CN107102048A - It is a kind of to be used to detect electrochemical electrode of copper ion and preparation method and application - Google Patents
It is a kind of to be used to detect electrochemical electrode of copper ion and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of copper ion detection electrochemical electrode and preparation method and application.In electrode modified material, SnO2As active material, RGO, RGO/ Mixture of Activated Carbon are used as active additive, it is possible to increase the selectivity of electrode.Carbon black, CNT are as conductive additive, and its high conductivity can play a part of signal amplification, electrode is obtained more obvious response current in the detection of trace copper ion, improve the accuracy of detection of electrode.Had the advantage that using the electrochemical electrode of the present invention：Electrode preparation method is simple, sensitivity is high, copper ion concentration and current-responsive intensity are low in good linear relationship, ion detection limit, is with a wide range of applications.
Description
Technical field
The invention belongs to electrochemical analysis detection technique field, and in particular to a kind of electrochemistry electricity for being used to detect copper ion
Pole and preparation method and application.
Background technology
Copper ion is a kind of essential trace element in organism, is all played an important role in many physiology courses.
But the copper ion of excess can cause senile dementia, Parkinson's, hepatolenticular degeneration and protein virus disease in vivo.With industry, agricultural,
The field such as traffic cupric massive discharge of pollutant, copper turns into a kind of important environmental contaminants.Therefore, design and develop spirit
The method that sensitivity is high, selectivity is good, has important practical significance to the quick detection of copper ion in biological sample and the aqueous solution.
Up to the present, the assay method of copper ion has colorimetric method, fluorescent spectrometry, atomic absorption spectrography (AAS), ion color
Spectrometry etc..Although these detection method preci-sion and accuracies are higher, detecting instrument is expensive, to laboratory and instrumentation degree
It is required that high, and during operating cost, analysis cost is expensive, is unfavorable for promoting the use of, it is difficult to adapt to great amount of samples and Site Detection
It is required that.Electrochemical analysis method and technology are with low cost with easy to operate, the simple advantage of detection architecture, in copper ion
Researcher is obtained in detection widely to pay attention to.
Document《SnO2/Reduced Graphene Oxide Nanocomposite for the Simultaneou
Electrochemical Detection of Cadmium(II),Lead(II),Copper(II),and Mercury(II):
An Interesting Favorable Mutual Interference》Disclose a kind of be used for while detecting various heavy
Electrochemical electrode of ion and preparation method thereof, utilizes SnO2/ RGO is repaiied as active additive to conductive substrates material
Decorations, to improve in electrode activity, but this method, electrode material therefor electric conductivity is poor, when being detected to trace copper ion, detection letter
Number weaker, accuracy of detection is relatively low.
Application number 201410298881.X Chinese patent discloses a kind of light propyl cellulose/carbon nano tube/graphene
The preparation and application of modified electrode.Light propyl cellulose can effectively improve the dispersiveness of CNT, add effective reaction
Site, improves effective specific surface area, and CNT can improve the selectivity of electrode as active material, but in this method,
Electrode material therefor activity is weaker, when being detected to trace copper ion, and detection signal is weaker, and accuracy of detection is relatively low.
The content of the invention
The present invention provides a kind of for detecting electrochemical electrode of copper ion and preparation method and application.By five hydrations four
The obtained SnO of stannic chloride reaction2As active material, RGO, RGO/ Mixture of Activated Carbon can improve electricity as active additive
The selectivity of pole.Carbon black, CNT are as conductive additive, and its high conductivity can play a part of signal amplification, detect trace
When measuring copper ion, detection signal intensity is significantly enhanced, and significantly improves accuracy of detection, is with a wide range of applications.
The invention discloses a kind of electrochemical electrode for being used to detect copper ion, it is characterised in that including being used as conductive base
The glass-carbon electrode or carbon paste electrode of bottom material and the decorative material being immobilized on electrode, the glass-carbon electrode is by polishing
Reason, the carbon paste electrode is filled with carbon paste and passes through grinding process.
The above-mentioned preparation method for being used to detect the electrochemical electrode of copper ion of the present invention, including glass-carbon electrode is carried out
Polishing；Prepare carbon paste electrode；Prepare decorative material and decorative material is immobilized on conductive substrates material.
Any of the above-described scheme is preferably, and the polishing method of the glass-carbon electrode is：
(1) electrode surface is gently wiped with the lens paper of moistening, removes dirt, it is ensured that electrode surface is smooth；
(2) on polishing cloth successively with 0.3 μm with 0.05 μm of aluminum oxide polishing powder by polishing electrode into " minute surface ", spend
Ionized water rinses electrode surface, electrode is immersed to 2~3min of ultrasonic cleaning in absolute ethyl alcohol, deionized water respectively, at room temperature certainly
So dry.
Any of the above-described scheme is preferably, and the preparation method of the carbon paste electrode is：
(1) it is 7 in mass ratio by graphite powder and atoleine：3 ratio mixed grinding is uniform, gained mixture fill to
It is compacted in clean carbon paste electrode sleeve pipe；
(2) carbon paste electrode is polishing to electrode surface on sand paper bright and clean smooth.
Any of the above-described scheme is preferably, and the method that the decorative material is immobilized on conductive substrates material is：
(1) active additive predecessor, conductive additive predecessor is taken to be put into deionized water, it is ultrasonically treated；
(2) active material predecessor is dissolved in deionized water and butter of tin solution is made, be added dropwise made in step (1)
Solution is placed in magnetic stirring apparatus after the solution obtained and stirred.
(3) supernatant will be abandoned after solution centrifugal made from step (2), heating obtains decorative material；
(4) absolute ethyl alcohol is added dropwise into obtained decorative material, it is ultrasonically treated, after decorative material is completely dissolved, it will mix
Drop is applied to conductive substrates material surface, drying at room temperature.
Any of the above-described scheme is preferably, and the active material predecessor in the step (2) comprises at least five hydration tetrachloros
Change tin；Active additive predecessor in step (1) includes at least one of graphene oxide and/or activated carbon, and conduction adds
Plus agent predecessor includes at least one of carbon black and/or CNT.
Any of the above-described scheme is preferably, the active material predecessor and active additive predecessor, conductive additive
The mass ratio of predecessor is 1:(7×10-4-3×10-2):(1.5×10-4-1.2×10-3)。
Any of the above-described scheme is preferably, and the sonication treatment time in the step (1) is 90 minutes, in step (2)
Mixing time is 5 hours in magnetic stirring apparatus.Centrifuge parameters in step (3) set rotating speed to be 8000r/min, centrifugation time
For 5 minutes.
Any of the above-described scheme is preferably, and 2h is heated in argon atmosphere, under the conditions of 500 DEG C in the step (3)
Obtain decorative material.
Any of the above-described scheme is preferably, and electrochemistry electricity is also included after decorative material is immobilized on conductive substrates material
The activation of pole, the activation method of electrochemical electrode is：Modified electrode as working electrode, silver chloride electrode as reference electrode,
Platinum electrode constitutes three-electrode system as to electrode；Entered in PBS in the range of -1V to+1V using cyclic voltammetry
Row test, Multiple-Scan to it is double institute test curve overlap when activation completion.
Any of the above-described scheme is preferably, the compound method of the PBS cushioning liquid：Take 4.9g phosphoric acid, 6.8g di(2-ethylhexyl)phosphates
Hydrogen potassium, the hypophosphite monohydrate hydrogen dipotassiums of 14.411g tri- and 2g sodium hydroxides, add 500mL distilled water and are well mixed, second is used before use
Acid for adjusting pH is to 5.0.
Any of the above-described scheme is preferably, and described reference electrode refers to：Using with identical conductive substrates in the present invention
Material and electrode fabrication process, and the different modified electrode of decorative material.The decorative material of reference electrode is only comprising activity
Material and redox graphene (RGO), prepare predecessor used in decorative material for Tin tetrachloride pentahydrate, graphene oxide
(GO), the two mass ratio is (1:6.7×10-4)。
The present invention also provide electrochemical electrode prepared by a kind of any of the above-described described preparation method be used to detecting copper from
Son.
Any of the above-described scheme is preferably, and the detection method to copper ion is：After the completion of electrode activation, in buffer solution by
It is secondary that the copper sulphate that 40 μ L concentration are 1.5mM is added dropwise, carry out electrochemical source of current detection using SWSV technologies
The technical scheme is that be achieved in that：
Graphite powder and atoleine are configured into carbon paste to fill into carbon paste electrode, polished flat on sand paper as conduction
Base material is standby；Glass-carbon electrode is processed by shot blasting, cleaned up as conductive substrates materials for later use.Before active material
Drive thing, active additive predecessor and conductive additive predecessor are mixed by certain mass ratio, by ultrasound, stirring, centrifugation, height
Temperature processing, brings it about redox reaction and decorative material is made, active material predecessor includes Tin tetrachloride pentahydrate, activity
Additive predecessor includes graphene oxide, activated carbon, and conductive additive predecessor includes carbon black, CNT.It will prepare
Decorative material absolute ethyl alcohol dissolve after drop coating to conductive substrates material surface, natural drying at room temperature.Modified electrode is used as work
Make electrode, silver chloride electrode is constituted after three-electrode system, electrode activation using SWSV as reference electrode, platinized platinum as to electrode
Determine copper ion concentration.
In the present invention, to ensure the purity and quality of decorative material, so as to avoid the impurity or material that are mixed into from figure
Influence of the state to electrode performance is, it is necessary to accomplish that raw material proportioning is accurate, and dilution is needed with ultra-pure water, it is necessary to be sufficiently stirred for for a long time,
Obtained decorative material finished product needs to be fully sealed to be stored in vacuum drying chamber., it is necessary to make material in absolute ethyl alcohol during dissolving
Middle dissolving is complete., it is necessary to avoid touching electrode surface during quantitative drop coating.
The operation principle of electrochemical electrode of the present invention is：
The present invention uses three-electrode system, is tested using SWSV technologies.Depositional phase, copper ion is in working electrode table
Reduction reaction occurs for face；In working electrode surface oxidation reaction occurs for dissolution stage, copper ion.
Conductive substrates material includes glass-carbon electrode, carbon paste electrode in the present invention, and decorative material adds comprising active material, activity
Plus agent and conductive additive.Wherein, active material includes tin ash；Active additive includes redox graphene, activity
Charcoal；Conductive additive includes carbon black, CNT.Decorative material is added by ultrasonic dissolution, stirring mixing, centrifugal treating and high temperature
Thermal technology's sequence is synthesized, and is combined by dissolving drop coating technique with conductive substrates material.
The performance of electrochemical electrode in the present invention is by the way that its testing result is compared with reference electrode testing result
Compared with and embody.
The conductive substrates material used in the present invention is glass-carbon electrode and carbon paste electrode, and the two is respectively provided with high conductivity, compared with
Good chemical stability.In decorative material, the copper ion that RGO can be in adsorbent solution makes copper ion obtain phase in electrode surface
Than the more enriching quantities of conductive substrates material in unvarnished material, so as to significantly improve the electrochemical response of copper ion；
Activated carbon has larger specific surface area, can also increase its adsorption capacity, is enriched with copper ion, and many synergies make to repair
The ability of decorations electrode detection copper ion is greatly increased；Carbon black, CNT play signal as conductive additive, its high conductivity
The effect of amplification, realizes and trace copper ion is detected.In addition, electric conductivity good RGO expands for signal also certain rush
Enter effect.
Beneficial effect
The present invention provides a kind of copper ion detection electrochemical electrode and preparation method and application.In electrode modified material,
SnO2As active material, RGO, RGO/ Mixture of Activated Carbon are used as active additive, it is possible to increase the selectivity of electrode.Carbon
Black, CNT is as conductive additive, and its high conductivity can play a part of signal amplification, make electrode in trace copper ion
Detection in obtain the higher detection signal of intensity, improve the accuracy of detection of electrode.Had using the electrochemical electrode of the present invention
There is following advantage：Electrode preparation method is simple, sensitivity is high, copper ion concentration and current-responsive intensity are in good linear pass
System, ion detection limit are low, are with a wide range of applications.
Brief description of the drawings
Fig. 1 is modified electrode structure chart；
Fig. 2 analyzes image for the X-ray energy spectrum of decorative material used in embodiment 1；
Fig. 3 is the SEM image of decorative material used in embodiment 1；
Fig. 4 is the X-ray diffractogram of decorative material used in embodiment 1；
Fig. 5 is reference electrode test curve in embodiment 1；
Fig. 6 is modified electrode test curve in embodiment 1；
Fig. 7 is modified electrode and reference electrode detection gained linear fit curve comparison in embodiment 1.
Embodiment
Following embodiments are further illustrating using as the explaination to the technology of the present invention content for present invention, but
The present invention substantive content be not limited in described in following embodiments, one of ordinary skill in the art can with and should know appoint
What simple change or replacement based on true spirit all should belong to protection domain of the presently claimed invention.
Embodiment 1
1) glassy carbon electrode surface is gently wiped with the lens paper of moistening, removes dirt.On polishing cloth successively with 0.3 μm and
Polishing electrode into " minute surface ", is used deionized water rinsing electrode surface by 0.05 μm of aluminum oxide polishing powder, and electrode is immersed respectively
It is cleaned by ultrasonic 2~3min in absolute ethyl alcohol, deionized water, spontaneously dries at room temperature, be used as conductive substrates materials for later use；
2) solution is prepared, wherein：The concentration of carbon black is 0.35g/L, and the concentration of graphene oxide is 0.2g/L, and solvent is to go
Ionized water, ultrasonically treated 90 minutes；
3) by 2.4g SnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
It is rapid 2) in obtained solution 8mL.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge
Separation 5 minutes, setting rotating speed is 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air, anti-oxidation；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；Obtained modified electrode structure is as shown in figure 1, wherein 1 is conductive substrates material, and 2 be electrode modification material
Material；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is used as control electricity as reference electrode, platinized platinum
Pole constitutes three-electrode system.Surveyed in 30mL PBSs in the range of -1V to+1V using cyclic voltammetry (CV)
Examination, Multiple-Scan to the double curve measured is essentially coincided, then activation is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 1.5mM copper-bath, use
SWSV technologies carry out electrochemical source of current detection, and solution is added dropwise to be carried out eight times altogether so that copper ion concentration is incremented to 16 μM by 0 μM.
Parameter setting：Deposition voltage be -1V, sedimentation time be 120V, take-off potential be -1.0V, to terminate current potential be 0.5V, square wave frequency
It is that 25mV, current potential increment are 4mV for 15Hz, amplitude；
Step 4) obtained by decorative material X-ray energy spectrum analyze image as shown in Fig. 2 the scanning electron of decorative material
Microscope imaging figure is as shown in figure 3, the X-ray diffractogram of decorative material is as shown in Figure 4；
Modified electrode test curve and reference electrode test curve are distinguished as shown in Figure 5, Figure 6 in the embodiment；
To test result carry out linear fit, can obtain modified electrode with according to document (《SnO2/Reduced
Graphene Oxide Nanocomposite for the Simultaneou Electrochemical Detection of
Cadmium(II),Lead(II),Copper(II),and Mercury(II):An Interesting Favorable
Mutual Interference》) prepare reference electrode detection gained linear fit curve as shown in fig. 7, analysis curve can
Know：Copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its equation of linear regression is I=0.212C
+ 2.601, linearly dependent coefficient is R=0.973.Reference electrode test gained equation of linear regression is I=0.168C+2.492,
Linearly dependent coefficient is R=0.931.Contrast can find that the modified electrode detection gained equation of linear regression in the present embodiment has
There are bigger slope, i.e. electrode that there is higher sensitivity；Copper ion concentration and current-responsive intensity have more excellent linear
Relation.
Embodiment 2
1) electrode surface is gently wiped with the lens paper of moistening, removes dirt.Successively with 0.3 μm and 0.05 on polishing cloth
μm aluminum oxide polishing powder by polishing electrode into " minute surface ", use deionized water rinsing electrode surface, electrode immersed to anhydrous respectively
It is cleaned by ultrasonic 2~3min in ethanol, deionized water, spontaneously dries at room temperature, be used as conductive substrates materials for later use；
2) solution is prepared, wherein：The concentration of CNT is 0.25g/L, and the concentration of graphene oxide is 0.2g/L, activity
The concentration of charcoal is 0.01g/L, and solvent is deionized water, ultrasonically treated 90 minutes；
3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
2) obtained solution 8mL in.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge and divides
From 5 minutes, setting rotating speed was 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 1.5mM copper-bath, use
SWSV technologies carry out electrochemical source of current detection, and solution is added dropwise to be carried out eight times altogether so that copper ion concentration is incremented to 16 μM by 0 μM.
Parameter setting：Deposition voltage be -1V, sedimentation time be 120V, take-off potential be -1.0V, to terminate current potential be 0.5V, square wave frequency
It is that 25mV, current potential increment are 4mV for 15Hz, amplitude；
Found by test, copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its is linear
Regression equation is I=1.018C+4.192, and linearly dependent coefficient is R=0.997, and detection is limited to 0.060 μM.According to document
(《SnO2/Reduced Graphene Oxide Nanocomposite for the Simultaneou
Electrochemical Detection of Cadmium(II),Lead(II),Copper(II),and Mercury(II):
An Interesting Favorable Mutual Interference》) prepare reference electrode test gained linear regression
Equation is I=0.675C+6.707, and linearly dependent coefficient is R=0.973, and detection is limited to 0.395 μM.Contrasting to find, this reality
There is modified electrode detection gained equation of linear regression in example bigger slope, i.e. electrode to have higher sensitivity；Copper from
Sub- concentration has more excellent linear relationship with current-responsive intensity.In addition, the modified electrode in this example has lower inspection
Survey limit.
Embodiment 3
1) electrode surface is gently wiped with the lens paper of moistening, removes dirt.Successively with 0.3 μm and 0.05 on polishing cloth
μm aluminum oxide polishing powder by polishing electrode into " minute surface ", use deionized water rinsing electrode surface, electrode immersed to anhydrous respectively
It is cleaned by ultrasonic 2~3min in ethanol, deionized water, spontaneously dries at room temperature, be used as conductive substrates materials for later use；
2) solution is prepared, wherein：The concentration of carbon black is 0.25g/L, and the concentration of graphene oxide is 0.2g/L, activated carbon
Concentration is 6g/L, and solvent is deionized water, ultrasonically treated 90 minutes；
3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
2) obtained solution 8mL in.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge and divides
From 5 minutes, setting rotating speed was 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 1.5mM copper-bath, use
SWSV technologies carry out electrochemical source of current detection, and solution is added dropwise to be carried out eight times altogether so that copper ion concentration is incremented to 16 μM by 0 μM.
Parameter setting：Deposition voltage be -1V, sedimentation time be 120V, take-off potential be -1.0V, to terminate current potential be 0.5V, square wave frequency
It is that 25mV, current potential increment are 4mV for 15Hz, amplitude；
Found by test, copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its is linear
Regression equation is I=0.692C+2.354, and linearly dependent coefficient is R=0.956.According to document (《SnO2/Reduced
Graphene Oxide Nanocomposite for the Simultaneou Electrochemical Detection of
Cadmium(II),Lead(II),Copper(II),and Mercury(II):An Interesting Favorable
Mutual Interference》) prepare reference electrode test gained equation of linear regression be I=0.168C+2.492, linearly
Coefficient correlation is R=0.931.Contrast can find that the modified electrode detection gained equation of linear regression in this example has bigger
Slope, i.e., electrode have higher sensitivity；Copper ion concentration has more excellent linear relationship with current-responsive intensity.
Embodiment 4
1) electrode surface is gently wiped with the lens paper of moistening, removes dirt.Successively with 0.3 μm and 0.05 on polishing cloth
μm aluminum oxide polishing powder by polishing electrode into " minute surface ", use deionized water rinsing electrode surface, electrode immersed to anhydrous respectively
It is cleaned by ultrasonic 2~3min in ethanol, deionized water, spontaneously dries at room temperature, be used as conductive substrates materials for later use；
2) solution is prepared, wherein：The concentration of CNT is 0.35g/L, and the concentration of graphene oxide is 0.2g/L, solvent
For deionized water, ultrasonically treated 90 minutes；
3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
2) obtained solution 8mL in.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge and divides
From 5 minutes, setting rotating speed was 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 1.5mM copper-bath, use
SWSV technologies carry out electrochemical source of current detection, and solution is added dropwise to be carried out eight times altogether so that copper ion concentration is incremented to 16 μM by 0 μM.
Parameter setting：Deposition voltage be -1V, sedimentation time be 120V, take-off potential be -1.0V, to terminate current potential be 0.5V, square wave frequency
It is that 25mV, current potential increment are 4mV for 15Hz, amplitude；
Found by test, copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its is linear
Regression equation is I=0.397C+3.695, and linearly dependent coefficient is R=0.987.According to document (《SnO2/Reduced
Graphene Oxide Nanocomposite for the Simultaneou Electrochemical Detection of
Cadmium(II),Lead(II),Copper(II),and Mercury(II):An Interesting Favorable
Mutual Interference》) prepare reference electrode test gained equation of linear regression be I=0.168C+2.492, linearly
Coefficient correlation is R=0.931.Contrast can find that the modified electrode detection gained equation of linear regression in this example has bigger
Slope, i.e., electrode have higher sensitivity；Copper ion concentration has more excellent linear relationship with current-responsive intensity.
Embodiment 5
1) it is 7 in mass ratio by graphite powder (325 mesh) and atoleine：3 ratio mixed grinding is uniform, gained mixture
Fill and be compacted into clean carbon paste electrode sleeve pipe.Carbon paste electrode is polishing on sand paper to electrode surface bright and clean smooth；
2) solution is prepared, wherein：The concentration of carbon black is 0.25g/L, and the concentration of graphene oxide is 0.2g/L, activated carbon
Concentration is 8g/L, and solvent is deionized water, ultrasonically treated 90 minutes；
3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
2) obtained solution 8mL in.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge and divides
From 5 minutes, setting rotating speed was 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 1.5mM copper-bath, use
SWSV technologies carry out electrochemical source of current detection.Parameter setting：Deposition voltage be -1V, sedimentation time be 120V, take-off potential for -
1.0V, to terminate current potential be that 0.5V, square wave frequency are that 15Hz, amplitude are that 25mV, current potential increment are 4mV；
Found by test, copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its is linear
Regression equation is I=0.548C+5.860, and linearly dependent coefficient is R=0.934.According to document (《SnO2/Reduced
Graphene Oxide Nanocomposite for the Simultaneou Electrochemical Detection of
Cadmium(II),Lead(II),Copper(II),and Mercury(II):An Interesting Favorable
Mutual Interference》) prepare reference electrode test gained equation of linear regression be I=0.168C+2.492, linearly
Coefficient correlation is R=0.931.Contrast can find that the modified electrode detection gained equation of linear regression in this example has bigger
Slope, i.e., electrode have higher sensitivity；Copper ion concentration has more excellent linear relationship with current-responsive intensity.
Embodiment 6
(1) it is 7 in mass ratio by graphite powder (325 mesh) and atoleine：3 ratio mixed grinding is uniform, gained mixing
Thing is filled to be compacted into clean carbon paste electrode sleeve pipe.Carbon paste electrode is polishing on sand paper to electrode surface bright and clean smooth；
(2) solution is prepared, wherein：The concentration of carbon black is 0.05g/L, and the concentration of graphene oxide is 0.2g/L, and solvent is
Deionized water, ultrasonically treated 90 minutes；
(3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
It is rapid 2) in obtained solution 8mL.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge
Separation 5 minutes, setting rotating speed is 8000r/min；
(4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
(5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
(6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
Utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 15mM copper-bath (be added dropwise first
60 μ L), electrochemical source of current detection is carried out using SWSV technologies, solution is added dropwise to be carried out eight times altogether so that copper ion concentration is by 30 μM
It is incremented to 170 μM.Parameter setting：Deposition voltage is that -1V, sedimentation time are that 120V, take-off potential are -1.0V, terminate current potential and be
0.5V, square wave frequency are that 15Hz, amplitude are that 25mV, current potential increment are 4mV；
Found by test, copper ion concentration and current-responsive intensity are in good linear relationship in buffer solution, and its is linear
Regression equation is I=0.039C+1.876, and linearly dependent coefficient is R=0.873.According to document (《SnO2/Reduced
Graphene Oxide Nanocomposite for the Simultaneou Electrochemical Detection of
Cadmium(II),Lead(II),Copper(II),and Mercury(II):An Interesting Favorable
Mutual Interference》) prepare reference electrode test gained equation of linear regression be I=0.009C+0.892, linearly
Coefficient correlation is R=0.860.Contrast can find that the modified electrode detection gained equation of linear regression in this example has bigger
Slope, i.e., electrode have higher sensitivity；Copper ion concentration has more excellent linear relationship with current-responsive intensity.
Embodiment 7
1) it is 7 in mass ratio by graphite powder (325 mesh) and atoleine：3 ratio mixed grinding is uniform, gained mixture
Fill and be compacted into clean carbon paste electrode sleeve pipe.Carbon paste electrode is polishing on sand paper to electrode surface bright and clean smooth；
2) solution is prepared, wherein：The concentration of CNT is 0.05g/L, and the concentration of graphene oxide is 0.2g/L, solvent
For deionized water, ultrasonically treated 90 minutes；
3) by 2.4gSnCl4·5H2O is dissolved in the SnCl that 0.24M is made in 20mL deionized waters4Solution, and add step
2) obtained solution 8mL in.Mixing resulting solution is placed in 5 hours of agitation in magnetic stirring apparatus, is subsequently placed in centrifuge and divides
From 5 minutes, setting rotating speed was 8000r/min；
4) centrifugation solution is abandoned after supernatant, gained material is in argon atmosphere, heat 2h under the conditions of 500 DEG C,
Electrode modified material is made, wherein, argon gas protection atmosphere is for isolation air；
5) 5 μ L absolute ethyl alcohols are added dropwise into decorative material, ultrasonically treated 5 minutes, drop-coated will be mixed to conductive base ground
Expect surface, drying at room temperature；
6) glass-carbon electrode of modified is as working electrode, and silver chloride electrode is as reference electrode, and platinized platinum is as to electrode
Constitute three-electrode system.CV tests, Multiple-Scan to continuous two are carried out in the range of -1V to+1V in 30mL PBSs
Secondary activation when essentially coinciding is completed；
7) utilize step 6) in three-electrode system, be gradually added dropwise 40 μ L concentration be 15mM copper-bath (drip first
Plus 60 μ L), use SWSV technologies to carry out electrochemical source of current detection, solution is added dropwise to be carried out eight times altogether so that copper ion concentration is by 30 μ
M is incremented to 170 μM.Parameter setting：Deposition voltage is that -1V, sedimentation time are that 120V, take-off potential are -1.0V, terminate current potential and be
0.5V, square wave frequency are that 15Hz, amplitude are that 25mV, current potential increment are 4mV；
8) found by test, copper ion concentration and current-responsive intensity are in good linear relationship, its line in buffer solution
Property regression equation be I=0.033C+0.465, linearly dependent coefficient is R=0.927.
According to document (《SnO2/Reduced Graphene Oxide Nanocomposite for the
Simultaneou Electrochemical Detection of Cadmium(II),Lead(II),Copper(II),and
Mercury(II):An Interesting Favorable Mutual Interference》) prepare reference electrode test
Gained equation of linear regression is I=0.009C+0.892, and linearly dependent coefficient is R=0.860.Contrast can be found, in this example
Modified electrode detection gained equation of linear regression have bigger slope, i.e. electrode have higher sensitivity；Copper ion is dense
Degree has more excellent linear relationship with current-responsive intensity.
Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without
Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. a kind of electrochemical electrode for being used to detect copper ion, it is characterised in that including the glass carbon electricity as conductive substrates material
Pole or carbon paste electrode and the decorative material being immobilized on electrode, the glass-carbon electrode pass through polishing, the carbon paste electrode
Filled with carbon paste and pass through grinding process.
2. a kind of preparation method as claimed in claim 1 for being used to detect the electrochemical electrode of copper ion, it is characterised in that bag
Include and carbon paste electrode is processed by shot blasting or prepared to glass-carbon electrode；Prepare decorative material and decorative material is immobilized on conductive substrates
On material.
3. the preparation method according to claim 2 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
The polishing method of glass-carbon electrode is：
(1) electrode surface is gently wiped with the lens paper of moistening, removes dirt, it is ensured that electrode surface is smooth；
(2) on polishing cloth successively with 0.3 μm with 0.05 μm of aluminum oxide polishing powder by polishing electrode into minute surface, use deionized water
Electrode surface is rinsed, electrode is immersed to 2~3min of ultrasonic cleaning in absolute ethyl alcohol, deionized water respectively, spontaneously dried at room temperature.
4. the preparation method according to claim 2 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
The preparation method of carbon paste electrode is：
(1) it is 7 in mass ratio by graphite powder and atoleine：3 ratio mixed grinding is uniform, and gained mixture is filled to cleaning
Carbon paste electrode sleeve pipe in be compacted；
(2) carbon paste electrode is polishing to electrode surface on sand paper bright and clean smooth.
5. the preparation method according to claim 2 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
The method that decorative material is immobilized on conductive substrates material is：
(1) active additive predecessor, conductive additive predecessor is taken to be put into deionized water, it is ultrasonically treated；
(2) active material predecessor is dissolved in deionized water and butter of tin solution is made, be added dropwise obtained by step (1)
Solution is placed in magnetic stirring apparatus after solution and stirred；
(3) supernatant will be abandoned after solution centrifugal made from step (2), heating obtains decorative material；
(4) absolute ethyl alcohol is added dropwise into obtained decorative material, it is ultrasonically treated, after decorative material is completely dissolved, drop will be mixed
It is applied to conductive substrates material surface, drying at room temperature.
6. the preparation method according to claim 5 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
Active material predecessor in step (2) comprises at least Tin tetrachloride pentahydrate；Active additive predecessor bag in step (1)
Containing at least one of graphene oxide and/or activated carbon, conductive additive predecessor is comprising in carbon black and/or CNT
It is at least one.
7. the preparation method according to claim 5 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
The mass ratio of active material predecessor and active additive predecessor, conductive additive predecessor is 1:(7×10-4-3×10-2):(1.5×10-4-1.2×10-3)。
8. the preparation method according to claim 5 for being used to detect the electrochemical electrode of copper ion, it is characterised in that described
Heating 2h obtains decorative material in argon atmosphere, under the conditions of 500 DEG C in step (3).
9. the preparation method according to claim 2 for being used to detect the electrochemical electrode of copper ion, it is characterised in that will repair
Exterior material also includes the activation of electrochemical electrode after being immobilized on conductive substrates material, and the activation method of electrochemical electrode is：
Modified electrode is as working electrode, and silver chloride electrode is as reference electrode, and platinum electrode constitutes three-electrode system as to electrode；
Tested in PBS in the range of -1V to+1V using cyclic voltammetry, Multiple-Scan to double gained is tested
Activate and complete during curve co-insides.
10. it is used to detect copper ion according to the electrochemical electrode that in claim 2-9 prepared by any described preparation method.
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| CN107589169A (en) * | 2017-08-31 | 2018-01-16 | 山东理工大学 | The apparatus and method of cadmium ion in a kind of detection water |
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| CN102636535A (en) * | 2012-04-10 | 2012-08-15 | 上海大学 | Method for constructing modified carbon paste electrode by hydrotalcite composite material as well as electrochemical determination method of super-trace heavy metal ions and application thereof |
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| CN107589169A (en) * | 2017-08-31 | 2018-01-16 | 山东理工大学 | The apparatus and method of cadmium ion in a kind of detection water |
| CN112881488A (en) * | 2021-01-18 | 2021-06-01 | 天津理工大学 | Core-shell Au @ tin oxide/vertical graphene microelectrode and preparation method and application thereof |
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