CN114527185B - Copper-silver-loaded few-layer graphene-based composite material and preparation method and application thereof - Google Patents
Copper-silver-loaded few-layer graphene-based composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000010949 copper Substances 0.000 claims abstract description 43
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- 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
Abstract
The invention relates to a copper-silver-loaded few-layer graphene-based composite material, and a preparation method and application thereof, and discloses a preparation method of the copper-silver-loaded few-layer graphene-based composite material, comprising the following steps of: s1: graphite powder, absolute ethyl alcohol, cyclohexane, anhydrous copper sulfate, tween 80, span 80, PVP and deionized water are taken as raw materials, and uniform and stable graphite water-in-oil emulsion is prepared by vortex mixing; s2: freezing the graphite water-in-oil emulsion prepared in the step S1 for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours; s3: adding sodium borohydride into the graphite water-in-oil emulsion treated in the step S2, then freezing for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours; s4: adding 2% PVP aqueous solution containing silver nitrate into the graphite water-in-oil emulsion treated in the step S3, then freezing for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours to obtain the few-layer graphene-based composite material Cu x O/Ag@FLG. The preparation method has simple synthesis process and high yield. Cu adopting the few-layer graphene-based composite material x The hydrogen peroxide sensor prepared from O/Ag@FLG has excellent sensing performance.
Description
Technical Field
The invention belongs to the field of hydrogen peroxide detection, and particularly relates to a copper-silver-loaded few-layer graphene-based composite material, a preparation method thereof and application thereof in hydrogen peroxide detection.
Background
Hydrogen peroxide is one of the byproducts of many classical enzymatic reactions, such as glucose oxidation, uric acid oxidation, oxalic acid oxidation, amino acid oxidation, glutamic acid, lysine oxidation, etc., which are of concern to human health. Therefore, the human body related physiological index can be monitored in a certain sense by detecting the content of hydrogen peroxide. At the same time, the hydrogen peroxide content in the body is also often considered as an important indicator of related diseases such as parkinson's disease, cancer, stroke, arteriosclerosis.
Hydrogen peroxide is an important signaling molecule (ROS), which is often considered more suitable for intracellular signaling due to its ability to penetrate the cell membrane directly, and its longer life cycle than other ROS molecules, and plays an important role in the regulation of various biological processes including intracellular proliferation, lesions, apoptosis, immune cell activation, vascular remodeling, stomatal closure, etc.
The hydrogen peroxide has strong oxidizing property, and can consume antioxidant substances in the body after being taken, so that the aging process of the human body is accelerated, and the resistance is reduced; the hydrogen peroxide in the body is excessive, a large amount of hydroxyl free radicals can be generated, the hydroxyl free radicals participate in electron transfer and hydroxylation reactions in the biochemical process, cells are damaged, gene mutation is induced, various diseases are caused, even cancer of human cells is caused, and the hydroxyl free radicals are the most toxic free radicals. The world health organization international cancer research organization published a list of carcinogens on 10 and 27 days 2017, with hydrogen peroxide appearing in the 3-class carcinogen list.
H 2 O 2 Is also widely used as a chemical raw material for chemicals and foods as an oxidizing agent, a bleaching agent or a bactericideAnd food medical industry and environmental monitoring. Thus H 2 O 2 Analytical detection of (c) has become an important way to monitor human health and control the quality of industrial products and processes related to our daily lives.
Currently applied to H 2 O 2 The detection method comprises the following steps: titration, spectroscopy, chromatography, chemiluminescence and electrochemistry. The electrochemical method has the advantages of simple operation, quick response, high cost efficiency, high selectivity sensitivity and the like.
First generation electrochemical H 2 O 2 The detector relies on the reaction of an enzyme with hydrogen peroxide. This enzyme-based technology is now mature and is now capable of providing high sensitivity, high selectivity and low background noise. Nevertheless, the complex process of immobilizing enzymes on electrodes, stringent conditions require maintenance of enzyme activity, and the long-term stability and reproducibility are inadequate to limit the large-scale application of this technology. More importantly, almost all enzymes are proteins that inhibit the electrochemical reaction of the electrode surface during electron transfer. Thus faster electron transport and higher non-enzymatically active electrochemical H 2 O 2 Detection has been developed to eliminate these drawbacks. For preparing enzyme-free H 2 O 2 Nanoparticles of the sensor include gold nanoparticles, silver nanoparticles, platinum nanoparticles, and palladium nanoparticles. The high cost, poor tolerance to toxic reaction intermediates and rare storage of noble metals greatly limit their commercial use. Therefore, there is a need to develop sensitive, reliable, low cost electrochemical sensing materials for hydrogen peroxide detection. To date, co 3 O 4 、Fe 3 O 4 、Cu 2 O、MnO 2 Has been successfully applied to H 2 O 2 Is a chemical detection of (a). Wherein, one-component Cu 2 The inherent characteristics of low sensitivity, narrow linear detection range and the like of the O sensor prevent the practical application of the O sensor. And the silver nano particles are used as noble metals, have large specific surface area, good stability and good biocompatibility, and have excellent conductivity and electrocatalytic activity. Thus Cu is to 2 O and Ag are compounded, so that the electrocatalytic performance is improved. However, metal composite nanoparticles are extremely easyOxidized and easily agglomerated due to van der Waals forces existing between the nanoparticles, limiting their electrocatalytic capacity. To improve this problem, it is necessary to find a suitable carrier to disperse the metal composite nanoparticles uniformly. Substrates that have been widely studied at present are typically carbon materials, such as ordered mesoporous carbon, carbon nanotubes, carbon nanofibers and graphene. The discovery of graphene brings new opportunities and challenges to the development and application of carbon materials in the catalysis field, wherein in the graphene material, carbon atoms are in sp 2 The hybrid form exists, so that the structure and chemical properties of the graphene are very stable, and meanwhile, the graphene has a large specific surface area and high electron transfer capacity due to the fact that the graphene has high specific surface area, good thermal stability, good conductivity and good stability, and the defect on the surface of the graphene can anchor metal nano particles, so that the graphene is an excellent carrier material. At present, most of related researches adopt graphene oxide prepared by a Hummers method as a carbon substrate to prepare a metal nanoparticle composite material, the preparation process is complex, and the distribution position and the size of metal particles are not uniform, so that the sensing performance of the composite material is affected.
Disclosure of Invention
The invention aims at solving the technical problems, and provides a preparation method of a copper-silver-loaded few-layer graphene-based composite material with simple process and high yield.
In order to achieve the above object, the present invention provides a method for preparing a copper-silver loaded few-layer graphene-based composite material, comprising the following steps:
s1: graphite powder, absolute ethyl alcohol, cyclohexane, anhydrous copper sulfate, tween 80, span 80, PVP and deionized water are taken as raw materials, and uniform and stable graphite water-in-oil emulsion is prepared by vortex mixing;
s2: freezing the graphite water-in-oil emulsion prepared in the step S1 for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours;
s3: adding sodium borohydride into the graphite water-in-oil emulsion treated in the step S2, then freezing for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours;
s4: adding 2% PVP containing silver nitrate into the graphite water-in-oil emulsion treated in the step S3Freezing the aqueous solution for 2 hours at low temperature, and performing ultrasonic treatment for 2 hours to obtain the few-layer graphene-based composite material Cu x O/Ag@FLG。
Compared with the prior art, the invention prepares the raw materials into the uniform and stable graphite water-in-oil emulsion and then directly adopts a freeze ultrasonic circulation method to synthesize the few-layer graphene-based composite material Cu by one-step method x O/Ag@FLG has simple process and yield higher than 90%. Synthetic few-layer graphene-based composite Cu x O/Ag@FLG has a certain reduction effect on hydrogen peroxide, and can be developed into an enzyme-free hydrogen peroxide sensor. Through comparison test, the few-layer graphene-based composite material Cu is adopted x Compared with the existing hydrogen peroxide sensor, the hydrogen peroxide sensor prepared by O/Ag@FLG has more positive initial potential, larger reduction current, higher sensitivity under smaller voltage, better catalytic performance and better sensing performance.
Preferably, the dosage ratio of the graphite powder, the absolute ethyl alcohol, the cyclohexane, the anhydrous copper sulfate, the tween 80, the span 80, the PVP, the deionized water, the sodium borohydride and the silver nitrate is 0.4g:0.05 to 0.2g:30mL:3g:4g:0.2g:10mL:0.057g: 0.05-0.2 g.
Preferably, the silver nitrate-containing 2% PVP aqueous solution is used in an amount of 2mL.
Preferably, the dosage ratio of the graphite powder, the absolute ethyl alcohol, the cyclohexane, the anhydrous copper sulfate, the tween 80, the span 80, the PVP, the deionized water, the sodium borohydride and the silver nitrate is 0.4g:0.15g:30mL:3g:4g:0.2g:10mL:0.057g:0.15g.
Preferably, in steps S2 to S4, the freezing temperature is-18 ℃.
The invention also provides a copper-silver-loaded few-layer graphene-based composite material prepared by the preparation method.
The invention also provides application of the copper-silver loaded few-layer graphene-based composite material in hydrogen peroxide detection.
Preferably, the application of the copper-silver-loaded few-layer graphene-based composite material in hydrogen peroxide detection is carried out according to the following steps: cu of few-layer graphene-based composite material x O/Ag@FLG dispersionPreparing 1mg/mL of catalyst ink in 0.5wt% Nafion ethanol solution; then, the catalyst ink is dripped on the pretreated glassy carbon electrode, and is dried for 15min under an infrared lamp to obtain Cu x And (3) detecting the O/Ag@FLG modified glassy carbon electrode in a solution to be detected by adopting a cyclic voltammetry method.
Preferably, the volume of the catalyst ink supported on the glassy carbon electrode is 5 μl.
Preferably, the electrolyte solution in the hydrogen peroxide detection is a phosphate buffer solution with ph=7.4, and the detection potential is-0.65V.
The invention provides a few-layer graphene-based composite Cu with simple preparation process and high yield x O/Ag@FLG, which has a certain reduction effect on hydrogen peroxide, can be used as a catalyst material of an enzyme-free hydrogen peroxide sensor. Through comparison test, the few-layer graphene-based composite material Cu is adopted x The enzyme-free hydrogen peroxide sensor prepared from O/Ag@FLG has good performance in hydrogen peroxide detection, has positive initial potential, larger reduction current, higher sensitivity under smaller voltage, better catalytic performance and excellent sensing performance.
Drawings
FIG. 1 is a composite Cu obtained in example 1 x SEM image of O/Ag@FLG
FIG. 2 is a composite Cu obtained in example 1 x EDX (electronic data X) graph of O/Ag@FLG
FIG. 3 shows Cu prepared with different silver nitrate contents x O/Ag@FLG containing 4mM H 2 O 2 CV diagram in PBS solution of (C)
FIG. 4 shows Cu prepared with different anhydrous copper sulfate contents x O/Ag@FLG containing 4mM H 2 O 2 CV diagram in PBS solution of (C)
FIG. 5 shows different volumes of catalyst modified electrode at 4mM H 2 O 2 CV diagram in PBS solution of (C)
FIG. 6 is 5. Mu.L of Cu x O/Ag@FLG containing 4mM H at different pH values 2 O 2 CV diagram in phosphate buffer solution
FIG. 7 is Cu x O/Ag@FLG containing 4mM H 2 O 2 CV plots scanned at 10,20,40,60,80,100,120mV/s in PBS solution, respectively
FIG. 8 is Cu x O/Ag@FLG containing 4mM H 2 O 2 The reduction peak-to-peak current versus scan rate for 10,20,40,60,80,100,120mV/s, respectively, in PBS solutions
FIG. 9 is Cu x O/Ag@FLG containing 4mM H 2 O 2 The reduction peak-to-peak current versus square root of scan rate for 10,20,40,60,80,100,120mV/s scans, respectively, in PBS solutions
FIG. 10 is a graph showing I-t curves of 1mM hydrogen peroxide added to a volume of PBS solution at 60s intervals at different potentials
FIG. 11 is Cu x H with different concentrations is added into PBS solution every 40s after O/Ag@FLG is electrolyzed for 1800s under constant potential of-0.65V 2 O 2 I-t curve of (C)
FIG. 12 is an enlarged view of a portion of FIG. 11
FIG. 13 shows GCE, ag@FLG, cu x O@FLG、Cu x O/Ag@FLG at 4mM H 2 O 2 CV diagram in (C)
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form or modification thereof.
Example 1:
the preparation method comprises the following steps of x O/Ag@FLG：
Taking 0.4g of graphite powder, 5ml of absolute ethyl alcohol, 30ml of cyclohexane, 0.15g of absolute copper sulfate, 3g of tween 80, 4g of span 80, 0.2g of PVP and 5ml of deionized water as raw materials, uniformly mixing by vortex to prepare uniform and stable graphite water-in-oil emulsion, freezing at the temperature of minus 18 ℃ for 2 hours, and then carrying out ultrasonic treatment for 2 hours; then adding 0.057g of sodium borohydride, and repeating the freezing and ultrasonic treatment for 2 hours; then adding 2ml of 2% PVP aqueous solution containing 0.15g of silver nitrate, and freezing and ultrasonic again for 2 hours to synthesize the few-layer graphene-based composite material Cu x O/Ag@FLG。
As shown in the SEM image of fig. 1, the partially aggregated spherical AgO nanoparticles and flower-like Cu nanoparticles were supported on the surface of the few-layer graphene; the EDX spectrum of FIG. 2 shows that the composite material contains C, cu, ag, O, S element, the element distribution is shown in FIG. 2, which shows that Cu and AgO nano particles are uniformly distributed on FLG (Few-layer Graphene), namely the embodiment successfully prepares a few-layer Graphene-based composite material Cu x O/Ag@FLG。
Example 2:
the hydrogen peroxide detection is carried out according to the following steps:
the few-layer graphene-based composite material Cu prepared in example 1 x O/Ag@FLG is dispersed in 0.5wt% Nafion ethanol solution, and 1mg/mL catalyst ink is prepared; then, 5. Mu.L of the catalyst ink was dropped on the pretreated glassy carbon electrode, and dried under an infrared lamp for 15 minutes to obtain Cu x The O/Ag@FLG modified glassy carbon electrode is characterized in that an electrolyte solution is a phosphoric acid buffer solution with pH=7.4, the selected potential is-0.65V, and the solution to be detected is detected by adopting a cyclic voltammetry method.
Test example 1: optimization of silver nitrate dosage
The test example optimizes the use amount of silver nitrate, and specifically, experiments are carried out according to the following steps: taking 0.4g of graphite powder, 5ml of absolute ethyl alcohol, 30ml of cyclohexane, 0.25g of absolute copper sulfate, 3g of tween 80, 4g of span 80, 0.2g of PVP and 10ml of deionized water as raw materials, and uniformly mixing by vortex to prepare uniform and stable graphite water-in-oil emulsion, wherein four parts are prepared; freezing at-18deg.C for 2 hr, and performing ultrasonic treatment for 2 hr; then adding 0.057g of sodium borohydride, and repeating the freezing and ultrasonic treatment for 2 hours; then respectively adding 2ml of 2% PVP aqueous solution containing 0.05g,0.10g,0.15g and 0.20g of silver nitrate into the four samples, and freezing and ultrasonic again for 2 hours to synthesize the few-layer graphene-based composite material Cu with different silver nitrate dosages x O/Ag@FLG. They were each activated by cyclic voltammetry at a rate of 100mV/s in hydrogen peroxide for 10 cycles and then tested at 50mV/s by adding hydrogen peroxide to a concentration of 4 mM. As shown in FIG. 3, the current response of the small-layer graphene prepared by adding 0.15g of silver nitrate to hydrogen peroxide was maximized, so 2ml containing 0.15g of silver nitrate was selectively added in example 12% PVP in water.
Test example 2: optimization of anhydrous copper sulfate dosage
The test example optimizes the dosage of anhydrous copper sulfate, and specifically, experiments are carried out according to the following steps: the following four raw materials are weighed respectively: 0.4g of graphite powder, 5ml of absolute ethyl alcohol, 30ml of cyclohexane, 3g of tween 80, 4g of span 80, 0.2g of PVP and 10ml of deionized water are respectively added into four raw materials, 0.05g,0.10g,0.15g and 0.20g of absolute copper sulfate are respectively added, and then four uniform and stable graphite water-in-oil emulsions are prepared through vortex mixing; freezing at-18deg.C for 2 hr, and performing ultrasonic treatment for 2 hr; then adding 0.057g of sodium borohydride, and repeating the freezing and ultrasonic treatment for 2 hours; then adding 2ml of 2% PVP aqueous solution containing 0.15g of silver nitrate into the four samples, and freezing and ultrasonic again for 2 hours respectively to synthesize the few-layer graphene-based composite materials Cu with different anhydrous copper sulfate dosages x O/Ag@FLG. They were each activated by cyclic voltammetry at a rate of 100mV/s in hydrogen peroxide for 10 cycles and then tested at 50mV/s by adding hydrogen peroxide to a concentration of 4 mM. As shown in fig. 4, the current response of the graphene with a small layer prepared by adding 0.15g of anhydrous copper sulfate to hydrogen peroxide was maximized, so that the amount of anhydrous copper sulfate used in example 1 was 0.15g.
Test example 3: optimization of catalyst ink volume
The test example optimizes the pH value of the electrolyte solution in the hydrogen peroxide detection, and specifically, the few-layer graphene-based composite material Cu prepared in the example 1 x O/Ag@FLG was dispersed in 0.5wt% Nafion ethanol solution to prepare a catalyst ink of 1 mg/ml. The catalyst ink was loaded on the glassy carbon electrode in a volume of 3. Mu.L, 4. Mu.L, 5. Mu.L, 6. Mu.L, and 7. Mu.L, respectively, and contained 4mM H 2 O 2 Is tested by cyclic voltammetry at-1 to 0V in PBS solution. As shown in FIG. 5, 5. Mu.L is the optimal loading volume for detecting hydrogen peroxide.
Test example 4: optimization of pH of electrolyte solution
The test example optimizes the pH value of the electrolyte solution in the hydrogen peroxide detection, and specifically, the few-layer graphene-based composite material Cu prepared in the example 1 x O/Ag@FLG componentDispersed in 0.5wt% Nafion ethanol solution to prepare 1mg/ml catalyst ink. The catalyst ink on the glassy carbon electrode had a loading volume of 5. Mu.L, and the electrolyte solution was phosphate buffer solutions each having a pH of 5,6,7,7.4,8,9 and containing 4mM H 2 O 2 Is tested by cyclic voltammetry at-1 to 0V in PBS solution. As shown in fig. 6, the phosphate buffer solution with ph=7.4 is the optimal electrolyte solution for detecting hydrogen peroxide.
Test example 5:
the few-layer graphene-based composite material Cu prepared in example 1 x O/Ag@FLG was dispersed in 0.5wt% Nafion ethanol solution to prepare 1mg/ml catalyst ink, the catalyst ink on the glassy carbon electrode was loaded at a volume of 5. Mu.L, and the electrolyte solution was a phosphate buffer solution having pH=7.4 containing 4mM H 2 O 2 The scan rates were 10,20,40,60,80,100,120mV/s in PBS at-1-0V, respectively, and were measured by cyclic voltammetry. And plotted as the abscissa, the scan rate or square root of the scan rate, and the reduction peak-to-peak current at each scan rate. As shown in fig. 7-9, the reduction peak-to-peak current shows a good linear relationship with the square root of the scan rate, indicating that the process of detecting hydrogen peroxide is diffusion control.
Test example 6: optimization of detection potential
The few-layer graphene-based composite material Cu prepared in example 1 x O/Ag@FLG is dispersed in 0.5wt% Nafion ethanol solution to prepare 1mg/ml catalyst ink, the loading volume of the catalyst ink on the glassy carbon electrode is 5 mu L, and the electrolyte solution is a phosphoric acid buffer solution with pH=7.4. The I-t curves were measured by amperometric time method at potentials of-0.3, -0.4, -0.5, -0.6, -0.65, -0.7, -0.75V, respectively. As shown in FIG. 10, the result shows that the current change value is maximum when the selected potential is-0.65V, so that-0.65V is selected as the detection potential in example 2.
Test example 7: detection range test
The few-layer graphene-based composite material Cu prepared in example 1 x O/Ag@FLG was dispersed in 0.5wt% Nafion ethanol solution to prepare a catalyst ink of 1mg/mlThe catalyst ink on the glassy carbon electrode has a loading volume of 5 mu L, the electrolyte solution is phosphoric acid buffer solution with pH=7.4, the potential is selected to be-0.65V, the test is carried out by an I-t curve method, after the constant potential is stabilized for 1800s, hydrogen peroxide with certain volumes and different concentrations is added every 40s, and the curve is in a stepped curve shape as shown in fig. 11 and 12, and the detection range is 20 mu M-20 mM.
Comparison test:
preparing Cu by using 0.4g graphite powder, 5ml absolute ethyl alcohol, 30ml cyclohexane, 3g tween 80, 4g span 80, 0.2g PVP and 10ml deionized water as raw materials and respectively using 0.15g absolute copper sulfate x O@FLG, preparation of Ag@FLG from 0.15g silver nitrate, preparation of Cu from 0.15g anhydrous copper sulfate and 0.15g silver nitrate x O/Ag@FLG. Respectively adopting bare electrode and 5 mu L of Cu with 1mg/ml x O@FLG、Ag@FLG、Cu x O/Ag@FLGNafion ethanol solution is coated on the glassy carbon electrode. In the presence of 4mM H 2 O 2 Is measured by cyclic voltammetry in a phosphate buffer solution at a scan rate of 50mV/s at 0 to-1.2 v vs. As shown in fig. 13, copper-silver co-modified few-layer graphene Cu x Compared with single copper or silver modified few-layer graphene, the O/Ag@FLG has more positive initial potential, larger reduction current, higher sensitivity under smaller voltage and better catalytic performance, so that the sensing performance is better.
The invention is not limited to the use of the description and embodiments listed, which can be applied to various fields suitable for the invention, and further modifications and variations can be easily realized by those skilled in the art without departing from the spirit and the essence of the invention, but these corresponding modifications and variations shall fall within the scope of protection claimed by the invention.
The above description is only a few examples of the present invention and is not intended to limit the embodiments and the protection scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious changes made by the content of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a copper-silver-loaded few-layer graphene-based composite material is characterized by comprising the following steps of: the method comprises the following steps:
s1: graphite powder, absolute ethyl alcohol, cyclohexane, anhydrous copper sulfate, tween 80, span 80, PVP and deionized water are taken as raw materials, and uniform and stable graphite water-in-oil emulsion is prepared by vortex mixing;
s2: freezing the graphite water-in-oil emulsion prepared in the step S1 for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours;
s3: adding sodium borohydride into the graphite water-in-oil emulsion treated in the step S2, then freezing for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours;
s4: adding 2% PVP aqueous solution containing silver nitrate into the graphite water-in-oil emulsion treated in the step S3, then freezing for 2 hours at low temperature, and then performing ultrasonic treatment for 2 hours to obtain the few-layer graphene-based composite material Cu x O/Ag@FLG；
The dosage ratio of the graphite powder, the absolute ethyl alcohol, the cyclohexane, the anhydrous copper sulfate, the tween 80, the span 80, the PVP, the deionized water, the sodium borohydride and the silver nitrate is 0.4g:0.05 to 0.2g:30mL:3g:4g:0.2g:10mL:0.057g: 0.05-0.2 g.
2. The method of manufacturing according to claim 1, characterized in that: in the step S4, the dosage of the 2% PVP aqueous solution containing silver nitrate is 2mL.
3. The method of manufacturing according to claim 1, characterized in that: the dosage ratio of the graphite powder, the absolute ethyl alcohol, the cyclohexane, the anhydrous copper sulfate, the tween 80, the span 80, the PVP, the deionized water, the sodium borohydride and the silver nitrate is 0.4g:0.15g:30mL:3g:4g:0.2g:10mL:0.057g:0.15g.
4. The method of manufacturing according to claim 1, characterized in that: in the steps S2 to S4, the freezing temperature is-18 ℃.
5. The utility model provides a little layer graphite alkene base combined material of load copper silver which characterized in that: is prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the copper-silver loaded few-layer graphene-based composite material according to claim 5 in hydrogen peroxide detection.
7. The use of the copper-silver loaded few-layer graphene-based composite material in hydrogen peroxide detection according to claim 6, wherein the use is characterized in that: the method comprises the following steps: cu of few-layer graphene-based composite material x O/Ag@FLG is dispersed in 0.5wt% Nafion ethanol solution, and 1mg/mL catalyst ink is prepared; then, the catalyst ink is dripped on the pretreated glassy carbon electrode, and is dried for 15min under an infrared lamp to obtain Cu x And (3) detecting the O/Ag@FLG modified glassy carbon electrode in a solution to be detected by adopting a cyclic voltammetry method.
8. The use of the copper-silver loaded few-layer graphene-based composite material according to claim 7 in hydrogen peroxide detection, wherein: the volume of the catalyst ink loaded on the glassy carbon electrode is 5 mu L.
9. The use of the copper-silver loaded few-layer graphene-based composite material according to claim 7 in hydrogen peroxide detection, wherein: the electrolyte solution in the hydrogen peroxide detection was a phosphate buffer solution with ph=7.4, and the detection potential was-0.65V.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779499A (en) * | 2014-02-10 | 2014-05-07 | 苏州新锐博纳米科技有限公司 | Graphene composite film material interspersed with Ag nanoparticles and preparation |
| CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
| CN110006974A (en) * | 2019-03-26 | 2019-07-12 | 西北工业大学深圳研究院 | A kind of high-efficiency soft enzyme-free glucose bio-sensing electrode and preparation method |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779499A (en) * | 2014-02-10 | 2014-05-07 | 苏州新锐博纳米科技有限公司 | Graphene composite film material interspersed with Ag nanoparticles and preparation |
| CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
| CN110006974A (en) * | 2019-03-26 | 2019-07-12 | 西北工业大学深圳研究院 | A kind of high-efficiency soft enzyme-free glucose bio-sensing electrode and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| Ag and Cu Monometallic and Ag/Cu Bimetallic Nanoparticle− Graphene Composites with Enhanced Antibacterial Performance;Anna Perdikaki 等;ACS Applied Materials & Interfaces;第8卷;第27498-27510页 * |
| 微波辅助法合成Ag/CuxCo1-xFe2O4/RGO及其在光催化降解亚甲基蓝的吸附性能研究;刘超 等;牡丹江师范学院学报(自然科学版)(第1期);第45-50页 * |
| 无酶过氧化氢电化学传感器材料的研究进展;李亮;庹鑫;李思博;佘潇;;武汉工程大学学报(第04期);第343-356页 * |
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