | 2004-02-27 | 2005-08-31 | 上海塞艾生物科技有限公司 | One-off simple rapid test kit for color matching formaldehyde and preparation method |
| CN101000310A (en) * | 2007-01-15 | 2007-07-18 | 浙江大学 | Method for investigating formol |
Non-Patent Citations (1)
| Title |
|---|
| JP平5-42000A 1993.02.23 |
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