CN102175675A - Method for detecting copper ions - Google Patents
Method for detecting copper ions Download PDFInfo
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- CN102175675A CN102175675A CN2011100228368A CN201110022836A CN102175675A CN 102175675 A CN102175675 A CN 102175675A CN 2011100228368 A CN2011100228368 A CN 2011100228368A CN 201110022836 A CN201110022836 A CN 201110022836A CN 102175675 A CN102175675 A CN 102175675A
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- complexing agent
- copper ion
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Abstract
The invention provides a method for detecting copper ions. In the method provided by the invention, a strong oxidizer and a complexing agent are added to gold nano particle sol, and the color of the solution is changed when the copper ions exist in the solution, thereby detecting the copper ions; the solution comprises the complexing agent, the strong oxidizer and a solvent, wherein the complexing agent comprises a complexing agent A and a complexing agent B; the complexing agent A is a compound containing sulfur, and the concentration of the complexing agent A is 5-20mM; the complexing agent B is an ammonia compound, and the concentration of the complexing agent B is 5-40mM; the strong oxidizer is hydrogen peroxide, and the concentration of the strong oxidizer is 5-50mM; and the solvent is water. Compared with the traditional nano gold aggregated coloration method, the method provided by the invention is stronger in interference resistance on the high salt, acid and ligand in an actual sample. In the method provided by the invention, the concentration of the copper ions in visual colorimetric measurement can reach 0.05mM, and the method is good in selectivity, does not need any instrument and equipment and can be conveniently and rapidly applied to the scene detection of the copper ions.
Description
Technical field
The present invention relates to a kind of method that detects copper ion, belong to the analyzing and testing field.
Background technology
Though copper ion is vegeto-animal indispensable element, similarly, the copper ion of excessive concentrations can cause the water body bacterium, and the death of algae also can cause the damage of human liver and kidney and the disorder of functions of intestines and stomach.Therefore, aspect environmental protection and the health, tool has very important significance to the detection of copper ion.Water environment quality standard (GB3838-2002), Han Liang ≦ 0.01 of copper ion (I class)～1.0 (V class) mg/L(0.15～15 mM) (annotate: the I class refers to I class protected location, and the V class refers to V class protected location).
With the detection method of traditional present copper ion, as atomic absorption method, the chromatography of ions, methods such as Electrochemical Detection are compared, and colourimetry has its original advantage.Such as, convenient, fast, can realize on-the-spot advantages such as analysis.
The present colourimetry of report has the method that develops the color based on the complex reaction of copper ion and organic molecule, and golden nanometer particle is induced the method for assembling down and developing the color at copper ion.Because the synthetic and separation of organic molecule is difficulty relatively, and the golden nanometer particle simple synthetic method, maturation, more meaningful in the application of reality.For example, in 2008, on Angew. Chem. Int. Ed., Xingyu Jiang reported the gathering of the golden nanometer particle that the click-reaction based on copper ion catalysis causes.Though this method has good selectivity to copper ion, detectability has only 50 mM.In addition, because some compositions in the actual sample matrix similarly can cause the gathering of golden nanometer particle as high salt, acid and part, thereby be subjected to certain restriction.
Summary of the invention
The objective of the invention is to be to provide a kind of method that detects copper ion with sensitivity.
To achieve these goals, technical scheme of the present invention is as follows:
The method of detection copper ion of the present invention is to add strong oxidizer and complexing agent in golden nanometer particle colloidal sol, and when having copper ion to exist in the solution, solution produces the variation on the color, thereby detects copper ion; Solution composition comprises: complexing agent is divided into complexing agent A and complexing agent B, and complexing agent A is a sulfocompound, and concentration is 5 ~ 20 mM, and complexing agent B is an ammoniac compounds, and concentration is 5 ~ 40 mM, and strong oxidizer is a hydrogen peroxide, and concentration is 5 ~ 50 mM, and solvent is a water.
Described complexing agent A is KSCN.
Described complexing agent B is the ammonia damping fluid.
The concentration of described golden nanometer particle colloidal sol is 5 ~ 40 mg/L.
Also comprise anti-mercury agent interfering in the solution composition, described anti-mercury agent interfering is a potassium iodide, and concentration is 0-20 mM.
The copper ion that in solution, has variable concentrations, solution produces the difference on the color, adopts the semi-quantitative analysis method to judge the concentration range of copper ion according to color distinction; Decision method is: add the copper ion of variable concentrations respectively in described solution, can produce the difference on the color, when the concentration of copper ion in the test sample, the difference of contrast color can be judged the concentration range of copper ion.
Owing to compare with the gathering of nm of gold, the oxidation of nm of gold is more difficult, generally needs the acting in conjunction of strong oxygenant and complexing agent in the method for the present invention.Therefore, has the better resisting interference ability for high salt, acid and part in the actual sample.The principle of this method is: add strong oxygenant, part and ammoniac compounds in golden nanometer particle colloidal sol, when having copper ion to exist in the solution, can generate cupric ammine complex.This cupric ammine complex can be under lower concentration, the decomposition of catalyzing hydrogen peroxide and reach the dissolving that suppresses golden nanometer particle effectively, thus produce the difference on the color.Just can reach the purpose of highly sensitive detection by method of the present invention.Assemble the method for colour developing with traditional nm of gold and compare, the present invention has following advantage:
(1) the present invention is owing to compare with the gathering of nm of gold, and the oxidation of nm of gold is more difficult, thereby anti-interference stronger to high salt, acid and part in the actual sample.
(2) concentration of utilizing the present invention to detect copper ion can reach 0.05 mM, is lower than the content of copper ion standard (GB3838-2002) in the surface water.
(3) the present invention and have good selectivity, other metallic ion is almost interference-free, as Hg(II), Ag(I), Zn(II), Cd(II), Pb (II), Fe(II), Co(II), Ni(II).
(4) need not by any instrument and equipment, detection method can be widely used in the detection of on-the-spot copper ion easily and fast.
Description of drawings
Fig. 1 is the transmission electron microscope picture of golden nanometer particle;
Fig. 2 is the colorimetric analysis figure of the copper ion of variable concentrations;
Fig. 3 adds the colorimetric analysis figure of the copper ion of the variable concentrations behind the dyestuff;
Fig. 4 is the interference of other metallic ion;
Fig. 5 is the interference of the mercury ion behind the adding KI;
The detection of the actual copper ion of Fig. 6.
Embodiment
Synthesizing of golden nanometer particle colloidal sol: the synthetic method that adopts the trisodium citrate reduction.Gold chloride solid (HAuCl with 1g
44H
2O) be dissolved in the aqueous solution of 100mL, take out 1mL and be diluted to 100mL, change that condensing reflux is heated to boiling in the flask over to.Inject the citric acid three sodium solution (C of 3mL then fast
6H
5Na
3O
72H
2O, 1.14g/100mL).Continue to reflux 40 minutes, can obtain golden nanometer particle colloidal sol.The synthetic nano particle grain size of this method is 17 nm, as shown in Figure 1.
Embodiment 1
Golden nanometer particle colloidal sol 30 mg/L
NH
3/NH
4Cl 10?mM
KSCN 10?mM
Hydrogen peroxide 20 mM
The compound method of solution: with complexing agent A KSCN, complexing agent B ammonia damping fluid, golden nanometer particle colloidal sol and hydrogen peroxide are made test fluid after mixing.The copper ion that adds various criterion concentration is put into 60 ℃ water-bath heating 8 minutes, and does not add comparing of tested thing.
Change the concentration (0 ~ 5 mM) of different copper ions, when not adding copper ion, solution is colourless, and when the concentration of copper ion was 5 mM, solution was peony, can obtain under the normal concentration, the nano-Au solution of the different colours degree of depth, as shown in Figure 2.In order further to improve its color resolution, we add the Copper Phthalocyanine of 10 mg/L in this solution, can present different colours.As shown in Figure 3, when not adding copper ion, it is blue that solution is, and when the concentration of copper ion is 0.05 mM, solution is bluish violet, when the concentration of copper ion was 0.5 mM, solution was purple, when the concentration of copper ion is 1 mM, solution is aubergine, when the concentration of copper ion was 5 mM, solution took on a red color, and can be used as the color standards of actual detected.
Embodiment 2
Golden nanometer particle colloidal sol 30 mg/L
NH
3/NH
4Cl 10?mM
KSCN 10?mM
Hydrogen peroxide 20 mM
The compound method of solution: with complexing agent A KSCN, complexing agent B ammonia damping fluid, golden nanometer particle colloidal sol and hydrogen peroxide are made test fluid after mixing.Add different interfering ions, put into 60 ℃ water-bath and heated 8 minutes, with comparing of adding copper ion.
The influence of different metal ion (concentration is 5uM) as shown in Figure 4, has only mercury ion to exist and disturbs.
Embodiment 3
Golden nanometer particle colloidal sol 25 mg/L
NH
3/NH
4Cl 10?mM
KSCN 10?mM
KI 10mM
Hydrogen peroxide 20 mM
The compound method of solution: with complexing agent A KSCN, complexing agent B ammonia damping fluid, anti-mercury agent interfering potassium iodide, golden nanometer particle colloidal sol and hydrogen peroxide are made test fluid after mixing.Add mercury ion, put into 60 ℃ water-bath and heated 8 minutes, with comparing of adding copper ion.
The influence (concentration is 5mM) of the mercury metallic ion behind the adding KI, as shown in Figure 5, the interference of mercury ion can be eliminated.
Application Example 1
Golden nanometer particle colloidal sol 30 mg/L
NH
3/NH
4Cl 10?mM
KSCN 10?mM
Hydrogen peroxide 20 mM
Copper Phthalocyanine 10mg/L
The compound method of solution: with complexing agent A KSCN, complexing agent B ammonia damping fluid, anti-mercury agent interfering potassium iodide, golden nanometer particle colloidal sol and hydrogen peroxide are made test fluid after mixing.Add testing sample (electroplating effluent, 100 times have been diluted), be purple in the solution, slightly blue, as shown in Figure 6, color distinction according to solution, can judge that the copper ion concentration scope is approximately 0.2 ~ 0.5 mM, the concentration range in the back testing sample that converts is 0.4 ~ 1 mM, is 0..84 mM and measure the result who comes with atom absorption method, more approaching, illustrated that this method is used for the feasibility of half-quantitative detection copper ion.
Claims (6)
1. method that detects copper ion is characterized in that: add strong oxidizer and complexing agent in golden nanometer particle colloidal sol, when having copper ion to exist in the solution, solution produces the variation on the color, thereby detects copper ion; Solution composition comprises: complexing agent is divided into complexing agent A and complexing agent B, and complexing agent A is a sulfocompound, and concentration is 5 ~ 20 mM, and complexing agent B is an ammoniac compounds, and concentration is 5 ~ 40 mM, and strong oxidizer is a hydrogen peroxide, and concentration is 5 ~ 50 mM, and solvent is a water.
2. the method for detection copper ion according to claim 1 is characterized in that: described complexing agent A is KSCN.
3. the method for detection copper ion according to claim 1 is characterized in that: described complexing agent B is the ammonia damping fluid.
4. the method for detection copper ion according to claim 1 is characterized in that: the concentration of described golden nanometer particle colloidal sol is 5 ~ 40 mg/L.
5. the method for detection copper ion according to claim 1 is characterized in that: also comprise anti-mercury agent interfering in the solution composition, described anti-mercury agent interfering is a potassium iodide, and concentration is 0-20 mM.
6. the method for detection copper ion according to claim 1 is characterized in that: have the copper ion of variable concentrations in solution, solution produces the difference on the color, adopts the semi-quantitative analysis method to judge the concentration range of copper ion according to color distinction; Decision method is: add the copper ion of variable concentrations respectively in described solution, can produce the difference on the color, when the concentration of copper ion in the test sample, the difference of contrast color can be judged the concentration range of copper ion.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100228368A CN102175675A (en) | 2011-01-20 | 2011-01-20 | Method for detecting copper ions |
| CN201210014101.5A CN102565050B (en) | 2011-01-20 | 2012-01-18 | Method for detecting copper ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100228368A CN102175675A (en) | 2011-01-20 | 2011-01-20 | Method for detecting copper ions |
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| CN102175675A true CN102175675A (en) | 2011-09-07 |
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ID=44518882
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| CN2011100228368A Pending CN102175675A (en) | 2011-01-20 | 2011-01-20 | Method for detecting copper ions |
| CN201210014101.5A Expired - Fee Related CN102565050B (en) | 2011-01-20 | 2012-01-18 | Method for detecting copper ions |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323312A (en) * | 2011-09-21 | 2012-01-18 | 福州大学 | Detection method and device for portable rapid visual detection of copper ion content |
| CN102565047A (en) * | 2012-01-04 | 2012-07-11 | 福州大学 | Method for detecting aluminium ion concentration |
| CN102634571A (en) * | 2011-10-17 | 2012-08-15 | 中国科学院广州生物医药与健康研究院 | Nucleic acid nano gold biological sensor for detecting copper ion |
| CN103487430A (en) * | 2013-08-29 | 2014-01-01 | 中国科学院宁波材料技术与工程研究所 | Trivalent aluminum ion detection reagent and method |
| CN103728228A (en) * | 2012-10-10 | 2014-04-16 | 三星Sdi株式会社 | Method for detecting non-magnetic metal particles contained in secondary battery materials |
| CN104062241A (en) * | 2014-03-15 | 2014-09-24 | 河南工程学院 | Nano-silver colorimetry for detecting copper ions |
| CN105527240A (en) * | 2016-01-21 | 2016-04-27 | 南昌大学 | Method for visually detecting cadmium ions based on silver nanoparticle |
| CN106053451A (en) * | 2016-05-20 | 2016-10-26 | 大连理工大学 | Gold nano particle with modified surface |
| CN106442513A (en) * | 2016-11-24 | 2017-02-22 | 桂林理工大学 | Instrument-free bivalent copper ion detection method based on timing strategy |
| CN106525824A (en) * | 2016-05-30 | 2017-03-22 | 南京农业大学 | Cu<2+> colorimetric detection method based on MarR protein regulation |
| CN110146497A (en) * | 2019-05-29 | 2019-08-20 | 哈尔滨商业大学 | A kind of copper ion detection method based on methane oxidation rhzomorph functional gold nanoparticles |
| CN114136957A (en) * | 2021-11-16 | 2022-03-04 | 中国中医科学院中药研究所 | Instrument-free dendrobium nobile producing area visual tracing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110262556A1 (en) * | 2005-01-05 | 2011-10-27 | American Silver, Llc | Silver/water, silver gels and silver-based compositions; and methods for making and using the same |
| CN101458242B (en) * | 2007-12-11 | 2010-12-08 | 郑州轻工业学院 | Nanogold Colloid for responding heavy metal ion and method for making same |
| CN101710076B (en) * | 2009-12-29 | 2012-07-04 | 东北师范大学 | Lead ion colorimetric detection probes and application method thereof |
-
2011
- 2011-01-20 CN CN2011100228368A patent/CN102175675A/en active Pending
-
2012
- 2012-01-18 CN CN201210014101.5A patent/CN102565050B/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323312A (en) * | 2011-09-21 | 2012-01-18 | 福州大学 | Detection method and device for portable rapid visual detection of copper ion content |
| CN102634571A (en) * | 2011-10-17 | 2012-08-15 | 中国科学院广州生物医药与健康研究院 | Nucleic acid nano gold biological sensor for detecting copper ion |
| CN102565047A (en) * | 2012-01-04 | 2012-07-11 | 福州大学 | Method for detecting aluminium ion concentration |
| CN103728228B (en) * | 2012-10-10 | 2020-03-31 | 三星Sdi株式会社 | Method for detecting non-magnetic metal particles contained in secondary battery material |
| CN103728228A (en) * | 2012-10-10 | 2014-04-16 | 三星Sdi株式会社 | Method for detecting non-magnetic metal particles contained in secondary battery materials |
| JP2014077789A (en) * | 2012-10-10 | 2014-05-01 | Samsung Sdi Co Ltd | Method of detecting non-magnetic substance metal particles contained in secondary cell material |
| CN103487430B (en) * | 2013-08-29 | 2018-08-14 | 中国科学院宁波材料技术与工程研究所 | A kind of trivalent aluminium ion detection reagent and detection method |
| CN103487430A (en) * | 2013-08-29 | 2014-01-01 | 中国科学院宁波材料技术与工程研究所 | Trivalent aluminum ion detection reagent and method |
| CN104062241B (en) * | 2014-03-15 | 2016-08-17 | 河南工程学院 | A kind of nanometer silver colorimetry detecting copper ion |
| CN104062241A (en) * | 2014-03-15 | 2014-09-24 | 河南工程学院 | Nano-silver colorimetry for detecting copper ions |
| CN105527240A (en) * | 2016-01-21 | 2016-04-27 | 南昌大学 | Method for visually detecting cadmium ions based on silver nanoparticle |
| CN106053451A (en) * | 2016-05-20 | 2016-10-26 | 大连理工大学 | Gold nano particle with modified surface |
| CN106525824A (en) * | 2016-05-30 | 2017-03-22 | 南京农业大学 | Cu<2+> colorimetric detection method based on MarR protein regulation |
| CN106442513A (en) * | 2016-11-24 | 2017-02-22 | 桂林理工大学 | Instrument-free bivalent copper ion detection method based on timing strategy |
| CN106442513B (en) * | 2016-11-24 | 2019-04-16 | 桂林理工大学 | Bivalent cupric ion detection method based on timing strategy |
| CN110146497A (en) * | 2019-05-29 | 2019-08-20 | 哈尔滨商业大学 | A kind of copper ion detection method based on methane oxidation rhzomorph functional gold nanoparticles |
| CN114136957A (en) * | 2021-11-16 | 2022-03-04 | 中国中医科学院中药研究所 | Instrument-free dendrobium nobile producing area visual tracing method |
| CN114136957B (en) * | 2021-11-16 | 2024-01-23 | 中国中医科学院中药研究所 | Instrument-free visual traceability method for dendrobium nobile producing area |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102565050A (en) | 2012-07-11 |
| CN102565050B (en) | 2014-03-26 |
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Open date: 20110907 |