CN113092555A - Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof - Google Patents
Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof Download PDFInfo
- Publication number
- CN113092555A CN113092555A CN202110343604.6A CN202110343604A CN113092555A CN 113092555 A CN113092555 A CN 113092555A CN 202110343604 A CN202110343604 A CN 202110343604A CN 113092555 A CN113092555 A CN 113092555A
- Authority
- CN
- China
- Prior art keywords
- boron
- doped graphene
- glassy carbon
- palladium nano
- carbon electrode
- 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.)
- Pending
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
Abstract
The invention discloses a preparation method of a boron-doped graphene/palladium nano electrochemical sensor, which is implemented according to the following steps: step 1, preparing a boron-doped graphene/palladium nano material: step 2, preparation of a modification liquid: ultrasonically dispersing the solid prepared in the step 1 in deionized water to obtain a modification liquid; step 3, processing the glassy carbon electrode: taking a glassy carbon electrode, polishing the surface of the glassy carbon electrode, cleaning the glassy carbon electrode, and drying for later use; step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode: and (3) uniformly dripping the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the glass carbon electrode. The method is simple and easy to operate. Also provides a preparation method and application of the boron-doped graphene/palladium nano electrochemical sensor.
Description
Technical Field
The invention belongs to the technical field of electrochemical analysis and detection, and particularly relates to a boron-doped graphene/palladium nano electrochemical sensor, and a preparation method and application of the boron-doped graphene/palladium nano electrochemical sensor.
Background
As a strong oxidant which can be mixed and dissolved with water in any proportion, hydrogen peroxide (commonly called hydrogen peroxide) is widely used in various aspects of environmental disinfection, food disinfection, industrial bleaching and the like. In addition, hydrogen peroxide is one of the important active oxygen species in organisms, and plays an important role in a series of biological processes (such as immune regulation, apoptosis and the like). Abnormal hydrogen peroxide concentrations can affect the structure and function of nucleic acids, protein destruction or cause apoptosis of cells, which in turn can lead to serious diseases such as cancer, neurodegenerative diseases, cardiovascular diseases, and the like. However, the instability of the properties increases the difficulty of detection due to the easy decomposition of hydrogen peroxide. Therefore, it is very significant to develop a sensor capable of detecting the hydrogen peroxide content in various environments, medicines and cells with high sensitivity and convenience.
In order to improve the detection sensitivity of hydrogen peroxide, researchers have utilized various carbon materials, particularly those having sp2Carbon materials of hybrid carbon atom structure, such as graphene, have excellent thermal and electrical conductivity and strong mechanical properties. The B-doped graphene has better electrocatalysis property due to the fact that the electron transmission performance is improved, and on the other hand, the graphene has lower oxidation-reduction potential, so that metal ions can be directly reduced into metal nano particles under the condition that no protective agent or reducing agent is added, the method for preparing the metal nano catalyst is simple and convenient, and the catalytic activity of the metal nano particles can be guaranteed to the greatest extent. The doped graphene with the large pi conjugated structure can have stronger interaction with the metal nanoparticles, so that the agglomeration of the metal nanoparticles can be prevented, binding sites are provided for the metal nanoparticles without adding any surface stabilizer, the dispersity and the catalytic activity of the metal nano-catalyst are improved, and the improvement on the dispersity and the catalytic activity of the metal nano-catalyst is realizedHigh analysis performance.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-doped graphene/palladium nano electrochemical sensor, which avoids the defect that a surfactant involved in the preparation process of the existing chemical reduction method occupies active sites of metal nano particles, enhances the active sites of the metal nano particles to a certain extent, improves the catalytic performance of a catalyst, and is simple in preparation method and easy to operate.
The second purpose of the invention is to provide a boron-doped graphene/palladium nano electrochemical sensor, which can increase the catalytic specific surface area and the active sites, thereby improving the detection sensitivity.
The third purpose of the invention is to provide the application of the boron-doped graphene/palladium nano electrochemical sensor.
The first technical scheme adopted by the invention is that the preparation method of the boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing to obtain a mixed solution, placing the mixed solution in an open ice bath and under a stirring condition for reaction, performing centrifugal treatment after the reaction, and washing and drying the centrifuged solid;
step 2, preparation of a modification liquid:
ultrasonically dispersing the solid prepared in the step 1 in deionized water to obtain a modification liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, polishing the surface of the glassy carbon electrode, cleaning the glassy carbon electrode, and drying for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the glass carbon electrode.
The present invention is also characterized in that,
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 2-4 mg/mL-1(ii) a Introducing nitrogen for 10-30 min; the concentration of the potassium chloropalladate solution is 10-50 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1.
in the step 1, the mixed solution is placed in an open ice bath for reaction for 30-40 min; the centrifugal rotating speed is 11000-14000 rpm; washing the centrifuged solid by deionized water for 3-6 times; the vacuum drying temperature is 40-60 ℃, and the drying time is 6-12 h.
In the step 2, the prepared modifying solution has the concentration of 2-4 mg/mL-1。
And 3, detecting the peak potential difference value of the cyclic voltammetry curve of the polished glassy carbon electrode surface by an electrochemical workstation to be 70-90 mV.
In step 4, the amount of the modification liquid is 2-6 μ L.
The second technical scheme adopted by the invention is that the boron-doped graphene/palladium nano electrochemical sensor is prepared by adopting the method.
The third technical scheme adopted by the invention is that the boron-doped graphene/palladium nano electrochemical sensor prepared by the method is applied to detection of hydrogen peroxide
The invention has the beneficial effects that:
(1) the method avoids the defects of few active sites and low catalytic performance of the catalytic material prepared by the existing chemical reduction method; the device is only an electrochemical workstation and a magnetic stirrer, is simple and convenient, can realize detection only by adopting an I-t scanning technology, and has the advantages of simple method, easy operation and higher result repeatability.
(2) The electrochemical sensor is boron-doped graphene/palladium nano-particles prepared based on electroless deposition, and the material can increase the catalytic specific surface area and active sites, so that the detection sensitivity is improved.
Drawings
Fig. 1 is a transmission electron microscope image of the boron-doped graphene/palladium nano-catalyst prepared in step 1 in the method of the present invention;
FIG. 2 is a cyclic voltammogram of a boron-doped graphene/palladium nano glassy carbon modified electrode, a boron-doped graphene glassy carbon modified electrode, and a bare glassy carbon electrode of the present invention in a 1mM hydrogen peroxide phosphate buffer solution;
FIG. 3 is an I-t response curve of boron-doped graphene/palladium nano-modified glassy carbon electrode prepared by the present invention placed in hydrogen peroxide phosphate buffer solutions of different concentrations;
fig. 4 is a graph of the current versus hydrogen peroxide concentration fitted from fig. 3.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a boron-doped graphene/palladium nano electrochemical sensor, which is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 2-4 mg/mL-1(ii) a Introducing nitrogen for 10-30 min; the concentration of the potassium chloropalladate solution is 10-50 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; placing the mixed solution in an open ice bath for reaction for 30-40 min; the centrifugal rotating speed is 11000-14000 rpm; washing the centrifuged solid by deionized water for 3-6 times; the vacuum drying temperature is 40-60 ℃, and the drying time is 12-24 h.
Step 2, preparation of a modification liquid:
dispersing 1-2 mg of the solid prepared in the step 1 in 500 mu L of deionized water, and performing ultrasonic treatment for 20-30 min to obtain 2-4 mg of mL-1A modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 70-90 mV; then fully washing with deionized water, respectively carrying out ultrasonic treatment in ethanol and deionized water for about 1-3 min, and drying with nitrogen for later use;
wherein, whether the surface of the polished glassy carbon electrode meets the requirement or not is detected, and the polished glassy carbon electrode can be placed at 1-5 mM K3Fe(CN)6In the method, a potential window is-0.2-0.6V, and is characterized by scanning through a cyclic voltammetry (the scanning speed is 50-100 mV/s), the peak potential difference of the cyclic voltammetry is 70-90mV, which meets the requirement, the cyclic voltammetry is fully rinsed with deionized water and dried at room temperature, and the treated bare glassy carbon electrode is used for a subsequent modified electrode for later use.
Step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 2-6 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
The invention also provides a boron-doped graphene/palladium nano electrochemical sensor prepared by the method.
The invention also provides application of the boron-doped graphene/palladium nano electrochemical sensor prepared by the method in detecting hydrogen peroxide, and the modified electrode serving as the sensor can be directly used for electrochemical determination of hydrogen peroxide, and the specific determination method comprises the following steps:
all electrochemical tests use a three-electrode system, namely a boron-doped graphene/palladium nano glassy carbon modified electrode is used as a working electrode, a reference electrode is Ag/AgCl (saturated KCl solution), and a platinum wire electrode is used as a counter electrode. The test work was done in an electrochemical cell at room temperature. And placing the boron-doped graphene/palladium nano glassy carbon modified electrode in a hydrogen peroxide phosphate buffer solution with the pH value of 7.4, and performing cyclic voltammetry scanning in a potential window of 0-1V to study the electrochemical behavior of hydrogen peroxide in the phosphate buffer solution on the surface of the modified electrode, including the position of a peak and the height of peak current.
As shown in fig. 3, at the working potential of 0.7V, the high concentration hydrogen peroxide solution was added to the phosphate solution with stirring by using a pipette at the same time intervals, and the I-t current value obtained at the workstation was increased stepwise for a short time after each addition of the high concentration hydrogen peroxide solution, resulting in a step response curve.
Fig. 3 is an I-t response curve of the boron-doped graphene modified glassy carbon electrode in hydrogen peroxide phosphate buffer solutions with different concentrations, as shown in fig. 3, the response current and the concentration present a good linear relationship within a concentration range of 2.5 μ M to 300 μ M, and the linear relationship between the current and the hydrogen peroxide concentration obtained by fitting in fig. 4 is I (μ a) ═ 0.087c (μ M) +1.39, so that the hydrogen peroxide concentration can be obtained by substituting the equation according to the I-t steady-state current value of the hydrogen peroxide solution to be measured.
Fig. 1 is a transmission electron microscope image of the boron-doped graphene/palladium nano-catalyst prepared in step 1 of the method of the present invention, and it can be seen from fig. 1 that the average diameter of the palladium nanoparticles is about 6.5nm, the distribution range is 5.2-7.8nm, and the dispersibility is good, which proves that the boron-doped graphene/palladium nano-catalyst with good dispersibility can still be prepared without adding a reducing agent and a protective agent additionally.
FIG. 2 is a cyclic voltammogram of a boron-doped graphene/palladium nano glassy carbon modified electrode, a boron-doped graphene glassy carbon modified electrode and a bare glassy carbon electrode in a 1mM hydrogen peroxide phosphate buffer solution, no obvious hydrogen peroxide oxidation peak is found in the corresponding cyclic voltammetry curve of the bare glassy carbon electrode, the boron-doped graphene/palladium nano glassy carbon modified electrode and the boron-doped graphene modified glassy carbon electrode respectively have oxidation peaks at 0.75V and 0.65V, the oxidation peak current of the boron-doped graphene/palladium nano material is high, so that the boron-doped graphene/palladium nano material has a good electrocatalytic effect on hydrogen peroxide, and the problem that the catalytic activity is reduced due to the defect that the surfactant occupies an active site of a metal nano particle and is easy to agglomerate is solved.
Example 1
A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 2 mg/mL-1(ii) a Introducing nitrogen for 10 min; the concentration of the potassium chloropalladate solution is 10 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; the mixed solution is placed in an open ice bath for reaction for 30 min; the rotating speed of the centrifugation is 11000 rpm; washing the centrifuged solid with deionized water for 3 times; the vacuum drying temperature is 60 ℃, and the drying time is 12 h.
Step 2, preparation of a modification liquid:
ultrasonically dispersing the solid prepared in the step 1 in deionized water for 20min to obtain 2mg mL-1Modifying liquid, and carrying out ultrasonic treatment to obtain modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 70 mV; then use itAfter the ionized water is fully washed, respectively carrying out ultrasonic treatment in ethanol and deionized water for 1min, and drying by nitrogen for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 2 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
Example 2
A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 4 mg/mL-1(ii) a Introducing nitrogen for 30 min; the concentration of the potassium chloropalladate solution is 50 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; the mixed solution is placed in an open ice bath for reaction for 40 min; the rotation speed of the centrifuge is 14000 rpm; washing the centrifuged solid with deionized water for 6 times; the vacuum drying temperature is 40 ℃, and the drying time is 24 h.
Step 2, preparation of a modification liquid:
dispersing the solid prepared in the step 1 in deionized water, and performing ultrasonic treatment for 30min to obtain 4mg mL-1A modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 90 mV; then fully washing with deionized water, respectively performing ultrasonic treatment in ethanol and deionized water for 3min, and drying with nitrogen for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 6 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
Example 3
A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 3 mg/mL-1(ii) a Introducing nitrogen for 20 min; the concentration of the potassium chloropalladate solution is 40 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; the mixed solution is placed in an open ice bath for reaction for 35 min; the rotating speed of the centrifugation is 13000 rpm; washing the centrifuged solid with deionized water for 5 times; the vacuum drying temperature is 50 ℃, and the drying time is 18 h.
Step 2, preparation of a modification liquid:
dispersing the solid prepared in the step 1 in deionized water, and performing ultrasonic treatment for 25min to obtain 3mg mL-1A modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 80 mV; then fully washing with deionized water, respectively performing ultrasonic treatment in ethanol and deionized water for 2min, and drying with nitrogen for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 2-6 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
Example 4
A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 3 mg/mL-1(ii) a Introducing nitrogen for 25 min; the concentration of the potassium chloropalladate solution is 20 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; the mixed solution is placed in an open ice bath for reaction for 30 min; the rotation speed of the centrifuge is 14000 rpm; washing the centrifuged solid by deionized water for 3-6 times; the vacuum drying temperature is 55 ℃, and the drying time is 15 h.
Step 2, preparation of a modification liquid:
dispersing the solid prepared in the step 1 in deionized water, and performing ultrasonic treatment for 20min to obtain 4mg mL-1A modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 70 mV; then fully washing with deionized water, respectively performing ultrasonic treatment in ethanol and deionized water for 1min, and drying with nitrogen for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 2-6 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
Example 5
A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is implemented according to the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing the solution with the boron-doped graphene dispersion liquid to obtain a mixed solution, placing the mixed solution in an open ice bath and stirring for reaction, performing centrifugal treatment after the reaction, washing and drying the centrifuged solid to obtain a black solid, namely the corresponding boron-doped graphene/palladium nano catalyst;
in the step 1, the concentration of the boron-doped graphene dispersion liquid is 4 mg/mL-1(ii) a Introducing nitrogen for 10 min; the concentration of the potassium chloropalladate solution is 10 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1; the mixed solution is placed in an open ice bath for reaction for 40 min; the rotation speed of the centrifuge is 14000 rpm; washing with deionized waterCentrifuging the solid for 5 times; the vacuum drying temperature is 40 ℃, and the drying time is 24 h.
Step 2, preparation of a modification liquid:
dispersing the solid prepared in the step 1 in deionized water, and performing ultrasonic treatment for 20min to obtain 4mg mL-1A modifying liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, firstly, sequentially using 0.3 mu m and 0.05 mu m of Al on polishing cloth2O3Grinding the powder, and detecting the peak potential difference value of a cyclic voltammetry curve on the surface of the ground glassy carbon electrode by an electrochemical workstation to be 70-90 mV; then fully washing with deionized water, respectively performing ultrasonic treatment in ethanol and deionized water for 1min, and drying with nitrogen for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping 4 mu L of the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the boron-doped graphene/palladium nano glassy carbon modified electrode, namely the boron-doped graphene/palladium nano electrochemical sensor.
Claims (8)
1. A preparation method of a boron-doped graphene/palladium nano electrochemical sensor is characterized by comprising the following steps:
step 1, preparing a boron-doped graphene/palladium nano material:
placing the boron-doped graphene dispersion liquid in a round-bottom flask, introducing nitrogen, adding a potassium chloropalladate solution into the boron-doped graphene dispersion liquid, mixing to obtain a mixed solution, placing the mixed solution in an open ice bath and under a stirring condition for reaction, performing centrifugal treatment after the reaction, and washing and drying the centrifuged solid;
step 2, preparation of a modification liquid:
ultrasonically dispersing the solid prepared in the step 1 in deionized water to obtain a modification liquid;
step 3, processing the glassy carbon electrode:
taking a glassy carbon electrode, polishing the surface of the glassy carbon electrode, cleaning the glassy carbon electrode, and drying for later use;
step 4, preparing the boron-doped graphene/palladium nano glassy carbon modified electrode:
and (3) uniformly dripping the prepared modification liquid on the surface of the glassy carbon electrode treated in the step (3), quickly covering the beaker upside down on the glassy carbon electrode, and slowly volatilizing the solution on the surface of the beaker to be dry at room temperature to obtain the glass carbon electrode.
2. The method for preparing a boron-doped graphene/palladium nano electrochemical sensor according to claim 1, wherein in the step 1, the concentration of the boron-doped graphene dispersion liquid is 2-4 mg-mL-1(ii) a Introducing nitrogen for 10-30 min; the concentration of the potassium chloropalladate solution is 10-50 mM; the volume ratio of the boron-doped graphene dispersion liquid to the chloropalladate solution is 10: 1.
3. the preparation method of the boron-doped graphene/palladium nano electrochemical sensor according to claim 1, wherein in the step 1, the mixed solution is placed in an open ice bath for a reaction time of 30-40 min; the centrifugal rotating speed is 11000-14000 rpm; washing the centrifuged solid by deionized water for 3-6 times; the vacuum drying temperature is 40-60 ℃, and the drying time is 12-24 h.
4. The method for preparing a boron-doped graphene/palladium nano electrochemical sensor according to claim 1, wherein in the step 2, the concentration of the prepared modification solution is 2-4 mg-mL-1。
5. The method for preparing a boron-doped graphene/palladium nano electrochemical sensor according to claim 1, wherein in step 3, the peak potential difference of the cyclic voltammetry curve detected on the surface of the polished glassy carbon electrode through an electrochemical workstation is 70-90 mV.
6. The method for preparing a boron-doped graphene/palladium nano electrochemical sensor according to claim 1, wherein in the step 4, the amount of the modification solution is 2 to 6 μ L.
7. A boron-doped graphene/palladium nano electrochemical sensor is characterized by being prepared by the method of any one of claims 1 to 6.
8. The application of the boron-doped graphene/palladium nano electrochemical sensor prepared by the method according to any one of claims 1 to 6 in detection of hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110343604.6A CN113092555A (en) | 2021-03-30 | 2021-03-30 | Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110343604.6A CN113092555A (en) | 2021-03-30 | 2021-03-30 | Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113092555A true CN113092555A (en) | 2021-07-09 |
Family
ID=76671969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110343604.6A Pending CN113092555A (en) | 2021-03-30 | 2021-03-30 | Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113092555A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532292A (en) * | 2022-06-27 | 2022-12-30 | 山西大学 | Preparation and application of nitrogen-doped carbon-supported monatomic palladium catalyst |
| CN115646486A (en) * | 2022-11-10 | 2023-01-31 | 辽宁大学 | Graphene-supported palladium nanoenzyme as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105024086A (en) * | 2015-06-10 | 2015-11-04 | 南京理工大学 | Palladium/nitrogen-doped graphene composite electrode catalyst and preparation method thereof |
| CN105562057A (en) * | 2016-01-30 | 2016-05-11 | 镇江市高等专科学校 | Palladium nano-composite catalyst loaded by N-doped three-dimensional graphene and preparing method and application thereof |
| CN109856208A (en) * | 2019-03-07 | 2019-06-07 | 广西师范学院 | The method for detecting concentration of hydrogen peroxide in solution |
| CN110787827A (en) * | 2019-10-23 | 2020-02-14 | 华中科技大学 | Monoatomic catalyst, preparation method and application thereof |
-
2021
- 2021-03-30 CN CN202110343604.6A patent/CN113092555A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105024086A (en) * | 2015-06-10 | 2015-11-04 | 南京理工大学 | Palladium/nitrogen-doped graphene composite electrode catalyst and preparation method thereof |
| CN105562057A (en) * | 2016-01-30 | 2016-05-11 | 镇江市高等专科学校 | Palladium nano-composite catalyst loaded by N-doped three-dimensional graphene and preparing method and application thereof |
| CN109856208A (en) * | 2019-03-07 | 2019-06-07 | 广西师范学院 | The method for detecting concentration of hydrogen peroxide in solution |
| CN110787827A (en) * | 2019-10-23 | 2020-02-14 | 华中科技大学 | Monoatomic catalyst, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| GENG-HUANG WU ET AL.: "An electrochemical ascorbic acid sensor based on palladium nanoparticles supported on graphene oxide", 《ANALYTICA CHIMICA ACTA》 * |
| LING MA ET AL.: "Hydrogen adsorption and storage on palladium-decorated grapheme with boron dopants and vacancy defects: A first-principles study", 《PHYSICAE》 * |
| WANYI XUE ET AL.: "Enzymeless electrochemical detection of hydrogen peroxide at Pd nanoparticles/porous grapheme", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532292A (en) * | 2022-06-27 | 2022-12-30 | 山西大学 | Preparation and application of nitrogen-doped carbon-supported monatomic palladium catalyst |
| CN115532292B (en) * | 2022-06-27 | 2024-03-12 | 山西大学 | Preparation and application of nitrogen-doped carbon-supported monoatomic palladium catalyst |
| CN115646486A (en) * | 2022-11-10 | 2023-01-31 | 辽宁大学 | Graphene-supported palladium nanoenzyme as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Preparation of highly sensitive Pt nanoparticles-carbon quantum dots/ionic liquid functionalized graphene oxide nanocomposites and application for H2O2 detection | |
| Li et al. | Electrochemical investigation of tryptophan at gold nanoparticles modified electrode in the presence of sodium dodecylbenzene sulfonate | |
| Ekram et al. | Electrochemistry of glucose at gold nanoparticles modified graphite/SrPdO3 electrode–towards a novel non-enzymatic glucose sensor | |
| Yang et al. | Hydrogen peroxide and glucose biosensor based on silver nanowires synthesized by polyol process | |
| CN113092555A (en) | Boron-doped graphene/palladium nano electrochemical sensor and preparation method and application thereof | |
| Rahsepar et al. | A new enzyme-free biosensor based on nitrogen-doped graphene with high sensing performance for electrochemical detection of glucose at biological pH value | |
| Wang et al. | Ultrathin two-dimension metal-organic framework nanosheets/multi-walled carbon nanotube composite films for the electrochemical detection of H2O2 | |
| Zhou et al. | An electrochemical sensor for the detection of p-nitrophenol based on a cyclodextrin-decorated gold nanoparticle–mesoporous carbon hybrid | |
| Yang et al. | Facile synthesis of silver nanoparticle-decorated graphene oxide nanocomposites and their application for electrochemical sensing | |
| Sahin et al. | Facile and rapid synthesis of microwave assisted Pd nanoparticles as non-enzymatic hydrogen peroxide sensor | |
| Ni et al. | Facile synthesis of Prussian blue@ gold nanocomposite for nonenzymatic detection of hydrogen peroxide | |
| Li et al. | Facile synthesis of NiO/CuO/reduced graphene oxide nanocomposites for use in enzyme-free glucose sensing | |
| Li et al. | High catalytic performance non-enzymatic H2O2 sensor based on Cu2O@ Cu9S5 yolk-shell nanospheres | |
| Liu et al. | Au nanoparticles attached Ag@ C core-shell nanocomposites for highly selective electrochemical detection of dopamine | |
| GB2603835A (en) | Enzyme-free glucose sensor, manufacturing method for same, and uses thereof | |
| CN104535633A (en) | Preparation method for PtAuNPs-CTAB-GR modified glassy carbon electrode | |
| Huang et al. | Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes | |
| Lv et al. | Cu2+ modified Zr-based metal organic framework-CTAB-graphene for sensitive electrochemical detection of sunset yellow | |
| Ouyang et al. | ZIFs derived polyhedron with cobalt oxide nanoparticles as novel nanozyme for the biomimetic catalytic oxidation of glucose and non-enzymatic sensor | |
| Kim et al. | Highly dispersive gold nanoparticles on carbon black for oxygen and carbon dioxide reduction | |
| CN114563454A (en) | Based on Au/Ti3C2TxDopamine electrochemical sensor for modifying glassy carbon working electrode and preparation method thereof | |
| Sakthinathan et al. | Multiwalled carbon nanotube supported Schiff base copper complex inorganic nanocomposite for enhanced electrochemical detection of dopamine | |
| Dong et al. | Amperometric Biosensor for Detection of Phenolic Compounds Based on Tyrosinase, N‐Acetyl‐L‐cysteine‐capped Gold Nanoparticles and Chitosan Nanocomposite | |
| Sun et al. | Electrochemical dopamine detection using electrochemically reduced graphene oxide/silver/metal organic framework composites | |
| Ren et al. | A novel superoxide anion radical nonenzymatic electrochemical sensor based on PtRuCu ternary alloy nanoparticles/graphene composite modified electrode |
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 |