CN109270139A - A kind of method detecting copper ion and its composite modified carbon paste electrode of ferrocene-EDTA- polyaniline used - Google Patents
A kind of method detecting copper ion and its composite modified carbon paste electrode of ferrocene-EDTA- polyaniline used Download PDFInfo
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- CN109270139A CN109270139A CN201811104801.7A CN201811104801A CN109270139A CN 109270139 A CN109270139 A CN 109270139A CN 201811104801 A CN201811104801 A CN 201811104801A CN 109270139 A CN109270139 A CN 109270139A
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Abstract
A kind of method detecting copper ion and its composite modified carbon paste electrode of ferrocene-EDTA- polyaniline used, the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline is in graphite powder, polyaniline, EDTA, ferrocene mass ratio has determined optimum mass ratio when being 2:1:2:1, is limited to 4.395 × 10 to the detection of copper ion in water‑7mol/L.Polyaniline has excellent electric conductivity and stability, and EDTA has excellent adsorption capacity, ferrocene not only stable structure to copper ion, but also has good redox reversible；Therefore, the detection effect to copper ion can be improved in the common decorating carbon paste electrode of the above different materials.In addition, electrode prepared by the present invention has stability high, strong interference immunity, sensitivity and the good advantage of reproducibility.
Description
Technical field
The present invention relates to a kind of method for detecting copper ion and its composite modified carbon of ferrocene-EDTA- polyaniline used
Paste electrode.
Background technique
Since 21 century, scientific and technical development is extremely rapid.It is raw that pollution caused by heavy metal ion has become the mankind
What dis environment was faced seriously threatens.Metallurgy, the untreated copper ion that the industries such as plating chemical industry generate are disposed to rivers
It when the sea of lake, is not easy to be biodegradable, seriously threatens the mankind and then vivo protein inactivates by making one under the action of food chain
Life security.The analysis processing of copper ion increasingly becomes the hot spot of research, it is well known that we are often used electrochemical analysis
Method, atomic absorption method, the detection means such as atomic fluorescence spectrometry detect Cu2+.Wherein electrochemical methods possess detection hand
Section is simple, and minute is short and spends the features such as at low cost.Preparing for carbon paste electrode is simple, low in cost, while in order to improve
The sensitivity and accuracy of carbon paste electrode detection, are generally selected and are modified using chemical modifier, such as nano material, and conduction is poly-
Close object and surfactant etc..
Summary of the invention
It is an object of that present invention to provide a kind of method for detecting copper ion and its ferrocene-EDTA- polyaniline used are multiple
Close decorating carbon paste electrode.
To achieve the above object, present invention provide the technical scheme that a kind of ferrocene-EDTA- polyaniline is composite modified
The preparation method of carbon paste electrode, the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline includes the following steps:
Step 1: ammonium persulfate and aniline are added in hydrochloric acid, it is stirred to react 3 ~ 5 hours, product is first cleaned with deionized water, then
With washes of absolute alcohol, polyaniline is obtained；
Step 2: the polyaniline that the first step is obtained and graphite powder, EDTA, ferrocene are according to mass ratio 1:2:2-2.2:0.9-
1.1 mixing, sonicated 50 ~ 70min obtain ferrocene-EDTA- Polyaniline；
Step 3: the atoleine of its quality 10-15% is added into ferrocene-EDTA- Polyaniline, it is stirred well to
Paste is inserted electrode tube and is compacted to get ferrocene-EDTA- Polyaniline-modified carbon paste electrode is arrived.
Preferred technical solution are as follows: the condition of ultrasonic treatment are as follows: ultrasonic frequency 25-35KHz, power density are
0.40-0.55w/cm2。
Preferred technical solution are as follows: shown deionized water cleaning refers to, and product is added in deionized water, then with 2500-
3500 rpm centrifugation, removes supernatant after centrifugation, repeats centrifugation until supernatant is limpid.
Preferred technical solution are as follows: the washes of absolute alcohol refers to deionized water is cleaned after obtained product nothing is added
In water-ethanol, then with 2500-3500 rpm centrifugation, supernatant is removed after centrifugation, repeats centrifugation until supernatant
It is limpid to get polyaniline.
To achieve the above object, present invention provide the technical scheme that it is a kind of detect copper ion method, using three electrodes
System, working electrode are the composite modified carbon paste electricity of ferrocene-EDTA- polyaniline described in claim 1 ~ 4 any claim
Pole, auxiliary electrode are platinum electrode, and reference electrode is saturated calomel electrode；Using cyclic voltammetry testing liquid copper from
Son, sweep speed are 150 ~ 250V/s.
Detailed description of the invention
Fig. 1 is the composite modified carbon paste electrode scanning of ferrocene-EDTA- polyaniline that mass ratio is 2:1:2:1.
The composite modified carbon paste electrode that Fig. 2 quality proportioning is 2:1:2:1 is 10 with different scanning speed measurement concentration-3M's
Cu2+The redox peak potential map obtained after solution.
The Polyaniline-modified carbon paste electrode that Fig. 3 quality proportioning is 2:1:2:1 detects Cu2+Gained standard curve.
The Polyaniline-modified carbon paste electrode that Fig. 4 quality proportioning is 2:1:2:1 detects Cu2+Gained fitting a straight line.
Fig. 5 cyclic voltammetry curve obtained by detecting electrode weekly.
Fig. 6 is doped hydrochloride polyaniline infrared spectroscopy infrared spectrogram.
Fig. 7 is doped hydrochloride polyaniline infrared spectroscopy.
Since above-mentioned technical proposal is used, the present invention has the advantage, that compared with prior art
Electrode of the invention possesses high-precision and outstanding stability and reproducibility and lower detection limits.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
Equipment as used in the following examples, reagent etc., are commercially available unless otherwise specified.
Embodiment one: a kind of method detecting copper ion and its composite modified carbon paste of ferrocene-EDTA- polyaniline used
Electrode
One, the preparation of polyaniline: weighing 0.5g ammonium persulfate, and 2ml aniline is added the hydrochloric acid solution of 75mL 0.1mol/L and stirs
It mixes 4 hours.Product is cleaned with deionized water, dry 12 h in 60 °C of baking ovens.Doped hydrochloride polyaniline made from the present embodiment
Infrared spectrogram is as shown in fig. 6, doped hydrochloride polyaniline infrared spectroscopy is as shown in Figure 7.
Two, polyaniline, graphite powder, EDTA and ferrocene are weighed by the mass ratio of 2:1:2:1, is vibrated in ultrasonic cleaning instrument
1 hour, suitable atoleine is added and stirs to paste, insert electrode tube and is compacted.By the polishing electrode after grinding and
It dries at room temperature to prepare ferrocene-EDTA- Polyaniline decorating carbon paste electrode.
Three, the present embodiment uses three-electrode system: working electrode: the chemically modified carbon paste electrode of production；Auxiliary electrode: platinum
Electrode makees back work electrode normal work；Reference electrode: saturated calomel electrode is contrasted with working electrode.In room temperature condition
Under, the bottom of at, liquid is under copper-bath by changing scanning speed, the quality proportioning of EDTA, polyaniline, ferrocene and graphite powder
Etc. carrying out cyclic voltammetry, post analysis is carried out to obtained cyclic voltammetry curve.
Copper ion is as shown in Figure 1 in the composite modified carbon paste electrode detection water of ferrocene-EDTA- polyaniline, it can be seen that figure
In have compared to mass ratio be 2:1:2 EDTA- Polyaniline-modified carbon paste electrode have more obvious redox peaks, potential difference
For 1.28V.Illustrate mass ratio be 2:1:2:1 the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline 10-1 mol / L
Cu2+To Cu in solution2+There is preferable response.It is demonstrated by good electrochemical behavior.
Sweep speed measures Cu to the composite modified carbon paste electrode of ferrocene2+Influence as shown in Fig. 2, 10-2Mol/L's
Cu2+In solution, respectively with 50 mV/ s, 100 mV/ s, 200 mV/ s, 300 mV/ s, sweep speed be to quality proportioning
Ferrocene-EDTA- Polyaniline the decorating carbon paste electrode of 2:1:2:1 carries out cyclic voltammetry scan.It can from Fig. 2
Out, under the scanning speed of 200mV/s, the oxidation spike potential highest of electrode, peak point current maximum.
Standard curve is as shown in Figure 3 and Figure 4 with detection limit, and Fig. 4 is the ferrocene-EDTA- that quality proportioning is 2:1:2:1
The composite modified carbon paste electrode of polyaniline is to various concentration Cu2+Standard curve and linear fit straight line.With Cu2+Concentration
Increase, the oxidation current peaks of electrode are also linearly increasing.
Its linear fit equation are as follows: Ipa=0.0423c-5.48E-5, R2=0.90358。
Detection is limited to 4.395 × 10-7mol/L。
The stability of electrode is with reproducibility as shown in figure 5, being that 2:1:2:1 ferrocene-EDTA- polyaniline is answered by quality proportioning
It closes decorating carbon paste electrode and measures 10 weekly-2 mol / L Cu2+Solution.The redox peak current of the cyclic voltammogram of acquisition,
Current potential and figure are almost the same.Prove that quality proportioning is the composite modified carbon paste electrode tool of 2:1:2:1 ferrocene-EDTA- polyaniline
There is good stability.
Embodiment two: a kind of method detecting copper ion and its composite modified carbon paste of ferrocene-EDTA- polyaniline used
Electrode
A kind of composite modified carbon paste electrode of ferrocene-EDTA- polyaniline, the composite modified carbon paste of ferrocene-EDTA- polyaniline
The preparation method of electrode includes the following steps:
Step 1: ammonium persulfate and aniline are added in hydrochloric acid, it is stirred to react 5 hours, product is first cleaned with deionized water, then is used
Washes of absolute alcohol obtains polyaniline；
Step 2: the polyaniline that the first step is obtained and graphite powder, EDTA, ferrocene are according to mass ratio 1:2:2.2:1.1
Mixing, sonicated 70min obtain ferrocene-EDTA- Polyaniline；
Step 3: the atoleine of its quality 15% is added into ferrocene-EDTA- Polyaniline, it is stirred well to paste
Shape is inserted electrode tube and is compacted to get ferrocene-EDTA- Polyaniline-modified carbon paste electrode is arrived.
Preferred technical solution are as follows: the condition of ultrasonic treatment are as follows: ultrasonic frequency 35KHz, power density 0.55w/
cm2。
Preferred technical solution are as follows: shown deionized water cleaning refers to, and product is added in deionized water, then with 3500
Rpm centrifugation, removes supernatant after centrifugation, repeats centrifugation until supernatant is limpid.
Preferred technical solution are as follows: the washes of absolute alcohol refers to deionized water is cleaned after obtained product nothing is added
In water-ethanol, then with 3500 rpm centrifugation, remove supernatant after centrifugation, repeat centrifugation until supernatant it is limpid,
Up to polyaniline.
A method of detection copper ion, using three-electrode system, working electrode is that ferrocene-EDTA- polyaniline is compound
Decorating carbon paste electrode, auxiliary electrode are platinum electrode, and reference electrode is saturated calomel electrode；Using cyclic voltammetry prepare liquid
The copper ion of body, sweep speed 250V/s.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (5)
1. a kind of composite modified carbon paste electrode of ferrocene-EDTA- polyaniline, it is characterised in that: the ferrocene-EDTA- polyphenyl
The preparation method of the composite modified carbon paste electrode of amine includes the following steps:
Step 1: ammonium persulfate and aniline are added in hydrochloric acid, it is stirred to react 3 ~ 5 hours, product is first cleaned with deionized water, then
With washes of absolute alcohol, polyaniline is obtained；
Step 2: the polyaniline that the first step is obtained and graphite powder, EDTA, ferrocene are according to mass ratio 1:2:2-2.2:0.9-
1.1 mixing, sonicated 50 ~ 70min obtain ferrocene-EDTA- Polyaniline；
Step 3: the atoleine of its quality 10-15% is added into ferrocene-EDTA- Polyaniline, it is stirred well to
Paste is inserted electrode tube and is compacted to get ferrocene-EDTA- Polyaniline-modified carbon paste electrode is arrived.
2. the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline according to claim 1, it is characterised in that: ultrasound
The condition of processing are as follows: ultrasonic frequency 25-35KHz, power density 0.40-0.55w/cm2。
3. the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline according to claim 1, it is characterised in that: shown
Deionized water cleaning refers to, and product is added in deionized water, then with 2500-3500 rpm centrifugation, after centrifugation in removal
Clear liquid repeats centrifugation until supernatant is limpid.
4. the composite modified carbon paste electrode of ferrocene-EDTA- polyaniline according to claim 1, it is characterised in that: described
Washes of absolute alcohol refers to deionized water is cleaned after obtained product be added to absolute ethanol, then with 2500-3500 rpm
Centrifugation, removes supernatant after centrifugation, repeats centrifugation until supernatant is limpid to get polyaniline.
5. a kind of method for detecting copper ion, it is characterised in that: use three-electrode system, working electrode is claim 1 ~ 4 times
The composite modified carbon paste electrode of ferrocene-EDTA- polyaniline described in one claim, auxiliary electrode are platinum electrode, reference electrode
For saturated calomel electrode；Using the copper ion of cyclic voltammetry testing liquid, sweep speed is 150 ~ 250V/s.
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| CN201811104801.7A CN109270139A (en) | 2018-09-21 | 2018-09-21 | A kind of method detecting copper ion and its composite modified carbon paste electrode of ferrocene-EDTA- polyaniline used |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113415857A (en) * | 2021-06-11 | 2021-09-21 | 安徽工业大学 | Method for harmless treatment of hexavalent Cr wastewater by adsorption and electroreduction through carbon paste electrode |
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| CN102928486A (en) * | 2012-10-19 | 2013-02-13 | 哈尔滨师范大学 | Method for preparing ethylene diamine tetraacetic acid (EDTA) modified carbon paste carbon nano tube membrane electrode |
| CN104569098A (en) * | 2014-12-16 | 2015-04-29 | 大连理工大学 | Preparation method and application of TiS2 nanosheet-polyaniline-based electrochemical sensor for trace copper ion detection |
| CN105806914A (en) * | 2016-03-18 | 2016-07-27 | 河南城建学院 | Copper ion selective electrode and preparation method thereof |
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2018
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| CN102928486A (en) * | 2012-10-19 | 2013-02-13 | 哈尔滨师范大学 | Method for preparing ethylene diamine tetraacetic acid (EDTA) modified carbon paste carbon nano tube membrane electrode |
| CN104569098A (en) * | 2014-12-16 | 2015-04-29 | 大连理工大学 | Preparation method and application of TiS2 nanosheet-polyaniline-based electrochemical sensor for trace copper ion detection |
| CN105806914A (en) * | 2016-03-18 | 2016-07-27 | 河南城建学院 | Copper ion selective electrode and preparation method thereof |
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| A. WALCARIUS ET.AL: "Selective monitoring of Cu<sup>(II)</sup> species using a silica modified carbon paste electrode", 《ANALYTICA CHIMICA ACTA》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113415857A (en) * | 2021-06-11 | 2021-09-21 | 安徽工业大学 | Method for harmless treatment of hexavalent Cr wastewater by adsorption and electroreduction through carbon paste electrode |
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