CN104977293B - A kind of method that electrochemical luminescence detects metal ion - Google Patents
A kind of method that electrochemical luminescence detects metal ion Download PDFInfo
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- CN104977293B CN104977293B CN201510400118.8A CN201510400118A CN104977293B CN 104977293 B CN104977293 B CN 104977293B CN 201510400118 A CN201510400118 A CN 201510400118A CN 104977293 B CN104977293 B CN 104977293B
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Abstract
The invention discloses a kind of method that electrochemical luminescence detects metal ion, including luminescent material, electrode, electrolyte solution and dual signal detection metal ion, the luminescent material is graphite phase carbon nitride polymer nanocomposite piece；The electrode is with glass-carbon electrode as substrate；The electrolyte is the cushioning liquid for including conducting medium, coreagent；The detection metal ion method is dual signal and drives potential to realize by adjusting.Electrochemical luminescence of the present invention detects metal ion, on the one hand builds the dual signal sensor driven with potential and detects nickel ion, effectively prevent the appearance of false positive results in actual sample detection；On the other hand, the luminescent material for using is graphite phase carbon nitride polymer nanocomposite piece, and raw material is cheap, heat endurance is high, stable luminescence.
Description
Technical field
The present invention relates to sensory field, and in particular to a kind of method that electrochemical luminescence detects metal ion.
Background technology
Electrogenerated chemiluminescence (Electrochemiluminescence, ECL) is one of three kinds of typical chemiluminescences, because
It is have the advantages that sensitivity is high, the range of linearity is wide, instrument is simple and is had a wide range of applications in analytical chemistry.Due to metal
The content of ion and health and the ecosystem have important relation, and the accurate and metal ion that reliably detects contains
Amount and species have very important significance.
Graphite phase carbon nitride polymer nanocomposite piece（Graphite-phase polymeric carbon nitride
Nanosheets, GPPCN nanometer sheet）Used as a kind of organic semiconducting materials, its electrogenerated chemiluminescence property is studied recently.
Compared with traditional electrogenerated chemiluminescence material, graphite phase carbon nitride polymer nanocomposite piece has that raw material are cheap, heat endurance
The high, advantage of stable luminescence；And the electrogenerated chemiluminescence of graphite phase carbon nitride polymer nanocomposite piece can be by the drive of potential
It is dynamic, realize simultaneously luminous in different potential ranges.But in actually detected, the interference of environmental factor, such as other metals from
Son, Chuan Tong Unit signal detections may cause the appearance of actually detected middle false positive results.
The content of the invention
Technical problem：It is luminescent material to use GPPCN nanometer sheets it is an object of the invention to provide one kind, by different potentials
Driving the detection of dual signal is realized to metal ion, solve the vacation sun caused due to factors such as environment in actual sample detection
Property result produced problem, and can realize Qualitative Identification different ions electrochemical luminescence detect metal ion method.
Technical scheme：The method that electrochemical luminescence of the invention detects metal ion, comprises the following steps：
1）Using electrochemiluminescdetection detection instrument, with saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is repaiied
The glass-carbon electrode of luminescent material is decorated with for working electrode, detects one group of metal ion sample of concentration known in electrolyte I respectively
Efficiency is quenched with electrolyte II；
2）The metal ion sample is drawn respectively, and efficiency is quenched with ion concentration in electrolyte I and in electrolyte II
Relation curve；
3）Detect that metal ion to be measured is quenched efficiency in electrolyte I and in electrolyte II using same method, and with
Step 1）The metal ion sample for measuring is quenched efficiency comparative in the electrolyte I and in electrolyte II, if metal to be measured from
Be quenched efficiency of the son in the electrolyte I and in electrolyte II each falls within metal ion sample efficiency is quenched in correspondence electrolyte
Number range, then it is assumed that metal ion to be measured is same metal ion species with metal ion sample；
For with the congener metal ion to be measured of metal ion sample, further according to the step 2）The relation for obtaining
Curve determines ion concentration.
Further, the luminescent material is graphite phase carbon nitride polymer nanocomposite piece.
Further, the cushioning liquid of conducting medium and coreagent, the conducting medium are dissolved with the electrolyte
It is KCl, K2SO4Or NaCl, in the electrolyte I, coreagent is that concentration is the K of 10mM ~ 200mM2S2O8、H2O2Or C2O4 2-,
In the electrolyte II, coreagent is the triethanolamine that concentration is 1mM ~ 100mM, triethylamine or the third triamine.
Further, the step 1）With step 3）It is middle to detect that the method that efficiency is quenched is：Apply potential in the electrolyte,
Scan-type electrochemical luminous intensity is I0, then to metal ion is added in electrolyte solution, rescaning electrochemical luminescence intensity is
Ic, according to（I0−Ic）/ I0It is calculated and efficiency is quenched.
Further, the potential for applying in the electrolyte I is 0 ~ -2.0V, the potential applied in electrolyte II for 0 ~
2.0V。
Further, the ion concentration range of the metal ion sample of one group of concentration known is 10 ~ 120nM, sample
Quantity is at least 5.
Principle of the invention is：GPPCN nanometer sheets are modified in glass carbon substrate, different potentials are applied successively so that material
The two poles of the earth all light, then again to certain density metal ion is added in electrolyte solution, at potential I, due to metal from
The redox potential of son is located between the band gap of GPPCN nanometer sheets, and the principle according to photo induced electron transfer causes luminous intensity
Weaken；And at potential II, have catalytic action for the luminescence process of GPPCN nanometer sheets due to specific metal ion so that
Luminous intensity strengthens；According to two kinds of unlike signals being caused by same metal ion at two potentials at the same determine a kind of target from
Son so that testing result is more credible, the appearance of the false positive results for effectively avoiding, according to each ion under different potentials
Response signal is different, Qualitive test other metal ions.
The present invention is luminescent material from GPPCN nanometer sheets, and dual signal is realized using simultaneously luminous in two potential ranges
Detect a kind of object simultaneously so that testing result is more credible, effectively avoid the appearance of false positive results, and according to not
Electrochemical response with metal ion in two potential ranges is different, realizes the different ion of Qualitative Identification.The present invention is with graphite
Phase carbon nitride polymer nanocomposite piece is luminescent material, the characteristic of, thermally-stabilised high, stable luminescence cheap with raw material.
Beneficial effect：The present invention compared with prior art, with advantages below：
1st, the GPPCN Nanoflake luminescent materials that the present invention is used, at potential I, due to the oxidation-reduction potential of nickel ion
The electricity during ground state is returned to of the GPPCN nanometer sheets in excitation state is caused between conduction band and valence band in GPPCN nanometer sheets
Son is intercepted and captured by nickel ion so that luminous intensity weakens；And at potential II, because nickel ion is luminous to GPPCN nanometer sheets wherein
One process has catalytic action so that luminous signal strengthens；Therefore being quenched and strengthen according to the signal under different potentials, with two
Signal is planted simultaneously to a kind of metal ion detection so that testing result is more credible, and being prevented effectively from Unit signal detections may lead
The appearance of the false positive of cause.
2nd, the sensor that the present invention builds does not introduce traditional target identification thing, i.e. markless detection, and instrument is simple, side
Just, it is therefore very with practical value.
3rd, the sensor that the present invention builds is successfully applied to the detection of nickel ion in Kowloon lake water and running water.
Brief description of the drawings
Fig. 1 show under different potentials nickel ion concentration and efficiency chart is quenched.
Fig. 2 is shown by taking nickel ion as an example, and nickel ion is in two different potential ranges to GPPCN nanometer sheet electrochemistry
It is luminous that the enhanced mechanism figure of work is quenched；
Specific embodiment
With reference to embodiment and Figure of description, the present invention is further illustrated.
A kind of method that electrochemical luminescence detects metal ion, including graphite phase carbon nitride polymer nanocomposite piece
（Graphite-phase polymeric carbon nitride nanosheets, GPPCN nanometer sheets）, glass-carbon electrode substrate
With electrolyte buffer solution, it is characterised in that the detection method is GPPCN Nanoflake luminescent materials in two different potential models
Enclose interior luminous, two signals can be provided specific heavy metal ion and be detected；The luminescent material is cheap, bio-compatible
The graphite phase carbon nitride polymer nanocomposite piece of the good, stable luminescence of property；
Embodiment 1
The raw material that the present embodiment is related to is purchased from Sigma-Aldrich of the U.S.；The electroluminescent chemistry hair of MPI-E types for using
Optical detector is purchased from Chinese Xi'an Rui Mai companies.
Graphite phase carbon nitride polymer nanocomposite piece luminescent material is prepared using the method that ultrasound is peeled off, specially：
The preparation of step one, body phase GPPCN luminescent materials
Graphite phase carbon nitride polybenzazole precursor thing is inserted into high-temperature calcination equipment, 500 are warmed up tooC, held for some time；
Graphite phase carbon nitride polybenzazole precursor thing is taken in crucible；
The preparation of step 2, GPPCN Nanoflake luminescent materials
The body phase GPPCN for taking step one preparation is dissolved in secondary water, is peeled off in ultrasonic cleaner ultrasound, is then centrifuged for taking
Supernatant is product.
Electrochemical luminescence according to claim 2 detects the method for metal ion, the graphite-phase in the step one
Nitridation carbon precursor polymer thing is cyanamide, dicyandiamide or urea.
GPPCN nanometer sheets are modified on glass-carbon electrode by following steps：
Step one, glass-carbon electrode use Al first2O3Powder is polished, then with secondary water ultrasound, N2Drying；
Step 2, take graphite phase carbon nitride polymer nanocomposite piece suspension and drop in the glass-carbon electrode table that the step one is obtained
Face, the drying at room temperature in drier；
Perfluorinated sulfonic acid is added dropwise again on step 3, the glass-carbon electrode obtained to the step 2, the drying at room temperature in drier,
Obtain the glass-carbon electrode of graphite phase carbon nitride polymer nanocomposite piece modification.
Specific detection method is realized by following steps：
, respectively in potential 0 ~ -1.6V of I, electrolyte solution includes 0.1M KCl for step one, the glass-carbon electrode that will be obtained,
150mM K2S2O80.01 M Tris-HCl pH 7.4 cushioning liquid in, in potential 0 ~ 1.4V of II, electrolyte solution bag
Include 0.1M KCl, sweep stabilization, recording light intensity I in 7.4 cushioning liquid of the 0.01 M Tris-HCl pH of 60mM TEA0。
One group of metal ion sample of concentration known is added in step 2, the dielectric solution to step one sweep stabilization
Product, record the luminous intensity Ic of each sample respectively.
Step 3, basis（I0−Ic）/ I0It is calculated and the working curve that efficiency obtains detecting metallic nickel ions is quenched.
The working curve that step 4, basis are obtained, detects actual by taking Kowloon lake water in the institution of higher education of the southeast and running water as an example
The concentration of nickel ion in water sample, it is 0.129 that lake water is quenched efficiency at potential I, and it is 0 that running water is quenched efficiency；At potential II
Lake water is quenched efficiency for -0.116, and it is 0 that running water is quenched efficiency, and nickel ion concentration in tap is obtained according to fitting operations curve
It is 0, nickel ion concentration is 8.83nM in the lake water of Kowloon.
Above-described embodiment is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill of the art
For personnel, under the premise without departing from the principles of the invention, some improvement and equivalent can also be made, these are to the present invention
Claim be improved with the technical scheme after equivalent, each fall within protection scope of the present invention.
Claims (5)
1. a kind of method that electrochemical luminescence detects metal ion, it is characterised in that the method is comprised the following steps：
1）Using electrochemiluminescdetection detection instrument, with saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is modified with
The glass-carbon electrode of luminescent material is working electrode, detects one group of metal ion sample of concentration known in electrolyte I and electricity respectively
Efficiency is quenched in solution matter II, the luminescent material is graphite phase carbon nitride polymer nanocomposite piece；
2）The relation that is quenched efficiency and ion concentration of the metal ion sample in electrolyte I and in electrolyte II is drawn respectively
Curve；
3）Detect that metal ion to be measured is quenched efficiency, and and step in electrolyte I and in electrolyte II using same method
1）The metal ion sample for measuring is quenched efficiency comparative in electrolyte I and in electrolyte II, if metal ion to be measured exists
The efficiency that is quenched in electrolyte I and in electrolyte II each falls within the numerical value that metal ion sample is quenched efficiency in correspondence electrolyte
Scope, then it is assumed that metal ion to be measured is same metal ion species with metal ion sample；
For with the congener metal ion to be measured of metal ion sample, further according to the step 2）The relation curve for obtaining
Determine ion concentration.
2. the method that electrochemical luminescence according to claim 1 detects metal ion, it is characterised in that in the electrolyte
The cushioning liquid of conducting medium and coreagent is dissolved with, the conducting medium is KCl, K2SO4Or NaCl, the electrolyte I
In, coreagent is that concentration is the K of 10mM ~ 200mM2S2O8、H2O2Or C2O4 2-, in the electrolyte II, coreagent is concentration
It is the triethanolamine of 1mM ~ 100mM, triethylamine or the third triamine.
3. the method that electrochemical luminescence according to claim 1 and 2 detects metal ion, it is characterised in that the step
1）With step 3）It is middle to detect that the method that efficiency is quenched is：Apply potential in the electrolyte, scan-type electrochemical luminous intensity is I0, then
To metal ion is added in electrolyte solution, electrochemical luminescence intensity is rescaned for Ic, according to（I0−Ic）/ I0It is calculated
Efficiency is quenched.
4. the method that electrochemical luminescence according to claim 3 detects metal ion, it is characterised in that the electrolyte I
The potential of middle applying is 0 ~ -2.0V, and the potential applied in electrolyte II is 0 ~ 2.0V.
5. the method that electrochemical luminescence according to claim 1 and 2 detects metal ion, it is characterised in that described a group
The ion concentration range of the metal ion sample of concentration known is 10 ~ 120nM, and sample size is at least 5.
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| CN108387572B (en) * | 2018-02-11 | 2021-03-16 | 青岛科技大学 | Electrochemiluminescence system and electrochemiluminescence detection method |
| CN108982478A (en) * | 2018-06-12 | 2018-12-11 | 华中师范大学 | Method based on carbonitride electrochemiluminescdetection detection chromium content |
| CN111122552A (en) * | 2019-12-11 | 2020-05-08 | 南京大学 | Method for monitoring cell to secrete copper ions by single-particle electrochemiluminescence imaging technology |
| CN111239111A (en) * | 2020-02-14 | 2020-06-05 | 西北师范大学 | g-C3N4VB (vitamin B) detection by nanosheet12In (1) |
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| KR101276612B1 (en) * | 2010-11-24 | 2013-06-19 | 한국과학기술원 | Synthesis of graphitic carbon nitride having 3d cubic nano structure and selective detection method of copper ion using the same |
| CN104677892A (en) * | 2015-03-27 | 2015-06-03 | 济南大学 | Method for preparing electrochemiluminescence biological sensing interface based on loaded graphite phase carbon nitride and application thereof |
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| KR101276612B1 (en) * | 2010-11-24 | 2013-06-19 | 한국과학기술원 | Synthesis of graphitic carbon nitride having 3d cubic nano structure and selective detection method of copper ion using the same |
| CN104677892A (en) * | 2015-03-27 | 2015-06-03 | 济南大学 | Method for preparing electrochemiluminescence biological sensing interface based on loaded graphite phase carbon nitride and application thereof |
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