CN111521653B - Tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, electrochemical sensor prepared from same and application of electrochemical sensor - Google Patents
Tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, electrochemical sensor prepared from same and application of electrochemical sensor Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
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- 239000011701 zinc Substances 0.000 title claims abstract description 30
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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Abstract
The invention discloses a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound, and an electrochemical sensor and application prepared by the same. The Nafion tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound is directly coated on the surface of the glassy carbon electrode by a one-step dripping method, and the method has the advantages of quick and simple operation, good reproducibility and the like. The prepared sensor has low cost, good stability and selectivity, wide detection range and low detection limit of 10nmol/L, can realize accurate, rapid and high-sensitivity detection of acetaminophen, and has potential application value in the fields of clinical diagnosis, drug analysis and the like.
Description
Technical Field
The invention relates to a water-soluble tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, and an electrochemical sensor prepared from the water-soluble tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound and application of the water-soluble tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, and belongs to the technical field of electrochemistry and nano materials.
Background
Paracetamol (AC), a relatively common antipyretic analgesic, has extremely wide application in clinical treatment. Normal doses of drugs are relatively safe to administer, but excessive use can lead to severe hepatotoxicity and nephrotoxicity and even death. Meanwhile, the water source is polluted to a certain extent when the water is metabolized into the environment after long-term and extensive use and abuse.
At present, the detection method of acetaminophen mainly comprises the technologies such as liquid chromatography, gas chromatography, liquid chromatography-mass spectrometry, and the like, but the technical methods are relatively time-consuming and labor-consuming, the operation is complex, the requirement on sample pretreatment is high, and the instruments are expensive. The electrochemical sensor has the advantages of low instrument price, simple operation, rapid and accurate determination and analysis, sensitivity, high selectivity and stability, simple sample pretreatment and the like, and has good application prospect. Therefore, it is of great significance to develop an accurate, simple, rapid and highly sensitive electrochemical sensor for detecting acetaminophen.
Phthalocyanines (Pcs) are similar to porphyrin compounds with 18-electron conjugated large pi systems, and metal ions such as copper, nickel, zinc, cobalt and the like can enter the center of a large conjugated ring through covalent and coordination to form highly stable Metal Phthalocyanines (MPCs), so that the phthalocyanine compounds have wide application in various fields. Particularly, the conjugated macrocyclic structure of the graphene oxide has excellent electrochemical activity and has important application value in the aspect of electrochemical sensors. However, metal phthalocyanine belongs to a semiconductor compound, and can block the transfer of electrons to a certain extent in an electrode reaction, the metal phthalocyanine has extremely poor solubility, is unevenly distributed in a solution, modifies an electrode in a suspension form, is easy to fall off, and seriously reduces the stability and reproducibility of an electrochemical reaction, thereby influencing the application of the metal phthalocyanine in electrochemistry.
Reduced graphene oxide (rGO) has the advantages of good conductivity and large specific surface area, and is widely applied to electrochemistry. However, due to the strong van der waals force existing between graphene sheets, the graphene sheets are easy to accumulate and agglomerate and difficult to disperse in water, and further application of the graphene is severely limited. Therefore, the development has important significance for the functional modification of the reduced graphene oxide. The graphene contains delocalized large pi bonds, phthalocyanine and other substances containing rich pi electrons are easily loaded on the graphene through non-covalent bond combination, the agglomeration between the phthalocyanine and between the graphene is effectively prevented, the specific surface area is increased, and the conjugated system is further prolonged, so that the electron transmission efficiency is enhanced.
Hydroxyl has good hydrophilicity, and hydroxyl functionalization is a good way for improving the water solubility of the compound, so that the tetrahydroxylated zinc phthalocyanine is synthesized, and the delocalized large pi bond with 18 electrons and the reduced graphene oxide are subjected to non-covalent combination to prepare the nano composite material. At present, no novel electrochemical sensor is constructed by taking water-soluble tetrahydroxy phthalocyanine-reduced graphene oxide as an electrode sensitive material, and is used for relevant reports of acetaminophen detection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a water-soluble zinc tetrahydroxy phthalocyanine-reduced graphene oxide nano composite, an electrochemical sensor prepared from the same and application of the electrochemical sensor.
In order to achieve the above object, one of the technical solutions of the present invention is:
a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite is prepared from water-soluble tetrahydroxy zinc phthalocyanine and reduced graphene oxide as raw materials. The preparation method comprises the following steps: dissolving 0.01g of tetrahydroxy zinc phthalocyanine in 300 mu L of DMF, adding 10mL of 1mg/mL reduced graphene oxide solution, stirring at room temperature for 12 hours, centrifuging, washing the obtained precipitate with water, and obtaining the tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite; dissolving the obtained tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound in 10mL of water to obtain a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound solution for later use.
The preparation method of the tetrahydroxy zinc phthalocyanine comprises the following steps: weighing 2.5mmol of 4-hydroxyphthalic nitrile and 2mmol of zinc acetate, adding the mixture into 5mL of n-amyl alcohol, then adding 0.5mL of 1, 8-diazabicyclo-bicyclo (5, 4, 0) -7-undecene, fully stirring, heating to 160 ℃ under the protection of nitrogen, condensing and refluxing for 7h, cooling to room temperature after the reaction is completed, then generating precipitate in the reaction solution, carrying out vacuum filtration, washing the precipitate with water until the filtrate is colorless, drying the precipitate, dissolving with methanol, filtering, and carrying out reduced pressure distillation to obtain a dark green solid, namely the tetrahydroxy zinc phthalocyanine.
Preparation of 4-hydroxyphthalionitrile: weighing 0.1mol of 4-nitrophthalonitrile, 0.1mol of sodium nitrite and 0.1mol of anhydrous potassium carbonate, dissolving the materials in 40mL of N, N-dimethylformamide, fully stirring, heating to 120 ℃ under the protection of nitrogen for reaction for 24 hours, cooling to room temperature after the reaction is finished, then carrying out vacuum filtration, adding concentrated hydrochloric acid into filtrate, adjusting the pH value to between 2 and 3, finally sealing and placing the filtrate at 4 ℃ for standing for 2 to 3 days, wherein flocculent precipitate appears in the solution, carrying out vacuum filtration, washing the precipitate to be neutral, and drying to obtain dark yellow solid, namely the 4-hydroxyphthalic nitrile.
One of the technical schemes of the invention is as follows:
a signal enhancement type electrochemical sensor based on the tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite is characterized in that the tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite is coated on the surface of a glassy carbon electrode by adopting a one-step dripping method. The specific method comprises the following steps: mixing the tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano composite solution with a Nafion solution with a mass concentration of 0.5% according to a volume ratio of 1.
The method for pretreating the glassy carbon electrode comprises the following steps: using 0.3 and 0.05. Mu.M Al, respectively 2 O 3 Polishing the glassy carbon electrode, carrying out ultrasonic cleaning by using absolute ethyl alcohol and ultrapure water in sequence, and airing at room temperature for later use.
One of the technical schemes of the invention is as follows:
the application of the electrochemical sensor in acetaminophen detection.
The soluble tetrahydroxy zinc phthalocyanine synthesis route is as follows:
the invention has the beneficial effects that:
1. according to the invention, the tetrahydroxy substituted zinc phthalocyanine is synthesized, the hydroxyl is a good hydrophilic group, 4-nitrophthalonitrile is used as a raw material, a series of reduction and hydrolysis reactions are carried out, firstly, 4-hydroxyphthalic nitrile is prepared, then, the 4-hydroxyphthalic nitrile is used as the raw material to prepare the hydroxylated zinc phthalocyanine, the obtained zinc phthalocyanine is the tetrahydroxy substituted zinc phthalocyanine, after the tetrahydroxy substitution, the water solubility of the zinc phthalocyanine is greatly improved, the zinc phthalocyanine can be well combined with reduced graphene oxide in a non-covalent bond manner, and the dispersibility of the reduced graphene oxide is effectively improved.
2. The prepared zinc tetrahydroxy phthalocyanine-reduced graphene oxide nano composite is formed by combining non-covalent bonds based on the existence of large pi bonds of water-soluble zinc tetrahydroxy phthalocyanine and reduced graphene oxide, the combination of the two takes the advantages of the two into consideration, and meanwhile, the defect of poor dispersibility of the two is improved.
3. The tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound is used as a modification material, so that a high-sensitivity electrochemical sensitive film can be obtained, and the detection sensitivity of the sensor is remarkably improved.
4. The Nafion tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound is directly coated on the surface of the glassy carbon electrode by a one-step dripping method, and the method has the advantages of quick and simple operation, good reproducibility and the like.
5. The prepared sensor has low cost, good stability and selectivity, wide detection range (0.03-100, 100-800 mu mol/L) and detection limit as low as 10nmol/L, can realize accurate, rapid and high-sensitivity detection of the acetaminophen, and has potential application value in the fields of clinical diagnosis, drug analysis and the like.
Drawings
FIG. 1 is a representation of synthesized zinc tetrahydroxy phthalocyanine, UV absorption spectrum (A); a fluorescence spectrum (B); an infrared spectrum (C); hydrogen nuclear magnetic resonance spectroscopy (D).
Fig. 2 is a scanning electron microscope image of the tetrahydroxy phthalocyanine zinc-reduced graphene oxide nanocomposite.
FIG. 3 is a cyclic voltammogram (A) and a linear relationship graph (B) of the square root of the sweep rate and the oxidation current of the ZnPc-rGO electrochemical sensor in a probe potassium ferricyanide solution at different sweep rates. In FIG. 3A, a → r represents sweep rates of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500mV/s, respectively.
FIG. 4 is a cyclic voltammogram of different modified electrodes in a probe potassium ferricyanide solution.
FIG. 5 is a cyclic voltammogram of acetaminophen under different electrode modification materials.
FIG. 6 is a linear cyclic voltammogram (A), a linear relation graph (B) of measured oxidation current and a linear relation graph (C) of measured reduction current for detection of acetaminophen by a ZnPc-rGO electrochemical sensor. In FIG. 6A, a → s respectively represent acetaminophen concentrations of 0.03, 0.1, 0.5, 1.0, 5.0, 10.0, 15.0, 20.0, 25.0, 50.0, 80.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 700.0, and 800.0. Mu. Mol/L.
FIG. 7 shows the results of analysis of the effect of ascorbic acid (A), dopamine (B), rutin (C) and uric acid (D) on the determination of acetaminophen at 30. Mu. Mol/L. In FIG. 7A, a → g respectively represents ascorbic acid concentrations of 0.9, 1.8, 2.7, 3.6, 4.5, 5.4, 6.3mmol/L, in FIG. 7B, a → D respectively represents dopamine concentrations of 60, 120, 180, 240. Mu. Mol/L, in FIG. 7C, a → D respectively represents rutin concentrations of 60, 150, 240, 330. Mu. Mol/L, and in FIG. 7D, a → e respectively represents uric acid concentrations of 125, 250, 375, 500, 625. Mu. Mol/L.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
The reduced graphene oxide used in the present invention was prepared using a modified Hummers method (William s. Hummers, j.r., richard e.offeman.preparation of graphic oxide. Journal of the American Chemical Society 1958, 80.
Example 1: preparation of tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano composite
(1) Preparation of 4-hydroxyphthalionitrile:
weighing 0.1mol of 4-nitrophthalonitrile, 0.1mol of sodium nitrite and 0.1mol of anhydrous potassium carbonate in a round-bottom flask, adding 40mL of N, N-Dimethylformamide (DMF) for dissolving, introducing nitrogen for 1h while stirring, placing on a constant-temperature magnetic stirrer under the protection of nitrogen, heating to 120 ℃ for reaction for 24h, cooling to room temperature after the reaction is finished, then carrying out vacuum filtration, wherein the solution is reddish orange, adding concentrated hydrochloric acid into the filtrate, adjusting the pH value to be between 2 and 3, sealing the filtrate, standing for 2 to 3 days at 4 ℃, generating a large amount of flocculent precipitates in the solution, carrying out vacuum filtration, washing the precipitates to be neutral, and drying in a vacuum drying oven for 24h to obtain dark yellow solid, namely the 4-hydroxyphthalic dinitrile.
(2) Preparation of tetrahydroxy zinc phthalocyanine:
weighing 2.5mmol of 4-hydroxyphthalionitrile and 2mmol of zinc acetate, adding 5mL of n-amyl alcohol into a round-bottom flask, then adding 0.5mL of 1,8 diazabicyclo-bicyclo (5, 4, 0) -7-undecene (DBU), introducing nitrogen for 30min while stirring (after introducing nitrogen, installing a condensing tube), placing the mixture on a constant-temperature magnetic stirrer under the protection of nitrogen, heating the mixture to 160 ℃, condensing and refluxing for 7h, cooling the mixture to room temperature after the reaction is finished, wherein the product is insoluble in n-amyl alcohol, at the moment, precipitates appear in a reaction solution are subjected to reduced pressure suction filtration, washing the precipitates with water until the filtrate is colorless, then placing the precipitates in a vacuum drying oven, drying the precipitates for 12h, dissolving the precipitates with methanol, filtering out impurities, and performing reduced pressure distillation to obtain a dark green solid, namely the zinc tetrahydroxy phthalocyanine (ZnPc-OH).
(3) Preparing a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite:
0.01g of (excessive) tetrahydroxy zinc phthalocyanine is dissolved in 300 muL of DMF, 10mL of 1mg/mL reduced graphene oxide solution is added, the mixture is stirred at room temperature for 12 hours, then the mixture is centrifuged at 4000rmp for 10 minutes, the obtained precipitate is washed for 3 times, and then the precipitate is dissolved in 10mL of water, so that a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite (ZnPc-rGO nano composite) solution is obtained.
Example 2: characterization of Zinc tetrahydroxy phthalocyanine
The prepared zinc tetrahydroxy phthalocyanine is characterized by ultraviolet absorption spectrum, fluorescence spectrum, infrared spectrum and nuclear magnetic resonance hydrogen spectrum, and the result is shown in figure 1. From the UV absorption spectrum (FIG. 1A), a characteristic absorption peak of phthalocyanine appears at 680nm, and the fluorescence spectrum shows (FIG. 1B) that 4-hydroxyphthalitrile has no fluorescence emission peak, while zinc tetrahydroxyphthalocyanine has a typical fluorescence emission peak of phthalocyanine ring at 692nm, indicating the formation of a complete phthalocyanine ring. From redAs shown in the external spectrum (FIG. 1C), the infrared spectrum of 4-nitrophthalonitrile (4-nitrophthalonitril) was 1539cm -1 And 1356cm -1 Two nitro stretching vibration peaks appear in the sample, and the sample is 1203cm in 4-hydroxyphthalitrile (4-hydroxypyhthalonitrile) -1 And 3103cm -1 And respectively shows the expansion vibration absorption peaks of C-O and O-H. And the tetrahydroxy metal phthalocyanine is at 1070cm higher than that of 4-nitrophthalonitrile -1 The peak of absorption of stretching vibration and 3439cm of new phthalocyanine ring appear -1 Stretching vibration peak of O-H of (2). In the NMR spectrum (FIG. 1D), the tetrahydroxy zinc phthalocyanine showed shifts of H on the phthalocyanine ring (Pc ring) of 7.45ppm and 7.65ppm, and also shifts of O-H on the benzene ring at 3.55ppm, which fully demonstrated the success of the preparation of tetrahydroxy phthalocyanine.
Example 3: preparation of electrochemical sensor
(1) Pretreating a glassy carbon electrode: using 0.3 and 0.05 μ M Al, respectively 2 O 3 Polishing a Glassy Carbon Electrode (GCE), carrying out ultrasonic cleaning by using absolute ethyl alcohol and ultrapure water in sequence, and airing at room temperature for later use;
(2) Mixing the ZnPc-rGO nano-composite solution with a Nafion solution (Nafion D-520 dispersion liquid) with the mass concentration of 0.5 percent according to the volume ratio of 1.
Example 4: electrochemical sensor performance analysis
1. Specific surface area
Scanning electron microscope analysis is carried out on the prepared ZnPc-rGO nano-composite, and the result is shown in figure 2. As can be seen from the figure, the nano-composite has a plurality of fold structures, and the specific surface area of the electrode is obviously improved. By utilizing cyclic voltammetry, a three-electrode working system is adopted, a glassy carbon electrode modified by a ZnPc-rGO nano composite is taken as a working electrode, ag/AgCl is taken as a reference electrode, a Pt wire electrode is taken as a counter electrode, and scanning speeds of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450 and 500mV/s pairs are sequentially changed on an electrochemical workstationPerforming cyclic voltammetry scanning on 0.5mmol/L potassium ferricyanide solution to obtain corresponding cyclic voltammetry result, and calculating the specific surface area of the sensor to be 0.455cm by establishing the relationship between the square root of scanning speed and current in probe potassium ferricyanide solution as shown in FIG. 3 2 And the specific surface area of the bare electrode is 0.108cm 2 It is shown that the specific surface area of the electrode is increased about 4 times by the modification of the nanocomposite.
2. Electrochemical performance
The electrochemical performance of the ZnPc-rGO nano-composite is characterized by utilizing a cyclic voltammetry method in a potassium ferricyanide electrochemical probe: FIG. 4 is a cyclic voltammogram of different modified electrodes in probe potassium ferricyanide, and a, b, c represent bare electrode, reduced graphene oxide modified electrode, and ZnPc-rGO nano-composite modified electrode, respectively. As can be seen from the figure, compared with a bare electrode, the electrochemical signal of the ZnPc-rGO nano composite modified electrode is obviously enhanced, which shows that the electron transmission capability of the modified electrode is obviously improved.
Example 5: detection of acetaminophen
The experimental method comprises the following steps: a cyclic voltammetry method is adopted, a glassy carbon electrode modified by a ZnPc-rGO nano composite is used as a working electrode, ag/AgCl is used as a reference electrode, a Pt wire electrode is used as a counter electrode, and the detection and analysis of the acetaminophen are realized in a 0.2mol/L Phosphate Buffer Salt (PBS) supporting dielectric medium with the scanning potential range of 0.2-0.9V and the pH value of 7.0 under the scanning speed of 125 mV/s.
1. Sensitivity of the probe
And (3) detecting the cyclic voltammograms of the acetaminophen under different electrode modified materials, wherein the experimental method is as above, and the result is shown in fig. 5. In fig. 5, a is a cyclic voltammogram of acetaminophen on a bare electrode, b is a cyclic voltammogram of acetaminophen on a reduced graphene oxide modified electrode, and c is a cyclic voltammogram of acetaminophen on a tetrahydroxy phthalocyanine-reduced graphene oxide composite modified electrode. After the tetrahydroxy phthalocyanine zinc and the reduced graphite oxide are compounded, the electrochemical detection signal of the acetaminophen is further greatly improved, and the modified electrode can be used for high-sensitivity detection of the acetaminophen.
Meanwhile, the detection characteristics of the sensor on acetaminophen are analyzed, wherein the concentrations of acetaminophen are respectively 0.03, 0.1, 0.5, 1.0, 5.0, 10.0, 15.0, 20.0, 25.0, 50.0, 80.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 700.0 and 800.0 mu mol/L, and as a result, as shown in fig. 6, the wide linear range of acetaminophen 0.03-100 and 100-800 mu mol/L is realized in a PBS buffer salt medium with pH of 7.0 by using a cyclic voltammetry method and the detection limit is 10 nmol/L.
2. Reproducibility and stability
The reproducibility, stability and selectivity of the sensor for detecting acetaminophen are analyzed, and cyclic voltammetry is adopted in an experiment, wherein the method is as above. The results show that 30. Mu. Mol/L acetaminophen was analyzed 6 consecutive times a day and the measured oxidation current RSD% was less than 2.63% and the measured oxidation current RSD% was less than 2.92% over three days, indicating that good reproducibility of acetaminophen detection was achieved. After the sensor is placed for 7 days in a dark place, the redox current signal of the acetaminophen is detected again, the redox current signal of the acetaminophen is basically not influenced, and after the sensor is placed for 20 days in the dark place, the detection signal can still keep 98.8% of the original signal, which indicates that the sensor has good detection stability.
3. Selectivity is
For 500 times concentration (compared with 30 mu mol/L paracetamol) of inorganic ions (including Zn) 2+ 、Al 3+ 、K + 、Mg 2 + 、SO 4 2- 、Cl - ) Analysis of the effect of glucose, urea, glycine and 2.5mg/mL bovine serum albumin on the determination of acetaminophen at 30. Mu. Mol/L revealed that there was almost no change in the redox current, indicating that the presence of these substances had substantially no effect on the detection of acetaminophen.
As a result of analyzing the influence of organic compounds such as Ascorbic Acid (AA), dopamine (DA), rutin (Rutin), uric Acid (UA), and the like, which may coexist, on the measurement of 30 μmol/L acetaminophen, wherein the ascorbic acid concentrations are 0.9, 1.8, 2.7, 3.6, 4.5, 5.4, 6.3mmol/L, the dopamine concentrations are 60, 120, 180, and 240 μmol/L, the Rutin concentrations are 60, 150, 240, and 330 μmol/L, and the uric acid concentrations are 125, 250, 375, 500, and 625 μmol/L, respectively, as shown in fig. 7, the oxidation current of acetaminophen is not substantially affected by 11 times of Rutin compared to 210 times of ascorbic acid, while the oxidation current of acetaminophen is not substantially affected by 8 times of dopamine, and the presence of uric acid at 20 times or more may affect the oxidation current of acetaminophen, but only the oxidation peak is irreversible reaction on the uric acid sensor, and the original amino acid concentration is not present, so that when the reduction peak is present, the reduction peak can be quantitatively analyzed. Therefore, the sensor has high selectivity for the detection of acetaminophen.
Claims (3)
1. A method for detecting acetaminophen by using an electrochemical sensor is characterized in that the preparation method of the electrochemical sensor comprises the following steps: mixing a tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano composite solution and a Nafion solution with the mass concentration of 0.5% according to the volume ratio of 1; the tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano composite is prepared by taking water-soluble tetrahydroxy zinc phthalocyanine and reduced graphene oxide as raw materials; wherein, the first and the second end of the pipe are connected with each other,
the preparation method of the tetrahydroxy zinc phthalocyanine comprises the following steps: weighing 2.5mmol of 4-hydroxyphthalionitrile and 2mmol of zinc acetate, adding the 4-hydroxyphthalionitrile and 2mmol of zinc acetate into 5mL of n-amyl alcohol, then adding 0.5mL of 1,8 diazabicyclo-bicyclo (5, 4, 0) -7-undecene, fully stirring, heating to 160 ℃ under the protection of nitrogen, condensing and refluxing for 7h, cooling to room temperature after the reaction is completed, then precipitating in a reaction solution, carrying out vacuum filtration, washing the precipitate with water until the filtrate is colorless, drying the precipitate, dissolving with methanol, filtering, and distilling under reduced pressure to obtain a dark green solid, namely the zinc tetrahydroxy phthalocyanine;
the preparation method of the 4-hydroxy phthalonitrile comprises the following steps: weighing 0.1mol of 4-nitrophthalonitrile, 0.1mol of sodium nitrite and 0.1mol of anhydrous potassium carbonate, dissolving in 40mL of N, N-dimethylformamide, fully stirring, heating to 120 ℃ under the protection of nitrogen for reaction for 24 hours, cooling to room temperature after the reaction is finished, then carrying out vacuum filtration, adding concentrated hydrochloric acid into the filtrate, adjusting the pH to between 2 and 3, finally sealing and placing the filtrate at 4 ℃ for standing for 2 to 3 days, wherein flocculent precipitates appear in the solution, carrying out vacuum filtration, washing the precipitates to be neutral, and drying to obtain dark yellow solids, namely the 4-hydroxyphthalic phthalonitrile.
2. The method for detecting acetaminophen by using an electrochemical sensor according to claim 1, wherein the specific preparation method of the tetrahydroxy phthalocyanine zinc-reduced graphene oxide nanocomposite comprises: 0.01 Dissolving tetrahydroxy zinc phthalocyanine in 300 muL DMF, adding 10mL of 1mg/mL reduced graphene oxide solution, stirring at room temperature for 12h, centrifuging, washing the obtained precipitate with water, and obtaining a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound; dissolving the obtained tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound in 10mL of water to obtain a tetrahydroxy zinc phthalocyanine-reduced graphene oxide nano compound solution for later use.
3. The method for detecting acetaminophen by using an electrochemical sensor according to claim 1, wherein the glassy carbon electrode is pretreated by a specific method comprising: using 0.3 and 0.05 μ M Al, respectively 2 O 3 Polishing the glassy carbon electrode, carrying out ultrasonic cleaning by using absolute ethyl alcohol and ultrapure water in sequence, and airing at room temperature for later use.
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| CN109100408A (en) * | 2018-09-25 | 2018-12-28 | 山西大学 | It is a kind of based on iron-phthalocyanine/nitrogen, the electrochemical sensor of boron doping redox graphene and its preparation method and application |
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