CN109752432B - Ascorbic acid sensor electrode with nano nickel manganate and preparation method thereof - Google Patents
Ascorbic acid sensor electrode with nano nickel manganate and preparation method thereof Download PDFInfo
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- CN109752432B CN109752432B CN201910097780.9A CN201910097780A CN109752432B CN 109752432 B CN109752432 B CN 109752432B CN 201910097780 A CN201910097780 A CN 201910097780A CN 109752432 B CN109752432 B CN 109752432B
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Abstract
The invention discloses an ascorbic acid sensor electrode with nano nickel manganate, which comprises a metal wire, a carbon film and nano nickel manganate, wherein the metal wire is used as a conductive substrate, an insulating layer is coated on the middle section of the metal wire, the carbon film is covered on the end surface of the metal wire, the nano nickel manganate is covered on the surface of the carbon film, and one end of the metal wire, which is covered with the carbon film and the nano nickel manganate, is used as a sensing surface. The method has the advantages of short response time, low detection limit, high sensitivity, good stability, wide application range and the like, and has high ascorbic acid detection efficiency and high accuracy. The invention also discloses a preparation method of the ascorbic acid sensor electrode with the nano nickel manganate, which has the advantages of simple process, lower cost, high production efficiency, suitability for large-scale production and popularization and application in preparing electrochemical sensor electrodes with other material combinations.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis and detection, in particular to an ascorbic acid sensor electrode with nano nickel manganate and a preparation method thereof.
Background
Ascorbic Acid (Ascorbic Acid), also known as vitamin C, is a water-soluble compound widely found in fruits, vegetables and beverages, and is also an effective drug for the treatment of scurvy, liver disease, allergic reactions and atherosclerosis, and can promote the growth of healthy cells, calcium absorption and the growth of normal tissues. Therefore, the development of a method capable of simply and rapidly detecting ascorbic acid is of great significance in the diagnosis of diseases and the judgment of food safety. In recent years, various analytical methods have been used for detecting ascorbic acid, such as titration analysis, chromatography, fluorimetry, spectrophotometry, electrochemical analysis, and the like. Among these measurement methods, electrochemical analysis has been widely recognized as one of the most potential effective analysis methods because of its high catalytic performance and low price.
The nano material has the special properties of high specific surface area, high activity and the like, and utilizesThe nano material as the detection electrode can obviously improve the performance of electrochemical analysis. A great number of nano materials are used for manufacturing ascorbic acid detection electrodes, such as metal Au, Pt and metal oxides CuO, ZnO and Fe2O3And the like, as well as graphene and some composite nanomaterials. Most of the detection electrodes based on the nano materials are prepared by coating and fixing the nano materials on the surface of a traditional glassy carbon electrode or a gold electrode through a film making technology, which inevitably causes larger interface resistance, and the nano materials modified on the electrode are easy to fall off after a plurality of electrochemical test processes. In addition, the traditional electrodes are difficult to be implanted into the body for real-time dynamic monitoring due to the limitation of the size of the traditional electrodes. The nickel manganate sheet-like nanomaterial has a large specific surface area and good electrochemical performance, and can be used for manufacturing high-performance electrochemical capacitors, so that attention is paid to the nickel manganate sheet-like nanomaterial in recent years. However, no relevant report is found at present when the nano nickel manganate is used for electrochemical analysis, particularly for detecting the concentration of ascorbic acid.
Disclosure of Invention
In order to overcome the defects of the existing ascorbic acid electrochemical detection technology, such as the nano material modified on the electrode is easy to fall off, the electrode has larger size, and thus implantable detection or micro-area concentration analysis is difficult to carry out, the invention provides an ascorbic acid sensor electrode with nano nickel manganate and a preparation method thereof.
The ascorbic acid sensor electrode with the nano nickel manganate comprises a metal wire, a carbon film and the nano nickel manganate, wherein the metal wire is used as a conductive substrate, an insulating layer is coated at the middle section of the metal wire, the carbon film covers the end surface of the metal wire, the nano nickel manganate covers the surface of the carbon film, and one end of the metal wire, which is covered with the carbon film and the nano nickel manganate, is a sensing surface.
Furthermore, the metal wire is made of nickel, copper or steel, the length of the metal wire is 1-5 cm, and the diameter of the metal wire is 20-500 mu m; the thickness of the carbon film is 4-10 mm; the nano nickel manganate is in a nano sheet shape, and the thickness of the nano sheet is 5-15 mm.
Furthermore, the nano nickel manganate nano-sheets form a three-dimensional network structure, and the nano-sheets have uniform appearance, are staggered with each other and are substantially perpendicular to the surface of the metal wire.
Furthermore, the insulating layer is made of plastic and has a thickness of 1-5 mm.
The electrode substrate is a metal wire with small diameter and good stability, and the metal wire is used as a needle electrode, can be used for detecting ascorbic acid in a traditional solution, can also penetrate into the interior of an object to be detected for real-time analysis, can also be used for determining the concentration of a micro-area in a microfluidic device, and has wider application range. The metal wire is coated with the carbon film, so that the biocompatibility is improved, the subsequent direct and uniform growth of nano materials is facilitated, and the repeatability and the performance stability of electrode preparation are improved; the functional material is preferably a nickel manganate nanosheet structure, has good electrochemical activity, low price and low toxicity, greatly increases the specific surface area after nanocrystallization, is favorable for improving the sensitivity of ascorbic acid detection, and reduces the detection limit.
A preparation method of an ascorbic acid sensor electrode with nano nickel manganate comprises the following steps:
step one, removing and shearing metal wires, cleaning and drying, standing and soaking in a glucose aqueous solution for 10-15 hours, taking out and drying, and performing high-temperature heat treatment in high-purity argon to obtain the metal wires with the surfaces covered with carbon films;
dissolving nickel nitrate and manganese chloride in deionized water, adding hexamethylenetetramine and urea, stirring, and uniformly mixing to obtain a mixed solution;
step three, transferring the mixed solution prepared in the step two into a high-pressure reaction kettle, adding the metal wire obtained by the step one into the mixed solution, carrying out hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished;
and step four, washing the reaction product obtained in the step three with deionized water, drying, carrying out high-temperature heat treatment in air, carrying out injection molding and packaging on the middle section of the obtained product, polishing one exposed end of the product to obtain an external conductive surface, and taking the other end of the product as a sensing surface to obtain the ascorbic acid sensor electrode with the nano nickel manganate.
Further, the concentration of the glucose aqueous solution in the first step is 0.02-0.05 mol/L; the temperature of the high-temperature heat treatment is 400-600 ℃, and the time is 2-5 hours.
Further, in the second step, the nickel nitrate is Ni (NO)3)2·6H2O, wherein the concentration of the O in the mixed solution is 10-30 mg/mL; manganese chloride is MnCl2·4H2O, wherein the concentration of the O in the mixed solution is 20-40 mg/mL; the concentration of hexamethylene tetramine in the mixed solution is 5-10 mg/mL; the concentration of urea in the mixed solution is 2-5 mg/mL;
further, the temperature of the hydrothermal reaction in the third step is 100-180 ℃, and the reaction time is 3-9 hours.
Further, the temperature of the high-temperature heat treatment in the fourth step is 350-550 ℃, and the heat treatment time is 1-3 hours.
The ascorbic acid sensor electrode with the nano nickel manganate can be directly used for rapid electrochemical determination of ascorbic acid, has the advantages of short response time, low detection limit, high sensitivity, good stability, wide application range and the like, and has high ascorbic acid resistance detection efficiency and high accuracy.
The nano nickel manganate is difficult to be directly attached to the surface of the metal wire, and a layer of carbon film is covered on the surface of the metal wire through soaking treatment and high-temperature heat treatment, so that a foundation is provided for the attachment of the nano nickel manganate, the bonding strength of the nano nickel manganate is ensured, and the electrode performance of the sensor is further improved.
The preparation method has the advantages of simple process, low cost and high production efficiency, is suitable for large-scale production, and can be popularized and used for preparing electrochemical sensor electrodes combined by other materials.
Drawings
FIG. 1 is a schematic diagram of the structure of an ascorbic acid sensor electrode with nano nickel manganate in accordance with the present invention;
FIG. 2 is an SEM image of an ascorbic acid sensor electrode with nano nickel manganate obtained in the first embodiment of the present invention, wherein a is a morphology image of a carbon film-coated metal wire and a nano nickel manganate metal wire, and b is a partially enlarged view of a showing a morphology structure of the nano nickel manganate metal wire;
FIG. 3 is an SEM image of an ascorbic acid sensor electrode with nano nickel manganate obtained by the second embodiment of the present invention;
FIG. 4 is an SEM image of an ascorbic acid sensor electrode with nano nickel manganate obtained by the third embodiment of the present invention;
FIG. 5 is an X-ray diffraction characterization of an ascorbic acid sensor electrode with nano nickel manganate obtained according to a first embodiment of the present invention;
FIG. 6 is a spectrum diagram of an ascorbic acid sensor electrode with nano nickel manganate obtained by the first embodiment of the present invention;
FIG. 7 is a timing current response diagram of an ascorbic acid sensor electrode with nano nickel manganate obtained by the method of the present invention when ascorbic acid with a concentration of 0.1mM is continuously added during detection
Fig. 8 is a corresponding timing current response diagram of the ascorbic acid sensor electrode with nano nickel manganate after adding a small concentration of ascorbic acid during detection according to the first embodiment of the present invention.
In the figure, 1-metal wire, 2-insulating layer, 3-nano nickel manganate, 4-carbon film.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
Referring to fig. 1, the ascorbic acid sensor electrode with nano nickel manganate comprises a metal wire 1, a carbon film 4 and nano nickel manganate 3, wherein the metal wire 1 is used as a conductive substrate, an insulating layer 2 is coated on the middle section of the metal wire 1, the carbon film 4 covers the end surface of the metal wire 1, the nano nickel manganate 3 covers the surface of the carbon film 4, and one end of the metal wire 1, which is covered with the carbon film 4 and the nano nickel manganate 3, is a sensing surface.
The metal wire 1 is made of nickel, copper or steel, the length is 1-5 cm, and the diameter is 20-500 mu m; the thickness of the carbon film 4 is 4-10 mm; the nano nickel manganate 3 is in a nano sheet shape, and the thickness of the nano sheet is 5-15 mm.
The insulating layer 2 is made of plastic and has a thickness of 1-5 mm.
In a first embodiment, a method for preparing an ascorbic acid sensor electrode with nano nickel manganate comprises the following steps:
cutting a metal nickel wire with the diameter of 0.2mm into a length of 3cm, respectively ultrasonically cleaning the metal nickel wire for 10min by using acetone, alcohol and deionized water, drying the metal nickel wire in an oven at 60 ℃, standing and soaking the metal nickel wire in a glucose aqueous solution with the concentration of 0.03mol/L, taking out the metal nickel wire for natural drying after soaking for 15 hours, and then carrying out high-temperature heat treatment in high-purity argon at the temperature of 500 ℃ for 3 hours;
step two, 0.58g of nickel nitrate Ni (NO) is added3)2·6H2O and 0.97g of MnCl2·4H2O is dissolved in 30mL of deionized water, and 0.21g of hexamethylenetetramine C is added6H12N4And 0.09g of Urea CH4N2O, stirring and mixing uniformly to obtain a clear mixed solution;
step three, transferring the mixed solution prepared in the step two into a 50mL high-pressure reaction kettle, adding the metal wire obtained by the step one into the mixed solution, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 6 hours, and naturally cooling to room temperature after the reaction is finished;
step four, repeatedly washing the reaction product obtained in the step three by using deionized water, placing the reaction product in a drying oven, drying the reaction product at the temperature of 60 ℃, and then placing the reaction product in air for high-temperature heat treatment, wherein the temperature of the heat treatment is 450 ℃, and the time of the heat treatment is 2 hours; and then, carrying out injection molding and packaging on the middle section of the obtained product, polishing one exposed end of the product to obtain an external conductive surface, and taking the other end of the product as a sensing surface to obtain the ascorbic acid sensor electrode with the nano nickel manganate.
The obtained target product was characterized by using a field emission scanning electron microscope SEM, see fig. 2a, with wires of consistent thickness and diameter of 0.2mm, and a layer of plush-like film material was uniformly coated on the surface. Referring to fig. 2b, the observation shows that the material covered by the surface is a nano-sheet structure, and the sheet structures have uniform appearance, are staggered with each other and are substantially vertical to the surface of the nickel wire, and the vertical arrangement is favorable for charge transmission and ion diffusion; meanwhile, the surfaces of the sheet structures are smooth, the thicknesses of the sheet structures are basically consistent and are about 5nm, and the widths of the sheet structures are basically in the range of hundreds of nanometers. Because the nano sheets are clustered with each other to form a three-dimensional network structure, wherein three nano sheets are surrounded by five nano sheets, and irregular pores are formed among the three nano sheets, the synthesized material not only has a larger surface area, but also is easy to be in full contact with a solution, the effective active area is increased, and the structure is very favorable for improving the performance of the sensor.
The phase structure of the obtained target product was characterized by using an X-ray diffractometer, and analysis showed that these nano-sheet structures were nickel manganate with face-centered cubic structure, see fig. 5. The elemental composition of the target product was characterized by using an energy dispersion spectrometer, and as can be seen from an observation in fig. 6, the obtained product was mainly composed of three elements, i.e., Ni, Mn, and O, further indicating that the product was nickel manganate, and also showing the presence of element C, indicating that the surface of the metal nickel wire was coated with a layer of carbon film.
An ascorbic acid sensor electrode with nano nickel manganate is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a platinum wire electrode is used as a counter electrode to form a three-electrode system. When electrochemical determination is carried out, the electrode is placed in 0.1mol/L NaOH solution which is stirred at a constant speed, then a constant potential of 0.55V is applied to a working electrode, a current time curve is recorded, after background current reaches a steady state, ascorbic acid solution samples with different concentrations are added by a microsyringe, current response is recorded, a corresponding timing current result when the corresponding ascorbic acid solution concentration is added is obtained, referring to fig. 7 and 8, the sensor has quick and sensitive response to the concentration change of the ascorbic acid, the response time is less than 5 seconds, when the ascorbic acid with the same concentration is continuously added, the corresponding current change is consistent and stable, and the sensitivity is calculated to be up to 3106 muA/mM cm2The detection limit can be calculated to be as low as 0.1 mu mol/L according to the signal-to-noise ratio of 3:1, which shows that the ascorbic acid sensor electrode with the nano nickel manganate has good catalytic capability on oxidation of ascorbic acid and can be directly used for high-sensitivity detection of ascorbic acid.
In a second embodiment, a method for preparing an ascorbic acid sensor electrode with nano nickel manganate comprises the following steps:
firstly, respectively ultrasonically cleaning a metal steel needle with the diameter of 0.25mm and the length of 5cm for 10min by using acetone, alcohol and deionized water, drying the metal steel needle in an oven at the temperature of 60 ℃, standing and soaking the metal steel needle in 0.02mol/L glucose aqueous solution, taking out the metal steel needle for natural drying after soaking for 15 hours, and then carrying out high-temperature heat treatment in high-purity argon at the temperature of 600 ℃ for 2 hours;
step two, 0.3g of nickel nitrate Ni (NO) is added3)2·6H2O and 0.6g of MnCl2·4H2Dissolving O in 30mL of deionized water, and respectively adding 0.15g of hexamethylenetetramine C6H12N4And 0.06g of Urea CH4N2O, stirring and mixing uniformly to obtain a clear mixed solution;
step three, transferring the mixed solution prepared in the step two into a 50mL high-pressure reaction kettle, adding the metal wire obtained by the step one into the mixed solution, carrying out hydrothermal reaction at the reaction temperature of 180 ℃ for 3 hours, and naturally cooling to room temperature after the reaction is finished;
step four, repeatedly washing the reaction product obtained in the step three by using deionized water, drying the reaction product in an oven at the temperature of 60 ℃, and then performing high-temperature heat treatment in air at the temperature of 550 ℃ for 1 hour; and then, carrying out injection molding and packaging on the middle part of the obtained product, polishing one exposed end of the product to obtain an external conductive surface, and taking the other end of the product as a sensing surface to obtain the ascorbic acid sensor electrode with the nano nickel manganate.
The obtained target product is characterized by using a field emission scanning electron microscope SEM, referring to fig. 3, the steel needle has a sharp front end, the surface is uniformly covered with a layer of plush-shaped film material, the material covered on the surface of the film material is a nano-sheet structure, the sheet structures have uniform appearance, are mutually staggered and are substantially perpendicular to the surface of the steel needle, the phase structure test, the element component test and the electrochemical sensing performance test results of the ascorbic acid sensor electrode with nano nickel manganate prepared in example two are similar to those of the example by using the same inspection method of the example one, and are not repeated herein.
In a third embodiment, a method for preparing an ascorbic acid sensor electrode with nano nickel manganate comprises the following steps:
firstly, ultrasonically cleaning a metal copper wire with the diameter of 0.02mm and the length of 1cm for 10min by using acetone, alcohol and deionized water respectively, drying the metal copper wire in an oven at the temperature of 60 ℃, standing and soaking the metal copper wire in 0.05mol/L glucose aqueous solution for 10 hours, taking out the metal copper wire for natural drying, and then carrying out high-temperature heat treatment in high-purity argon at the temperature of 400 ℃ for 5 hours;
step two, 0.9g of nickel nitrate Ni (NO) is added3)2·6H2O and 1.2g of MnCl2·4H2Dissolving O in 30mL of deionized water, and respectively adding 0.3g of hexamethylenetetramine C6H12N4And 0.15g of Urea CH4N2O, stirring and mixing uniformly to obtain a clear mixed solution;
step three, transferring the mixed solution prepared in the step two into a 50mL high-pressure reaction kettle, adding the metal wire obtained by the step one into the mixed solution, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 9 hours, and naturally cooling to room temperature after the reaction is finished;
step four, repeatedly washing the reaction product obtained in the step three by using deionized water, drying the reaction product in an oven at the temperature of 60 ℃, and then performing high-temperature heat treatment in air at the temperature of 350 ℃ for 3 hours; and then, carrying out injection molding and packaging on the middle part of the obtained product, polishing one exposed end of the product to obtain an external conductive surface, and taking the other end of the product as a sensing surface to obtain the ascorbic acid sensor electrode with the nano nickel manganate.
The obtained target product is characterized by using a field emission scanning electron microscope SEM, referring to FIG. 4, the thickness of the metal wire is consistent, a layer of plush-shaped film material is uniformly covered on the surface of the metal wire, the material covered on the surface of the film material is a nano flaky structure, the flaky structures are uniform in appearance, mutually staggered and generally perpendicular to the surface of the copper wire, the phase structure test, the element component test and the electrochemical sensing performance test results of the ascorbic acid sensor electrode with the nano nickel manganate prepared in the third embodiment are similar to those of the first embodiment by adopting the same test method of the first embodiment, and are not repeated herein.
The raw materials used in the embodiment of the invention are purchased in the market or prepared by a conventional method, and the specific parameters of the raw materials are as follows: the purity of the nickel wire, the copper wire and the steel wire used as the electrode conductive matrix is more than or equal to 99.99 percent; analytically pure nickel nitrate, manganese chloride, hexamethylenetetramine, urea, glucose, acetone and alcohol; the purity of Ar gas is more than or equal to 99.99 percent; the resistivity of the deionized water was 18 M.OMEGA.cm.
Although the present invention has been described with reference to the preferred embodiments, it is not limited thereto, and those skilled in the art can make modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is subject to the scope defined by the claims.
Claims (9)
1. An ascorbic acid sensor electrode with nano nickel manganate is characterized in that: the conductive carbon film comprises a metal wire, a carbon film and nano nickel manganate, wherein the metal wire is used as a conductive substrate, and an insulating layer is coated at the middle section of the metal wire;
soaking a metal wire in a glucose aqueous solution, and performing high-temperature heat treatment to form a carbon film, wherein the carbon film covers the surface of the end part of the metal wire;
dissolving nickel nitrate and manganese chloride in deionized water, adding hexamethylenetetramine and urea, stirring, uniformly mixing to obtain a mixed solution, placing the metal wire covered with the carbon film in the mixed solution, performing hydrothermal reaction to obtain nano nickel manganate, covering the nano nickel manganate on the surface of the carbon film, and taking one end of the metal wire covered with the carbon film and the nano nickel manganate as a sensing surface.
2. The ascorbic acid sensor electrode with nano nickel manganate of claim 1, wherein: the metal wire is made of nickel, copper or steel, the length of the metal wire is 1-5 cm, and the diameter of the metal wire is 20-500 mu m; the thickness of the carbon film is 4-10 mm; the nano nickel manganate is in a nano sheet shape, and the thickness of the nano sheet is 5-15 mm.
3. The ascorbic acid sensor electrode with nano nickel manganate of claim 2, wherein: the nano nickel manganate nanosheets form a three-dimensional network structure.
4. The ascorbic acid sensor electrode with nano nickel manganate according to claim 1 or 2, wherein: the insulating layer is made of plastic and has a thickness of 1-5 mm.
5. A preparation method of an ascorbic acid sensor electrode with nano nickel manganate is characterized by comprising the following steps: the method comprises the following steps:
step one, removing and shearing metal wires, cleaning and drying, standing and soaking in a glucose aqueous solution for 10-15 hours, taking out and drying, and performing high-temperature heat treatment in high-purity argon to obtain the metal wires with the surfaces covered with carbon films;
dissolving nickel nitrate and manganese chloride in deionized water, adding hexamethylenetetramine and urea, stirring, and uniformly mixing to obtain a mixed solution;
step three, transferring the mixed solution prepared in the step two into a high-pressure reaction kettle, adding the metal wire obtained by the step one into the mixed solution, carrying out hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished;
and step four, washing the reaction product obtained in the step three with deionized water, drying, carrying out high-temperature heat treatment in air, carrying out injection molding and packaging on the middle section of the obtained product, polishing one exposed end of the product to obtain an external conductive surface, and taking the other end of the product as a sensing surface to obtain the ascorbic acid sensor electrode with the nano nickel manganate.
6. The method for preparing the ascorbic acid sensor electrode with nano nickel manganate according to claim 5, wherein: the concentration of the glucose aqueous solution in the first step is 0.02-0.05 mol/L; the temperature of the high-temperature heat treatment is 400-600 ℃, and the time is 2-5 hours.
7. The method for preparing the ascorbic acid sensor electrode with nano nickel manganate according to claim 5, wherein: in the second step, the nickel nitrate is Ni (NO)3)2·6H2O, wherein the concentration of the O in the mixed solution is 10-30 mg/mL; manganese chloride is MnCl2·4H2O, wherein the concentration of the O in the mixed solution is 20-40 mg/mL; the concentration of hexamethylene tetramine in the mixed solution is 5-10 mg/mL; the concentration of the urea in the mixed solution is 2-5 mg/mL.
8. The method for preparing the ascorbic acid sensor electrode with nano nickel manganate according to claim 5, wherein: the temperature of the hydrothermal reaction in the third step is 100-180 ℃, and the reaction time is 3-9 hours.
9. The method for preparing the ascorbic acid sensor electrode with nano nickel manganate according to claim 5, wherein: the temperature of the high-temperature heat treatment in the fourth step is 350-550 ℃, and the heat treatment time is 1-3 hours.
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| CN105289643A (en) * | 2015-11-11 | 2016-02-03 | 东华大学 | Nickel manganese/carbon nanotube composite catalyst and preparation and application thereof |
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