CN111707718A - Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof - Google Patents
Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof Download PDFInfo
- Publication number
- CN111707718A CN111707718A CN202010387758.0A CN202010387758A CN111707718A CN 111707718 A CN111707718 A CN 111707718A CN 202010387758 A CN202010387758 A CN 202010387758A CN 111707718 A CN111707718 A CN 111707718A
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- gce
- electrode
- free sensor
- enzyme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
-
- 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
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention relates to a functionalized black phosphorus-based enzyme-free sensor and a preparation method and application thereof, wherein the method comprises the following steps: (1) the black phosphorus nanometer suspension is dripped and coated on the surface of a glassy carbon electrode GCE, and is put in nitrogen N2Drying in the air under the atmosphere to obtain a BP GCE modified electrode; (2) depositing copper nanoparticles on the surface of a BP GCE modified electrode, and then airing in nitrogen; (3) and dripping the Nafion solution on the surface of the electrode, and airing in nitrogen to obtain the functional black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE. Compared with the prior art, the method has the advantages of uniform dispersion of copper nanoparticles, large effective surface area, high electron transfer rate, high conductivity, strong catalytic activity, simple and quick electro-catalytic detection, high sensitivity, good stability and the like.
Description
Technical Field
The invention relates to the technical field of electrochemical sensing, in particular to a functionalized black phosphorus-based modified enzyme-free sensor and a preparation method and application thereof.
Background
Hydrogen peroxide H2O2Not only various enzymatic reactions in living systemsThe reaction by-products are also important substances indispensable in the fields of biomedicine, food, textile, pharmacy, environmental analysis and the like. Therefore, the accurate, sensitive, credible and convenient H is developed2O2The quantitative detection method has great significance.
Conventional H2O2The core of the electrochemical sensor is catalase using ferriporphyrin as a prosthetic group. Although the enzyme sensor has the characteristics of high sensitivity, strong selectivity and the like, the enzyme is expensive, the enzyme immobilization process is complex and volatile, and the stability of the electrochemical enzyme sensor is poor and the use cost is high because the enzyme activity is greatly influenced by factors such as temperature, pH, humidity and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a functionalized black phosphorus-based enzyme-free sensor with uniform copper nanoparticle dispersion, large effective surface area, high electron transfer rate, high conductivity, strong catalytic activity, simple, convenient and quick electro-catalytic detection, high sensitivity and good stability, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
h based on metal nano material2O2Enzyme-free sensors are an advantageous alternative to conventional enzyme sensors. The copper nanoparticles CuNPs have small particle size, large specific surface area, good biocompatibility, strong electron transmission capability, higher electrochemical activity and low price, and are used for constructing H2O2Good motifs for enzyme-free electrochemical sensors. However, the copper nanoparticles CuNPs are easy to agglomerate on the surface of the electrode, so that the effective active area of the electrode is reduced, and the catalytic activity of the electrode is reduced. Therefore, it is very important to prepare a matrix capable of uniformly supporting CuNPs.
Two-dimensional Black Phosphorus (BP) has excellent conductivity and large specific surface area, and is an ideal element for supporting copper nanoparticles (CuNPs) to construct an electrochemical biosensor. However, black phosphorus is hydrophobic and has fewer surface active functional groups. In order to expand the application of the sensor in the sensing field, on the basis of keeping high specific surface area and high conductivity of black phosphorus, the sensor has better water solubility and stability through functional composite modification, and a new-generation electrochemical enzyme-free sensor is prepared. The enzyme-free sensor and the electrode are a concept, and the specific scheme is as follows:
a preparation method of a functionalized black phosphorus-based enzyme-free sensor comprises the following steps:
(1) the Black Phosphorus (BP) nano suspension is dripped on the surface of a glassy carbon electrode GCE and is added in nitrogen N2Drying in air under the atmosphere to prepare a BPGCE modified electrode;
(2) depositing copper nanoparticles (CuNPs) on the surface of a BP GCE modified electrode, and then airing in nitrogen;
(3) and dripping the Nafion solution on the surface of the electrode, and airing in nitrogen to obtain the functional black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE.
Further, the step (2) is specifically;
(2-1) adding CuCl2Dissolving in chitosan/acetic acid (Chit/HAc) solution to form copper nanoparticle (CuNPs) dispersion;
and (2-2) placing the BP GCE modified electrode in the copper nanoparticle dispersion liquid, electrochemically depositing the copper nanoparticles on the surface of the BP GCE by using cyclic voltammetry, and then naturally airing.
Furthermore, the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is (6.36-19.06): (10-30): 0.018-0.042.
Further, the volume ratio of the black phosphorus nano suspension to the Nafion solution is (3-6): 1.
Further, the concentration of the black phosphorus nano suspension is 3-7mg/mL, and the concentration of the Nafion solution is 0.1-1 wt%.
Further, the concentration of the chitosan/acetic acid solution is 0.1-0.3 g/mL.
Further, CuCl is contained in the copper nanoparticle dispersion liquid2The concentration of (A) is 10-30 mmol/L.
Furthermore, during electrochemical deposition, the voltage of an electrochemical window is-0.8-0.3V, and the scanning rate is 50 mV/s.
A functionalized black phosphorus-based enzyme-free sensor prepared as described above.
Application of functionalized black phosphorus-based enzyme-free sensor as described above in H2O2Enzyme-free electrochemical detection of (1).
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the black phosphorus-based enzyme-free electrochemical sensor CuNPs-Chit-BP GCE is simple, and the CuNPs are uniformly dispersed on a Chit-BP substrate and are not easy to agglomerate;
(2) and conventional H2O2Compared with an enzyme sensor, due to the introduction of two-dimensional BP, the CuNPs-Chit-BP GCE has the advantages of large effective surface area, high electron transfer rate, high conductivity and strong catalytic activity;
(3) compared with a constant potential deposition method, the cyclic voltammetry deposition method has the advantages that the enzyme-free sensor obtained by the cyclic voltammetry deposition method shows better electrode stability when being scanned by a cyclic voltammetry curve;
(4) the CuNPs-Chit-BP GCE enzyme-free electrochemical sensor is applied to the electro-catalysis detection of hydrogen peroxide, the method is simple, convenient and quick, the sensitivity is high, the stability is good, and when the content of the hydrogen peroxide is 1.0 × 10-5-9.5×10-4The linear relationship is good when the mol/L is in the process, and the detection limit is 0.722 mu mol/L.
Drawings
FIG. 1 is a plot of cyclic voltammetric scans of the enzyme-free sensors obtained in example 1, comparative example 1, and comparative example 2;
FIG. 2 is a cyclic voltammogram of the enzyme-free sensor obtained in example 2 in a three-electrode system in 100mmol/L PBS phosphate buffer solution at different pH values;
FIG. 3 is a cyclic voltammogram of the enzyme-free sensors obtained in example 3 and comparative example 5 in 100mmol/L PBS phosphate buffer at pH 7.0;
FIG. 4 shows the enzyme-free sensor pair H obtained in example 2, comparative example 3 and comparative example 42O2Testing the performance of reduction;
FIG. 5 shows the enzyme-free sensors obtained in example 1 at different concentrations H2O2An ampere-time curve in solution;
FIG. 6 shows enzyme-free sensor pair H obtained in example 1, comparative example 1 and comparative example 22O2And (5) testing the performance of reduction.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
In N 26 μ L,5mg/mL BP dispersion was applied dropwise to a polished GCE surface in an ambient vacuum glove box, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Placing the BP GCE composite electrode in a container containing 20mmol/L CuCl20.2% (w/v) chip/HAc solution, CuNPs were electrochemically deposited on the BP GCE surface using cyclic voltammetry, electrochemical window: -0.8-0.3V, scan rate of 50mV/s, N2Naturally drying in the atmosphere.
And (3) dropwise coating 1 mu L of Nafion solution (0.5 wt%) on the surface of an electrode, and naturally airing in a glove box to obtain the functionalized black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE, wherein the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is 12.71: 20: 0.03.
comparative example 1
Placing the polished glassy carbon electrode GCE in a container containing 20mmol/L CuCl20.2% (w/v) Chit/HAc solution, electrochemical deposition of CuNPs on the GCE surface using cyclic voltammetry, N2Naturally airing under the atmosphere, dripping 1 mu of LNafion solution (0.5wt percent) and airing again to prepare the CuNPs-Chit GCE composite electrode. Wherein the mass ratio of the copper nanoparticles to the chitosan is 12.71: 20.
comparative example 2
In N 26 μ L,5mg/mL BP dispersion was applied dropwise to a polished GCE surface in an ambient vacuum glove box, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Example 2
In N 26 μ L,3mg/mL BP dispersion was applied dropwise to a polished GCE surface in an ambient vacuum glove box, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Placing BP GCE composite electrode in a containerHas 10mmol/L CuCl20.1% (w/v) chip/HAc solution, CuNPs were electrochemically deposited on the BP GCE surface using cyclic voltammetry, electrochemical window: -0.8-0.3V, scan rate of 50mV/s, N2Naturally drying in the atmosphere.
And dripping 1 mu L of Nafion solution (0.5 wt%) on the surface of the electrode, and naturally drying in a glove box to obtain the functionalized black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE. Wherein the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is 6.36: 10: 0.018.
comparative example 3
Placing the polished glassy carbon electrode GCE in a container containing 10mmol/L CuCl20.1% (w/v) Chit/HAc solution, electrochemical deposition of CuNPs on the GCE surface using cyclic voltammetry, N2Naturally airing under the atmosphere, dripping 1 mu L of Nafion solution (0.5 wt%) and airing again to prepare the CuNPs-Chit GCE composite electrode. Wherein the mass ratio of the copper nanoparticles to the chitosan is 6.36: 10.
comparative example 4
In N 26 μ L,3mg/mL BP dispersion was applied dropwise to a polished GCE surface in an ambient vacuum glove box, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Example 3
In N 26 μ L,6mg/mL BP dispersion was applied dropwise to a polished GCE surface in an ambient vacuum glove box, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Placing the BP GCE composite electrode in a solution containing 25mmol/L CuCl20.25% (w/v) chip/HAc solution, CuNPs were electrochemically deposited on the BP GCE surface using cyclic voltammetry, electrochemical window: -0.8-0.3V, scan rate of 50mV/s, N2Naturally drying in the atmosphere.
And dripping 1 mu L of Nafion solution (0.5 wt%) on the surface of the electrode, and naturally drying in a glove box to obtain the functionalized black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE. Wherein the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is 15.89: 25: 0.036.
comparative example 5
In N2Taking 6 μ L of 6mg/m in an atmosphere vacuum glove boxThe L BP dispersion liquid is dripped on the surface of the GCE which is polished clean, N2And (5) drying in the air under the atmosphere to obtain the BP-GCE composite electrode.
Placing BP GCE composite electrode in N2Saturated solution containing 25mmol/L CuCl20.25% (w/v) Chit/HAc solution, electrochemical deposition of CuNPs on the BP GCE surface by potentiostatic method, deposition potential: 0.4V, deposition time 480s, N2Naturally drying in the atmosphere.
And dripping 1 mu L of Nafion solution (0.5 wt%) on the surface of the electrode, and naturally drying in a glove box to obtain the functionalized black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE-constant potential deposition. Wherein the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is 15.89: 25: 0.036.
the functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in the embodiment 1 of the invention, the composite electrode (CuNPs-Chit GCE) obtained in the comparative example 1 and the composite electrode (BP GCE) obtained in the comparative example 2 are used as working electrodes, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, and the counter electrode is placed in 100mmol/L PBS phosphate buffer solution with pH of 7.0 to form a three-electrode system. And performing cyclic voltammetry scanning within the range of-0.8 to 0.3V, wherein the scanning speed is 20 mV/s.
FIG. 1 is a cyclic voltammogram scan of the functionalized black phosphorus-based enzyme-free sensors (CuNPs-Chit-BP GCE), the composite electrode (CuNPs-Chit GCE) and the composite electrode (BP GCE) obtained in example 1, comparative example 1 and comparative example 2 of the present invention.
As can be seen from fig. 1, the composite electrode BP-GCE obtained in comparative example 2 exhibited only non-faradaic characteristics under the test conditions. The composite electrode CuNPs-Chit GCE obtained in comparative example 1 presents two reduction peaks at-0.19V and-0.25V, corresponding to the reduction of Cu (II) → Cu (I) and Cu (I) → Cu (0). An oxidation peak appears at-0.05V, corresponding to the oxidation of Cu (0) → Cu (I)/Cu (II). The functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in example 1 has the advantages that the redox current of CuNPs is remarkably increased and the redox peak shape is better due to the introduction of the high-conductivity black phosphorus BP. An oxidation peak of Cu (0) → Cu (I)/Cu (II) was observed at 0.1V, and a reduction peak of Cu (II) → Cu (I) and Cu (I) → Cu (0) with more symmetrical peak shapes was observed at-0.22V and-0.35V. This indicates that the introduction of two-dimensional BP greatly promotes the electron transport efficiency of CuNPs on the surface of the modified electrode.
FIG. 2 is a cyclic voltammogram of the functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in example 2 of the present invention in the above three-electrode system at different pH values in 100mmol/L PBS phosphate buffer solution, wherein the pH values are 2.5,4.0,7,8.5, and 10.
As can be seen from fig. 2, the functionalized black phosphorus-based enzyme-free sensor CuNPs-chi-BP GCE obtained in example 2 can exhibit the characteristic redox behavior of CuNPs in a relatively wide pH range, i.e., pH 2.5-10. In a 100mmol/L PBS phosphate buffer solution with the pH value of 7, the CuNPs-Chit-BP GCE modified electrode has the best electron transfer capability, and two characteristic reduction peak peaks of the CuNPs are complete and symmetrical.
FIG. 3 is a cyclic voltammogram of the functionalized black phosphorus-based enzyme-free sensor obtained in example 3 of the present invention (CuNPs-Chit-BP GCE-cyclic voltammogram) and the functionalized black phosphorus-based enzyme-free sensor obtained in comparative example 5 (CuNPs-Chit-BP GCE-constant potential deposition) in 100mmol/L PBS phosphate buffer solution at pH 7.0.
As can be seen from FIG. 3, the oxidation peak current of the functionalized black phosphorus-based enzyme-free sensor obtained by the potentiostatic deposition method of comparative example 5 is slightly higher than that of the functionalized black phosphorus-based enzyme-free sensor obtained by the cyclic voltammetry method of example 3, but the reduction peak current is significantly lower than that of example 3, and only Cu (II) → Cu (I) has one reduction peak. In addition, the current response of the modified electrode obtained by the potentiostatic deposition method in comparative example 5 is continuously reduced along with the increase of the number of scanning cycles when the cyclic voltammetry scanning is carried out, the time required for current stabilization is long, and the electrode stability is obviously lower than that of the modified electrode obtained by the cyclic voltammetry method in example 3.
FIG. 4 shows a functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in example 2 of the present invention and a composite electrode (CuNPs-Chit GCE) obtained in comparative example 3, the composite electrode (BP GCE) obtained in comparative example 4 is against H2O2And (5) testing the performance of reduction. The functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in example 2 of the invention, the composite electrode (CuNPs-Chit GCE) obtained in comparative example 3 and the composite electrode (BP GCE) obtained in comparative example 4 are used as working electrodes, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrodeAnd placing the solution in 100mmol/L PBS phosphate buffer solution with pH value of 7.0 to form a three-electrode system. 2mM H was added2O2Separately test for addition of H2O2And testing the catalytic performance by cyclic voltammetry scanning on front and back cyclic voltammograms (the scanning range is-0.8-0.3V, and the scanning speed is 20 mV/s).
As can be seen from FIG. 4, 2mM H was added2O2Thereafter, the oxidation peak of the functionalized black phosphorus-based non-enzyme sensor (CuNPs-Chit-BP GCE) obtained in example 2 is significantly reduced, the reduction peak of Cu (I) → Cu (0) is nearly disappeared, and instead a new reduction peak appears at-0.55V, and the peak current of the reduction peak is sharply increased. Comparative example 4 composite electrode (BPGCE) pair H2O2The reduction has no catalytic effect. Comparative example 3 composite electrode (CuNPs-ChitGCE) pair H2O2The catalytic action of the reduction is obviously smaller than that of the functionalized black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE obtained in the embodiment 3. This indicates H2O2Electrochemical reduction is carried out under the catalytic action of a functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) which is used for H2O2Has high electrocatalytic activity.
FIG. 5 shows the functionalized black phosphorus-based enzyme-free sensor (CuNPs-Chit-BP GCE) obtained in example 1 of the present invention at different low concentrations of H2O2Ampere-time curve in solution. It was found that H appears at-0.55V2O2The magnitude of the catalytic reduction peak, the magnitude of the current of the peak and H2O2The concentration is in a linear relation, and the linear range is 1.0 × 10-5-9.50×10-4mol/L, correlation coefficient 0.9991, signal-to-noise ratio (S/N) equal to 3, calculated to a limit of 0.722. mu. mol/L for hydrogen peroxide detection.
The black phosphorus-based enzyme-free electrochemical sensor (CuNPs-Chit-BP GCE) prepared in example 2 was used for H2O2Catalysis, and the appearance of H at-0.54V is found2O2The magnitude of the catalytic reduction peak, the magnitude of the current of the peak and H2O2The concentration is in a linear relation, and the linear range is 0.99 × 10-5-9.50×10-4mol/L, correlation coefficient of 0.9990, and signal-to-noise ratio (S/N) of 3, calculatingThe limit of detection of hydrogen peroxide was 0.720. mu. mol/L.
The black phosphorus-based enzyme-free electrochemical sensor (CuNPs-Chit-BP GCE) prepared in example 3 was used for H2O2Catalysis, and the appearance of H at-0.55V2O2The magnitude of the catalytic reduction peak, the magnitude of the current of the peak and H2O2The concentration is in a linear relation, and the linear range is 0.98 × 10-5-9.50×10-4And when the mol/L, the correlation coefficient is 0.9993 and the signal-to-noise ratio (S/N) is equal to 3, calculating that the detection limit of the hydrogen peroxide is 0.723 mu mol/L.
FIG. 6 shows a pair of H-H composite electrodes (CuNPs-Chit-BP GCE) obtained in example 1 and a pair of H-H composite electrodes (BP GCE) obtained in comparative example 12O2And (5) testing the performance of reduction. The comparison result is consistent with the analysis of FIG. 4.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a functionalized black phosphorus-based enzyme-free sensor is characterized by comprising the following steps:
(1) the black phosphorus nanometer suspension is dripped and coated on the surface of a glassy carbon electrode GCE, and is put in nitrogen N2Drying in the air under the atmosphere to obtain a BP GCE modified electrode;
(2) depositing copper nanoparticles on the surface of a BP GCE modified electrode, and then airing in nitrogen;
(3) and dripping the Nafion solution on the surface of the electrode, and airing in nitrogen to obtain the functional black phosphorus-based enzyme-free sensor CuNPs-Chit-BP GCE.
2. The method for preparing the functionalized black phosphorus-based enzyme-free sensor according to claim 1, wherein the step (2) is specifically;
(2-1) adding CuCl2Dissolving in chitosan/acetic acid solution to form copper nanoparticle dispersion liquid;
and (2-2) placing the BP GCE modified electrode in the copper nanoparticle dispersion liquid, electrochemically depositing the copper nanoparticles on the surface of the BP GCE by using cyclic voltammetry, and then naturally airing.
3. The method as claimed in claim 1, wherein the mass ratio of the copper nanoparticles to the chitosan to the black phosphorus is (6.36-19.06): (10-30): (0.018-0.042).
4. The method for preparing the functionalized black phosphorus-based enzyme-free sensor according to claim 1, wherein the volume ratio of the black phosphorus nanosuspension to the Nafion solution is (3-6): 1.
5. The method as claimed in claim 1, wherein the concentration of the black phosphorus nanosuspension is 3-7mg/mL, and the concentration of the Nafion solution is 0.1-1 wt%.
6. The method as claimed in claim 2, wherein the concentration of the chitosan/acetic acid solution is 0.1-0.3 g/mL.
7. The method as claimed in claim 2, wherein the copper nanoparticle dispersion liquid contains CuCl2The concentration of (A) is 10-30 mmol/L.
8. The method as claimed in claim 2, wherein during electrochemical deposition, the voltage of electrochemical window is-0.8-0.3V, and the scan rate is 50 mV/s.
9. A functionalized black phosphorus-based enzyme-free sensor prepared according to the method of any one of claims 1-8.
10. Use of the functionalized black phosphorus-based enzyme-free sensor of claim 9 in the application of H2O2Enzyme-free electrochemical detection of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010387758.0A CN111707718B (en) | 2020-05-09 | 2020-05-09 | Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010387758.0A CN111707718B (en) | 2020-05-09 | 2020-05-09 | Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111707718A true CN111707718A (en) | 2020-09-25 |
| CN111707718B CN111707718B (en) | 2023-04-28 |
Family
ID=72537186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010387758.0A Active CN111707718B (en) | 2020-05-09 | 2020-05-09 | Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111707718B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116593557A (en) * | 2023-05-17 | 2023-08-15 | 海南师范大学 | Molybdenum disulfide/black phosphazene composite material, electrochemical sensor prepared from molybdenum disulfide/black phosphazene composite material and application of electrochemical sensor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106377770A (en) * | 2016-09-27 | 2017-02-08 | 中南大学 | Nanocomposite of black phosphorus nanosheet/copper sulfide nanoparticles as well as preparation method and application thereof |
| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
| CN107462619A (en) * | 2017-07-25 | 2017-12-12 | 海南师范大学 | A kind of preparation of the protein electrochemistry senser element based on black phosphorus modified electrode and electro-catalysis application |
| CN108333238A (en) * | 2018-01-16 | 2018-07-27 | 上海应用技术大学 | It is a kind of to be used to detect black phosphorus base modified electrode of hydrogen peroxide and preparation method thereof |
| CN108686685A (en) * | 2018-05-09 | 2018-10-23 | 南京邮电大学 | A kind of copper nano particles/black phosphorus nanosheet composite material and the preparation method and application thereof |
| CN109142487A (en) * | 2018-09-07 | 2019-01-04 | 上海应用技术大学 | A kind of functionalization black phosphorus base modified electrode and preparation method thereof for detecting sodium nitrite |
-
2020
- 2020-05-09 CN CN202010387758.0A patent/CN111707718B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106377770A (en) * | 2016-09-27 | 2017-02-08 | 中南大学 | Nanocomposite of black phosphorus nanosheet/copper sulfide nanoparticles as well as preparation method and application thereof |
| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
| CN107462619A (en) * | 2017-07-25 | 2017-12-12 | 海南师范大学 | A kind of preparation of the protein electrochemistry senser element based on black phosphorus modified electrode and electro-catalysis application |
| CN108333238A (en) * | 2018-01-16 | 2018-07-27 | 上海应用技术大学 | It is a kind of to be used to detect black phosphorus base modified electrode of hydrogen peroxide and preparation method thereof |
| CN108686685A (en) * | 2018-05-09 | 2018-10-23 | 南京邮电大学 | A kind of copper nano particles/black phosphorus nanosheet composite material and the preparation method and application thereof |
| CN109142487A (en) * | 2018-09-07 | 2019-01-04 | 上海应用技术大学 | A kind of functionalization black phosphorus base modified electrode and preparation method thereof for detecting sodium nitrite |
Non-Patent Citations (3)
| Title |
|---|
| SHANLI YANG 等: "Fabrication of nano-copper/carbon nanotubes/chitosan film by one-step electrodeposition and its sensitive determination of nitrite", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 王莹: "纳米材料修饰电极及其在葡萄糖生物传感器中的应用研究", 《中国优秀硕博论文全文数据库》 * |
| 郭伟兰: "纳米结构的黑磷传感性能研究", 《中国优秀硕博论文全文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116593557A (en) * | 2023-05-17 | 2023-08-15 | 海南师范大学 | Molybdenum disulfide/black phosphazene composite material, electrochemical sensor prepared from molybdenum disulfide/black phosphazene composite material and application of electrochemical sensor |
| CN116593557B (en) * | 2023-05-17 | 2024-01-23 | 海南师范大学 | Electrochemical sensor prepared from molybdenum disulfide @ black phosphazene composite material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111707718B (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hira et al. | Ultrasensitive detection of hydrogen peroxide and dopamine using copolymer-grafted metal-organic framework based electrochemical sensor | |
| Zhang et al. | A novel glucose biosensor based on direct electrochemistry of glucose oxidase incorporated in biomediated gold nanoparticles–carbon nanotubes composite film | |
| Ragupathy et al. | Electrocatalytic oxidation and determination of ascorbic acid in the presence of dopamine at multiwalled carbon nanotube–silica network–gold nanoparticles based nanohybrid modified electrode | |
| Haghighi et al. | Electrochemical behavior and application of Prussian blue nanoparticle modified graphite electrode | |
| Kang et al. | Glucose biosensors based on platinum nanoparticles-deposited carbon nanotubes in sol–gel chitosan/silica hybrid | |
| Fang et al. | A non-enzymatic hydrogen peroxide sensor based on poly (vinyl alcohol)–multiwalled carbon nanotubes–platinum nanoparticles hybrids modified glassy carbon electrode | |
| Xiang et al. | Direct electrochemistry and enhanced electrocatalysis of horseradish peroxidase based on flowerlike ZnO–gold nanoparticle–Nafion nanocomposite | |
| Lu et al. | Carbon nanofiber-based composites for the construction of mediator-free biosensors | |
| Shahrokhian et al. | Application of thionine-nafion supported on multi-walled carbon nanotube for preparation of a modified electrode in simultaneous voltammetric detection of dopamine and ascorbic acid | |
| Jia et al. | Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in sol–gel-derived tin oxide/gelatin composite films | |
| Dung et al. | NiO-decorated single-walled carbon nanotubes for high-performance nonenzymatic glucose sensing | |
| Cui et al. | Direct electrochemistry and electrocatalysis of glucose oxidase on three-dimensional interpenetrating, porous graphene modified electrode | |
| Liu et al. | Electrochemical characteristics of glucose oxidase adsorbed at carbon nanotubes modified electrode with ionic liquid as binder | |
| Yu et al. | Electrocatalytical oxidation of nitrite and its determination based on Au@ Fe3O4 nanoparticles | |
| Yuan et al. | Polyethylenimine-bridged graphene oxide–gold film on glassy carbon electrode and its electrocatalytic activity toward nitrite and hydrogen peroxide | |
| Ma et al. | Amperometric hydrogen peroxide biosensor based on the immobilization of HRP on DNA–silver nanohybrids and PDDA-protected gold nanoparticles | |
| Che et al. | Amperometric glucose biosensor based on Prussian blue–multiwall carbon nanotubes composite and hollow PtCo nanochains | |
| Salimi et al. | Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor | |
| Chen et al. | A novel biosensor based on electro-co-deposition of sodium alginate-Fe 3 O 4-graphene composite on the carbon ionic liquid electrode for the direct electrochemistry and electrocatalysis of myoglobin | |
| CN107328839A (en) | Preparation and its electrocatalysis characteristic research based on Nafion/ hemoglobins/nitrogen-doped graphene quanta dot modified electrode | |
| Wang et al. | A novel nitrite biosensor based on direct electron transfer of hemoglobin immobilized on a graphene oxide/Au nanoparticles/multiwalled carbon nanotubes nanocomposite film | |
| Ozdokur et al. | Pyranose oxidase and Pt–MnOx bionanocomposite electrode bridged by ionic liquid for biosensing applications | |
| Chekin et al. | The porous chitosan–sodium dodecyl sulfate–carbon nanotube nanocomposite: direct electrochemistry and electrocatalysis of hemoglobin | |
| Hamidi et al. | Fabrication of bulk-modified carbon paste electrode containing α-PW12O403− polyanion supported on modified silica gel: Preparation, electrochemistry and electrocatalysis | |
| Shi et al. | Application of titanium dioxide nanowires for the direct electrochemistry of hemoglobin and electrocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |