CN109487370A - MOF-235-500 DEG C of material of spinning and its preparation method and application - Google Patents
MOF-235-500 DEG C of material of spinning and its preparation method and application Download PDFInfo
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Abstract
The invention discloses MOF-235-500 DEG C of materials of spinning and its preparation method and application, prepare presoma with the ethanol solution of MOF-235 and PVP composite material.The presoma is calcined under 500 DEG C of high temperature, MOF-235-500 DEG C of material of spinning is made.MOF-235-500 DEG C of material of spinning of synthesis is modified in glassy carbon electrode surface, MOF-235-500 DEG C of spinning/Nafion/GCE sensor has been constructed.The linear relationship of dopamine (DA) peak current and concentration is investigated using I-T curve method.The result shows that: in the Acetic acid-sodium acetate solution system of pH=4, DA shows good electrochemical behavior on the sensor.In addition, MOF-235-500 DEG C of spinning/Nafion/GCE sensor of preparation has preferable reproducibility, stability and selectivity, and the sensor is used successfully to analysis injection sample actual sample.
Description
Technical field
The present invention relates to new materials, and in particular to MOF-235-500 DEG C of material of spinning and its preparation method and application.
Background technique
Dopamine (DA) is one of most important neurotransmitter, is that mammal and the important information of mankind's nervous centralis pass
Substance is passed, vital role is play in central nervous system, renal system, Hormone system, cardiovascular system.DA exists
The intracorporal abnormal transmission of people can cause schizophrenia, the diseases such as parkinsonism, and the concentration of DA also influences the learning and memory of people
Ability.Therefore, effectively monitoring is carried out quickly and accurately to the content of DA, either from cure the disease, physiological Study, or in control medicine
Amount of substance etc. all has positive effect very much.But the DA concentration range in organism is down to 0.01-1 μM, to its quantitative detection
It is very difficult.In recent years, the methods of many advanced analysis methods such as gas-chromatography, liquid chromatogram, mass spectrum, Capillary Electrophoresis quilt
Apply in the measurement of DA concentration, electrochemical analysis method because have response is fast, in operation simply, high sensitivity, expense it is low and
The advantages that time-consuming is few, the application in terms of detecting small-molecule substance attracts extensive attention.
Metal-organic framework materials (metal-organic frameworks, MOFs) are a kind of matching with three-dimensional structure
Position polymer, is made up of organic ligand and metal ion self assembly, is a kind of novel porous material.The tool of MOFs material
There are big specific surface area, higher Kong Rong, aperture, structure and vdiverse in function.Currently, be applied to hydrogen storage, drug carrier,
It sensor, gas absorption and separates etc..In recent years, MOFs material is in terms of electroanalysis using as research hotspot.MOF-
235 are made up of with terephthalic acid (TPA) ligand coordinate bond as important one of MOFs material, by Fe ion, through high-temperature calcination
Afterwards, there is biggish specific surface area, be suitable as sensor dressing agent.Currently, synthesis MOF-235 MATERIALS METHODS mainly has steam
Xiang Fa, ion thermal synthesis method, diffusion method and hydro-thermal method.This experiment carries out hydro-thermal method using reaction kettle and synthesizes MOF-235 material, tool
There are the advantages such as the reaction time is shorter, crystal growth not high to temperature requirement is perfect and equipment is simple.
Electrostatic spinning is come across earliest in the 1930s, early in 1934, and Formhals has applied for the first time in electrostatic field
Middle first patent that fiber is prepared using high-pressure electrostatic, is acknowledged as the origin of electrostatic spinning technique.Electro spinning nano fiber
Have the characteristics that large specific surface area, porosity are high, so that its surface and activity is enable to increase, so that interfacial effect is produced, this
A little peculiar properties make it be applied to many fields.High-voltage electrostatic spinning technology is to provide number kilovoltage by high-voltage DC power supply,
The anode of power supply is connected with the fine needle of syringe when spinning, and cathode is connect with aluminum foil plate.Now, have and be much synthetically prepared nanometer
The method of fiber, such as split-phase method, template synthesis method, method of reeling off raw silk from cocoons, white construction from part etc..It is for the more other methods of method of electrostatic spinning
Most simple and effective method.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides MOF-235-500 DEG C of materials of spinning and preparation method thereof
And application.
The technical scheme is that a kind of preparation method of MOF-235-500 DEG C of material of spinning, MOF-235 material add
Enter into the ethanol solution of polyvinylpyrrolidone and acetic acid is added after continuously stirring, after the completion turns MOF-235 composite material
It moves on in the plastic injector with small pinhead, and syringe needle is connected to can generate the high voltage power supply of DC voltage just
Pole；The cathode of the power supply is connected with aluminum foil plate, carries out electrostatic spinning after applying the voltage of 16.5kV, makes after the completion of electrostatic spinning
MOF-235 presoma composite nano fiber, nanofiber with the speed of 5 DEG C/min is risen to 500 DEG C in N2 and at this
At a temperature of keep 5h, be made MOF-235-500 DEG C of material of spinning.
Further improvement of the present invention includes:
The mass ratio 1:10 of the MOF-235 material and polyvinylpyrrolidone.
2.02g polyvinylpyrrolidone is dissolved in 6mL ethanol solution by the method, and is uniformly stirred at room temperature
1h is mixed to make it completely dissolved；Then, the MOF-235 material of 0.20g is added in the ethanol solution of polyvinylpyrrolidone simultaneously
6h is continuously stirred, 0.5mL acetic acid is then added；Finally, the MOF-235 composite material of 5mL is transferred to the 5mL with small pinhead
In plastic injector；Then the syringe needle phase of the up to high-voltage power cathode of the DC voltage of 30kV and syringe will be generated
Even, the cathode of power supply is connected with aluminum foil plate；Electrostatic spinning is carried out under the voltage of 16.5kV.Between syringe needle and receiver sheet
Distance is maintained at 15cm；By MOF-235 presoma composite nano fiber obtained place in vacuum drying oven at room temperature 12h with
Remove the solvent residues in nanofiber；Finally, nanofiber is risen to 500 DEG C simultaneously with the speed of 5 DEG C/min in N2
5h is kept at such a temperature, and MOF-235-500 DEG C of material of spinning is made.
The molecular weight of the polyvinylpyrrolidone is 10000.
Another object of the present invention is to provide MOF-235-500 DEG C of materials of spinning obtained according to the method described above.
The present invention further provide MOF-235-500 DEG C of material of above-mentioned spinning preparation MOF-235-500 DEG C of spinning/
Application in Nafion/GCE sensor.
The application is that MOF-235-500 DEG C of material of spinning is taken to be placed in a beaker respectively, and distilled water is then added, ultrasound
10min makes nano material be uniformly dispersed, and obtains suspension；Hanging drop is pipetted to be added in processed glassy carbon electrode surface,
The dry 10min under infrared lamp, make MOF-235-500 DEG C of material of spinning in a short time it is uniform curing on the electrode；With moving back
It takes 0.5%Nafion solution to be in kind added dropwise at the electrode surface, dries at room temperature, keep modified electrode more stable, make
Obtain MOF-235-500 DEG C of spinning/Nafion/GCE sensor.
It is diluted to obtain 0.5%Nafion solution with the dehydrated alcohol of 9mL with the Nafion mother liquor that pipette pipettes 1mL
It uses.
The present invention also provides application of MOF-235-500 DEG C of the spinning/Nafion/GCE sensor in detection dopamine.
It is 1-170 μM to the range of linearity of dopamine detection in the application, detection is limited to 0.21 μM.
The present invention has synthesized MOF-235 material using hydro-thermal method.And using the method for electrostatic spinning, will contain
The ethanol solution of MOF-235 and PVP (Polyvinylpyrrolidone) composite material is prepared into MOF-235 forerunner
Body.The presoma is calcined under 500 DEG C of high temperature, MOF-235-500 DEG C of material of spinning is made.Using infrared spectroscopy and XRD pairs
MOF-235 material is characterized.MOF-235-500 DEG C of material of spinning of synthesis is modified in glassy carbon electrode surface, spinning has been constructed
Silk MOF-235-500 DEG C/Nafion/GCE sensor.Condition optimizing is carried out to experiment by cyclic voltammetry, and bent using I-T
The linear relationship of collimation method investigation dopamine (DA) peak current and concentration.The result shows that: in the Acetic acid-sodium acetate solution body of pH=4
In system, DA shows good electrochemical behavior on the sensor, and the concentration range of linearity of DA is 1-170 μM, and detection is limited to
0.21 μM (S/N=3).In addition, preparation MOF-235-500 DEG C of spinning/Nafion/GCE sensor have preferable reproducibility,
Stability and selectivity, and the sensor is used successfully to analysis injection sample actual sample.
The present invention obtains MOF-235 presoma nanofiber using electrostatic spinning technique, then passes through high-temperature calcination, preparation
MOF-235-500 DEG C of material modified electrode of spinning, MOF-235-500 DEG C of spinning/Nafion/GCE sensor has been constructed, to DA
With preferable electrochemical response.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of MOF-235.
Fig. 2 is the XRD diffraction pattern of MOF-235.
Fig. 3 (a) is bare electrode (i), MOF-235-500 DEG C of spinning/Nafion/GCE sensor (ii), MOF-235-500
DEG C/Nafion/GCE sensor (iii), the cyclic voltammetry curve in 5mM K3 [Fe (CN) 6] (KCl containing 0.1mM) solution.
Fig. 3 (b) is this Tequ line of the energy of the electrode sensor of bare electrode and modification.
Fig. 4 is the cyclic voltammogram that the sensor that bare electrode and different materials modified electrode are constructed detects DA, from it is lower to
On be successively bare electrode (a), MOF-235/Nafion/GCE sensor (b), MOF-235-500 DEG C/Nafion/GCE sensor
(c) and MOF-235-500 DEG C of spinning/Nafion/GCE sensor (d).
The cyclic voltammogram of dopamine, HAc-NaAc (a), NaH2PO4- are detected when Fig. 5 is different electrolyte solutions
Na2HPO4(b)、NaH2PO4-Na2HPO4(c)、Na2HPO4-C6H8O7(d)、C6H8O7-Na3C6H5O7·2H2O(e)
Fig. 6 be various concentration MOFs modified electrode detection DA cyclic voltammogram, 10mg/mL (c), 12mg/mL (b),
15mg/mL(a)、18mg/mL(d)、20mg/mL(e)、22mg/mL(f)。
Fig. 7 (a) is the cyclic voltammogram that dopamine is detected under condition of different pH, indicated from a to f pH be respectively 6,5.5,5,
4.5,4,3.5 electrolyte solution.
Fig. 7 (b) is the electric current line chart of redox peaks under different pH.
Fig. 7 (c) is the linear relationship between DA oxidizing potential and pH.
Fig. 8 (a) is the cyclic voltammogram of different scanning rates, successively indicate 10 from a to p, 20,40,60,80,100,
120、140、160、180、200、220、240、260、280、300mV/s。
Fig. 8 (b) is the linear graph of different scanning rates.
Fig. 9 (a) be the DA concentration of solution system in i-t curve graph be followed successively by 1,2,3,5,7,9,10,20,30,40,50,
60,70,80,90,100,110,120,130,140,150,160,170 μM and
Fig. 9 (b) is i-c linear graph.
The reproducibility of Figure 10 (a) Different electrodes and (b) same electrode.
Figure 11 (a) indicates that anti-inorganic ions interferes i-t curve graph.
Figure 11 (b) indicates that anti-organic matter interferes i-t curve graph.
Dopamine concentration measures i-t curve graph in Figure 12 (a) injection sample.
Figure 12 (b) is the i-c linear graph of standard sample.
Specific embodiment
It elaborates with reference to the accompanying drawing to the present invention.
Embodiment
Instrument and reagent
1 key instrument of table
2 main agents of table
The preparation of MOF-235
The N-N dimethylformamide (DMF) of 100mL is added into the large beaker of 250mL, accurately weighs 1.43g to benzene two
Formic acid and 2.38g FeCl3·6H2O is dissolved in DMF.Mixed liquor and ethanol solution are pipetted by the volume ratio of 1:1, after mixing
It is placed in reaction kettle, so that it is reacted 12h under conditions of 85 DEG C, washed respectively after product centrifugation with distilled water, ethyl alcohol, repeat this
Operation 3 times.Product after cleaning is placed in drying in 100 DEG C of vacuum drying oven and for 24 hours, obtains MOF-235 material, store for future use.
The preparation of electrostatic spinning MOF-235 presoma
Firstly, 2.02g PVP (Mw=10000) is dissolved in 6mL ethanol solution, and uniform stirring 1h makes at room temperature
It is completely dissolved.Then, the MOF-235 material of 0.20g is added in PVP solution and is continuously stirred 6h, 0.5mL is then added
Acetic acid.Finally, being transferred to the MOF-235 composite material of 5mL in the 5mL plastic injector with small pinhead.Then will
The high-voltage power cathode of DC voltage for generating up to 30kV is connected with the syringe needle of syringe, cathode and the aluminum foil plate phase of power supply
Even.Electrostatic spinning is carried out under the voltage of 16.5kV.The distance between syringe needle and receiver sheet are maintained at 15cm.By MOF-
12h is in the vacuum drying oven of 235 presoma composite nano fibers placement at room temperature to remove the solvent residues in nanofiber.
Finally, by nanofiber in N2In rise to 500 DEG C with the speed of 5 DEG C/min and keep 5h at such a temperature, spinning is made
MOF-235-500 DEG C of material stores for future use.
The preparation of working electrode
Pretreatment of glassy carbon electrode
The aluminum oxide polishing powder polishing 3min that glass-carbon electrode is successively used to 0.3 and 0.05 μM, so that electrode surface is smooth
Then cleaning completely removes aluminium oxide on electrode with distilled water flushing, then successively put the electrodes into the sulfuric acid containing 0.5M, nitre
Acid: in the beaker of distilled water (1:1), dehydrated alcohol and distilled water, ultrasound 10min, uses distilled water flushing, then respectively after taking-up
Naturally dry is spare.
Modified electrode preparation
The MOF-235-500 DEG C of material of spinning for weighing different quality respectively is placed in each small beaker, is then added 1mL's
Distilled water, ultrasonic 10min make nano material be uniformly dispersed, obtain suspension.It pipettes 5 μ L hanging drops and is added to processed glass
In carbon electrodes, the dry 10min under infrared lamp, make MOF-235-500 DEG C of material of spinning in a short time it is uniform curing
On electrode.The 0.5%Nafion solution for then pipetting 5 μ L (pipettes the anhydrous second of the Nafion mother liquor 9mL of 1mL with pipette
Alcohol, which dilutes to obtain 0.5%Nafion solution, can be used) it is in kind added dropwise at the electrode surface, it dries, makes at room temperature
Modified electrode is more stable, and MOF-235-500 DEG C of spinning/Nafion/GCE sensor is made.
Electrochemical determination method
All experiment tests are all completed on electrochemical workstation, using traditional three-electrode system: bare electrode or modification
Glass-carbon electrode be working electrode, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode.Three electrodes are connected to
On electrochemical workstation, select HAc-NaAc as electrolyte, compound concentration is 5 × 10-4The DA solution of M, in sweeping for 100mV/s
It retouches within the scope of rate and scanning voltage -0.3~0.8V and carries out electrochemical behavior measurement using CV method.
Characterization
Infrared spectrum characterization
The infrared spectrogram of MOF-235 sample is as shown in Figure 1, in 1592cm-1The characteristic peak at place is C=C stretching vibration,
1392cm-1The characteristic peak at place is C=C skeletal vibration, in 1017cm-1The characteristic peak at place is the C-O vibration in carboxyl, is shown
Contain-COOH group in MOF-235 material.
X-ray diffraction (XRD) phenogram of MOF-235-synthesized sample as shown in Fig. 2, its between 5-50 °
There is in diffraction angular region high crystallinity, main diffraction peak appears in 2 θ=9.4 °, and 10.7 °, 12.6 °, 18.9 ° and 22 °.And
And the opposite diffracted intensity of MOF-235-synthesized and the normal data of MOF-235-simulated are essentially identical, show
The successful synthesis of MOF-235 material.
Electrochemical Characterization
The electrochemical properties of Different electrodes sensor are investigated by CV and electrochemical impedance spectroscopy (EIS) method.As seen from the figure,
Redox peaks show as completely reversibility, redox peaks potential difference (Δ Ep) on the cyclic voltammetry curve that bare electrode (i) scans
For 148mV.Compared with bare electrode, the electrode Δ Ep value of MOF-235-500 DEG C of material modified of spinning is down to 135mV, but aoxidizes
The value of reduction peak current, which reduces, shows that the electrode resistance of composite material material modification is larger；Compared with curve (i) and (ii), curve
(iii) redox peaks become smaller, and show K3[Fe(CN)6] probe solution is in MOF-235-500 DEG C/Nafion/GCE sensor
On impedance it is maximum.
This corresponding semi-circular portions of spy's spectrum high frequency of energy represent dynamic control process, and half diameter of a circle represents charge and turns
Move resistance (Rct), the diameter of circular arc is bigger, and resistance is bigger, and electron transfer capacity just weakens.As seen from the figure, different sensors
RctValue follows sequence below: MOF-235-500 DEG C/Nafion/GCE sensor > MOF-235-500 DEG C of spinning/Nafion/GCE
Sensor > naked GCE, shows the material of spinning, and the sensor constructed after calcining compares the resistance of non-spinning in probe solution
Small, this is consistent with CV result.
Electrochemical behavior of the DA in different sensors
By CV method, 5 × 10 are investigated-4M DA (pH=4) is in bare electrode, MOF-235/Nafion/GCE sensor, MOF-
Electrochemical behavior in 235-500 DEG C/Nafion/GCE sensor and MOF-235-500 DEG C of spinning/Nafion/GCE sensor
(Fig. 4).As seen from the figure, bare electrode and MOF-235/Nafion/GCE sensor do not have apparent electrochemical response, MOF- to DA
235-500 DEG C/Nafion/GCE sensor has certain current-responsive to DA, and MOF-235-500 DEG C of spinning/Nafion/GCE
Sensor is most strong to the response of DA.This is because MOF-235-500 DEG C of spinning dispersion is more uniform, glass carbon is modified as dressing agent
The sensor that electrode is constructed can greatly improve the specific surface area of sensor, promote DA that oxygen preferably occurs in sensor surface
Change reduction reaction.
Detection of the different electrolyte solutions to DA
HAc-NaAc, H are chosen in experiment2NaPO4-Na2HPO4、NaH2PO4-Na2HPO4、Na2HPO4-
C6H8O7、C6H8O7-Na3C6H5O7·2H2Five kinds of different electrolyte solutions of O.5 × 10 are prepared respectively-4DA (the pH of M
=4) after solution, investigating different electrolytes using CV method influences DA electrochemical behavior.As shown in Figure 5, HAc-NaAc is selected to make
For electrolyte solution, the current-responsive of DA on a sensor is most strong.Therefore the HAc-NaAc that 0.2M is chosen in this experiment does electrolyte.
Measurement of MOFs-235-500 DEG C of various concentration to DA
The MOFs-235-500 DEG C of material of spinning for weighing 10mg, 12mg, 15mg, 18mg, 20mg and 22mg respectively, is dissolved into
In the distilled water of 1mL, making concentration is respectively 10mg/mL, 12mg/mL, 15mg/mL, 18mg/mL, 20mg/mL, 22mg/mL
Suspension, after ultrasonic 10min, modified glassy carbon electrode constructs corresponding electrochemical sensor.It is 5 × 10 in pH=4, concentration-4M
Solution in, investigate influence (Fig. 6) of the sensor to DA current-responsive.The result shows that: concentration is the MOFs-235- of 15mg/mL
The sensor of 500 DEG C of modifications is best to DA response effect.
Optimization to electrolyte pH
Using CV method, investigating different pH value, (solution concentration is 5 × 10 on the influence of the current-responsive of DA-4M), as a result such as Fig. 7
It is shown.As seen from the figure, DA response first with pH increase and enhance, after weaken, the electric current in pH=4 with the increase of pH
Response is most strong, therefore the optimal pH of this experiment electrolyte solution is 4.The oxidation spike potential of pH value of solution can also be obtained from figure
There is good linear relationship between pH value of solution.
Influence of the sweep speed to dopamine determination
By investigating influence of the sweep speed to the redox electrochemical behavior of DA, spinning MOF-235-500 is had studied
DEG C/kinetics (Fig. 8) of Nafion/GCE sensor.It can be seen from the figure that with the raising of sweep speed, DA electric current
Response is more and more stronger, and there is good linear relationships between the response current and sweep speed of redox peaks, this shows
There are granule surface contral dynamic process, equations of linear regression on modified electrode surface are as follows:
Oxidation peak Ip (μ A)=- 0.2118v-23.0489 (mV/s), R2=0.9937；
Reduction peak Ip (μ A)=0.2362v+22.0177 (mV/s), R2=0.9955.
In subsequent experiment, selection 100mV/s is sweep speed.
Amperometric Determination
(detection current potential+0.6V, electrolyte is HAc-NaAc solution, volume 5mL) under the best experimental conditions, every
The DA standard solution of certain volume is added into electrolyte by 200s, controls the concentration of DA in electrolyte and carries out ampere survey to it
It is fixed, steady-state current-response time (i-t) curve is obtained, the electric current for showing DA as a result as shown in Fig. 9 (a) and time are in ladder
Shape variation.Good linear relationship, and linear equation are presented by the electric current and concentration that shown in 9 (b), show DA are as follows: Ip (μ A)=
0.0375+0.0078c(μM)(R2=0.9946).The range of linearity of DA is 1-170 μM, and detection is limited to 0.21 μM.
Working electrode stability and reproducibility
The reproducibility of Different electrodes and same electrode is investigated by CV method.Measurement result is as shown in Figure 10, seven not simultaneous interpretations
The RSD of sensor is 3.31%.The RSD that same root electrode continuously does seven times is 1.41%.Therefore, which has preferable weight
Existing property.In order to investigate MOF-235-500 DEG C of spinning/Nafion/GCE sensor stability, place a sensor in refrigerator
It saves, tests after two months, it is found that the sensor remains to retain its original value 91.2% to the current-responsive of DA, show the biography
Sensor has preferable stability.
The anti-interference of working electrode
A large amount of inorganic ions and organic matter are rich in human plasma.Therefore anti-interference measurement is also biosensor
One critically important factor of detection, the testing result of anti-interference can be obtained by Amperometric Determination method (i-t curve method), most
Under good determination condition, the interference of inorganic ions and organic matter to detection dopamine is investigated respectively, in 5mL HAc-NaAc solution
The concentration for being continuously added to 50 μ L respectively is 1 × 10-2Inorganic interfering substance (the BaCl of M2、MgCl2、NiCl2、KCl、CaCl2) and 50 μ L
Concentration be 1 × 10-3M dopamine solution and the concentration of 50 μ L are 1 × 10-2M organic interfering substance (terramycin (OTC), VB3、
VB6, lactose, sucrose, glucose, maltose) and 50 μ L concentration be 1 × 10-3M dopamine solution.As a result as shown in figure 11, do
The current-responsive for disturbing substance is smaller, can ignore, and shows that the sensor has good selectivity.
The measurement of DA concentration is (detection current potential+0.6V, electrolyte under optimum experimental condition in medical injection sample
For HAc-NaAc solution, liquid product in bottom is 5mL) it carries out.The injection sample for the 10mg/mL for accurately pipetting 1mL is placed in
Injection sample is diluted 25 times by 25mL volumetric flask HAc-NaAc solution constant volume, and the rate of recovery of DA is to pass through Standard entertion
What method obtained, then concentration is 1 × 10 by the DA solution after 40 μ L dilution is added into 5mL electrolyte solution-2M standard DA sample
Product are added in the electrolyte containing actual sample, and as shown in figure 12,3 data of table are calculated in summary, standard DA sample
The rate of recovery is 98.63%, the linear equation of experiment are as follows:
Ip (μ A)=0.2390+0.01154c (μM/L) (R2=0.9987)
3 DA injection measurement result of table
The present invention has successfully constructed MOF-235-500 DEG C of spinning/Nafion sensor, rings to DA with good electrochemistry
It answers, with optimal conditions, DA has good linear relationship on the sensor.The range of linearity of DA is 1-170 μM, detection limit
It is 0.21 μM.Moreover, the sensor has good reproducibility, stability and selectivity.This method is successfully applied in DA injection
In the detection of liquid, and the rate of recovery having had.This method has preparation process simple, and Costco Wholesale is lower, fast response time, rings
The advantages such as induction signal is strong and stability is good, provide good reference for the detection of other electroactive substances.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of preparation method of MOF-235-500 DEG C of material of spinning, which is characterized in that MOF-235 material is added to polyethylene
Acetic acid is added in the ethanol solution of pyrrolidones and after continuously stirring, MOF-235 composite material is transferred to small after the completion
In the plastic injector of syringe needle, and syringe needle is connected to the high-voltage power cathode that can generate DC voltage；The electricity
The cathode in source is connected with aluminum foil plate, carries out electrostatic spinning after applying the voltage of 16.5kV, MOF-235 is made after the completion of electrostatic spinning
Nanofiber is risen to 500 DEG C in N2 with the speed of 5 DEG C/min and kept at such a temperature by presoma composite nano fiber
MOF-235-500 DEG C of material of spinning is made in 5h.
2. the method according to claim 1, wherein the matter of the MOF-235 material and polyvinylpyrrolidone
Amount is than being 1:10.
3. the method according to claim 1, wherein it is molten that 2.02g polyvinylpyrrolidone is dissolved in 6mL ethyl alcohol
In liquid, and uniform stirring 1h makes it completely dissolved at room temperature；Then, the MOF-235 material of 0.20g is added to polyethylene pyrrole
In the ethanol solution of pyrrolidone and 6h is continuously stirred, 0.5mL acetic acid is then added；Finally, by the MOF-235 composite material of 5mL
It is transferred in the 5mL plastic injector with small pinhead；Then the high voltage power supply of the up to DC voltage of 30kV will be generated
Anode is connected with the syringe needle of syringe, and the cathode of power supply is connected with aluminum foil plate；Electrostatic spinning is carried out under the voltage of 16.5kV
's.The distance between syringe needle and receiver sheet are maintained at 15cm；MOF-235 presoma composite nano fiber obtained is placed on room
12h is in vacuum drying oven under temperature to remove the solvent residues in nanofiber；Finally, by nanofiber in N2 with 5 DEG C/
The speed of min rises to 500 DEG C and keeps 5h at such a temperature, and MOF-235-500 DEG C of material of spinning is made.
4. the method according to claim 1, wherein the molecular weight of the polyvinylpyrrolidone is 10000.
5. a kind of MOF-235-500 DEG C of material of spinning, which is characterized in that be made according to any one of claim 1-4 the method.
6. a kind of MOF-235-500 DEG C of material of spinning answering in preparation MOF-235-500 DEG C of spinning/Nafion/GCE sensor
With.
7. application according to claim 6, which is characterized in that MOF-235-500 DEG C of material of spinning is taken to be placed in beaker respectively
In, distilled water is then added, ultrasonic 10min makes nano material be uniformly dispersed, obtains suspension；It pipettes hanging drop and is added to and located
In the glassy carbon electrode surface managed, dry 10min, keeps MOF-235-500 DEG C of material of spinning equal in a short time under infrared lamp
Even solidification is on the electrode；It then pipettes 0.5%Nafion solution to be in kind added dropwise at the electrode surface, dry in the air at room temperature
It is dry, keep modified electrode more stable, MOF-235-500 DEG C of spinning/Nafion/GCE sensor is made.
8. application according to claim 7, which is characterized in that pipette the nothing of the Nafion mother liquor 9mL of 1mL with pipette
Water-ethanol, which dilutes to obtain 0.5%Nafion solution, can be used.
9. application of MOF-235-500 DEG C of the spinning/Nafion/GCE sensor in detection dopamine.
10. application according to claim 9, which is characterized in that the range of linearity to dopamine detection is 1-170 μM, inspection
Survey is limited to 0.21 μM.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980287A (en) * | 2021-11-29 | 2022-01-28 | 南京工业大学 | Preparation method and catalytic application of iron-based MOF material |
| CN114733497A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | Light-reproducible metal-organic framework composite film and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395094A (en) * | 2002-07-18 | 2003-02-05 | 武汉大学 | Electrochemical sensor for determining dopamine |
| EP1923423A1 (en) * | 2006-11-14 | 2008-05-21 | Sociedad Anonima Minera Catalano-Aragonesa | Process for the additivation of synthetic fibres, artificial fibres and polymers with special properties |
| US9307790B2 (en) * | 2011-08-01 | 2016-04-12 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
| CN106835363A (en) * | 2017-01-18 | 2017-06-13 | 南京理工大学 | A kind of preparation method of the hollow carbon fiber material for ultracapacitor |
| CN106835362A (en) * | 2017-01-16 | 2017-06-13 | 中国科学院长春应用化学研究所 | Micron ball carbon fibre composite of codope and preparation method thereof |
| CN107727720A (en) * | 2017-11-29 | 2018-02-23 | 河南科技学院 | HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared |
| KR20180065493A (en) * | 2016-12-08 | 2018-06-18 | 한국과학기술원 | Gas sensor and member using metal oxide nanotubes including nanoscale heterogeneous catalysts by using metal-organic framework, and manufacturing method thereof |
| CN108630921A (en) * | 2018-04-24 | 2018-10-09 | 西安科技大学 | The preparation method of ferriferous oxide/carbon fiber composite lithium ion battery cathode material |
-
2018
- 2018-11-08 CN CN201811328027.8A patent/CN109487370A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395094A (en) * | 2002-07-18 | 2003-02-05 | 武汉大学 | Electrochemical sensor for determining dopamine |
| EP1923423A1 (en) * | 2006-11-14 | 2008-05-21 | Sociedad Anonima Minera Catalano-Aragonesa | Process for the additivation of synthetic fibres, artificial fibres and polymers with special properties |
| US9307790B2 (en) * | 2011-08-01 | 2016-04-12 | Massachusetts Institute Of Technology | Porous catalytic matrices for elimination of toxicants found in tobacco combustion products |
| KR20180065493A (en) * | 2016-12-08 | 2018-06-18 | 한국과학기술원 | Gas sensor and member using metal oxide nanotubes including nanoscale heterogeneous catalysts by using metal-organic framework, and manufacturing method thereof |
| CN106835362A (en) * | 2017-01-16 | 2017-06-13 | 中国科学院长春应用化学研究所 | Micron ball carbon fibre composite of codope and preparation method thereof |
| CN106835363A (en) * | 2017-01-18 | 2017-06-13 | 南京理工大学 | A kind of preparation method of the hollow carbon fiber material for ultracapacitor |
| CN107727720A (en) * | 2017-11-29 | 2018-02-23 | 河南科技学院 | HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared |
| CN108630921A (en) * | 2018-04-24 | 2018-10-09 | 西安科技大学 | The preparation method of ferriferous oxide/carbon fiber composite lithium ion battery cathode material |
Non-Patent Citations (4)
| Title |
|---|
| LUIZ CARLOS DOMINGOS BATISTA ET AL.: "Metal organic framework - 235 (MOF-235) modified carbon paste electrode for catechol determination in water", 《ELECTROANALYSIS》 * |
| MAO XUANXIANG ET AL.: "beta-Cyclodextrin functionalization of metal-organic framework MOF-235 with excellent chemiluminescence activity for sensitive glucose biosensing", 《TALANTA》 * |
| 何聿 等: "金属有机骨架材料MOF-235的合成及其对甲基橙吸附性能的研究", 《福州大学学报》 * |
| 葛华丽: "基于功能化金属有机框架化合物在电化学分析中的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980287A (en) * | 2021-11-29 | 2022-01-28 | 南京工业大学 | Preparation method and catalytic application of iron-based MOF material |
| CN114733497A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | Light-reproducible metal-organic framework composite film and preparation method and application thereof |
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