CN110194445A - The three-dimensional porous graphene-based electrochemical electrode material of one kind and its preparation and application - Google Patents
The three-dimensional porous graphene-based electrochemical electrode material of one kind and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of three-dimensional porous graphene-based electrochemical electrode material and its preparation and application, three-dimensional porous graphene is prepared using hydro-thermal method, it is with nano-pore in three dimensional micron hole abundant and two-dimensional surface, three-dimensional porous graphene-based electrochemical electrode material, which is used, is added to substrate center for the hanging drop of above-mentioned graphene, and the method for vacuum drying obtains at room temperature.Three-dimensional porous graphene-based electrochemical electrode material in the present invention is used in electrochemical sensor, can the content of Ascorbic Acid, uric acid or nitrite detected, have that high sensitivity, response time be short, strong antijamming capability, advantage reproducible, long-time stability are good, the rate of recovery is high.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to the three-dimensional porous graphene-based electrochemical electrode material of one kind, preparation
Method and its application in electrochemical sensor.
Background technique
The electro-chemical activities biomolecule such as ascorbic acid (AA), uric acid (UA), nitrite rise emphatically in human lives
It acts on.Wherein, ascorbic acid is also known as vitamin C, is the important of synthesis collagen, cartilage, tendon, blood vessel and neurotransmitter
Compound, its abnormal level can be used to diagnose many diseases, as diabetes, high cholesterol, kidney, the nervous system disease with
And other various diseases；Uric acid is the final product of purine metabolism, if generating excessive uric acid in vivo has little time excretion or uric acid
Excretion mechanism is degenerated, then internal uric acid is detained excessive, is easy to cause human body fluid souring, is influenced the normal function of human body cell,
Gout will be caused by ignoring for a long time；Nitrite is naturally occurring in entire environment, the food being often used as in food industry
Product additive, but Excess free enthalpy nitrite constitutes huge risk to human health.Therefore, sensitive, quickly and accurately examine
The content for surveying AA, UA and nitrite is clinical diagnosis and the task of top priority of food safety.However, AA, UA and nitrite exist
Electroxidation on exposed working electrode needs very high overpotential, interferes with each other so as to cause with other biological activities molecule.
Traditional detection method mainly includes spectrophotometry, chromatography and fluorescence method etc., these conventional methods have inspection
Survey the disadvantages of slow, cumbersome.In recent years, based on quick, sensitive advantage, electrochemical sensor is gradually widely used in electrification
Learn the quick detection of active biomolecule.Wherein, grapheme material has the porous structure of biggish specific surface area and opening, energy
So that electrolyte ion is easy to enter from bone porous surface the inside, thus there is excellent chemical property, graphene material
Application study of the material for electrochemical sensor is also paid close attention to by industry.
Currently, grapheme material is used in the preparation of the electrochemical sensor of the substances such as nitrite by some researchers.
Such as: Chinese invention patent CN104634848A is deposited in working electrode surface by the method for electrochemical reduction oxidation graphene
Reproducibility graphene oxide is prepared for quickly detecting the electrochemical sensor of nitrite；Chinese invention patent
CN103604849A modifies working electrode using graphene oxide and mesoporous ferriferrous oxide composite material, is prepared for examining simultaneously
Survey the electrochemical sensor of dopamine, ascorbic acid and uric acid；Chinese invention patent CN108318556A discloses a kind of graphite
The preparation method of alkene cobalt acid nickel sensor material improves cobalt acid nickel fractions, sufficiently sends out by three-dimensional grapheme in conjunction with cobalt acid nickel
The synergistic effect for waving three-dimensional grapheme and heterogeneous structure enhances the sensitivity of sensor, is used for ascorbic acid non-enzymatic electrochemical sensing
In device.But graphene oxide employed in these patents or three-dimensional grapheme all exist in application process reunites, again
Folded phenomenon greatly affected the repeatability and stability of sensor.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of three-dimensional porous graphite
Alkenyl electrochemical electrode material and its preparation and application can make the electro-chemical activity of current graphene-based electrochemical electrode material
Site is more, and assigns the higher sensitivity of electrochemical sensor prepared by this kind of electrode material and anti-interference ability, and
Good repeatability and stability.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of three-dimensional porous graphene, method includes the following steps:
1) it after mixing graphene oxide solution with hydrogenperoxide steam generator, is ultrasonically treated later, obtains mixed liquor；
2) mixed liquor is placed in reaction vessel and carries out hydro-thermal reaction, by washing, drying to get more to the three-dimensional
Hole graphene.
Further, in step 1), the graphene oxide solution is the aqueous solution of graphene oxide, the oxidation
In graphene solution, the mass concentration of graphene oxide is 1.5-2.5mg/mL；The hydrogenperoxide steam generator is hydrogen peroxide
Aqueous solution, in the hydrogenperoxide steam generator, the mass percentage of hydrogen peroxide is 0.5-0.75%；The oxidation stone
The volume ratio of black alkene solution and hydrogenperoxide steam generator is 8-12:1.
Further, in step 1), the time of the ultrasonic treatment is 10-15min.
Further, in step 2), the temperature of the hydro-thermal reaction is 170-190 DEG C, time 4-6h.
Further, in step 2), the washing process are as follows: be immersed in the water reaction product 1-3 days.
Further, in step 2), the drying is freeze-drying, the drying process are as follows: washed product exists
Be rapidly frozen in liquid nitrogen, be placed in freeze-dryer and be freeze-dried.In freezing dry process, temperature be -55 DEG C to -
45 DEG C, time 10-15h.
A kind of three-dimensional porous graphene, the three-dimensional porous graphene are prepared using the method.Three-dimensional porous stone
The specific surface area of black alkene is 100-130m2/ g, characteristic peak positions of the three-dimensional porous graphene under Raman spectrum are 1345cm-1With
1590cm-1。
A kind of preparation method of three-dimensional porous graphene-based electrochemical electrode material, this method are as follows: the three-dimensional is more
Hole graphene is configured to dispersion liquid, and is added dropwise to glass-carbon electrode substrate center, obtains after vacuum drying at room temperature described
Electrochemical electrode material.
A kind of three-dimensional porous graphene-based electrochemical electrode material, the electrochemical electrode material are prepared using the method
It forms.
A kind of application of three-dimensional porous graphene-based electrochemical electrode material, the electrochemical electrode material is for electrification
It learns in sensor, the content of Ascorbic Acid, uric acid or nitrite is detected.
In the present invention, three-dimensional porous graphene not only has microcellular structure on three-dimensional space, equally has in two-dimensional surface
There is nano-pore in face, these pore structures abundant effectively increase the exposed amount of edge and defect concentration of graphene, to press down
Reunion of the graphene nanometer sheet on sensor substrate has been made, and has made graphene that there is bigger specific surface area, electrochemistry is living
Property site is increased, and the electric conductivity of three-dimensional porous graphene is improved.
In addition, by experiment it is found that the electricity prepared using graphene-based electrochemical electrode material three-dimensional porous in the present invention
Chemical sensor, with high sensitivity, the response time is short, strong antijamming capability, reproducible, long-time stability are good, the rate of recovery
High advantage has applications well potentiality in ascorbic acid, uric acid and the quick context of detection of content of nitrite.
Compared with prior art, the invention has the characteristics that:
1) the three-dimensional porous graphene-based electrochemical electrode material that the present invention prepares can be used in electrochemical sensor, energy
The concentration of enough quickly detection ascorbic acid, uric acid and nitrite, have short high sensitivity, response time, strong antijamming capability,
Feature reproducible, long-time stability are good, the rate of recovery is high, in the quick side of detection of ascorbic acid, uric acid and content of nitrite
Face has applications well potentiality；
2) three-dimensional porous graphene is prepared using hydrogen peroxide as etching agent using hydro-thermal method in the present invention, is had abundant
Three dimensional micron hole and two-dimensional surface in nano-pore, and specific surface area is high, and three-dimensional porous graphene-based electrochemical electrode material uses
The hanging drop of above-mentioned graphene is added to substrate center, at room temperature the method deposition three-dimensional porous graphene of vacuum drying and
, it prepares simple and quick.
Detailed description of the invention
Fig. 1 is the SEM figure for the three-dimensional porous graphene being prepared in embodiment 2；
Fig. 2 is the TEM figure for the three-dimensional porous graphene being prepared in embodiment 2；
Fig. 3 is the three-dimensional porous graphene-based electrochemical electrode (3D-HG/GCE) being prepared in embodiment 2 and common glass
Carbon electrode (GCE) is containing there are three types of the cyclic voltammetry curve figures in the 0.1M phosphate buffer (pH=7.4) of detection substance；
Fig. 4 be in embodiment 2 the three-dimensional porous graphene-based electrochemical electrode that is prepared respectively in 0.1M phosphoric acid buffer
AA, UA of a series of concentration and the differentiated pulse volt-ampere curve figure after sodium nitrite solution are sequentially added in liquid (pH=7.4),
In, it (c) is NaNO that it (b) is UA that (a), which is AA,2；
Fig. 5 be in embodiment 2 the three-dimensional porous graphene-based electrochemical electrode that is prepared respectively in 0.1M phosphoric acid buffer
A series of the quasi- of AA, UA of concentration and the differentiated pulse volt-ampere curve after sodium nitrite solution is sequentially added in liquid (pH=7.4)
Close curve graph, wherein (a) is AA, (b) is UA, (c) is NaNO2；
Fig. 6 is that the differentiated pulse volt-ampere measured after the interfering substance that 100 times of concentration is added in substance solution is detected at three kinds
Peak current, wherein (a) be AA, (b) be UA, (c) be NaNO2。
Fig. 7 is a three-dimensional porous graphene-based electrochemical electrode respectively containing there are three types of the 0.1M phosphoric acid of detection substance is slow
The repeated histogram of electrode after fliud flushing (pH=7.0) is reused 10 times, wherein (a) is AA, is (b) UA, (c) is
NaNO2；
Fig. 8 is that the three-dimensional porous graphene-based electrochemical electrode being prepared in embodiment 2 is being detected containing there are three types of respectively
21 days long-time stability histograms in the 0.1M phosphate buffer (pH=7.0) of substance, wherein (a) is AA, (b) is UA,
It (c) is NaNO2。
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1:
Three-dimensional porous grapheme material, specific steps are prepared using hydro-thermal method are as follows: take 10mL graphene oxide (2mg/mL)
Aqueous solution is added 1mL hydrogenperoxide steam generator (0.75wt.%), 10min is ultrasonically treated, then by graphene oxide and peroxidating
The mixed liquor of hydrogen is transferred in autoclave, and 4h is reacted under 180 DEG C of high temperature, and products therefrom, which immerses in ultrapure water, to be washed 2 days
To remove excessive hydrogen peroxide impurity, it is rapidly frozen in liquid nitrogen later, and continue to be freeze-dried in freeze-dryer
12h obtains three-dimensional porous grapheme material solid.
Three-dimensional porous graphene-based electrochemical electrode material is prepared using following steps: taking the 6 three-dimensional porous graphenes of μ L outstanding
Supernatant liquid (0.1mg/mL) is added drop-wise to the center of electrode base sheet, at room temperature vacuum drying, that is, obtains three-dimensional porous graphene-based electricity
Chemical electrode material.
Embodiment 2:
Three-dimensional porous grapheme material, specific steps are prepared using hydro-thermal method are as follows: take 10mL graphene oxide (2mg/mL)
Aqueous solution is added 1mL hydrogenperoxide steam generator (0.5wt.%), 13min is ultrasonically treated, then by graphene oxide and hydrogen peroxide
Mixed liquor be transferred in autoclave, react 5h under 180 DEG C of high temperature, products therefrom immerse in ultrapure water wash 2 days with
Excessive hydrogen peroxide impurity is removed, is rapidly frozen in liquid nitrogen later, and continues to be freeze-dried 12h in freeze-dryer,
Obtain three-dimensional porous grapheme material solid.
Three-dimensional porous graphene-based electrochemical electrode material is prepared using following steps: taking the 6 three-dimensional porous graphenes of μ L outstanding
Supernatant liquid (0.2mg/mL) is added drop-wise to the center of electrode base sheet, at room temperature vacuum drying, that is, obtains three-dimensional porous graphene-based electricity
Chemical electrode material, and three-dimensional porous graphene-based electrochemical electrode is further made using the material.
Electron microscope (SEM) and transmitted electron are scanned to the three-dimensional porous graphene being prepared in embodiment 2
Microscope (TEM) characterization.Scheme as shown in Figure 1 for the SEM of three-dimensional porous graphene, it is abundant to show that this kind of grapheme material has
Three-dimensional network micropore, range of aperture size are 0.1-10 μm；It is illustrated in figure 2 the TEM figure of three-dimensional porous graphene, shows stone
Nano-pore in a large amount of two-dimensional surface, range of aperture size 1-20nm are dispersed on mertenyl baseplane.
Three-dimensional porous graphene-based electrochemical electrode detection AA (1mM), UA (0.1mM) being prepared using embodiment 2
And NaNO2(1mM) mixed solution obtains cyclic voltammogram, sweep speed 0.05V/s.As a result as shown in figure 3, in 0.1M phosphorus
1mM AA, 0.1mM UA and 1mM NaNO are continuously added in acid buffer (pH=7.4)2, glass-carbon electrode in 0.291V and
Two peak values are only shown when 0.956V, it means that AA, UA and NO cannot be detected simultaneously by bare glassy carbon electrode2 -.But implement
The three-dimensional porous graphene-based electrochemical electrode that example 2 is prepared be observed that 3 in 0.003V (AA), 0.283V (UA) and
0.801V(NO2-) under good discrimination peak, it was demonstrated that the three-dimensional porous graphene-based electrochemical electrode material can detect simultaneously AA,
UA and NO2 -, and will not interfere with each other.
Three-dimensional porous graphene-based electrochemical electrode detection various concentration AA, the UA being prepared using embodiment 2 and Asia
Nitrate solution obtains differentiated pulse voltammogram, and as a result (a) in such as Fig. 4, (b), (c) are shown respectively, the results show that
Three kinds of substances are continuously added in 0.1M phosphate buffer (pH=7.4) respectively, with the increase of solution concentration, peak current is gradually
Increase.The linear relationship chart of electrode peak current and AA concentration at fitting -0.072V voltage, in Fig. 5 shown in (a), when AA concentration
When between 0.2-3.2mM, the R of linear fit equation2=0.992；It is fitted electrode peak current and UA concentration at 0.24V voltage
Linear relationship chart, in Fig. 5 shown in (b), when UA concentration is between 2-200 μM, the R of linear fit equation2=0.9995；It is quasi-
The linear relationship chart for closing electrode peak current and nitrite concentration at 0.745V voltage works as nitrite in Fig. 5 shown in (c)
When concentration is between 0.05-500 μM, the R of linear fit equation2=0.9944, when nitrite concentration is between 0.5-10mM
When, the R2=0.9901 of linear fit equation.It is above-mentioned statistics indicate that between AA, UA and the concentration and electrode peak current of nitrite
With good linear relationship.
Three-dimensional porous graphene-based electrochemical electrode detection AA, UA and the NaNO being prepared using embodiment 22And other
Interfering substance, such as: NaCl, KCl, sodium citrate (Sodium citrate), MgCl2、Na2SO4, L-cysteine (L-
Cysteine), D- (+)-glucose (D- (+)-Glucose), FeCl3、ZnCl2、(NH4)2CO3、K2HPO4、KH2PO4、CuSO4、
H2O2、NH4Cl、KNO3、CaCl2、NaF、C2H5OH obtains differentiated pulse volt-ampere peak current and responds histogram.Using differentiated pulse
Voltammetry is first respectively in AA (0.1mM), UA (0.1mM) and NaNO2The 0.1M phosphate buffer (pH=7.4) of (0.05 μM) is slow
Rush record AA, UA and NaNO in solution2Differentiated pulse volt-ampere peak current, be then respectively adding a variety of interference of 100 times of concentration
Substance, as a result (a), (b), (c) are shown such as in Fig. 6, when the concentration of above-mentioned interfering substance is to detect 100 times of material concentration,
AA, UA and NaNO are detected to three-dimensional porous graphene-based electrochemical electrode2The influence of current-responsive can be ignored.This illustrates base
The electrochemical sensor of three-dimensional porous graphene-based electrochemical electrode material is to detection AA, UA and NaNO in the present invention2Have
Good selectivity and anti-interference ability.
Three-dimensional porous graphene-based electrochemical electrode detection AA, UA and the NaNO being prepared using embodiment 22, obtain
Repeated histogram.Using Differential Pulse Voltammetry by a three-dimensional porous graphene-based electrochemical electrode 0.1mM AA,
0.1mM UA and 0.1mM NaNO2Replication 10 times in standard solution, as a result (a), (b), (c) are shown such as in Fig. 7, three kinds of inspections
The relative standard deviation RSD for surveying substance is respectively less than 2.01%, show three-dimensional porous graphene-based electrochemical electrode to AA, UA and
NaNO2Detection have good repeatability.
Three-dimensional porous graphene-based electrochemical electrode detection AA, UA and the NaNO being prepared using embodiment 22, obtain
The histogram of long-time stability.(a), (b), (c) are shown in Fig. 8, using Differential Pulse Voltammetry to 0.1mM AA, 0.1mM
UA and 0.1mM NaNO2Standard solution detected, the primary three-dimensional porous graphene-based electrochemical electrode inspection of record every three days
Survey AA, UA and NaNO2Peak current response, 21 days (three weeks) peak currents of continuous record respond, non-detection time three-dimensional porous stone
Black alkene modified electrode is stored in 4 DEG C of refrigerators, and after three weeks, three-dimensional porous graphene-based electrochemical electrode detects the peak of three kinds of substances
Electric current is all larger than detects the 96% of peak current for the first time, and it is long-term well to illustrate that three-dimensional porous graphene-based electrochemical electrode has
Stability.
The Victoria C in three-dimensional porous graphene-based electrochemical electrode detection tablet that is prepared using embodiment 2, human body morning
Content of nitrite in uric acid and tap water in urine, the results are shown in Table 1, and test method uses standard addition method, is containing
AA, UA and NaNO of various concentration are separately added into the phosphate buffer (pH=7.4) for having certain volume test sample2, record
The differentiated pulse volt-ampere curve measured every time calculates AA, UA and NaNO in detection solution according to normal equation curve2Content.By
Table 1 is as can be seen that three kinds of substances have the good rate of recovery, and alluvial is up between 99.73-102.05%, RSD less than 5%,
Should the result shows that, can be fine based on the electrochemical sensor of graphene-based electrochemical electrode material three-dimensional porous in the present invention
Ground is applied to carry out AA, UA and NaNO in actual sample2Detection.
Table 1
| Sample | Additive amount (μM) | Detected value (μM) | The rate of recovery (%) | RSD (n=5, %) |
| AA | 50 | 100.5 | 100.5 | 2.25 |
| 100 | 102.05 | 102.05 | 1.53 | |
| 150 | 199.48 | 99.74 | 2.55 | |
| 200 | 250.80 | 100.32 | 2.15 | |
| 250 | 300.4 | 100.13 | 1.98 | |
| UA | 20 | 30.65 | 102.16 | 1.35 |
| 40 | 50.93 | 101.86 | 1.52 | |
| 60 | 70.90 | 101.29 | 1.36 | |
| 100 | 110.20 | 100.18 | 1.28 | |
| 140 | 149.60 | 99.73 | 1.25 | |
| NaNO2 | 10 | 10.15 | 101.5 | 1.73 |
| 50 | 49.91 | 99.82 | 1.22 | |
| 100 | 102.05 | 102.05 | 1.53 |
Embodiment 3:
Three-dimensional porous grapheme material, specific steps are prepared using hydro-thermal method are as follows: take 10mL graphene oxide (2mg/mL)
Aqueous solution is added 1mL hydrogenperoxide steam generator (0.75wt.%), 15min is ultrasonically treated, then by graphene oxide and peroxidating
The mixed liquor of hydrogen is transferred in autoclave, and 6h is reacted under 180 DEG C of high temperature, and products therefrom, which immerses in ultrapure water, to be washed 2 days
To remove excessive hydrogen peroxide impurity, it is rapidly frozen in liquid nitrogen later, and continue to be freeze-dried in freeze-dryer
12h obtains three-dimensional porous grapheme material solid.
Three-dimensional porous graphene-based electrochemical electrode material is prepared using following steps: taking the 6 three-dimensional porous graphenes of μ L outstanding
Supernatant liquid (0.3mg/mL) is added drop-wise to the center of electrode base sheet, at room temperature vacuum drying, that is, obtains three-dimensional porous graphene-based electricity
Chemical electrode material.
Embodiment 4:
A kind of three-dimensional porous graphene, preparation method includes the following steps:
1) after mixing graphene oxide solution with hydrogenperoxide steam generator, ultrasonic treatment 10min is carried out later, is mixed
Liquid；Wherein, graphene oxide solution is the aqueous solution of graphene oxide, in graphene oxide solution, the quality of graphene oxide
Concentration is 2.5mg/mL；Hydrogenperoxide steam generator is the aqueous solution of hydrogen peroxide, in hydrogenperoxide steam generator, the quality hundred of hydrogen peroxide
Dividing content is 0.5%；Graphene oxide solution and the volume ratio of hydrogenperoxide steam generator are 12:1.
2) mixed liquor is placed in reaction vessel and carries out hydro-thermal reaction, temperature is 170 DEG C, time 6h, later will reaction
Product is immersed in the water 1 day and is washed, then washed product is rapidly frozen in liquid nitrogen, be placed in freeze-dryer and carry out
It is freeze-dried to get three-dimensional porous graphene is arrived.
A kind of three-dimensional porous graphene-based electrochemical electrode material, preparation method are as follows: by above-mentioned three-dimensional porous graphene
It is configured to dispersion liquid, and is added dropwise to glass-carbon electrode substrate center, obtains electrochemical electrode material after vacuum drying at room temperature.
The electrochemical electrode material is in electrochemical sensor, the content of Ascorbic Acid, uric acid or nitrite to be detected.
Embodiment 5:
A kind of three-dimensional porous graphene, preparation method includes the following steps:
1) after mixing graphene oxide solution with hydrogenperoxide steam generator, ultrasonic treatment 15min is carried out later, is mixed
Liquid；Wherein, graphene oxide solution is the aqueous solution of graphene oxide, in graphene oxide solution, the quality of graphene oxide
Concentration is 1.5mg/mL；Hydrogenperoxide steam generator is the aqueous solution of hydrogen peroxide, in hydrogenperoxide steam generator, the quality hundred of hydrogen peroxide
Dividing content is 0.75%；Graphene oxide solution and the volume ratio of hydrogenperoxide steam generator are 8:1.
2) mixed liquor is placed in reaction vessel and carries out hydro-thermal reaction, temperature is 190 DEG C, time 4h, later will reaction
Product is immersed in the water 3 days and is washed, then washed product is rapidly frozen in liquid nitrogen, be placed in freeze-dryer and carry out
It is freeze-dried to get three-dimensional porous graphene is arrived.
A kind of three-dimensional porous graphene-based electrochemical electrode material, preparation method are as follows: by above-mentioned three-dimensional porous graphene
It is configured to dispersion liquid, and is added dropwise to glass-carbon electrode substrate center, obtains electrochemical electrode material after vacuum drying at room temperature.
The electrochemical electrode material is in electrochemical sensor, the content of Ascorbic Acid, uric acid or nitrite to be detected.
Embodiment 6:
A kind of three-dimensional porous graphene, preparation method includes the following steps:
1) after mixing graphene oxide solution with hydrogenperoxide steam generator, ultrasonic treatment 12min is carried out later, is mixed
Liquid；Wherein, graphene oxide solution is the aqueous solution of graphene oxide, in graphene oxide solution, the quality of graphene oxide
Concentration is 2mg/mL；Hydrogenperoxide steam generator is the aqueous solution of hydrogen peroxide, in hydrogenperoxide steam generator, the quality percentage of hydrogen peroxide
Content is 0.6%；Graphene oxide solution and the volume ratio of hydrogenperoxide steam generator are 10:1.
2) mixed liquor is placed in reaction vessel and carries out hydro-thermal reaction, temperature is 180 DEG C, time 5h, later will reaction
Product is immersed in the water 2 days and is washed, then washed product is rapidly frozen in liquid nitrogen, be placed in freeze-dryer and carry out
It is freeze-dried to get three-dimensional porous graphene is arrived.
A kind of three-dimensional porous graphene-based electrochemical electrode material, preparation method are as follows: by above-mentioned three-dimensional porous graphene
It is configured to dispersion liquid, and is added dropwise to glass-carbon electrode substrate center, obtains electrochemical electrode material after vacuum drying at room temperature.
The electrochemical electrode material is in electrochemical sensor, the content of Ascorbic Acid, uric acid or nitrite to be detected.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of three-dimensional porous graphene, which is characterized in that method includes the following steps:
1) it after mixing graphene oxide solution with hydrogenperoxide steam generator, is ultrasonically treated later, obtains mixed liquor；
2) mixed liquor is placed in reaction vessel and carries out hydro-thermal reaction, arrive the three-dimensional porous stone by washing, drying
Black alkene.
2. a kind of preparation method of three-dimensional porous graphene according to claim 1, which is characterized in that in step 1), institute
The graphene oxide solution stated is the aqueous solution of graphene oxide, in the graphene oxide solution, the matter of graphene oxide
Amount concentration is 1.5-2.5mg/mL；The hydrogenperoxide steam generator is the aqueous solution of hydrogen peroxide, the hydrogenperoxide steam generator
In, the mass percentage of hydrogen peroxide is 0.5-0.75%；The body of the graphene oxide solution and hydrogenperoxide steam generator
Product is than being 8-12:1.
3. a kind of preparation method of three-dimensional porous graphene according to claim 1, which is characterized in that in step 1), institute
The time for the ultrasonic treatment stated is 10-15min.
4. a kind of preparation method of three-dimensional porous graphene according to claim 1, which is characterized in that in step 2), institute
The temperature for the hydro-thermal reaction stated is 170-190 DEG C, time 4-6h.
5. a kind of preparation method of three-dimensional porous graphene according to claim 1, which is characterized in that in step 2), institute
The washing process stated are as follows: be immersed in the water reaction product 1-3 days.
6. a kind of preparation method of three-dimensional porous graphene according to claim 1, which is characterized in that in step 2), institute
The drying stated is freeze-drying, the drying process are as follows: washed product is rapidly frozen in liquid nitrogen, to be placed on freezing dry
It is freeze-dried in dry device.
7. a kind of three-dimensional porous graphene, which is characterized in that the three-dimensional porous graphene is used such as any one of claim 1 to 6
The method is prepared.
8. a kind of preparation method of three-dimensional porous graphene-based electrochemical electrode material, which is characterized in that this method are as follows: by right
It is required that three-dimensional porous graphene described in 7 is configured to dispersion liquid, and is added dropwise to glass-carbon electrode substrate center, vacuumize at room temperature
The electrochemical electrode material is obtained after drying.
9. a kind of three-dimensional porous graphene-based electrochemical electrode material, which is characterized in that the electrochemical electrode material is used as weighed
Benefit require 8 described in method be prepared.
10. a kind of application of three-dimensional porous graphene-based electrochemical electrode material as claimed in claim 9, which is characterized in that
The electrochemical electrode material is in electrochemical sensor, the content of Ascorbic Acid, uric acid or nitrite to be examined
It surveys.
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