CN109187698B - Hydrogen peroxide electrochemical sensor based on nickel sulfide nanoenzyme - Google Patents
Hydrogen peroxide electrochemical sensor based on nickel sulfide nanoenzyme Download PDFInfo
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- CN109187698B CN109187698B CN201810902200.4A CN201810902200A CN109187698B CN 109187698 B CN109187698 B CN 109187698B CN 201810902200 A CN201810902200 A CN 201810902200A CN 109187698 B CN109187698 B CN 109187698B
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Abstract
The invention discloses a hydrogen peroxide electrochemical sensor based on nickel sulfide nanoenzyme. The invention utilizes metal ion complexes as precursors to synthesize NiS nano materials by electrochemical deposition and ion exchange methods. Subsequently, NiS-based electrochemical sensors were constructed to detect H2O2. The invention provides a novel electrodeposition method using metal ion complex as precursor, which adopts metal ion complex hydrolyzed by thioacetamide and S2‑Compared with the conventional electrodeposition method, the slow ion reaction controls the production rate of NiS, so that the production rate of NiS is controllable, and conditions are provided for practical application. The preparation process is simple, the size of the synthesized NiS particles is smaller than that of the NiS particles prepared by the conventional electrodeposition method, and the synthesized electrochemical sensor has high sensitivity and low detection limit.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors and electrodeposition, in particular to an electrochemical sensor for detecting hydrogen peroxide by using a nickel sulfide nano material prepared based on a novel electrodeposition technology.
Background
Hydrogen peroxide as a strong oxidantDue to the unique electrochemical property, the electrochemical material is widely applied to the fields of food, medicine, clinical diagnosis, environmental monitoring and the like. At present, various analysis methods, such as a fluorescence spectroscopy method, a chemiluminescence method and an electrochemical method, are applied to the detection of hydrogen peroxide, wherein the electrochemical method is widely applied due to high sensitivity, low detection limit and low cost. Upike and Hicks developed the first glucose oxidase electrode in the world in 1967 for quantitatively detecting the content of a grape sheath in serum. Since then, enzymatic electrochemical sensors have received high attention from scientists in various fields. Most hydrogen peroxide sensors used in the current market are electrochemical enzyme sensors, and although the sensors have the advantages of high sensitivity, high selectivity and the like, the electrochemical enzyme sensors are high in cost, short in service life and poor in stability due to the fact that the preparation and purification of the enzyme are difficult and the activity of the enzyme is greatly influenced by the environment. Recently, transition metal oxides (e.g., MnO) have been utilized2、Co3O4) The modified electrode constructs a plurality of enzyme-free electrochemical hydrogen peroxide sensors. Such as BSaha et al, utilize Mn (CH)3COO)2、Na2SO4For electrolyte, MnO is prepared by electrodeposition2An electrode is modified, and a hydrogen peroxide sensor (B.S, S.K.J, S.B, electrically-degraded nanostructured MnO2 for non-enzymatic hydrogen peroxide sensing, Solid State Physics (2015), 050097-1-050097-2.) with higher sensitivity is constructed. However, the current enzyme-free electrochemical sensor still has the defects of low sensitivity and poor selectivity, so that a hydrogen peroxide sensor with low cost, good stability and low detection limit is urgently needed in the industrial field.
In recent years, Transition Metal Sulfides (TMS) have attracted considerable attention due to their high electrical conductivity. Compared with transition metal hydroxides and transition metal oxides, TMS has inherent advantages of low cost, low toxicity, good biocompatibility and the like, and is increasingly used in the fields of lithium ion batteries, photocatalysis and the like. Among these TMS compounds, NiS has excellent charge storage capacity and electron conductivity, and is often used for supercapacitors and sensitized solar cells. Recently, many reports have found that NiS has excellent electrochemical catalytic performance and is used as an electrode active material for detecting various substances.
Therefore, the invention provides a hydrogen peroxide sensor based on nickel sulfide nanoenzyme. In the present invention, S2-And sodium citrate is used to form stable metal ion complexes. And then synthesizing the NiS nano-material by using an electrochemical deposition and ion exchange method by using the metal ion complex as a precursor. Subsequently, NiS-based electrochemical sensors were constructed to detect H2O2。
Disclosure of Invention
The invention aims to provide a nickel sulfide nanoenzyme hydrogen peroxide electrochemical sensor and a preparation method thereof.
The invention provides a nickel sulfide nanoenzyme hydrogen peroxide electrochemical sensor which is composed of a glassy carbon electrode and a nickel sulfide nanomaterial electrodeposited on the surface of the electrode. The linear range of the sensor is 1 mu mol/L-1000 mu mol/L, and the detection limit is 0.3 mu mol/L.
The nickel sulfide nanoenzyme hydrogen peroxide electrochemical sensor adopts the following preparation method, specifically:
(1) polishing glassy carbon electrode on polishing paper uniformly, and sequentially using Al with grain size of 1, 0.3 and 0.05 mu m2O3And (5) polishing the powder. And then cleaning the glassy carbon electrodes in an ultrasonic instrument for 3-5 min respectively by using absolute ethyl alcohol and deionized water. Blow-drying with nitrogen.
(2) The nickel containing compound and sodium citrate in a molar ratio of 2:3 were dissolved in 50ml of deionized water and stirred for 1 h.
(3) And (3) adding thioacetamide with the molar ratio of 5:1 to the nickel-containing compound into the mixed solution obtained in the step (2), and performing ultrasonic treatment for 10-15 min to obtain a reaction solution.
(4) Electrodeposition is carried out by a three-electrode electrochemical workstation (Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, a glassy carbon electrode is used as a working electrode) by cyclic voltammetry, the deposition potential of NiS is-0.9 mv-0.7 mv, and scanning is carried out for 10 periods at the scanning speed of 5 mv/s.
(5) And (5) cleaning the glassy carbon electrode by using ultrapure water to remove impurity ions.
(6) And (4) drying the cleaned glassy carbon electrode under an infrared lamp for 30-40 minutes.
Compared with the prior art, the invention has the outstanding advantages that:
(1) the invention provides a novel electrodeposition method using metal ion complex as precursor, which adopts metal ion complex hydrolyzed by thioacetamide and S2-Compared with the conventional electrodeposition method, the slow ion reaction controls the production rate of NiS, so that the production rate of NiS is controllable, and conditions are provided for practical application.
(2) The preparation process is simple, the size of the synthesized NiS particles is smaller than that of the NiS particles prepared by the conventional electrodeposition method, and the synthesized electrochemical sensor has high sensitivity and low detection limit.
Drawings
FIG. 1 is a FESEM image of NiS, wherein a and b are electron micrographs of the electrodeposited substrate with sodium citrate added at a resolution of 2 μm and 200nm, c is a 2 μm resolution electron micrograph of the electrodeposited substrate without sodium citrate added, and d is an EDX image of the electrodeposited substrate with sodium citrate added;
FIG. 2 is a graph showing the results of an electrochemical performance study of NiS, wherein a is a value in the concentration of 0.5mM [ Fe (CN)6]3-And cyclic voltammetry characteristics of bare glassy carbon electrode and NiS modified electrode in 0.1MKCl solution, b is in a solution containing 0.5mM [ Fe (CN)6]3-/4-And an electrochemical impedance spectrum analysis chart of the bare glass carbon electrode and the NiS modified electrode in the 0.5MKCl solution (an inset is an equivalent circuit diagram);
FIG. 3 is a graph which shows the electrocatalytic performance of NiS under investigation of the concentrations of different electrodeposition substrates, wherein a, b, and c are voltammetric curves of NiS-modified electrodes (sodium citrate added, sodium citrate not added, double nickel-containing compound and sodium citrate) in a solution containing 0.1M NaOH, respectively;
fig. 4 is a performance analysis diagram of the sensor for detecting hydrogen peroxide, wherein a is a time current curve of a NiS modified electrode in a solution containing 0.1M NaOH for detecting hydrogen peroxide with different concentrations, and b is a linear relation between the peak current of hydrogen peroxide and the corresponding concentration.
Detailed Description
The invention is further examined with the aid of specific examples and with the aid of the accompanying drawings.
Example 1:
preparation method of electrochemical sensor for preparing nickel sulfide nano material and detecting hydrogen peroxide in one step based on novel electrodeposition method
(1) Polishing glassy carbon electrode on polishing paper uniformly, and sequentially using Al with grain size of 1, 0.3 and 0.05 mu m2O3And (5) polishing the powder. And then sequentially cleaning the glassy carbon electrode in an ultrasonic instrument for 5-10 min by using absolute ethyl alcohol and deionized water. And blowing the glass by using nitrogen after cleaning.
(2) The nickel containing compound and sodium citrate in a molar ratio of 2:3 were dissolved in 50ml of deionized water and stirred for 1 h.
(3) And (3) adding thioacetamide with the molar ratio of 5:1 to the nickel-containing compound into the mixed solution obtained in the step (2), and performing ultrasonic treatment for 10-15 minutes to obtain a reaction solution.
(4) Pouring the reaction solution into an electrolytic bath, connecting a working station, carrying out electrodeposition by using a three-electrode electrochemical working station (Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode) by using a cyclic voltammetry method, wherein the deposition potential of NiS is-0.9 mv-0.7 mv, and scanning is carried out at the scanning speed of 5mv/s for 10 periods.
(5) And (5) cleaning the glassy carbon electrode by using ultrapure water to remove impurity ions.
(6) And (4) drying the cleaned glassy carbon electrode under an infrared lamp for 30-40 minutes.
The synthesized NiS is shown in fig. 1 a and b, d is energy dispersive X-ray spectroscopy (EDX), and it can be seen that the prepared nanoparticles with a molar ratio of 1:1 are proved to be NiS.
Example 2:
research on synthetic NiS particle size by adding sodium citrate into electrodeposition substrate
The procedure was as in example 1 except that sodium citrate was not added in step (2), and as shown in a and c in FIG. 1, it can be seen that the particle diameter of NiS without sodium citrate was larger than that of sodium citrate.
Example 3:
electrochemical performance analysis of nickel sulfide nanoenzyme hydrogen peroxide electrochemical sensor
0.5mM [ Fe (CN) ]6]3-/4-And 0.5M KCl,pouring the mixed solution into an electrolytic tank, connecting the work stations, adopting a three-electrode work station (Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode) to carry out voltammetry characteristic analysis on a bare glassy carbon electrode and a NiS modified electrode by using a cyclic voltammetry method, wherein the sweep speed is 50mv/s, the sweep potential is 0-0.8 v, and shown by a in figure 2, the oxidation-reduction peaks of the bare electrode are 0.225v and 0.153v, which correspond to Fe3+/Fe2+The pair of strong redox peaks of the NiS modified electrode is 0.618v and 0.534v, corresponding to the redox couple of NiS/NiSOH, and the pair of weak redox couples is 0.465v and 0.432v, corresponding to Fe3+/Fe2+Redox couples.
The EIS is adopted to further study the reaction kinetics of the NiS modified electrode except CV, an equivalent circuit diagram and software are adopted to fit to obtain a Nyquist curve, and as shown in b of figure 2, the electron transfer impedance of the NiS modified electrode is analyzed to be 208.30 omega cm-218.83 omega cm larger than that of a bare electrode-2Much larger, which may be that NiS modified electrodes are less conductive than bare electrodes, thereby impeding electron transfer.
Example 4:
effect of electrodeposition substrate concentration on NiS electrocatalytic Performance
Respectively preparing a nickel-containing compound, sodium citrate, NaOH (0.1mol) and thioacetamide; a nickel-containing compound, NaOH (0.1mol), thioacetamide; double nickel containing compound, double sodium citrate, NaOH, thioacetamide electrodeposition substrate solution, corresponding to a, b, c in fig. 3. Respectively pouring 3 substrates into an electrolytic cell, connecting the work stations, and adopting a three-electrode work station (Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode) to perform voltammetry characteristic analysis on a NiS modified electrode by using a cyclic voltammetry method, wherein the sweep rate is 50mv/s, the sweep potential is 0-0.8 v, as shown in a and b in figure 3, the NiS obtained by adding sodium citrate in the substrate has large oxidation peak current to hydrogen peroxide catalysis, because the NiS obtained by adding sodium citrate has small particle size, large specific surface area and high electron transfer efficiency, as shown in figure 3c, the NiS obtained by doubling the substrate concentration has smaller oxidation peak current to hydrogen peroxide than a, because the NiS obtained by doubling the substrate concentration has larger particle size, and the electron transfer efficiency is reduced.
Example 5:
detection range and detection limit of nickel sulfide nanoenzyme hydrogen peroxide sensor
Hydrogen peroxide solutions with concentrations of 1 mu mol/L, 5 mu mol/L, 10 mu mol/L, 100 mu mol/L, 200 mu mol/L, 500 mu mol/L and 1000 mu mol/L are prepared, the hydrogen peroxide solutions with the concentrations are respectively poured into an electrolytic bath, 0.1MNaOH is added, after magnetic stirring is carried out for 5 minutes, a three-electrode workstation (Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode) is connected with the workstation, and the NiS modified electrode is analyzed by using a time-current method, wherein as shown in figure 4a, corresponding current is gradually increased along with the increase of the concentration of the hydrogen peroxide solution in the reaction solution. FIG. 4b shows the linear relationship between the hydrogen peroxide concentration and the corresponding peak current value, and it can be seen that the sensor has a good linear range within 1 μ M to 1000 μ M, with a detection limit of 0.3 μ M.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (1)
1. A hydrogen peroxide electrochemical sensor based on nickel sulfide nanoenzyme is characterized by being prepared by the following method:
(1) polishing glassy carbon electrode on polishing paper uniformly, and sequentially using Al with grain size of 1, 0.3 and 0.05 mu m2O3Polishing the powder; then, cleaning the glassy carbon electrodes in an ultrasonic instrument for 3-5 min by using absolute ethyl alcohol and deionized water respectively; drying by using nitrogen;
(2) dissolving a nickel-containing compound and sodium citrate with a molar ratio of 2:3 in 50ml of deionized water, and stirring for 1 h;
(3) adding thioacetamide with the molar ratio of 5:1 to the nickel-containing compound into the mixed solution obtained in the step (2), and performing ultrasonic treatment for 10-15 min to obtain a reaction solution;
(4) performing electrodeposition by using a three-electrode electrochemical workstation and a cyclic voltammetry, wherein the deposition potential of NiS is-0.9 mV-0.7 mV, and scanning for 10 periods at the sweep rate of 5 mV/s; wherein Ag/AgCl in the three-electrode electrochemical workstation is a reference electrode, a platinum wire electrode is a counter electrode, and a glassy carbon electrode is a working electrode;
(5) washing the glassy carbon electrode with ultrapure water to remove impurity ions;
(6) and (4) drying the cleaned glassy carbon electrode under an infrared lamp for 30-40 minutes.
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