CN111239217A - N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof - Google Patents
N-doped carbon-wrapped Co @ Co3O4Core-shell particle polyhedron and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
Abstract
The invention discloses N-doped carbon-coated Co @ Co3O4Polyhedron of core-shell particles (Co @ Co)3O4-NC) and a preparation method and application thereof. Said Co @ Co3O4-the method for preparing NC comprises the following steps: 1) carbonizing the ZIF-67 crystal in an inert atmosphere, and naturally cooling to room temperature to obtain a Co-NC composite material; 2) placing Co-NC composite material in air of 220 deg.C for 2 deg.C min‑1And carrying out heat treatment at the heating rate for 24 hours to obtain the product. Benefit from Co @ Co3O4Special structure and nitrogen doping of-NC, Co @ Co3O4NC has high performance for non-enzymatic electrochemical glucose sensing. By Co @ Co3O4The sensitivity of the sensor made of NC can reach 251.9 mu AmM‑1cm‑2The detection limit can be as low as 0.3 μ M (S/N-3) with a linear range of 0.01-4 mM. Conveying applianceThe sensing electrode is also feasible in actual sample analysis.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to N-doped carbon-coated Co @ Co3O4A core-shell particle polyhedron and a preparation method and application thereof.
Background
The development of reliable and cost-effective and high-performance sensing devices in clinical research, bioprocessing and the food industry is considered to be an important technological means for accurate and rapid detection of glucose. In the aspect of detection technology, the electrochemical technology has the advantages of uniqueness, simplicity, sensitivity, quick response time, low detection limit, long-term stability, quick detection and the likeThe characteristics are widely concerned. Electrochemical glucose sensors are largely divided into enzyme-based sensing and non-enzymatic glucose sensing. However, enzymatic sensors have always relied on catalytic enzymes, such as glucose oxidase. Under the catalysis of the oxygen, the glucose is oxidized into gluconolactone and H by the oxygen2O2. The hydrogen peroxide produced is reduced by the mediator, causing a small change in the current response. Moreover, many studies have focused on the development of non-enzymatic agents for use in electrochemical glucose sensors due to their instability, high cost, and difficulty in immobilizing enzyme sensors.
Recently, Co with various structures and sizes due to high earth content, environmental friendliness and cost effectiveness3O4Nanoparticle (NPs) -based composites have attracted attention worldwide. However, Co3O4The conductivity of NPs is detrimental to the non-enzymatic detection of glucose. Co3O4The preparation of composite structures of NPs and conductive carbon materials is a versatile method for increasing the conductivity of electrode materials. Such as Co3O4NPs and graphene composites, Co3O4NPs and carbon nanotube composites and other porous carbon materials. However, Co3O4Composites of NPs and conductive carbon materials often suffer from aggregation, reduced activity, and the like. To date, Metal Organic Frameworks (MOFs) are a well-defined hollow material synthesized by self-assembly of metal ions and organic molecules. Also, because MOFs have high surface area and porous mass transport pathways, they are excellent sacrificial templates for fabricating porous carbon support metals or metal oxides to exhibit potential catalytic activity. In addition, small sized metal or metal oxide particles can be embedded in the carbon skeleton in situ without aggregation. Thus, MOF-derived nanocomposites have recently been investigated as effective catalysts.
Disclosure of Invention
An object of the present invention is to provide an N-doped carbon-wrapped Co @ Co3O4A core-shell particle polyhedron.
The N-doped carbon-coated Co @ Co provided by the invention3O4Polyhedron of core-shell particles (Co @ Co)3O4-NC) is prepared according to a process comprising the following steps:
1) carrying out carbonization treatment on ZIF-67 crystals (zeolite imidazole ester Framework-67, Zeolite Imidazolate Framework-67) in an inert atmosphere, and naturally cooling to room temperature to obtain a Co-NC composite material;
2) heating the Co-NC composite material to 220 +/-20 ℃ in air, and preserving the heat for 24 +/-5 hours at 200 +/-1 ℃ to form Co @ Co3O4-NC。
In the step 1) of the method, the inert atmosphere may be nitrogen, the carbonization temperature is 800 ± 50 ℃ (800 ℃ may be specific), and the carbonization time is 1 to 3 hours (2 hours may be specific). The temperature rise rate from the room temperature to the carbonization temperature can be 1-5 ℃ min-1(specifically, it may be 5 ℃ C. min-1)。
In the step 1) of the method, the ZIF-67 crystal is prepared by the following steps: reacting cobalt nitrate and 2-MeIM (2-methylimidazole) in an ethanol solution, and centrifuging and collecting precipitates after the reaction is finished; and washing the precipitate with ethanol and drying to obtain the product.
Wherein the mass ratio of the cobalt nitrate to the 2-MeIM is 0.727: 1.64. the reaction is specifically a stirred reaction at room temperature for 2 hours. The drying is carried out in a vacuum oven at 80 ℃ overnight.
The heating rate in the step 2) of the method is 2 +/-1 ℃ min-1。
According to an embodiment of the present invention, the step 2) of the method may specifically be: heating the Co-NC composite material to 220 ℃ in air, and preserving heat for 24h at 200 ℃ to form Co @ Co3O4-NC。
It is another object of the present invention to provide the above N-doped carbon-wrapped Co @ Co3O4Polyhedron of core-shell particles (Co @ Co)3O4-NC).
The invention provides an application of Co @ Co3O4-use of NC for the preparation of a non-enzymatic electrochemical glucose sensor.
It is a further object of the present invention to provide a non-enzymatic electrochemical glucose sensor.
The non-enzymatic electrochemical glucose sensor provided by the invention comprises a working electrode, a counter electrode and a reference electrode, wherein the surface of the working electrode is modified with Co @ Co3O4-a base electrode of NC layer.
The base electrode may be specifically a Glassy Carbon Electrode (GCE). Co @ Co in the working electrode3O4-NC may be used in an amount of 0.357 mg-cm relative to the base electrode-2。
Co-NC/GCE and Co in the invention3O4The preparation method of the (E) -NC/GCE is the same as that described above.
The counter electrode may specifically be a platinum electrode.
The reference electrode may specifically be Hg/HgO.
The invention also provides a method for detecting glucose.
The method comprises the following steps: the solution containing glucose was electrochemically detected by the above non-enzymatic electrochemical glucose sensor.
The non-enzymatic electrochemical glucose sensor has an operating voltage of 0.64V (reference electrode Hg/HgO).
The concentration of glucose in the glucose containing solution may be 0.01-4 mM.
The glucose-containing solution contains 0.1M KOH or NaOH.
The solution containing glucose also contains Dopamine (DA) and/or Uric Acid (UA) and/or Ascorbic Acid (AA).
The inventor prepares Co @ Co by a simple pyrolysis method3O4Core-shell particle encapsulated N-doped carbon polyhedrons (Co @ Co)3O4-NC). Benefit from special structure and nitrogen doping, Co @ Co3O4NC has high performance for non-enzymatic electrochemical glucose sensing. By Co @ Co3O4The sensitivity of the sensor made of NC can reach 251.9 mu A mM-1cm-2The detection limit can be as low as 0.3 μ M (S/N-3) with a linear range of 0.01-4 mM. Sensing electrodes are also feasible in actual sample analysis.
Drawings
FIG. 1 shows (a) Co-NC, Co3O4-NC and Co @ Co3O4-XRD pattern of NC; (b) Co-NC, Co3O4-NC and Co @ Co3O4-raman spectra of NC; (c) co @ Co3O4-nitrogen adsorption-desorption isotherm of NC; (d) co @ Co3O4-XPS spectra of NC; (e) co @ Co3O4-high resolution Co 2p spectra of NC; (f) high resolution XPS spectra of N1 s.
FIG. 2 is (a) an SEM image of Co-NC; (b) TEM image of Co-NC; (c) HRTEM image of Co-NC; (d) co @ Co3O4-SEM image of NC; (e) co @ Co3O4-TEM images of the NC; (f) co @ Co3O4-HRTEM images of NC; (g) co3O4-SEM image of NC; (h) co3O4-TEM images of the NC; (i) HRTEM image of Co3O 4-NC.
FIG. 3 shows (a) naked GCE, Co-NC/GCE, Co @ Co in 0.1M KOH with or without 5mM glucose3O4-NC/GCE and Co3O4CV curve of NC/GCE. (b) Bare GCE and Co @ Co3O4NC/GCE at 5mM K3Fe(CN)6CV curves in 0.1M KCl solution.
FIG. 4 shows (a) a scanning speed of 2-200mV s in a 0.1M KOH solution-1Time Co @ Co3O4CV curve of/GCE. (b) Peak current density versus scan rate.
FIG. 5 shows (a) Co @ Co3O4The amperometric response of the GCE to continuously add glucose to 0.1M KOH at 0.64V; (b) calibration curves of current versus glucose concentration, error bars represent standard deviations of three independent measurements made at different electrodes; (c) co @ Co3O4Anti-interference testing of GCE in 0.1M KOH solution in the presence of 0.1mM glucose and 0.1mM of different interferents; (d) co @ Co3O4Long term stability of the/GCE electrode.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The 2-methylimidazole (2-MeIM, 99%) used in the examples below was purchased from Macklin. Cobalt nitrate hexahydrate (Co (NO)3)·6H298.5 percent of O), potassium hydroxide (KOH, more than or equal to 85.0 percent) and methanol (CH)3OH > 99.7%) was purchased from Chinese medicine. Glucose (99%) was purchased from Acros organics. Ascorbic acid (AA, ≧ 99.0%), uric acid (UA, ≧ 99.0%) and Dopamine (DA) were purchased from Sigma-Aldrich. All other reagents were analytically pure and used without further purification. All solutions were prepared with Deionized (DI) water.
Example 1 preparation of Co @ Co3O4Core-shell particle encapsulated N-doped carbon polyhedrons (Co @ Co)3O4-NC)
1.1 preparation of ZIF-67
0.727g of cobalt nitrate was dissolved in 25mL of methanol, which was then poured into 25mL of methanol containing 1.64g of 2-MeIM (2-methylimidazole). After mixing, the solution was stirred at room temperature for 2 hours. The resulting precipitate was collected by centrifugation, washed 3 times with methanol, and dried in a vacuum oven at 80 ℃ overnight to give ZIF-67 crystals (Zeolite Imidazolate Framework-67) in a purple color.
1.2 preparation of Co-NC complexes
ZIF-67 crystal in N2Carbonizing at 800 deg.C for 2h under atmosphere, and heating at 5 deg.C for 5 min-1(i.e., at 5 ℃ for min-1Raising the temperature to 800 ℃, then preserving the heat for 2 hours), and naturally cooling to room temperature to obtain Co-NC.
1.3 preparation of Co @ Co3O4-NC complexes
The Co-NC composite material is arranged in the air at the temperature of 2 ℃ for min-1Heating to 220 ℃ at a heating rate and keeping the temperature at 200 ℃ for 24h to form Co @ Co3O4-NC。
1.4 preparation of Co3O4-NC complexes
The Co-NC composite material is arranged in the air at the temperature of 2 ℃ for min-1Heating to 220 deg.C and maintaining at 200 deg.C for 48h to form Co @ Co3O4-NC。
1.5 characterization and test methods
The structure and morphology of the catalyst was characterized by field emission scanning electron microscopy (FESEM, JSM-6701) and transmission electron microscopy (TEM, JEOLJEM-2100). measurement of X-ray diffraction (XRD) was with radiation of CuK α
X-ray photoelectron spectroscopy (XPS) analysis was recorded on a Thermoscientific Escapab 250 spectrometer using an AlK α X-ray source the Raman spectra were obtained using an XploRA Raman microscope with an excitation wavelength of 785nm and a BET specific surface area determined by nitrogen adsorption at 77.35K using Nova2000E electrochemical measurements were performed on a CHI660E electrochemical workstation based on a three electrode system consisting of a working electrode, a platinum sheet counter electrode and an Hg/HgO reference the electrolyte was 0.1M KOH and deoxygenated before the experiment.
2.1 characterization of the materials
XRD analysis was performed to confirm Co @ Co3O4-design structure of NC (fig. 1 a). Diffraction peaks appear at 44.2 ° and 51.5 ° corresponding to reflections from the (111) and (200) planes of the face centered (fcc) metallic Co phase (JCPDS number 15-0806). At the same time, another peak appears at 31.2 °, 36.9 °, 44.8 °, 59.3 ° and 65.2 ° and corresponds to cubic (220), (311), (400), (511) and (440) reflective spinel Co, respectively3O4Phase (JCPDS number 42-1467). Co3O4The NC samples were oxidized for longer periods in air and showed cubic spinel Co3O4The diffraction peak of (a) is stronger. Whereas the Co-NC sample obtained without further oxidation treatment in air showed only diffraction peaks of the metallic Co phase. Co @ Co3O4Raman spectrum of-NC indicates the presence of spinel Co on the surface3O4Structure, typical multiple Raman shift at 482cm-1、521cm-1、621cm-1And 692cm-1(FIG. 1 b). Co3O4NC sample shows Co3O4The raman shift signal of (a) is stronger because the metallic Co nanoparticles are completely oxidized, and the oxidation time in air is longer. The Co-NC sample showed no Raman signal over the range tested.
Co@Co3O4N of-NC2The adsorption-desorption isotherm curve is shown in FIG. 1 c. The average pore diameter was about 5nm, Co @ Co, as a result of pore diameter calculation using the BJH method3O4BET surface area and cumulative pore diameter of-NC 322.807 m2g-1And 0.279cm3g-1。Co@Co3O4The high surface area and pores of the NC may increase the available space to diffuse glucose and electrolyte to the catalyst surface.
Co@Co3O4XPS survey spectra of-NC showed that the surface consisted mainly of C (64.2 at%), N (2.9 at%), O (23.6 at%) and Co (9.3 at%) (FIG. 1 d). Co 2p3/2High resolution XPS spectra in the signal region (FIG. 1e) were fit into a typical metallic Co phase of 778.9eV and a Co phase of 780.4eV by a curve3O4。29N actually comes from the decomposed organic ligand and provides evidence for successful doping. Due to spin-orbit coupling, the high-resolution N1s spectrum (FIG. 1f) can be deconvoluted into three sub-peaks, including pyridine-N (399.5eV), graphite-N (401.3 eV), and oxidized-N (405.2 eV).
These results are in good agreement with the designed catalyst structure of partially oxidized Co particles anchored in the nitrogen-doped carbon backbone.
Co @ Co was studied by SEM and TEM3O4-morphology of NC catalyst. Co @ Co3O4SEM images of-NC (FIG. 2d) show a regular dodecahedral morphology, with average particle diameter of about 350nm, similar to the original ZIF-67 crystals and Co-NC (FIG. 2 a). However, as the oxidation time increases, the carbon skeleton is pulverized to various degrees. Especially in FIG. 2g, Co3O4NC shows a more disordered structure. Co @ Co3O4Enhanced High Resolution TEM (HRTEM) image of NC (FIG. 2f) shows pronounced interplanar spacings of 0.242nm and 0.466 nm, corresponding to cubic Co with (311) and (111) lattice fringes3O4. These stripes were found around a different domain with a planar spacing of 0.204nm, corresponding to metallic Co with (111) lattice stripes. For comparison, Co-NC (FIG. 2c) and Co3O4HRTEM image of-NC (FIG. 2i) shows interplanar spacings of 0.204nm and 0.242nm, corresponding to (111) lattice striations of Co (JCPDS No.15-0806) and to Co3O4(311) lattice fringes (JCPDS No. 42-1467). Obviously, the carbon layer surrounds Co @ Co3O4Around the particles. These results are consistent with the expectation for partially oxidized Co nanoparticles anchored in the carbon backbone.
2.2 glucose in Co @ Co3O4Cyclic voltammetry on NC/GCE
As can be seen in FIG. 3a, Co @ Co3O4-NC/GCE and Co3O4-NC/GCE (preparation method Co @ Co3O4-NC/GCE) both showed two pairs of redox peaks, anodic peaks at about 0.64V and 0.3V, cathodic peaks at about 0.55V and 0.25V. A pair of redox peaks at about 0.55V and 0.64V correspond to Co3+And Co4+Reversible transition between, and peaks of about 0.25V and 0.55V can be assigned to Co2+And Co3+To be transformed in between. These two reversible reactions can be schematically expressed as:
and
after addition of glucose, Co @ Co3O4NC/GCE showed a distinct catalytic current peak at an intensity of 0.64V, of about 2.78mAcm-2. In contrast, Co3O4The redox peaks of-NC/GCE and Co-NC/GCE increased slightly, while the bare GCThe oxidation reaction of E to glucose is very weak. In FIG. 3b, we investigated GCE and Co @ Co by cyclic voltammetry3O4-NC/GCE at 5mMK3Fe(CN)6Electrochemical activity in 0.1M KCl solution. It can be seen that Co @ Co3O4The degree of peak potential separation at NC/GCE is lower than at GCE, indicating Co @ Co3O4The presence of NC can accelerate the electron transfer rate. According to the Randles-Sevcik equation, with 0.063cm2Compared with GCE of Co @ Co3O4The electroactive area of-NC/GCE is larger and is 0.093cm2。
Co @ Co at different scan rates was obtained in 0.1M KOH3O4CV of NC/GCE. The results show that the peak currents of the anode and the cathode are both 2 to 200mV s-1Increases in the range of (1) (fig. 4 a). Figure 4b shows a good linear relationship between the anode and cathode peak currents and the scan rate, indicating a surface controlled electrochemical process.
2.3 glucose sensing
As shown in FIG. 3a, the current increase for the addition of glucose at the anodic peak of 0.64V was much stronger than the current increase at the anodic peak of 0.3V, which might indicate that the electrooxidation of glucose is mainly by Co3+/Co4+Mediating, rather than more alkaline, Co in solution2+/Co3+. Therefore, a potential of 0.64V vs. hg/HgO was used for the following amperometric detections. The current-time curve of Co @ Co in 0.1M KOH was further evaluated at a current of 0.64Vvs3O4Reliability of NC/GCE on glucose oxidation. Fig. 5a shows a voltammogram of a staircase box and a stepwise increase in ampere current at different glucose concentrations. The current response reached a steady state current within 5s (fig. 5a inset), revealing the fast charge carrier kinetics involved in the glucose electrooxidation process. The fitted curve for this glucose sensor is shown in fig. 5 b. Since glucose is in Co3S4Electrochemical oxidation on-G is a surface-catalyzed reaction, so Langmuir isothermal theory is used to fit curves32. According to Langmuir isothermal theory, the glucose concentration adsorbed on the catalyst surface (Cglucose S) can be expressed as:
wherein, KAIs the adsorption equilibrium constant, CtIs Co3S4Total molarity of active sites on G, which is constant, and CglucoseIs the concentration of glucose in the bulk electrolyte. Thus, at a given applied potential, electrochemical oxidation of glucose produces current density responses J and Cglucose SApproximately proportional, with a rate constant of KB. Thus, by defining a new constant, J may be represented as K ═ KAKBCt：
As shown in fig. 5, K in this equation is 0.447 and KA0.126 may possess a good fit constant (R0.986) so J may be expressed as:
furthermore, the calibration curve of the glucose sensor shows a linear range of 0.01-4mM and the sensitivity of the sensor at signal-to-noise ratio 3 is 251.9 μ A mM-1cm-2The detection limit was 0.3. mu.M.
In biological systems, Dopamine (DA), Uric Acid (UA) and Ascorbic Acid (AA) are often present with glucose, which may affect the detection of glucose. Therefore, selectivity is an important parameter of glucose sensors. The interference experiments were performed by the sequential addition of 0.1mM glucose and 0.1mM other interferents in 0.1M NaOH. As can be seen in FIG. 5c, Co @ Co3O4NC/GCE has a significant response to glucose, but a negligible response to interfering substances, and the current density increases again with the additional addition of glucose. Considering that the concentration of glucose in the physiological environment is more than 30 times higher than these interfering species,Co@Co3O4the selectivity of-NC/GCE is advantageous. By measuring the amperometric response over a long period of time, Co @ Co was studied3O4Stability of NC/GCE. FIG. 5d shows the amperometric response to 0.1mM glucose over 7 days. After 7 days, the final amperometric response was approximately 95.2% of the original response, indicating Co @ Co3O4the-NC/GCE has excellent stability. Also by measuring five Co @ Co3O4The cyclic voltammetry response of the-NC/GCE parallel electrode to 1mM glucose in 0.1m NaOH evaluated Co @ Co3O4Repeatability of NC/GCE. The Relative Standard Deviation (RSD) of the peak current density of the anode was 5.6%, indicating good reproducibility.
2.4 practical applications of glucose sensor
To prove Co @ Co3O4Feasibility of NC/GCE in practical analysis, the glucose concentration in medical glucose injections was tested amperometrically. Recovery of glucose and RSD for glucose injection was performed by spiking three known levels of glucose according to standard addition methods. Electrochemical measurements were performed three times (n-3). The glucose injection is not treated before use. The recovery of the three tests was between 97% and 104% and the RSD of the three tests was less than 2.6%, indicating a temperature at Co @ Co3O4Efficient and sensitive determination of glucose on NC/GCE. This indicates Co @ Co3O4NC/GCE has great potential in practical and reliable glucose analysis.
In summary, Co @ Co3O4NC/GCE has been shown to be an effective catalyst electrode for glucose oxidation under alkaline conditions. When used as non-enzymatic glucose electrochemical sensor, it shows high sensitivity and selectivity, and has satisfactory stability and repeatability. Moreover, the sensor shows a great potential for determining glucose in practical analyses.
Claims (10)
1. N-doped carbon-coated Co @ Co3O4The preparation method of the polyhedron of the core-shell particles comprises the following steps:
1) carbonizing the ZIF-67 crystal in an inert atmosphere, and cooling to room temperature to obtain a Co-NC composite material;
2) heating the Co-NC composite material to 220 +/-20 ℃ in air, and preserving heat for 24 +/-5 hours at 200 +/-1 ℃ to obtain the N-doped carbon-coated Co @ Co3O4A core-shell particle polyhedron.
2. The method of claim 1, wherein: in the step 1), the inert atmosphere is specifically nitrogen, the carbonization temperature is 800 +/-50 ℃, and the time is 1-3 h; the temperature rise rate from room temperature to the carbonization temperature is 1-5 ℃ min-1。
3. The method according to claim 1 or 2, characterized in that: in the step 1), the ZIF-67 crystal is prepared according to the following method: reacting cobalt nitrate and 2-methylimidazole in an ethanol solution, and centrifuging and collecting precipitates after the reaction is finished; and washing the precipitate with ethanol and drying to obtain the product.
4. The method according to any one of claims 1-3, wherein: in the step 1), the heating rate is 2 +/-1 ℃ min-1。
5. N-doped carbon-coated Co @ Co prepared by the method of any one of claims 1 to 43O4A core-shell particle polyhedron.
6. The N-doped carbon-wrapped Co @ Co of claim 43O4Application of the core-shell particle polyhedron in preparing a non-enzymatic electrochemical glucose sensor.
7. A non-enzymatic electrochemical glucose sensor comprising a working electrode, wherein: the working electrode is Co @ Co with the surface modified with the N-doped carbon coating according to claim 43O4And a base electrode of the core-shell particle polyhedron layer.
8. The non-enzymatic electrochemical glucose sensor of claim 7 wherein: the substrate electrode is a glassy carbon electrode; n-doped carbon-coated Co @ Co in working electrode3O4The dosage of the core-shell particle polyhedron relative to the substrate electrode is 0.357 mg-cm-2；
The non-enzymatic electrochemical glucose sensor takes a platinum electrode as a counter electrode, Hg/HgO as a reference electrode and KOH or NaOH as electrolyte.
9. A method of detecting glucose, comprising the steps of: electrochemical detection of a solution containing glucose using the non-enzymatic electrochemical glucose sensor of claim 7 or 8.
10. The method of claim 9, wherein: the solution containing glucose also contains at least one of the following substances: dopamine, uric acid and ascorbic acid;
the reference electrode in the non-enzymatic electrochemical glucose sensor is Hg/HgO, and the working voltage of the non-enzymatic electrochemical glucose sensor is 0.64V.
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