CN117127214A - Preparation method and application of Ce-MOF-CNT/PVA membrane electrode - Google Patents
Preparation method and application of Ce-MOF-CNT/PVA membrane electrode Download PDFInfo
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- CN117127214A CN117127214A CN202311397691.9A CN202311397691A CN117127214A CN 117127214 A CN117127214 A CN 117127214A CN 202311397691 A CN202311397691 A CN 202311397691A CN 117127214 A CN117127214 A CN 117127214A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 229940116269 uric acid Drugs 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 229910000510 noble metal Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method and application of a Ce-MOF-CNT/PVA membrane electrode, relating to the technical field of membrane electrode preparation, and specifically comprising the following steps: s1: preparing a PVA organic film; s2: preparation of Ce-MOF-CNT/PVA film electrode: adding cerium nitrate hexahydrate and CNT into a beaker, adding the PVA organic film prepared in the step S1 and secondary distilled water, carrying out ultrasonic treatment, and uniformly mixing to obtain a mixed solution A; taking terephthalic acid and N, N-dimethylformamide in a beaker, and stirring to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, performing water bath reaction, taking out after the reaction is finished, and drying the surface to obtain the Ce-MOF-CNT/PVA membrane electrode. The membrane electrode material has the advantages of high sensitivity, good stability, strong anti-interference performance, wide detection range, low cost and dual-function performance of identifying uric acid and oxygen evolution.
Description
Technical Field
The invention relates to the technical field of membrane electrode preparation, in particular to a preparation method and application of a Ce-MOF-CNT/PVA membrane electrode.
Background
Uric Acid (UA) is a basic product of purine metabolism, and is also a major component of biological fluids such as serum and urine, and excessive uric acid in serum can damage the circulatory system of the human body. Therefore, it is important to study a method for identifying UA. Currently, commonly used detection techniques for uric acid include colorimetry, spectrometry, fluorescence, chemiluminescence, high performance liquid chromatography, ion chromatography, electrochemistry and the like. The use of enzymes in biosensors results in limited storage stability, and non-enzymatic sensors have the significant advantages of long storage stability, simple manufacturing steps, etc., compared to enzymatic biosensors. The traditional sensor has the characteristics of poor sensitivity, narrow detection limit and poor stability, and experimental repeatability is poor due to experimental data errors.
With the current energy conversion, hydrogen energy is considered to be an ideal clean renewable energy source due to its efficient, environment-friendly and sustainable development. Electrolytic water hydrogen production is widely regarded as a promising fuel hydrogen production technology, and OER electrocatalysts mainly rely on noble metal oxides (RuO 2 And IrO 2 ) However, the scarcity and the cost limit industrial application, and in order to change the current situation, researchers start from electrode materials, and find that metal-organic framework Materials (MOFs) have high specific surface areas, obviously enhance unsaturated active centers and faster electron and mass transfer rates through continuous exploration, and have great effects in improving OER performance, and MOFs and composite materials thereof are considered as suitable materials for preparing efficient OER catalysts.
The rare earth-based MOF material has the advantages of high porosity, large specific surface area, controllable structure and the like of the MOF material, and the prepared sensor has the characteristics of strong stability and high sensitivity. Cerium salt is an important rare earth compound, and is widely used in catalytic reactions because of its advantages of being rich in oxygen cavities, non-toxic, good in biocompatibility, and relatively easy to convert between Ce (III) and Ce (IV). Meanwhile, ce has good electrochemical application potential as lanthanoid, and besides the common trivalent state like other rare earth elements, ce also exists in the tetravalent state, which is more beneficial to the unique electronic properties of oxidation and reduction reactions. Therefore, by combining the advantages of Ce and MOF materials, the development of the Ce-MOF material with dual functions of identifying uric acid and oxygen evolution, high sensitivity, good stability and low cost is very significant.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and application of a Ce-MOF-CNT/PVA membrane electrode.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a Ce-MOF-CNT/PVA membrane electrode, which specifically comprises the following steps:
s1: preparation of PVA organic film: adding polyethylene glycol (PEG) and polyvinyl alcohol (PVA) into a round-bottom flask, adding secondary distilled water, and stirring for reaction to obtain a mixed solution; after standing and defoaming, pouring the mixed solution into a culture dish, freezing and crosslinking, and then thawing at room temperature to form 1 freeze-thawing cycle, wherein after 5 freeze-thawing cycles are carried out, a PVA/PEG matrix is obtained; immersing the PVA/PEG matrix in secondary distilled water to remove PEG, thus obtaining a porous PVA organic film;
s2: preparation of Ce-MOF-CNT/PVA film electrode: adding cerium nitrate hexahydrate and Carbon Nano Tubes (CNT) into a beaker, adding the PVA organic film prepared in the step S1 and secondary distilled water, carrying out ultrasonic treatment, and uniformly mixing to obtain a mixed solution A; taking terephthalic acid and N, N-dimethylformamide in a beaker, and stirring to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, performing water bath reaction, taking out after the reaction is finished, and drying the surface to obtain the Ce-MOF-CNT/PVA membrane electrode.
Further, in the step S1, the mass of PEG is 0.2g, the mass of PVA is 2g, the volume of secondary distilled water is 41.8mL, the temperature of stirring reaction is 90 ℃, and the time of stirring reaction is 1h.
Further, in the step S1, the diameter of the culture dish is 8cm; the temperature of freezing and crosslinking is-20 ℃, and the time of freezing and crosslinking is 10 hours; thawing at room temperature for 2 hours; the PVA/PEG matrix was immersed in the secondary distilled water for 24 hours.
Further, in the step S2, the amount of the cerium nitrate hexahydrate is 1mmol; the dosage of the CNT is one of 0mg, 10mg, 20mg and 30 mg; the dosage of the PVA organic film is half; the volume of the secondary distilled water is 10mL; the amount of terephthalic acid material was 1mmol; the volume of the N, N-dimethylformamide is 10mL; the temperature of the water bath reaction was 50℃and the time was 3 hours.
The invention also provides an application of the Ce-MOF-CNT/PVA membrane electrode prepared by the preparation method of the Ce-MOF-CNT/PVA membrane electrode in identification of uric acid and oxygen evolution electrolytic water.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the electrochemical performance of the material is improved by combining Ce-MOF with the active substance carbon nano tube; the Ce-MOF and the carbon nano tube are directly grown on the organic film, so that the integrated flexible Ce-MOF-CNT/PVA film electrode is prepared, the preparation work of a working electrode is reduced, the electrode preparation time is shortened, and the working efficiency and the stability and repeatability of materials are improved. The membrane electrode material has the function of identifying uric acid, can detect uric acid in a larger concentration range, and has high sensitivity and good anti-interference performance; meanwhile, the membrane electrode also has certain oxygen evolution performance, can be used as an oxygen evolution working electrode for carrying out electrolytic water reaction, and is applied to the field of electrolytic water. Thus, the method is applicable to a variety of applications. The membrane electrode material has the advantages of high sensitivity, good stability, strong anti-interference performance, wide detection range, low cost and dual-function performance of identifying uric acid and oxygen evolution.
Drawings
FIG. 1 is a schematic view of a Ce-MOF-CNT/PVA film electrode according to the present invention;
FIG. 2 is a graph showing uric acid recognition performance test and electrode screening results of the membrane electrode material of the present invention;
FIG. 3 is a graph showing the results of oxygen evolution reaction performance test of the membrane electrode material of the present invention;
FIG. 4 is a graph showing CV test results of the membrane electrode material of the present invention at different sweep rates;
FIG. 5 is a graph of the peak current versus sweep rate for the present invention;
FIG. 6 is a graph of DPV test results of membrane electrode materials of the present invention for uric acid at different concentrations;
FIG. 7 is a linear fit of peak current versus concentration for the present invention;
FIG. 8 is a graph of the results of an anti-interference test of the membrane electrode material of the present invention;
fig. 9 is a graph of the stability test results of the membrane electrode material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples in order to make the objects and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The instruments, reagents, materials, etc. used in the following examples are conventional instruments, reagents, materials, etc. known in the art, and are commercially available. The experimental methods, detection methods, and the like in the following examples are conventional experimental methods, detection methods, and the like existing in the prior art unless otherwise specified.
In this example, the solution was prepared:
0.2M PBS solution: 0.1M disodium hydrogen phosphate and potassium dihydrogen phosphate are weighed respectively, dissolved in 1L of double distilled water, and pH is adjusted to 7.4 by NaOH.
Uric Acid (UA) solution at 5 mM: preparing uric acid solution as electrolyte solution for material identification test. 0.025g uric acid is weighed, and 30mL PBS solution is added for ultrasonic dissolution.
1M KOH solution: 56.1g of KOH was weighed, 1L of redistilled water was added for dissolution, and finally a solution having a constant volume of 1M was used as an electrolyte solution for electrolysis of water.
Interfering substance solution: the concentration of the interfering substance to be tested was determined to be 0.1mM, and then the mass of the interfering substance required was calculated according to the formula M=CV, and after weighing, it was dissolved in the above PBS solution, and the interfering substance was added to uric acid solution as an interfering substance to test its selectivity. Taking glucose as an example: after 1mL of glucose was added, the solution system was 31mL and the glucose concentration was 0.1mM, so that 0.00056g of glucose was weighed, 1mL of the prepared PBS solution was added for dissolution, and the solution was removed by a 1000. Mu.L pipette and added to the test solution at the time of testing.
Example 1
The embodiment provides a preparation method of a Ce-MOF-CNT/PVA membrane electrode, which specifically comprises the following steps:
s1: preparation of PVA organic film: adding 0.2g of PEG and 2g of PVA into a round-bottom flask, adding 41.8mL of double distilled water, and stirring at 90 ℃ for reaction for 1 hour to obtain a mixed solution; after standing and defoaming, pouring the mixed solution into a culture dish with the diameter of 8cm, freezing and crosslinking for 10 hours at the temperature of minus 20 ℃, and then thawing for 2 hours at room temperature to form 1 freeze-thawing cycle, wherein 5 freeze-thawing cycles are carried out to obtain a PVA/PEG matrix; immersing the PVA/PEG matrix in secondary distilled water for 24 hours, and removing PEG to obtain a porous PVA organic film;
s2: preparation of Ce-MOF-CNT/PVA film electrode: adding 1mmol of cerium nitrate hexahydrate and 0mg of CNT into a beaker, adding the half PVA organic film prepared in the step S1 and 10mL of secondary distilled water, carrying out ultrasonic treatment, and uniformly mixing to obtain a mixed solution A; taking 1mmol of phthalic acid and 10mL of N, N-dimethylformamide in a beaker, and stirring to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, carrying out water bath reaction for 3 hours at 50 ℃, taking out after the reaction is finished, and drying the surface to obtain the Ce-MOF-CNT/PVA membrane electrode. As shown in figure 1, the prepared membrane electrode is a flexible electrode and can be directly used for detecting uric acid and oxygen evolution reaction.
The embodiment also provides an application of the Ce-MOF-CNT/PVA membrane electrode prepared by the preparation method of the Ce-MOF-CNT/PVA membrane electrode in identification of uric acid and oxygen evolution electrolyzed water.
Example 2
The difference from example 1 is that the CNT amount is 10mg.
Example 3
The difference from example 1 is that the CNT amount is 20mg.
Example 4
The difference from example 1 is that the CNT amount is 30mg.
The membrane electrode was tested as follows:
1. uric acid identification performance test
And under the voltage of 0.2-1.2V, the scanning speed is 100mV/s, and the identification performance of the membrane electrode material is tested.
As shown in figure 2, through testing CV in PBS solution and uric acid PBS solution, obvious oxidation peaks are found in the test of uric acid-containing solution, which shows that the material can identify uric acid, meanwhile, the test in uric acid-containing solution shows that the current of the membrane electrode added with 20mg of CNT is strongest, the performance is best, and the electrode is selected for subsequent test of uric acid.
2. Oxygen evolution reaction OER Performance test
The OER performance of the membrane electrode material was tested at a sweep rate of 5mV/s at a voltage of 0-1.8V.
As shown in FIG. 3, the OER performance of the membrane electrode material was tested in a 1M KOH solution at 10mA/cm 2 According to formula E at current density overpotential =E RHE E it was found that the membrane electrode doped with 20mg of CNT had the best performance, with an overpotential of 530mV, with OER performance.
3. CV test and linear fitting of different sweep rates
As shown in FIG. 4, CV tests at different sweep rates of 10-100mV/s were tested in PBS solution containing 5mM UA at a voltage of 0.2-1.2V. As shown in fig. 5, a linear fit was made to the oxidation peak current and the sweep rate, and a linear relationship between the peak current and the sweep rate was found, which indicates that the recognition reaction was affected by diffusion and that the material performance was good.
4. DPV test and linear fitting of uric acid at different concentrations
As shown in FIG. 6, uric acid of different concentrations (0-9 mM) was detected under a voltage range of 0-1V using the prepared membrane electrode as a working electrode. As shown in FIG. 7, the peak current and the concentration are subjected to linear fitting, and the linear fitting degree is good, so that the performance is good, the detection can be performed in a large detection range, and meanwhile, the range contains the normal uric acid concentration of a human body, so that the method can be applied to clinical detection.
5. Anti-interference performance test
As shown in FIG. 8, the specificity of the membrane electrode material is examined by adopting a current time method, a test is carried out in a blank PBS solution, 0.1mM uric acid and different 0.1mM interfering substances (glucose, fructose, beta-lactose, sodium chloride, potassium nitrate, ammonium chloride, sodium sulfate, urea, L-alanine, DL-methionine, L-phenylalanine, glycine, DL-glutamic acid, cytosine, adenine, guanine, xanthine, sucrose and calcium chloride) are respectively added subsequently, the environment of human body fluid is simulated, and it can be found from FIG. 8 that the current rises rapidly after uric acid is added, which shows that the membrane electrode material has better response to uric acid and high sensitivity, but the current generated by the interfering substances added later is smaller, compared with uric acid can be ignored, and the anti-interference performance of the membrane electrode material is better.
6. Stability performance test
As shown in fig. 9, the stability of the membrane electrode material was examined. The membrane electrode material was placed in a solution containing 5mM uric acid, and the stability test of the recognition function was performed by cyclic voltammetry. The oxidation peak current of the first circle is taken as the initial current Io, the subsequent current I is divided by the initial current Io respectively, and after 50 circles of tests, the current is found to be reduced by 22%, which indicates that the membrane electrode material has good stability in recognition. In a 1M KOH solution, a stability test of the water electrolysis function is carried out by adopting a chronopotentiometry, and the voltage is found to reach 1.8V rapidly within 5 hours, and is basically unchanged after the voltage is increased. After up to 25 hours of testing, it was found to be stable in electrolytic function.
In the embodiment, the electrochemical performance of the material is improved by combining the Ce-MOF and the active substance carbon nano tube; the Ce-MOF and the carbon nano tube are directly grown on the organic film, so that the integrated flexible Ce-MOF-CNT/PVA film electrode is prepared, the preparation work of the working electrode is reduced, the electrode preparation time is shortened, and the working efficiency is improved. The membrane electrode material has the function of identifying uric acid, can detect uric acid in a larger concentration range, and has high sensitivity and good anti-interference performance; meanwhile, the membrane electrode also has certain oxygen evolution performance, can be used as an oxygen evolution working electrode for carrying out electrolytic water reaction, and is applied to the field of electrolytic water.
In conclusion, the membrane electrode material of the embodiment has the advantages of high sensitivity, good stability, strong anti-interference performance, wide detection range, low cost (compared with noble metal materials and the like), and has the dual-function performance of identifying uric acid and oxygen evolution.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A preparation method of a Ce-MOF-CNT/PVA membrane electrode is characterized by comprising the following steps: the method specifically comprises the following steps:
s1: preparation of PVA organic film: adding PEG and PVA into a round-bottom flask, adding secondary distilled water, and stirring for reaction to obtain a mixed solution; after standing and defoaming, pouring the mixed solution into a culture dish, freezing and crosslinking, and then thawing at room temperature to form 1 freeze-thawing cycle, wherein after 5 freeze-thawing cycles are carried out, a PVA/PEG matrix is obtained; immersing the PVA/PEG matrix in secondary distilled water to remove PEG, thus obtaining a porous PVA organic film;
s2: preparation of Ce-MOF-CNT/PVA film electrode: adding cerium nitrate hexahydrate and CNT into a beaker, adding the PVA organic film prepared in the step S1 and secondary distilled water, carrying out ultrasonic treatment, and uniformly mixing to obtain a mixed solution A; taking terephthalic acid and N, N-dimethylformamide in a beaker, and stirring to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, performing water bath reaction, taking out after the reaction is finished, and drying the surface to obtain the Ce-MOF-CNT/PVA membrane electrode.
2. The method for preparing the Ce-MOF-CNT/PVA film electrode according to claim 1, characterized in that: in the step S1, the mass of PEG is 0.2g, the mass of PVA is 2g, the volume of secondary distilled water is 41.8mL, the temperature of stirring reaction is 90 ℃, and the time of stirring reaction is 1h.
3. The method for preparing the Ce-MOF-CNT/PVA film electrode according to claim 1, characterized in that: in the step S1, the diameter of the culture dish is 8cm; the temperature of freezing and crosslinking is-20 ℃, and the time of freezing and crosslinking is 10 hours; thawing at room temperature for 2 hours; the PVA/PEG matrix was immersed in the secondary distilled water for 24 hours.
4. The method for preparing the Ce-MOF-CNT/PVA film electrode according to claim 1, characterized in that: in the step S2, the amount of the cerium nitrate hexahydrate is 1mmol; the dosage of the CNT is one of 0mg, 10mg, 20mg and 30 mg; the dosage of the PVA organic film is half; the volume of the secondary distilled water is 10mL; the amount of terephthalic acid material was 1mmol; the volume of the N, N-dimethylformamide is 10mL; the temperature of the water bath reaction was 50℃and the time was 3 hours.
5. A Ce-MOF-CNT/PVA membrane electrode prepared by the method for preparing a Ce-MOF-CNT/PVA membrane electrode according to any of claims 1 to 4, for use in identification of uric acid and oxygen evolution electrolyzed water.
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