CN109270140A - The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor - Google Patents
The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor Download PDFInfo
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Abstract
The preparation method of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor, comprising the following steps: A: the preparation of high dispersive graphene；B: the preparation of the graphene-supported Zn Base Metal organic framework composite material of high dispersive；C: the preparation of electrochemical sensor.High dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor and application, it is directly used in Electrochemical Detection hydrogen peroxide, method is as follows: using electrochemical sensor as working electrode, Ag/AgCl is reference electrode, platinum electrode as auxiliary electrode, forms three-electrode system；Three-electrode system is placed in phosphate buffer solution；Under -0.40V constant potential, record current-time graph is added hydrogen peroxide in phosphate buffer solution, hydrogen peroxide concentration can be obtained according to electric current.This electrochemical sensor is quick in simple, accurate, low price, detection.
Description
Technical field
The present invention relates to a kind of high dispersive graphene/Zn Base Metal organic framework composite material non-enzymatic dioxygen aqueous electrochemicals
The preparation method of sensor, belongs to chemical field.
Background technique
H2O2Many important biologies and chemical reaction are taken part in, and has played important function in many fields, for example, food
Product, pharmacy, industry and environmental analysis.Therefore, it is necessary to establish it is a kind of reliable, sensitive, quickly, detect H in real time2O2
Method.In electrochemical method, the participation of electrochemical sensor and enzyme can accelerate electrode and H2O2Between electronics transfer.So
And there are some FAQs in the sensor based on enzyme, such as experiment material expensive, electrode stability are poor, operating environment is wanted
Ask harsh, electrode prepares fixed routine is complicated, enzyme is apt to deteriorate etc..And non-enzymatic hydrogen peroxide electrochemical sensor can be avoided enzyme
The some shortcomings of electrochemical sensor, it will have bigger development space, make it have better sensitivity, higher selection
Property and accuracy.
Graphene due to its preferable bio-compatible environment, high electronic conductivity and more chemical active sites,
Greatly paid attention to by researcher；But graphene has lower dispersion degree in aqueous solution and organic solvent, the group of being easy
Be polymerized to bulky grain, carry out compound active site this not only lowers graphene and other materials, moreover it is possible to affect graphene with
Interaction between other materials not can effectively improve the catalytic performance of composite material.It is therefore desirable to continue to explore high dispersive
Graphene activates the preparation method of Zn Base Metal organic backbone, to give full play to the excellent properties of graphene in the composite,
To prepare highly sensitive non-enzymatic hydrogen peroxide electrochemical sensor.
Zn Base Metal organic backbone electrode material specific capacitance with higher, and Zn2+Belong to hard lewis acid, with carboxylic
Base has stronger binding force, and structural stability is stronger, is a kind of novel electrode material, but due to the office of MOF material itself
It is sex-limited, if particle is larger, it is not easy evenly dispersed, conductivity is lower, and stability is poor, limits its answering in electrochemical sensor
With.Ideal strategy is with the preferable Material cladding of electric conductivity to improve its limitation.Graphene is one kind by carbon atom structure
At single layer sheet nano structural material, have high specific surface area (2630 m2/ g) and high electron-transport efficiency.Correlation is ground
Study carefully proof: by MOF Material cladding on graphene, can effectively inhibit the reunion of MOF particle；MOF material is in graphite simultaneously
The performance that the compound can effectively be improved on alkene, embodies their synergistic effect.
Currently, being disclosed in patent (CN105713024A) a kind of based on ZnⅡMetal organic framework and its preparation side
Method and application；The invention is related to using ZnCl2For soluble-salt, terphenyl-hexacarboxylic acid is organic ligand, N, N- dimethyl methyl
Amide is solvent, under high temperature 358K, high-temperature high-voltage reaction 3 days, obtains target product, which has
Fluorescent effect.Since the particle of Zn-MOF is larger, it is not easy evenly dispersed, conductivity is lower, and stability is poor, limits it in electrification
Learn the application in sensor.Ideal strategy be with the preferable Material cladding of electric conductivity, it is such as compound with graphene, to improve it
Limitation.Disclosed in patent (CN 105355873B) it is some by Fe base MOF material with graphene is compound prepares electrode material
Report, by the way that n,N-Dimethylformamide is organic or the direct dispersed graphite alkene of deionized water dissolving, then with Fe3+And terephthaldehyde
Acid-mixed for a long time, is prepared for Fe metal organic framework (Fe- by hydro-thermal reaction together in high temperature of 120 DEG C~170 DEG C, the h of 2 h~24
MOF)/Graphene electrodes material.However, graphene has lower dispersion degree in aqueous solution and organic solvent, it is easy to reunite
At bulky grain, the excellent performance of graphene cannot be embodied adequately.It is therefore desirable to continue to explore low temperature timesaving high score
The preparation method of graphene activation Zn Base Metal organic backbone is dissipated, to give full play to the superiority of graphene in the composite
Can, and be applied in electrochemical sensor.
Summary of the invention
The purpose of the present invention is to provide a kind of high dispersive graphene/Zn Base Metal organic framework composite material electrochemistry
The preparation method and application of sensor.
To achieve the purpose of the present invention, using following technical solutions: high dispersive graphene/Zn Base Metal organic backbone
The preparation method of the electrochemical sensor of composite material, comprising the following steps:
A: the preparation of high dispersive graphene: used each material is using following amounts or using identical with following amounts in this step
Ratio, the graphene oxide solution of 1 mg/mL of the mL equal volume amounts of 100 mL~300 are uniformly mixed with 0.5 wt% chitosan solution
It closes, until obtaining the solution of uniform brown color；Solution is transferred in the water-bath of the oC of 80oC~95, is vigorously stirred 4 h~6
H, until solution colour is completely converted into black by brown color；Product be centrifuged, wash 2~3 times, dehydrated alcohol
Washing 2~3 times, by product in n,N-Dimethylformamide ultrasonic disperse, ultrasonic power and frequency are respectively 100W and 40
The graphene of polymolecularity can be obtained in KHz；
B: the preparation of the graphene-supported Zn Base Metal organic framework composite material of high dispersive: in the high dispersive graphite that step A is obtained
Zn (NO is added in alkene3)2 · 6H2O 200 mg~500 mg, 2-methylimidazole 200 mg~500 mg, PVP 1g~4g,
The methanol ml of 150 ml~500, is stirred to react 10~13 h at room temperature, and reaction precipitate is centrifuged, dehydrated alcohol washs,
It is dried in vacuo at 30 DEG C~60 DEG C, obtains the graphene-supported Zn Base Metal organic framework composite material of high dispersive；
C: the preparation of electrochemical sensor: the graphene-supported Zn Base Metal organic backbone of high dispersive obtained by step B is compound
Material: graphite powder: paraffin oil is 0.5:2:0.8 feeding in mass ratio, and hand operated mixing mixes about 1h~2h, uniform until being formed
Carbon paste；The glass tube that carbon paste filling glass bore is 3 mm is taken, is inserted into a copper wire as electrode from the other end
Connector；Obtain high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor.
Further；Zn- in the graphene-supported Zn Base Metal organic framework composite material of high dispersive obtained in step B
MOF is spherical shape.
Further；Stone in the graphene-supported Zn Base Metal organic framework composite material of high dispersive obtained in step B
The mass percentage of black alkene is wt7.01%~13.10%.
Further；Revolving speed is 3000~4000 rmp when step A is centrifugated.
High dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor and application, use is above-mentioned
Electrochemical sensor obtained, the electrochemical sensor are directly used in Electrochemical Detection hydrogen peroxide, and application method is as follows:
Using prepared high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor as working electrode, fill out
The Ag/AgCl of the KCl of 3 M of filling liquid is reference electrode, platinum electrode as auxiliary electrode, forms three-electrode system；When measurement,
Three-electrode system is placed in the phosphate buffer solution of 0.1 M, pH 7.0 of 10 mL；Under -0.40V constant potential, record
Current versus time curve, when background current is stable, under stiring, with microsyringe to 0.1 M, pH 7.0 of 10 mL
Hydrogen peroxide is added in phosphate buffer solution, hydrogen peroxide concentration can be obtained according to electric current.
Positive beneficial effect of the invention is: one there is provided a kind of new methods, are prepared for a kind of high dispersive graphene
Activate Zn-MOF composite material.Compared with pure graphene, high dispersive graphene, which activates Zn-MOF composite material, to be had newly
Property；Second is that chitosan used in this method provides the reduction and high dispersive for realizing graphene simultaneously, avoid using toxic
Reducing agent (such as hydrazine hydrate), mild condition are environmental-friendly；Third is that PVP(polyvinylpyrrolidone used in this method), have
Effect prevents the reunion of Zn-MOF ball, realizes Zn-MOF ball uniform load on high dispersive graphene.Preparation method is simple, is produced into
This is cheap；Fourth is that electrochemical sensor of the invention is when detecting hydrogen peroxide, easy to operate, response is rapid, favorable repeatability, valence
Lattice are cheap, have lower detection limit and better choice, reach through practice examining sensor of the invention detection limit
0.05 μM, the similar MOF sensor detection limit relative to existing announcement promotes 10 times or so, so this method was not only prepared
Journey is simple, and the performance of electrochemical sensors finally obtained is superior, this electrochemical sensor is being used for hydrogen peroxide detection process
In do not need cumbersome extraction step, be it is a kind of simple, accurate, at a low price, the quick electrochemical sensor of detection, in food, medicine
Product, reagent, clinical diagnosis of health industry, especially hydrogen peroxide concentration detection etc. is with good application prospect.
Detailed description of the invention
A is graphene oxide dispersion in Fig. 1, and b is high dispersive graphene dispersing solution prepared by the present invention, and c is not
Surface-functionalized graphene dispersing solution.
Fig. 2 is the scanning electron microscope (SEM) photograph of Zn-MOF.
Fig. 3 is the scanning electron microscope (SEM) photograph of composite material of the present invention.
Fig. 4 is the X ray diffracting spectrum (XRD) of composite material of the present invention.
The score of the x-ray photoelectron spectroscopy (XPS) of Fig. 5 composite material of the present invention.
The x-ray photoelectron spectroscopy (XPS) of the Zn element of Fig. 6 composite material of the present invention.
Fig. 7 is the phosphate (pH of 0.1 M of electrochemical sensor of the invention being free of and containing 10.0 mM hydrogen peroxide
7.0) the cyclic voltammogram in the liquid of bottom.
Fig. 8 be Zn-MOF decorating carbon paste electrode, naked carbon paste electrode 0.1 M containing 10.0 mM hydrogen peroxide phosphate
Cyclic voltammogram in the bottom liquid of (pH 7.0).
Fig. 9 is the bottom liquid of the phosphate (pH 7.0) for 0.1 M that graphene modified carbon paste electrode contains 10.0 mM hydrogen peroxide
In cyclic voltammogram.
Figure 10 is electrochemical sensor prepared by the present invention under stiring in the bottom liquid of the phosphate (pH 7.0) of 0.1 M
In sequentially add label concentration hydrogen peroxide solution current versus time curve.
Figure 11 is the hydrogen peroxide concentration measured using electrochemical sensor prepared by the present invention and the linear relationship of its electric current
Figure.
Figure 12 be using electrochemical sensor prepared by the present invention at optimum conditions, be added various concentration hydrogen peroxide and
Amion acetic acid, ascorbic acid, uric acid, glucose, the current versus time curve figure that whens chaff interferents such as NaCl generates.
Specific embodiment
The present invention is explained in detail below, for the ease of comparison, it is organic that applicant has carried out Zn Base Metal first
The preparation of skeleton, the method is as follows: by the Zn (NO of 300 mg3)2 · 6H2The organic ligand 2- methyl of O soluble-salt and 350 mg
Imidazoles, 1.0 g PVP, 200 mL methanol uniformly mix, and stir evenly 10 h at room temperature, and reaction precipitate is passed through with 4000 rmp
Revolving speed be centrifugated out sediment, dehydrated alcohol wash 3 times, 30 DEG C at be dried in vacuo.It is electric using scanning to the material of synthesis
Sub- microscope has carried out morphology characterization, as shown in Figure 2.Fig. 2 clearly illustrates the spheroidal Zn-MOF structure of morphological rules, says
The synthetic method that the bright present invention uses maintains the typical structure of Zn-MOF well；
The preparation side of high dispersive graphene provided by the present invention/Zn Base Metal organic framework composite material electrochemical sensor
Method, its step are as follows:
A: 100 mL of graphene oxide water solution of 1 mg/mL the preparation of high dispersive graphene: is prepared first.It is by deacetylated
75% Chitosan powder is added in glacial acetic acid (1 wt%), is vigorously stirred, makes it completely dissolved, and then adjusts pH value of solution 5 ~ 6,
With chitosan solution (0.5 wt%) 100 mL, it is then that the graphene oxide solution of 1 mg/mL and 0.5 wt% chitosan is molten
The isometric ultrasonic mixing of liquid is uniform, until obtaining the solution of a uniform brown color, then, solution is transferred to the water of 90 oC
In bath, be vigorously stirred 5 h, until solution colour is completely converted into black by brown color, finally, product through 4000 rmp
Revolving speed centrifugation, wash 3 times, dehydrated alcohol washs 2 times, then with n,N-Dimethylformamide ultrasonic disperse, ultrasonic power and frequency
Rate is respectively 100W and 40 KHz, has both obtained graphene (graphene of chitosan functionalization) dispersion liquid of 1mg/mL high dispersive.
The dispersion liquid for having stood 7 days when as shown in Figure 1, Fig. 1 clearly illustrate high dispersive graphene dispersing solution energy prepared by the present invention
It is stabilized；
B: high dispersive graphene the preparation of the graphene-supported Zn Base Metal organic framework composite material of high dispersive: is made in step A
In dispersion liquid, by the Zn (NO of 300 mg3)2 · 6H2O soluble-salt, the organic ligand 2-methylimidazole of 350 mg, 1.0 g
PVP(polyvinylpyrrolidone), 200 mL methanol sequentially add wherein, stir evenly 10 h at room temperature, uniformly mix, through washing
It washs, dry, the graphene-supported Zn-MOF electrode material of high dispersive is made；Yield is 94.0%；Graphene content is in product
8.06at.%, Zn content are 8.14at.%.Morphology characterization is carried out using scanning electron microscope to the composite material of synthesis, such as
Shown in Fig. 3.Fig. 3 clearly illustrates the spheroidal Zn-MOF structure of morphological rules, illustrates the synthetic method of the invention used very
The good typical structure for maintaining Zn-MOF, and it is finely dispersed on the surface of graphene, substantially increase the ratio table of composite material
Area.
Fig. 4 to fig. 6 is the related assays of Zn Base Metal organic framework composite material graphene-supported to high dispersive, and Fig. 4 is
The corresponding XRD spectrum of product.The peak a in figure at 26.0 ° belongs to the characteristic feature peak of graphene；In figure the characteristic peak of Zn-MOF with
Document [J. Am. Soc. 2010,132,12645] is reported completely the same, illustrates that composite material prepared by the invention is protected
The characteristic feature of Zn-MOF is stayed；Fig. 5 is that the XPS scanning of the graphene-supported Zn Base Metal organic framework composite material of high dispersive is total
Map, from figure 5 it can be seen that there are C in composite material prepared by phase, O and Zn element successfully exists；It can by XPS quantitative analysis
Know, Zn content 8.14at.% in product
Fig. 6 is the XPS swarming of the Zn 2p of the graphene-supported Zn Base Metal organic framework composite material of middle high dispersive, therefrom can be with
Two swarmings of 1022.5 eV and 1045.6 eV are clearly observed, they are belonging respectively to Zn 2p3/2 and Zn 2p1/2, it was demonstrated that
Zn2+'s is successfully introduced into.
C: the preparation of electrochemical sensor, by the graphene-supported Zn Base Metal organic backbone composite wood of 0.25 g high dispersive
Material, 1.0 g graphite powders and 0.4 paraffin oil 1 h of hand-ground in mortar are uniformly mixed, paraffin oil are added to above-mentioned mixing
Ground and mixed about 1 hour, forms uniform carbon paste in object；By carbon paste be filled in a glass tube end (diameter be 3 mm,
Long 5 cm), the other end is inserted into copper wire and provides electrical contact to get high dispersive graphene/Zn Base Metal organic framework composite material is arrived
Electrochemical sensor.
High dispersive graphene prepared by the present invention/Zn Base Metal organic framework composite material electrochemical sensor purposes and
Application method: the purposes of the electrochemical sensor is the electrochemical gaging for being directly used in hydrogen peroxide；
Application method is as follows: by high dispersive graphene prepared by the present invention/Zn Base Metal organic framework composite material electrochemistry
Sensor is as working electrode, and Ag/AgCl (KCl of 3 M of filling liquid) is reference electrode, platinum electrode is auxiliary electrode, composition
Three-electrode system；Three-electrode system is put in 10 mL, 0.1 M(pH 7.0 when measuring hydrogen peroxide) phosphate buffer solution in；
Then apply certain constant potential on the working electrode (s, record current-time graph is stirring after background current, which reaches, to be stablized
It is lower that certain density hydrogen peroxide standard solution is successively added into buffer solution with microsyringe；It is 1.0-in hydrogen peroxide concentration
Within the scope of 625 μM, the linear relationship curve of obtained electric current and hydrogen peroxide concentration, linearly dependent coefficient is r=0.9978,
Analysis detection is carried out to hydrogen peroxide using calibration curve method.The hair when investigating has the substance of potential interference behavior to dioxygen aquametry
It is existing, under physiological proportions concentration, when evaluated error≤10%, electrode to chaff interferent (for example, amion acetic acid, ascorbic acid, uric acid,
Glucose, NaCl etc.) response will not interfere the measurement of hydrogen peroxide.
Catalytic action as non-enzymatic hydrogen peroxide electrochemical sensor characterizes: Fig. 7 to Fig. 9 is electrochemical sensing of the invention
Device, Zn-MOF decorating carbon paste electrode, naked carbon paste electrode, graphene modified carbon paste electrode are to the respective cycle volt-ampere of dioxygen aquametry
Figure,
Fig. 7 is the phosphate (pH 7.0) of 0.1 M of electrochemical sensor of the invention being free of and containing 10.0 mM hydrogen peroxide
Bottom liquid in cyclic voltammogram.It can be seen that phosphate (pH 7.0) solution in 0.1 M containing hydrogen peroxide from Fig. 8 to Fig. 9
In, apparent peak is all not observed in three kinds of electrodes, and electric current has almost no change, and illustrates the three classes electrode to the electrification of hydrogen peroxide
Reduction is learned without catalytic action；And on high dispersive graphene activation Zn-MOF decorating carbon paste electrode, (electrochemistry i.e. of the invention is passed
Sensor), with the addition of hydrogen peroxide, reduction current signal obviously acutely increases, and current responsing signal is Zn-MOF modification electricity
200 times or so of pole show high dispersive graphene activation Zn Base Metal organic framework composite material to hydrogen peroxide electrochemical reduction
With excellent catalytic action, it can significantly accelerate electron transmission.
Electrochemical Detection hydrogen peroxide
Under optimum test condition, high dispersive graphene activation Zn Base Metal organic framework composite material electrification prepared by the present invention
Sensor is learned to respond as shown in Figure 10 the current-vs-time of hydrogen peroxide.As seen from Figure 10, the time for reaching 95% steady-state current is small
In 5 s, with the increase of hydrogen peroxide concentration, sensor is also gradually increased the response current of hydrogen peroxide, in 1.0-625 μM of models
In enclosing, response current and hydrogen peroxide concentration are (see Figure 11) in a linear relationship, calculate its lowest detection and are limited to 0.05 μM, such as Figure 10
It is shown.It is measured according to electrode active area, high dispersive graphene activation Zn Base Metal organic framework composite material electricity is calculated
Chemical sensor is up to 401 μ A mM to the measurement sensitivity of hydrogen peroxide-1 cm-2。
The stability and reproducibility of non-enzymatic hydrogen peroxide electrochemical sensor prepared by the present invention are excellent.For the same dioxygen
Water sensor, the relative standard deviation of 10 measurements are 2.01%, for 5 groups of hydrogen peroxide sensors, the relative standard of 5 measurements
Deviation is 7.31%.Room temperature stores a week to electrode when not used, and electric current is maintained as the 90% of initial current.Allowing evaluated error
When≤10%, the substances such as amion acetic acid (Glycine), ascorbic acid (MAA), uric acid (MUA), glucose (glucose), NaCl
Figure 12 is shown in hardly interference measurement, interference measurement.
Claims (5)
1. the preparation method of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor, feature exist
In the following steps are included:
A: the preparation of high dispersive graphene: used each material is using following amounts or using identical with following amounts in this step
Ratio, the graphene oxide solution of 1 mg/mL of the mL equal volume amounts of 100 mL~300 are uniformly mixed with 0.5 wt% chitosan solution
It closes, until obtaining the solution of uniform brown color；Solution is transferred in the water-bath of the oC of 80oC~95, is vigorously stirred 4 h~6
H, until solution colour is completely converted into black by brown color；Product be centrifuged, wash 2~3 times, dehydrated alcohol
Washing 2~3 times, by product in n,N-Dimethylformamide ultrasonic disperse, ultrasonic power and frequency are respectively 100W and 40
The graphene of polymolecularity can be obtained in KHz；
B: the preparation of the graphene-supported Zn Base Metal organic framework composite material of high dispersive: in the high dispersive graphite that step A is obtained
Zn (NO is added in alkene3)2 · 6H2O 200 mg~500 mg, 2-methylimidazole 200 mg~500 mg, PVP 1g~
4g, the methanol ml of 150 ml~500, are stirred to react 10~13 h, reaction precipitate is centrifuged, dehydrated alcohol is washed at room temperature
It washs, is dried in vacuo at 30 DEG C~60 DEG C, obtain the graphene-supported Zn Base Metal organic framework composite material of high dispersive；
C: the preparation of electrochemical sensor: the graphene-supported Zn Base Metal organic backbone of high dispersive obtained by step B is compound
Material: graphite powder: paraffin oil is 0.5:2:0.8 feeding in mass ratio, and hand operated mixing mixes about 1h~2h, uniform until being formed
Carbon paste；The glass tube that carbon paste filling glass bore is 3 mm is taken, is inserted into a copper wire as electrode from the other end
Connector；Obtain high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor.
2. high dispersive graphene according to claim 1/Zn Base Metal organic framework composite material electrochemical sensor
Preparation method, it is characterised in that: in the graphene-supported Zn Base Metal organic framework composite material of high dispersive obtained in step B
Zn-MOF be spherical shape.
3. high dispersive graphene according to claim 1/Zn Base Metal organic framework composite material electrochemical sensor
Preparation method, it is characterised in that: in the graphene-supported Zn Base Metal organic framework composite material of high dispersive obtained in step B
Graphene mass percentage be wt7.01%~13.10%.
4. high dispersive graphene according to claim 1/Zn Base Metal organic framework composite material electrochemical sensor
Preparation method, it is characterised in that: step A be centrifugated when revolving speed be 3000~4000 rmp.
5. the application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor, using claim 1
Electrochemical sensor obtained, it is characterised in that: the electrochemical sensor is directly used in Electrochemical Detection hydrogen peroxide, answers
Use method as follows: using prepared high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor as
Working electrode, the Ag/AgCl of the KCl of 3 M of filling liquid are reference electrode, platinum electrode as auxiliary electrode, form three electrodes
System；When measurement, three-electrode system is placed in the phosphate buffer solution of 0.1 M, pH 7.0 of 10 mL；In -0.40V
Under constant potential, record current-time graph, when background current is stable, under stiring, with microsyringe to the 0.1 of 10 mL
M, hydrogen peroxide is added in the phosphate buffer solution of pH 7.0, hydrogen peroxide concentration can be obtained according to electric current.
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| CN109920655A (en) * | 2019-03-20 | 2019-06-21 | 北京理工大学 | Porous carbon electrodes preparation method derived from a kind of MOF |
| CN110037052A (en) * | 2019-04-11 | 2019-07-23 | 浙江工商大学 | A kind of photo-catalyst agent and its preparation method and application |
| CN110057878A (en) * | 2019-02-20 | 2019-07-26 | 云南大学 | A kind of molecular imprinting electrochemical detection method of ketamine drugs |
| CN110467821A (en) * | 2019-08-30 | 2019-11-19 | 济南大学 | A kind of preparation method and application of the chitosan/oxidized graphene chirality composite material of Co-MOF/ |
| CN111751421A (en) * | 2020-07-14 | 2020-10-09 | 江西农业大学 | Electrochemical sensor for quickly and efficiently detecting lead ions |
| CN116037130A (en) * | 2023-02-03 | 2023-05-02 | 上海宇昂水性新材料科技股份有限公司 | Graphene-supported copper-zinc-aluminum catalyst and preparation method and application thereof |
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