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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- formaldehyde
- aqueous solution
- electrochemiluminescence
- ruthenium
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004020 luminiscence type Methods 0.000 title 1
- 239000000243 solution Substances 0.000 claims abstract description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 11
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910021397 glassy carbon Inorganic materials 0.000 claims 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 claims 1
- 238000004445 quantitative analysis Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Abstract
本发明涉及利用三联吡啶钌电化学发光测定水溶液中甲醛的方法。取含有甲醛的水溶液样品与pH值为8.6的浓度为1毫摩尔/升三联吡啶钌溶液混合，其中，与三联吡啶钌溶液混合前甲醛的水溶液浓度为0.9-300毫克/升；之后在0.2-1.5伏范围内进行循环伏安扫描，扫速0.1伏/秒，在进行循环伏安扫描的同时测量电化学发光强度；电化学发光测定的工作电极是玻碳电极，然后根据电化学发光强度和甲醛的浓度在一定范围内呈线性关系，对水溶液中甲醛进行定量分析。该方法可以测定0.9-300毫克/升范围内甲醛的含量。利用三联吡啶钌电化学发光的方法检测甲醛具有操作简单，测定速度快，分析仪器相对便宜等优点，可望用于日常分析。The invention relates to a method for measuring formaldehyde in aqueous solution by using terpyridine ruthenium electrochemiluminescence. Take an aqueous solution sample containing formaldehyde and mix it with a concentration of 1 mmol/L ruthenium terpyridyl solution with a pH value of 8.6, wherein the aqueous solution concentration of formaldehyde is 0.9-300 mg/L before mixing with the ruthenium terpyridyl solution; Carry out cyclic voltammetry scanning in the range of 1.5 volts, scan rate 0.1 volts/second, measure electrochemiluminescence intensity while performing cyclic voltammetry scanning; The concentration of formaldehyde has a linear relationship within a certain range, and the formaldehyde in the aqueous solution is quantitatively analyzed. The method can determine the content of formaldehyde in the range of 0.9-300 mg/L. The detection of formaldehyde by ruthenium tertiary pyridine electrochemiluminescence has the advantages of simple operation, fast determination speed, relatively cheap analytical instruments, etc., and it is expected to be used in 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)
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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 |
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| CN102042977B (en) * | 2010-10-19 | 2012-10-17 | 广西师范大学 | Capillary electrophoresis-terpyridine ruthenium electrochemiluminescence method for indirect determination of formaldehyde content in air or water |
| 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 |
| CN106645337B (en) * | 2016-11-18 | 2019-02-12 | 常州大学 | A kind of method of immobilizing ruthenium terpyridine and electrochemiluminescence detecting bright blue |
| CN106596666B (en) * | 2016-11-18 | 2018-12-04 | 常州大学 | A method for immobilizing ruthenium terpyridine and detecting Allura Red by electrochemiluminescence |
| 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)
| 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 |
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2009
- 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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