CN107478695B - Electrode modified based on nano copper sulfide-multiwalled carbon nanotube compound and preparation method and application thereof - Google Patents
Electrode modified based on nano copper sulfide-multiwalled carbon nanotube compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrode modified based on a nano copper sulfide-multi-walled carbon nanotube composite. Also provides a preparation method and application thereof. The nano copper sulfide-multi-walled carbon nanotube composite modified electrode has good electrocatalytic activity, is low in preparation cost, good in reproducibility and stability and high in determination sensitivity, and is particularly suitable for analysis of bioactive substances. The nano copper sulfide-multi-walled carbon nanotube composite is used as a working electrode to form a three-electrode system which is used as a sensor to measure Paracetamol (PCT), and the sensitivity is high.
Description
Technical Field
The invention belongs to the field of electrochemical analysis, and particularly relates to an electrode modified by a nano copper sulfide-multi-walled carbon nanotube compound, and a preparation method and application thereof.
Background
Paracetamol (PCT), also known as paracetamol or N-methyl-p-aminophenol, is one of the over-the-counter drugs widely used in the world and has antipyretic and analgesic effects. However, excessive use can cause serious liver damage and other adverse effects. Therefore, accurate determination of the amount of paracetamol in a drug helps to control drug safety and patient safety. At present, the common analytical chemical methods for measuring Paracetamol (PCT) mainly include spectrophotometry, high performance liquid chromatography, capillary electrophoresis, chemiluminescence, electrochemical methods, titration, and the like. Among them, the electrochemical analysis method has the characteristics of high sensitivity, high analysis speed, simple instrument, simple operation and low cost, and has been widely used for the determination of bioactive molecules.
Electrochemical sensors developed based on electrochemical methods are a class of sensors that use electrodes as signal transducers to measure electrical potential or current. The electrochemical system realizes input or output of electric energy by means of an electrode, so as to obtain an electric signal of an electrode surface modification substance, and a three-electrode system is commonly used. The three-electrode system comprises a working electrode, an auxiliary electrode (also called a counter electrode) and a reference electrode, wherein the counter electrode is a platinum electrode, the reference electrode is a saturated calomel electrode, and the working electrode is a glassy carbon electrode. However, the electrochemical analysis method for measuring Paracetamol (PCT) has the technical problem that the electrochemical response of paracetamol on a bare electrode is poor.
The nano material is a material with the average particle size of less than l00nm, has new and different physical and chemical characteristics which are not possessed by a plurality of macroscopic objects, and is a multi-component substance dispersion system and a novel material. The nano material has special properties which are not possessed by a plurality of solids, such as volume effect, surface effect, quantum size effect, macroscopic quantum tunneling effect, dielectric confinement effect and the like, so that the nano material has microwave absorption performance, high surface activity, strong oxidizing property, superparamagnetism, obvious blue shift or red shift phenomenon represented by an absorption spectrum and the like, and is widely applied. Such as: the nano copper sulfide (CuS) is used as a novel wide bandgap semiconductor photocatalytic material, and has good biocompatibility and high electron transfer characteristic; carbon Nanotubes (CNTs), a hollow tubular nanocarbon material formed by winding single-layer or multi-layer graphene sheets, can be used as an electrode material to promote electron transfer of electroactive substances, accelerate electron exchange, and enhance electrochemical reaction activity.
Disclosure of Invention
The invention aims to provide an electrode modified by a nano copper sulfide-multi-walled carbon nanotube composite, and simultaneously provides a corresponding preparation method and application thereof.
Based on the purpose, the invention adopts the following technical scheme:
the electrode is modified based on the nano copper sulfide-multi-walled carbon nanotube composite, the surface of the electrode is covered with the nano copper sulfide/multi-walled carbon nanotube composite, and the electrode is a glassy carbon electrode.
The preparation method of the electrode modified based on the nano copper sulfide-multi-walled carbon nanotube compound comprises the following steps: 1) dissolving 12-20 mg polyvinylpyrrolidone in 15-25 mL solution with concentration of 0.08-1.5 mg mL-1Sequentially adding 0.02-0.03 mmol of CuCl into the MWCNTs aqueous solution2、0.056～0.094mmol Na2S, mixing to obtain a suspension, sealing the suspension, heating at 160-200 ℃ for 20-26h, cooling, centrifuging, washing, and drying at 45-55 ℃ for 10-14 h to obtain a nano copper sulfide/multi-walled carbon nanotube compound;
2) dissolving 1.2-2.0 mg of the nano copper sulfide/multi-walled carbon nanotube composite obtained in the step 1) in 1.5mL of distilled water, ultrasonically mixing, dripping the mixture on the surface of an electrode, and drying.
And 2) grinding, polishing, cleaning and airing the electrode, dissolving the nano copper sulfide/multi-walled carbon nanotube composite obtained in the step 1) in water, ultrasonically mixing, and then dropwise coating the surface of the nano copper sulfide/multi-walled carbon nanotube composite.
Based on the application of the electrode modified by the nano copper sulfide-multi-walled carbon nanotube composite, the modified electrode is used as a working electrode, and forms a three-electrode system with a counter electrode and a reference electrode for measuring paracetamol.
The counter electrode is a platinum electrode, and the reference electrode is a saturated calomel electrode.
Compared with the prior art, the invention has the following beneficial effects:
1. the nano copper sulfide-multi-walled carbon nanotube composite modified electrode has good electrocatalytic activity, is low in preparation cost, good in reproducibility and stability and high in determination sensitivity, and is particularly suitable for analysis of bioactive substances. The nano copper sulfide-multi-walled carbon nanotube composite is used as a working electrode to form a three-electrode system which is used as a sensor to measure Paracetamol (PCT), and the sensitivity is high.
2. The preparation method is simple and low in cost.
Drawings
FIG. 1 cyclic voltammograms of different electrodes in potassium ferricyanide solution;
FIG. 2 is a cyclic voltammogram of different electrodes in the determination of PCT;
FIG. 3 is a graph of the AC impedance of various electrodes;
FIG. 4 is a graph of the potential window behavior on different electrodes;
FIG. 5 is a timing coulombic behavior on different electrodes;
FIG. 6 is a cyclic voltammogram of PCT at CuS/MWCNTs/GCE at different sweep rates;
FIG. 7 is a cyclic voltammogram of PCT at different pH values at CuS/MWCNTs/GCE;
FIG. 8 is a differential pulse voltammogram of PCT at different concentrations.
Detailed Description
Example 1
The electrode is modified based on a nano copper sulfide-multi-walled carbon nanotube composite, and the surface of the electrode (glassy carbon electrode) is covered with the nano copper sulfide/multi-walled carbon nanotube composite.
The preparation method of the electrode modified based on the nano copper sulfide-multi-walled carbon nanotube compound comprises the following steps: 1) 16mg of polyvinylpyrrolidone was dissolved in 20mL of 0.1mg mL-1Then 0.025mmol of CuCl is added into the MWCNTs aqueous solution2、0.075mmol Na2S, slowly stirring for 30min at room temperature, mixing to obtain a suspension, sealing the suspension, heating for 24h at 180 ℃, naturally cooling, centrifuging for 10 min at 12000rpm, removing supernatant, washing the lower precipitate with distilled water for three times, and drying for 12h at 50 ℃ to obtain the nano copper sulfide/multi-walled carbon nanotube composite;
2) grinding a Glassy Carbon Electrode (GCE) on abrasive paper, and then polishing the glass plate twice until the surface of the electrode is smooth (when polishing for the first time, polishing powder on the glass plate is alumina powder with the particle size of 0.3 mu m; during the second polishing, the polishing powder on the glass plate is alumina powder with the particle size of 0.05 mu m), then the glass plate is sequentially subjected to ultrasonic cleaning in absolute ethyl alcohol and distilled water, washed by secondary distilled water and dried for later use;
3) dissolving 1.5mg of the nano copper sulfide/multi-walled carbon nanotube composite obtained in the step 1) in 1.5mL of secondary distilled water, mixing, performing ultrasonic treatment for 2h to obtain a black suspension, sucking 5 mu L of the black suspension by using a pipette, uniformly dripping the black suspension on the surface of an electrode, and drying under an infrared lamp.
Based on the application of the electrode modified by the nano copper sulfide-multi-walled carbon nanotube composite, the dried glassy carbon electrode obtained in the step 3) is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system for measuring paracetamol.
Example 2
The preparation method of the electrode modified based on the nano copper sulfide-multi-walled carbon nanotube compound comprises the following steps: 1) 12mg of polyvinylpyrrolidone was dissolved in 15mL of 1.5mg mL-1Then sequentially adding 0.02mmol of CuCl into the MWCNTs aqueous solution2、0.056mmol Na2S, slowly stirring for 30min at room temperature, mixing to obtain a suspension, sealing the suspension, heating for 26h at 160 ℃, naturally cooling, centrifuging for 10 min at 12000rpm, removing a supernatant, washing a lower precipitate with distilled water for three times, and drying for 14h at 45 ℃ to obtain the nano copper sulfide/multi-walled carbon nanotube composite;
2) grinding a glassy carbon electrode on sand paper, and then polishing the glassy carbon electrode on a glass plate twice until the surface of the electrode is smooth (when polishing for the first time, polishing powder on the glass plate is alumina powder with the particle size of 0.3 mu m; during the second polishing, the polishing powder on the glass plate is alumina powder with the particle size of 0.05 mu m), and then the glass plate is sequentially subjected to ultrasonic cleaning in absolute ethyl alcohol and distilled water and washed by secondary distilled water for later use;
3) dissolving 1.2mg of the nano copper sulfide/multi-walled carbon nanotube composite obtained in the step 1) in 1.5mL of secondary distilled water, mixing, performing ultrasonic treatment for 2h to obtain a black suspension, sucking 5 mu L of the black suspension by using a pipette, uniformly dripping and coating the black suspension on the surface of an electrode, and drying under an infrared lamp.
The rest is the same as example 1.
Example 3
The preparation method of the electrode modified based on the nano copper sulfide-multi-walled carbon nanotube compound comprises the following steps: 1) 20mg of polyvinylpyrrolidone was dissolved in 25mL of 0.08mg mL-1Then sequentially adding 0.03mmol of CuCl into the MWCNTs aqueous solution2、0.094mmol Na2S, slowly stirring at room temperature for 30min, mixing to obtain suspension, sealing the suspension, heating at 200 deg.C for 20h, naturally cooling, centrifuging at 12000rpm for 10 min, removing supernatant, and precipitating the lower layerWashing the precipitate with distilled water for three times, and drying at 55 deg.C for 10h to obtain nanometer copper sulfide/multi-walled carbon nanotube composite;
2) grinding a glassy carbon electrode on sand paper, and then polishing the glassy carbon electrode on a glass plate twice until the surface of the electrode is smooth (when polishing for the first time, polishing powder on the glass plate is alumina powder with the particle size of 0.3 mu m; during the second polishing, the polishing powder on the glass plate is alumina powder with the particle size of 0.05 mu m), and then the glass plate is sequentially subjected to ultrasonic cleaning in absolute ethyl alcohol and distilled water and washed by secondary distilled water for later use;
3) dissolving 2.0mg of the nano copper sulfide/multi-walled carbon nanotube composite obtained in the step 1) in 1.5mL of secondary distilled water, mixing, performing ultrasonic treatment for 2h to obtain a black suspension, sucking 5 mu L of the black suspension by using a pipette, uniformly dripping and coating the black suspension on the surface of an electrode, and drying under an infrared lamp.
The rest is the same as example 1.
Example 4 test example
The test method comprises the following steps: the electrochemical behaviors of the modified electrodes in a potassium ferricyanide solution and an acetic acid-sodium Acetate Buffer Solution (ABS) containing a Paracetamol (PCT) analyte are respectively researched by Cyclic Voltammetry (CV). The effect of different concentrations of Paracetamol (PCT) on the oxidation peak current was measured using Differential Pulse Voltammetry (DPV). And simultaneously, the impedance, the potential window, the timing coulomb, the sweep rate, the pH and the like are analyzed and measured. During the measurement, paracetamol was diluted with an ABS buffer solution of a certain pH. The entire experimental procedure was carried out at room temperature.
Instruments and reagents: CHI660D electrochemical workstation (shanghai chenhua instruments corporation); electronic balance (shanghai yueping scientific instruments ltd); pHS-3C precision pH meter (Shanghai Dapu Instrument factory); KQ2200E model ultrasonic cleaner (kunshan ultrasonic instruments ltd); an XK96-B rapid mixer (Xinkang medical instruments Co., Ltd., Jiangyan); MS-2000 magnetic stirrers (good science instruments, Inc. in south of the river); three-electrode system: the nano copper sulfide-carbon nano tube composite nano material modified glassy carbon electrode (d is 3.0mm) is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a platinum electrode is used as a counter electrode.
Paracetamol(PCT): analytically pure, shanghai pharmaceutical company; MWCNTs: chinese academy of sciences Chengdu organic chemistry, Inc.; nano copper sulfide nano material (self-made); nano copper sulfide/carbon nano tube composite material (self-made); potassium ferricyanide solution: concentration 1mmol/L K3[Fe(CN)6]Solution, 1mmol/L K4[Fe(CN)6]Preparing a solution and 0.1mol/L KCl; ABS buffer solution: prepared by 0.1mol/L mixed solution of acetic acid and sodium acetate; the reagents used in the experiment are analytically pure; the experimental water is double distilled water.
4.1 CV electrochemical behavior characterization of different electrodes in Potassium ferricyanide solution
Respectively using a Glassy Carbon Electrode (GCE), a nano copper sulfide modified electrode (CuS/GCE, the preparation method of which is the same as that of example 1 except that the MWCNTs aqueous solution is replaced by distilled water), and a carbon nanotube modified electrode (MWCNTs/GCE, the preparation method of which does not add CuCl)2The rest is the same as example 1, and the same is below), the nano copper sulfide-carbon nanotube composite nanomaterial modified electrode (CuS/MWCNTs/GCE) of example 1 of the present invention is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a platinum electrode is used as a counter electrode to form a three-electrode system. Preparation of Fe (CN)6 3-/4-Mixed aqueous solution with KCl, Fe (CN) in the mixed aqueous solution6 3-/4-Is 1mmol/L (i.e., Fe (CN))6 3-And Fe (CN)6 4-The concentration of (B) is 1mmol/L, the concentration of KCl is 0.1mol/L (abbreviated as 1mmol/L Fe (CN)6 3-/4-+0.1mol/L KCl) in the concentration of 1mmol/L Fe (CN)6 3-/4-In +0.1mol/L KCl solution, cyclic voltammetry scanning is carried out at a scanning speed of 100mv/s, and the electrochemical behaviors of different electrodes are researched, and the results are shown in figure 1. In FIG. 1, a is GCE; b is CuS/GCE; c, MWCNTs/GCE; and d is CuS/MWCNTs/GCE, and the following marks are the same.
As can be seen from FIG. 1, the peak current measured by the modified electrode prepared by the method is maximum, and the peak shape is basically symmetrical, so that the modified electrode prepared by the method has good electrocatalytic activity, and the analysis sensitivity can be obviously improved.
4.2 CV electrochemical behavior characterization of different electrode assays PCT
0.1mol/L of ABS with pH value of 5.0 is used as a solvent to prepare 0.5mmol/L of PCT solution, and then a glassy carbon electrode, a nano copper sulfide modified electrode, a carbon nano tube modified electrode and the nano copper sulfide-carbon nano tube composite nano material modified electrode in the embodiment 1 of the invention are used as working electrodes respectively, a saturated calomel electrode is used as a reference electrode, and a platinum electrode is used as a counter electrode to form a three-electrode system. In the prepared PCT solution, cyclic voltammetry scans were performed at a scan rate of 100mV/s, and the electrochemical behavior of the different electrodes was studied, and the specific results are shown in FIG. 2.
As can be seen from FIG. 2, the peak current was also the largest in the PCT solution with the modified electrode of the present invention, and the oxidation peak and the reduction peak exhibited good symmetry. Therefore, the nano copper sulfide and the carbon nano tube have good conductivity, so that the sensitivity of electrode measurement is obviously improved.
4.3 AC impedance study
At 1mmol/L Fe (CN)6 3-/4-In +0.1mol/L KCl mixed solution, the impedance of the glassy carbon electrode, the nano copper sulfide modified electrode, the carbon nanotube modified electrode, and the nano copper sulfide-carbon nanotube composite nanomaterial modified electrode of example 1 of the present invention was studied, and the results are shown in FIG. 3.
As can be seen from fig. 3, compared with the bare electrode (glassy carbon electrode), the impedance on the nano copper sulfide modified electrode is slightly reduced, while the impedance on the MWCNTs modified glassy carbon electrode (curve c) is significantly reduced, and the impedance on the CuS-MWCNTs composite modified glassy carbon electrode (curve d) is also smaller than that on the bare electrode. Therefore, the CuS-MWCNTs composite modified electrode disclosed by the invention is small in impedance and good in conductivity, and can effectively promote the electron transfer rate on the surface of the electrode.
4.4 potential Window study
The potential windows of the glassy carbon electrode, the nano copper sulfide modified electrode, the carbon nanotube modified electrode, and the nano copper sulfide-carbon nanotube composite nanomaterial modified electrode of example 1 of the present invention were analyzed and studied using an ABS solution with a pH of 5.0 of 0.1mol/L, and the results are shown in fig. 4.
As can be seen from fig. 4, compared with the bare electrode (curve a), the potential window on the nano copper sulfide modified electrode is slightly reduced (curve b), while the potential window on the MWCNTs modified electrode is also reduced (curve c), the potential window on the CuS-MWCNTs composite modified electrode is also reduced to some extent relative to the bare electrode, and the range of the potential window on the CuS-MWCNTs composite modified electrode is: -1.5V to 1.5V.
4.5 chronometric coulometry study
Analytical studies were performed on timed coulombs on bare electrodes and CuS-MWCNTs/GCE electrodes of example 1 of the invention using 0.1mmol/L potassium ferricyanide solution, and the results are shown in FIG. 5.
As can be seen from fig. 5, the chronocoulombs on the CuS-MWCNTs composite modified glassy carbon electrode (curve d) are significantly reduced compared to the bare electrode (curve a).
According to the Anson formula
Q＝2nFAcD1/2t1/2π1/2+Qdc+Qds
Where A is the working electrode surface area, c is the substrate concentration, Qdc is the double layer charge that can be eliminated, Qds is the Faraday charge, other symbols have the usual meaning.
By experimental determination analysis, Q-t of bare electrode1/2The relationship curve is:
Q(μC)＝-1.68t-0.027
therefore, the surface area of the bare electrode is calculated to be 0.01782cm according to the Anson formula2。
Q-t of CuS-MWCNTs/GCE electrode1/2The relationship curve is:
Q(μC)＝-9.46t-0.88
therefore, the surface area of the CuS-MWCNTs/GCE electrode is calculated to be 0.10035cm according to the Anson formula2。
As can be seen, the specific surface area of the CuS-MWCNTs/GCE electrode is 4 times larger than that of the bare electrode, so that the CuS-MWCNTs/GCE electrode material can accelerate electron transfer, enhance electrochemical reaction activity and improve reaction sensitivity.
4.6 study of the Effect of different sweeping rates on PCT electrochemical behavior
The sweep rate was varied from 20mV/s to 600mV/s using an ABS solution containing 0.5mmol/L PCT at pH 5.0 (ABS solvent concentration of 0.1mol/L (pH 5.0)), and a sweep study was performed using cyclic voltammetry using the CuS/MWCNTs/GCE of inventive example 1 as the working electrode, the results of which are shown in FIG. 6. Scan rates (a-k) of 20, 50, 80, 120, 150, 180, 200, 300, 400, 500, 600 mV/s.
As can be seen from FIG. 6, when the sweep rate was varied from 20 to 600mV/s, the oxidation peak current and the reduction peak current were increased continuously as the sweep rate was increased. The square root of the oxidation peak current and the reduction peak current and the sweep rate show better linear relation. Wherein, the linear equation of the oxidation peak current is as follows: i (μ a) ═ 2.3091v1/2+0.4376, linear correlation coefficient R is 0.996, and the linear equation for the reduction peak current is: i (μ a) ═ 1.1711v1/2+0.8507, linear correlation coefficient R0.997, indicating that the redox process of PCT on the electrode is diffusion controlled. In order to reduce the background current and improve the signal-to-noise ratio, 100mV/s was chosen as the scanning rate in this experiment.
4.7 Effect of buffer solutions of different pH on PCT electrochemical behavior
Scanning studies using cyclic voltammetry were performed using a series of ABS solutions containing 0.5mmol/L PCT at different pH, using the CuS/MWCNTs/GCE modified electrode of example 1 of the present invention as the working electrode, and the results are shown in fig. 7, with a-f being pH 3, 3.5, 4, 4.5, 5, 5.5, respectively.
As can be seen from fig. 7, the oxidation peak potential Ep of PCT and the pH value satisfy the linear equation: ep (v) ═ -0.0633pH +0.8025, linear correlation coefficient R ═ 0.999. The slope of the oxidation peak potential versus pH was close to-56 mV/pH, indicating that PCT has an equal number of electrons and protons during the oxidation reaction. For oxidation peak current, it was observed that as pH increased, the current increased first and then decreased, and at pH 5.0, the oxidation peak current reached a maximum. Therefore, ABS buffer solution with pH 5.0 can be considered as the best supporting electrolyte.
4.8 investigation of Linear Range and detection Limit
A series of PCT solutions with different concentrations were prepared from 0.1mol/L ABS buffer solution with pH 5.0, and the Differential Pulse Voltammetry (DPV) was used to study and analyze electrochemical behavior using the CuS/MWCNTs/GCE modified electrode of example 1 of the present invention as the working electrode, and the PCT concentrations are shown in fig. 8: 2. 15, 30, 60, 100 and 200 mu mol/L.
As can be seen from fig. 8, as the concentration of the PCT solution increased, the oxidation peak current also gradually increased, and the oxidation peak current exhibited good linearity with the concentration, with the linear equation of I (μ a) — 0.16c (μmol/L) -0.04, the linear correlation coefficient of 0.998, and the detection limit of 2 μmol/L.
In conclusion, the nano copper sulfide-multi-walled carbon nanotube composite modified electrode has good electrocatalytic activity, is low in preparation cost, good in reproducibility and stability and high in determination sensitivity, and is particularly suitable for biological activity analysis. The nano copper sulfide-multi-walled carbon nanotube composite is used as a working electrode to form a three-electrode system which is used as a sensor to measure Paracetamol (PCT), and the sensitivity is high.
Claims (3)
1. The application of the electrode modified based on the nano copper sulfide-multi-wall carbon nanotube compound is characterized in that the modified electrode is used as a working electrode, a three-electrode system is formed by the modified electrode, a counter electrode and a reference electrode and used for measuring paracetamol, the surface of the electrode is covered with the nano copper sulfide/multi-wall carbon nanotube compound, and the preparation method of the electrode comprises the following steps of 1) dissolving 12 ~ 20mg of polyvinylpyrrolidone into 15 ~ 25mL of MWCNTs aqueous solution with the concentration of 0.08 ~ 1.5.5 mg mL-1, and then sequentially adding 0.02mmol of CuCl 0.02 ~ 0.03.03 mmol of CuCl 3512、0.056~0.094mmol Na2And S, mixing to obtain a suspension, sealing the suspension, heating at 160 ~ 200 ℃ for 20-26h, cooling, centrifuging, washing, and drying at 45 ~ 55 ℃ for 10 ~ 14h to obtain the nano copper sulfide/multi-walled carbon nanotube composite.
2. The application of the electrode modified by the nano copper sulfide-multi-walled carbon nanotube composite as claimed in claim 1, wherein the electrode obtained in step 2) is ground, polished, cleaned and dried, and then the nano copper sulfide/multi-walled carbon nanotube composite obtained in step 1) is dissolved in water, ultrasonically mixed and then dripped on the surface of the electrode.
3. The use of the electrode based on modification of a nanocopper sulfide-multiwalled carbon nanotube composite of claim 1, wherein the counter electrode is a platinum electrode and the reference electrode is a saturated calomel electrode.
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| CN1902477A (en) * | 2003-10-31 | 2007-01-24 | 生命扫描苏格兰有限公司 | Method of reducing interferences in an electrochemical sensor using two different applied potentials |
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