CN114957684A - TCPP (Ni) -Co electrode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a TCPP (Ni) -Co electrode material and a preparation method thereof. By means of synergistic use of microwave hydrothermal and ultrasonic means, product crystallization is completed at low temperature, so that the synthetic yield of the bimetal TCPP (Ni) -Co with the ultrathin two-dimensional structure characteristic reaches 68% -75%. Respectively preparing Ni metal by using a step-by-step assembly strategy 2+ And Co 2+ The double metal is fixed at the nitrogen coordination center and the carboxyl coordination center of 5,10,15, 20-tetracarboxyphenylporphyrin, so that the Co-coordination of double metals in TCPP (Ni) -Co is realized, two types of active sites are provided, and the high-selectivity electrochemical detection of theophylline is realized.
Description
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a TCPP (Ni) -Co electrode material and a preparation method thereof.
Background
Theophylline is a common purine alkaloid in diet and exists in various beverages and natural food materials, however, theophylline has the toxicological characteristics at the same time, and improper intake of theophylline can cause convulsion, tachycardia and gastrointestinal tract problems. Therefore, it is very important to detect theophylline by electrochemical methods with high sensitivity and strong anti-interference.
The electrochemical sensor is one of the most commonly used means for detecting theophylline, wherein an electrode modification material plays a very key role in the working process of the electrochemical sensor, and a two-dimensional layered metal-porphyrin framework material (M-TCPPMOF) is gradually developed into a high-performance electrode modification material due to the unique extremely high specific surface, two-dimensional layered structure, larger porosity and unsaturated metal sites.
The problems commonly faced by the metal-porphyrin framework modified electrode commonly used for theophylline detection at present are as follows:
first, the interference resistance is not strong, which is because the specific adsorption and recognition ability of a single type of active site in the electrode to theophylline is not enough, so that the practical application ability of the electrode in the coexistence environment of multiple reducing substances is limited, and the problem of insufficient specificity exists.
Secondly, because porphyrin has a plane macromolecular conjugated structure, the reactivity of porphyrin under the conventional hydrothermal-solvothermal condition is low, and the precipitation efficiency of the generated ultrathin two-dimensional layered structure in the natural cooling process is low, so that the yield of the two-dimensional metal-porphyrin framework material is low, the yield of the general mechanical stripping method is only about 15%, and the yield of the intercalation chemical stripping method can reach 57%, and the problem of low yield exists in the prior art.
Disclosure of Invention
The invention provides a TCPP (TCNi) -Co electrode material and a high-yield preparation method thereof, aiming at solving the problems of insufficient specificity and low yield of a metal-porphyrin framework ultrathin two-dimensional layered material in the existing theophylline detection.
In order to achieve the purpose of the invention, the technical scheme provided by the invention is as follows: a TCPP (Ni) -Co electrode material and a preparation method thereof comprise the following steps:
step 1: weighing 0.3-0.5 mmol 5,10,15, 20-tetracarboxyphenylporphyrin (H) 2 TCPP), putting the weighed medicines into a 100mL quartz reaction bottle, and adding 30-50 mLN, N-dimethyl methylAmide, stirring and heating to 50 ℃, and completely dissolving the medicine to form a solution A;
and 2, step: weighing 3-5 mmol NiSO 4 ·6H 2 Dissolving O in 6-10 mL of N, N-dimethylformamide to form a solution B, and then dropwise adding the solution B into the solution A to form a solution C;
and step 3: placing the solution C in a microwave ultrasonic reactor, and setting the microwave reaction temperature to be 80 ℃, the ultrasonic frequency to be 26 KHz-28 KHz and the reaction time to be 40-60 minutes in a temperature control mode; after the reaction is finished, placing the reaction bottle in a low-temperature environment of-20 ℃ for cooling for 2 hours to obtain TCPP (Ni) dark purple crystals, wherein the yield is about 83-88%;
and 4, step 4: weighing 0.3-0.5 mmol of CoSO 4 ·7H 2 Placing the medicine into a 50mL quartz reaction bottle, adding 20-30 mL mixed solution (volume ratio of N, N-dimethylformamide to absolute ethyl alcohol is 3:1), mixing and stirring for 30min, completely dissolving the medicine to obtain solution D, placing the solution D into a microwave ultrasonic reaction instrument, and setting microwave reaction temperature of 150 ℃ and ultrasonic frequency of 26-28 KHz in a temperature control mode for 1-2 hours; after the reaction is finished, the reaction bottle is placed in a low-temperature environment of minus 20 ℃ for cooling for 2 hours, washed and centrifuged for 3 times by ethanol, and dried to obtain a TCPP (Ni) -Co dark purple product. The yield is about 68-75%.
Compared with the prior art, the invention has the advantages that:
1. the invention completes product crystallization by low temperature through synergistic use of microwave hydrothermal and ultrasonic means, and respectively prepares metal Ni by using a step-by-step assembly strategy 2+ And Co 2+ The coordination center of nitrogen and the coordination center of carboxyl of 5,10,15, 20-tetracarboxyphenylporphyrin are fixed, the coordination of bimetal in TCPP (Ni) -Co is realized, and two types of active sites are provided. Therefore, the anti-interference capability is effectively improved, and the specificity is obviously enhanced.
2. The preparation method provided by the invention can improve the synthesis yield of the two-dimensional metal-porphyrin framework to 68-75%, and improve the utilization efficiency of raw materials and the yield of products.
3. The preparation method is simple, the raw materials are easy to obtain, the microwave hydrothermal reaction time is short, and the energy consumption is low.
Drawings
FIG. 1 is an SEM image of TCPP (Ni) -Co synthesized according to the present invention;
FIG. 2 is an XRD pattern of TCPP (Ni) -Co synthesized according to the present invention;
FIG. 3 is a graph of the amperometric response in the presence of various interfering substances.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
a high-yield preparation method of TCPP (Ni) -Co electrode material comprises the following steps:
step 1: 0.3mmol of 5,10,15, 20-tetracarboxyphenylporphyrin (H) was weighed 2 TCPP) is put into a 100mL quartz reaction bottle, 30mL of N, N-dimethylformamide is added, the mixture is stirred and heated to 50 ℃, and the medicine is completely dissolved to form a solution A;
step 2: weighing 3mmol of NiSO 4 ·6H 2 Dissolving O in 6mL of N, N-dimethylformamide to form a solution B, and then dropwise adding the solution B into the solution A to form a solution C;
and step 3: placing the solution C in a microwave ultrasonic reaction instrument, setting the microwave reaction temperature to be 80 ℃, the ultrasonic frequency to be 28KHz, and reacting for 60 minutes; after the reaction is finished, the reaction bottle is placed in an environment with the temperature of-20 ℃ for cooling for 2 hours to obtain TCPP (Ni) dark purple crystals, and the yield is about 88 percent.
And 4, step 4: 0.3mmol of CoSO was weighed 4 ·7H 2 Placing O and 0.1mmol TCPP (Ni) into a 50mL quartz reaction bottle, adding 20mL mixed solution (volume ratio of N, N-dimethylformamide: absolute ethyl alcohol is 3:1), mixing and stirring for 30min, completely dissolving the medicine to obtain suspension D, placing the suspension D into a microwave ultrasonic reaction instrument, setting microwave reaction temperature at 150 ℃, ultrasonic frequency at 28KHz, and reacting2 hours; and after the reaction is finished, placing the reaction bottle in an environment with the temperature of-20 ℃ for cooling for 2 hours, washing and centrifuging for 3 times by using ethanol, and drying to obtain a TCPP (Ni) -Co dark purple product with the yield of about 75%. Referring to fig. 1, the morphology of tcpp (ni) -Co can be seen as a porous flower-ball structure formed by self-assembly of nano-flakes, and referring to fig. 2, tcpp (ni) -Co can be seen to have better crystallinity.
Example 2:
a high-yield preparation method of TCPP (Ni) -Co electrode material comprises the following steps:
step 1: 0.5mmol of 5,10,15, 20-tetracarboxyphenylporphyrin (H) was weighed 2 TCPP) is put into a 100mL quartz reaction bottle, 50mL of N, N-dimethylformamide is added, the mixture is stirred and heated to 50 ℃, and the medicine is completely dissolved to form a solution A;
and 2, step: weighing 5mmol of NiSO 4 ·6H 2 Dissolving O in 10mL of N, N-dimethylformamide to form a solution B, and then dropwise adding the solution B into the solution A to form a solution C;
and step 3: placing the solution C in a microwave ultrasonic reactor, setting the microwave reaction temperature at 80 ℃ and the ultrasonic frequency at 26KHz, and reacting for 40 minutes; after the reaction is finished, the reaction bottle is placed in an environment with the temperature of-20 ℃ for cooling for 2 hours to obtain TCPP (Ni) dark purple crystals, and the yield is about 83 percent.
And 4, step 4: 0.5mmol CoSO was weighed 4 ·7H 2 Placing O and 0.2mmol of TCPP (Ni) into a 50mL quartz reaction bottle, adding 30mL of mixed solution (the volume ratio of N, N-dimethylformamide to absolute ethyl alcohol is 3:1), mixing and stirring for 30min, completely dissolving the medicine to obtain suspension D, placing the suspension D into a microwave ultrasonic reaction instrument, setting the microwave reaction temperature at 150 ℃ and the ultrasonic frequency at 26KHz, and reacting for 1 hour; and after the reaction is finished, placing the reaction bottle in an environment with the temperature of-20 ℃ for cooling for 2 hours, washing and centrifuging for 3 times by using ethanol, and drying to obtain a TCPP (Ni) -Co dark purple product. The yield was about 68%.
Example three:
a high-yield preparation method of TCPP (Ni) -Co electrode material comprises the following steps:
step 1: 0.4mmol of 5,10,15, 20-tetracarboxyphenylporphyrin (H) was weighed 2 TCPP) is put inAdding 40mL of N, N-dimethylformamide into a 100mL quartz reaction bottle, stirring and heating to 50 ℃, and completely dissolving the medicine to form a solution A;
and 2, step: weighing 4mmol of NiSO 4 ·6H 2 Dissolving O in 8mL of N, N-dimethylformamide to form a solution B, and then dropwise adding the solution B into the solution A to form a solution C;
and 3, step 3: placing the solution C in a microwave ultrasonic reactor, setting the microwave reaction temperature at 80 ℃, and the ultrasonic frequency at 27KHz, and reacting for 50 minutes; after the reaction is finished, the reaction bottle is placed in an environment with the temperature of-20 ℃ for cooling for 2 hours to obtain TCPP (Ni) dark purple crystals, and the yield is about 85 percent.
And 4, step 4: 0.4mmol of CoSO was weighed 4 ·7H 2 Placing O and 0.15mmol of TCPP (Ni) into a 50mL quartz reaction bottle, adding 25mL of mixed solution (the volume ratio of N, N-dimethylformamide to absolute ethyl alcohol is 3:1), mixing and stirring for 30min, completely dissolving the medicine to obtain suspension D, placing the suspension D into a microwave ultrasonic reaction instrument, setting the microwave reaction temperature at 150 ℃ and the ultrasonic frequency at 26KHz, and reacting for 1.5 hours; and after the reaction is finished, placing the reaction bottle in an environment with the temperature of-20 ℃ for cooling for 2 hours, washing and centrifuging for 3 times by using ethanol, and drying to obtain a TCPP (Ni) -Co dark purple product. The yield was about 72%.
The above example 1 is the best example, and the TCPP (Ni) -Co electrode prepared in the example 1 is used for the electrochemical detection of theophylline, and comprises the following steps:
step 1: grinding 30mg of TCPP (Ni) -Co by using a grinding bowl, putting the ground TCPP (titanium chloride) (Ni) -Co into a sample tube, adding 3mL of deionized water into the sample tube, performing ultrasonic dispersion uniformly, adding 2mL of Nafion (5 wt%) solution into the sample tube, and performing ultrasonic dispersion for 30min to obtain the required modified electrode suspension E. Glassy Carbon Electrodes (GCE) were each polished on the surface of the fur for 15 minutes to a bright mirror surface using alumina slurries having particle diameters of 0.3 μm and 0.05 μm, respectively. Then the surface of the GCE electrode is cleaned by secondary distilled water under the ultrasonic condition and is dried by nitrogen. And (3) sucking 3 mu L of modified electrode suspension liquid E by using a microsyringe, dropwise adding the modified electrode suspension liquid E to the surface of the glassy carbon electrode, naturally drying the glassy carbon electrode at room temperature to obtain the required TCPP (trichloropropylidene phosphate) (Ni) -Co @ GCE electrode, and finally storing the electrode in a refrigerator at 4 ℃ for testing.
And 2, step: TCPP (Ni) -Co @ GCE is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and 0.2mol/L, pH-4.5 of Na is used 2 HPO 4 -C 4 H 2 O 7 For the electrolyte solution, nitrogen was introduced into the solution before the test to remove oxygen from the solution.
And 3, step 3: TCPP (Ni) -Co @ GCE is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and 0.2mol/L, pH-4.5 of Na is used 2 HPO 4 -C 4 H 2 O 7 For the electrolyte solution, nitrogen was introduced into the solution before the test to remove oxygen from the solution. 0.125mmol/L theophylline solution is continuously dripped into the electrolyte for 4 times by a microsyringe, 4 mu L is dripped each time, then 10 times concentration interferent including ascorbic acid, sucrose, glucose, sodium citrate, glycine and sodium chloride is added, the amperometric current response of 1.0V is recorded after each dripping, and finally an amperometric current anti-interference response curve is obtained, which is shown in figure 3 and shows that the TCPP (Ni) -Co electrode modified material has excellent anti-interference performance on the theophylline when the theophylline is detected.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (4)
1. A preparation method of TCPP (Ni) -Co electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) weighing 0.3-0.5 mmol of 5,10,15, 20-tetracarboxyphenyl porphyrin, adding 30-50 mLN, N-dimethylformamide, stirring and heating to 50 ℃, and dissolving the medicine completely to form a solution A;
2) weighing 3-5 mmol of NiSO 4 ·6H 2 Dissolving O in 6-10 mL of N, N-dimethylformamide to form a solution B, and then dropwise adding the solution B into the solution A to form a solution C;
3) placing the solution C in a microwave ultrasonic reactor for reaction, and after the reaction is finished, placing a reaction bottle in a low-temperature environment of-20 ℃ for cooling for 2 hours to obtain TCPP (Ni) dark purple crystals;
4): weighing 0.3-0.5 mmol of CoSO 4 ·7H 2 Placing O and 0.1-0.2 mmol TCPP (Ni) into a 50mL quartz reaction bottle, adding 20-30 mL of mixed solution, mixing and stirring for 30min, obtaining a suspension D after the medicine is completely dissolved, placing the suspension D into a microwave ultrasonic reaction instrument, setting the microwave reaction temperature at 150 ℃, the ultrasonic frequency at 26 KHz-28 KHz, and the reaction time at 1-2 hours; after the reaction is finished, the reaction bottle is placed in a low-temperature environment of minus 20 ℃ for cooling for 2 hours, washed and centrifuged for 3 times by ethanol, and dried to obtain a TCPP (Ni) -Co dark purple product.
2. The method for preparing TCPP (Ni) -Co electrode material according to claim 1, wherein: in the step 3), the ultrasonic reaction is to place the solution C in a microwave ultrasonic reactor, set the microwave reaction temperature to be 80-90 ℃, the ultrasonic frequency to be 26 KHz-28 KHz, and the reaction time to be 40-60 minutes.
3. The method for preparing a TCPP (Ni) -Co electrode material according to claim 1 or 2, wherein: the mixed solution in the step 4) is N, N-dimethylformamide and absolute ethyl alcohol, and the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 3: 1.
4. The TCPP (Ni) -Co electrode material prepared by the preparation method according to claim 1.
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| CN115608355A (en) * | 2022-10-10 | 2023-01-17 | 河南师范大学 | Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet |
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| CN115608355A (en) * | 2022-10-10 | 2023-01-17 | 河南师范大学 | Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet |
| CN115608355B (en) * | 2022-10-10 | 2024-04-26 | 河南师范大学 | Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets |
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