CN111044587A - 2D porphyrin MOF nano material for electrochemical sensor and preparation method thereof - Google Patents
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Abstract
The invention discloses a 2D porphyrin MOF nano material for an electrochemical sensor, which comprises the following components: the volume ratio of the N, N-dimethylformamide to the ethanol is 1:3, the cobalt nitrate hexahydrate is 15mg, the polyvinylpyrrolidone is 20mg, and the 4-carboxyphenylporphyrin is 12 mg. The invention also discloses a preparation method of the nano material and a method for smearing the nano material on an electrode of an electrochemical sensor. The nitrite electrochemical sensor with high sensitivity, good stability, long service life and wide linear range is obtained by a method for preparing the electrochemical sensor electrode based on the nanocomposite material and a cheap and environment-friendly material based on the excellent performance of the 2D MOF nanomaterial.
Description
Technical Field
The invention belongs to the technical field of quantum chemistry, and particularly relates to a 2D porphyrin MOF nano material for an electrochemical sensor and a preparation method of the material.
Background
Biosensors are a special class of chemical sensors that use enzymes as the biosensing element, a detector that is highly selective for the target being measured. It captures the reaction between the target and the sensitive element through various physical and chemical signal converters, and then expresses the reaction degree by discrete or continuous electric signals, thus obtaining the concentration of the measured object.
Nitrite is a food additive, is a common food preservative, can effectively inhibit the propagation of microorganisms in food, and is widely applied to the processing, storage and fresh keeping of food. However, excess nitrite can be a serious life threatening safety. The intake of nitrite is 0.3-0.5 g, which can cause poisoning, and more than 3g can kill the disease. Nitrite is detected by a variety of methods, such as colorimetry, spectrophotometry, gas chromatography, liquid chromatography, electrochemical sensing, and the like. Compared with other methods, the electrochemical sensing has the advantages of high selectivity, low cost, high precision and the like. Electrochemical sensing for detecting nitrite has become a great research hotspot in recent years, and especially how to further improve the performance of the electrochemical sensor for nitrite is concerned by the majority of researchers.
Due to the specificity of the scale and the structure, the nano material shows special physical effects which are not possessed by a plurality of block materials, such as macroscopic quantum tunneling effect, coulomb blocking effect, small-size effect, surface effect and the like. Therefore, there is also a study to introduce nanomaterials into the study of electrochemical sensors. And with the expansion of the application range of the electrochemical sensor in the aspects of food, medicine, environmental monitoring and the like, higher requirements are put on the sensor, so that the development of a novel electrochemical detection technology based on the nano material becomes the development trend of the electrochemical sensor.
Among the numerous nanomaterials, Metal Organic Framework (MOF) nanomaterials are receiving attention from researchers, and their preparation and use have become a focus of research in recent years. The MOF is a crystalline porous material and is formed by matching metal ions and organic ligands. The MOF has ultrahigh porosity and a surprising internal specific surface area due to a unique three-dimensional pore structure, and the pore size of the MOF is controllable due to the spatial arrangement of metal atom centers and various organic ligands. Furthermore, the MOFs can also be made to exhibit compositional and structural diversity by functionalization of ligands and use of different metal ions. Among a plurality of MOF materials, the TCPP MOF material taking porphyrin (TCPP) as a ligand has the characteristics of biomimetic enzyme, shows excellent catalytic capability and brings new inspiration for electrochemical sensing research. Recent research has been mainly directed towards three-dimensional (3D) bulk MOF nanomaterials. Relatively few reports have been made on two-dimensional (2D) MOF nanomaterials, particularly on ultra-thin 2D MOF nanomaterials. In fact, compared to 3D bulk nanomaterials, nanolayers, nanofilms, and the like, 2D, the MOF and 2D materials have many more advantages due to their unique structures, such as large specific surface area, good ductility, many more active sites that are easily exposed, and the like.
In view of the properties of 2D MOF nano materials, the material in the prior art is also applied to electrochemical sensors, but basically is a noble metal and oxide material thereof, the price is high, the preparation process is complicated, and the cost of the sensor is high, so that the development of an electrochemical sensor which has the advantages of simple preparation process, low cost, economy, environmental protection, good stability, high sensitivity and wide detection limit range is necessary by fully utilizing common metals and metal oxides with wide sources.
Disclosure of Invention
The invention aims to provide a 2D porphyrin MOF nano material for an electrochemical sensor, which solves the problems of high price, complex preparation process and high sensor cost of noble metals and oxide materials thereof adopted in the existing electrochemical sensor.
The invention also aims to provide a preparation method of the high nano material, and the nitrite electrochemical sensor with high sensitivity, good stability, long service life and wide linear range is obtained by using cheap and environment-friendly materials and a simple preparation method.
The technical scheme adopted by the invention is that the 2D porphyrin MOF nanometer material for the electrochemical sensor comprises the following components: the volume ratio of the N, N-dimethylformamide to the ethanol is 1:3, the cobalt nitrate hexahydrate is 15mg, the polyvinylpyrrolidone is 20mg, and the 4-carboxyphenylporphyrin is 12 mg.
The invention also provides a preparation method of the nano material, which comprises the following specific preparation processes:
step 1: prefabricated building block
Respectively adding N, N-dimethylformamide and ethanol in a volume ratio of 1:3 into a beaker by adopting a hydrothermal method, uniformly mixing to obtain a mixed solution, and then weighing 15mg of cobalt nitrate hexahydrate and 20mg of polyvinylpyrrolidone to dissolve in the mixed solution to obtain a prefabricated solution;
step 2: reaction of
Slowly adding 12mg of 4-carboxyphenylporphyrin in the step 1 into the prefabricated liquid under the condition of magnetic stirring, fully and uniformly mixing under the ultrasonic condition, further transferring the mixture into a reaction kettle, and placing the reaction kettle into an oven for primary drying;
and step 3: treatment of
And taking out the reaction kettle after the reaction is finished, naturally cooling to room temperature, centrifuging, washing, and drying for the second time to obtain the 2D porphyrin MOF nano material expressed as Co-TCPP MOF.
The invention is also characterized in that:
the beaker in step 1 was 25 ml.
The condition of primary drying in the step 2 is reaction for 24 hours at 80 ℃.
The conditions of centrifugation in step 3 were: centrifuging for 10min under the condition of 10000 revolutions per minute of the centrifuge, wherein the washing condition is as follows: washing with ethanol for 3 times, wherein the conditions of secondary drying are as follows: drying for 6h at 50 ℃.
The other technical scheme of the invention is that the method for coating the electrode of the electrochemical sensor with the nano material comprises the following specific steps:
step 1: pretreatment of glassy carbon electrodes
Before modification, polishing and grinding the glassy carbon electrode by using 1.0 mu m and 0.3 mu m alumina powder respectively until the surface is a mirror surface, then ultrasonically cleaning the surface in ethanol and water respectively, then washing the surface by using distilled water for 3 times, and drying the surface by using nitrogen to obtain a standby glassy carbon electrode;
step 2: preparation of the Mixed solution
Weighing 1.0mg of 2D porphyrin MOF nano material, fusing the 2D porphyrin MOF nano material in 1mL of 5% chitosan, and thoroughly dispersing the 2D porphyrin MOF nano material under the ultrasonic treatment condition to obtain a mixed solution;
and step 3: dispensing
And transferring 7 mu L of the mixed solution, dripping the mixed solution on the surface of the standby glassy carbon electrode, and naturally drying at room temperature for 12h to obtain the modified glassy carbon electrode, which is expressed as Co-TCPP/GCE.
The invention has the beneficial effects that:
the nitrite electrochemical sensor with high sensitivity, good stability, long service life and wide linear range is obtained by a method for preparing the electrochemical sensor electrode based on the nanocomposite material and a cheap and environment-friendly material based on the excellent performance of the 2D MOF nanomaterial.
Drawings
FIG. 1 is a representation of a scanning electron microscope with a Co-TCPP MOF scale bar of 10 μm;
FIG. 2 is a representation of a scanning electron microscope with a scale bar of Co-TCPP MOF of 2 μm;
FIG. 3 is a representation of a transmission electron microscope with a Co-TCPP MOF scale bar of 500 μm;
FIG. 4 is a representation of the X-ray energy spectrum of Co-TCPP MOF;
FIG. 5 is a representation of the X-ray diffraction pattern of Co-TCPP MOF;
FIG. 6 shows the reaction of GCE (a, b) and Co-TCPP/GCE (c, d) in sodium nitrite (NaNO)2) Adding a post-addition CV curve;
FIG. 7 shows the concentration of sodium nitrite (NaNO) in Co-TCPP/GCE2) A CV curve measured in the presence;
FIG. 8 shows the concentration of sodium nitrite (NaNO) in Co-TCPP/GCE2) A linear relationship graph;
FIG. 9 is a graph of the I-t response test of Co-TCPP/GCE to continuous addition of 10. mu.L of 0.1M nitrite at different catalytic potentials:
FIG. 10 is a graph of the I-t curve and the linear relationship of Co-TCPP/GCE for different concentrations of nitrite;
FIG. 11 is an I-t response curve for Co-TCPP/GCE after continuous addition of 1mM nitrite and 1mM other interfering substances to a pH 7 phosphate buffered PBS base.
Wherein, a to i in fig. 7 are: 0. 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5 mM; in fig. 8, the base solutions were tested: 1M Phosphate Buffered (PBS) solution (pH 7), sweep rate: 0.1V/s; in fig. 9 a to e are: 0.7V, 0.8V, 0.85V, 0.9V, 1.0V, nitrite 10 μ L0.1M.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A2D porphyrin MOF nanometer material for an electrochemical sensor comprises the following components: the volume ratio of the N, N-dimethylformamide to the ethanol is 1:3, the cobalt nitrate hexahydrate is 15mg, the polyvinylpyrrolidone is 20mg, and the 4-carboxyphenylporphyrin is 12 mg.
The preparation method of the nano material comprises the following specific preparation processes:
step 1: prefabricated building block
Respectively adding N, N-dimethylformamide and ethanol in a volume ratio of 1:3 into a 25ml beaker by adopting a hydrothermal method, uniformly mixing to obtain a mixed solution, and then weighing 15mg of cobalt nitrate hexahydrate and 20mg of polyvinylpyrrolidone to dissolve in the mixed solution to obtain a prefabricated solution;
step 2: reaction of
Slowly adding 12mg of 4-carboxyphenylporphyrin in the step 1 into the prefabricated liquid under the condition of magnetic stirring, fully and uniformly mixing under the ultrasonic condition of 80KHz/100W, further transferring into a reaction kettle, placing the reaction kettle into an oven, and reacting for 24 hours at 80 ℃ for primary drying;
and step 3: treatment of
And after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifuging for 10min under the condition of 10000 revolutions per min by a centrifuge, washing for 3 times by using ethanol, and drying for 6h at 50 ℃ to obtain the 2D porphyrin MOF nano material, namely Co-TCPP MOF.
The method for smearing the electrode of the electrochemical sensor by the nano material comprises the following specific steps:
step 1: pretreatment of glassy carbon electrodes
Before modification, polishing and grinding the glassy carbon electrode by using 1.0 mu m and 0.3 mu m alumina powder respectively until the surface is a mirror surface, then ultrasonically cleaning the surface in ethanol and water respectively, then washing the surface by using distilled water for 3 times, and drying the surface by using nitrogen to obtain a standby glassy carbon electrode;
step 2: preparation of the Mixed solution
Weighing 1.0mg of 2D porphyrin MOF nano material, fusing the 2D porphyrin MOF nano material in 1mL of 5% chitosan, and thoroughly dispersing the 2D porphyrin MOF nano material under the ultrasonic treatment condition to obtain a mixed solution;
and step 3: dispensing
And transferring 7 mu L of the mixed solution, dripping the mixed solution on the surface of the standby glassy carbon electrode, and naturally drying at room temperature for 12h to obtain the modified glassy carbon electrode, which is expressed as Co-TCPP/GCE.
Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) are respectively adopted to characterize Co-TCPP, as can be seen from figures 1, 2 and 3, the prepared Co-TCPP MOF material presents 2D sheet-like morphology, the diameter of the Co-TCPP MOF material is in micron level, as can be seen from figure display data, the material surface is smooth, the thickness of the Co-TCPP MOF material is thin, and the prepared Co-TCPP MOF material is 2D sheet-like nanometer material.
Further, as can be seen from fig. 4, the nanomaterial prepared contains C, N, O, Co elements as a result of the X-ray spectroscopy (EDS) analysis of the material. In addition, the characterization results of X-ray diffraction (XRD) are shown in fig. 5. Comparing the characterization results of TCPP and Co-TCPP MOF in fig. 5, it can be found that, first, both exhibit the characteristic diffraction peak of TCPP around 20 °; secondly, the peak shape of TCPP is sharp and strong, while the peak intensity of Co-TCPP MOF is weak. This is probably because the more the prepared Co-TCPP MOF nanomaterials tend to be amorphous, i.e. 2D, state compared to pure TCPP. According to the characterization results of a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), an X-ray energy spectrum (EDS) and X-ray diffraction (XRD), the 2D Co-TCPP MOF nano material is successfully prepared through the experiment.
Figure 6 shows CV curves measured before and after the addition of 1mM NaNO2 to phosphate buffered saline PBS base solution at pH 7 using naked GCE and Co-TCPP/GCE, respectively. For the bare electrode GCE, it can be seen that there is almost no peak current response in Phosphate Buffered Saline (PBS) without the addition of NaNO2 (fig. 6 a); while 1mM NaNO was added2After that, the potential was observedAt 0.9V, an oxidation peak appeared with a peak current value of about 6. mu.A. This indicates that the bare electrode GCE has some catalytic oxidation effect on nitrite. For the modified electrode Co-TCPP/GCE, NaNO is not added2In the case of (1), at a potential of 0.8V, an oxidation peak appears, which is an oxidation peak of the Co-TCPP material itself, and the peak current value thereof is about 13. mu.A; while 1mM NaNO was added2After that, it was observed that the current response was greatly increased, and at a potential of 0.9V, the oxidation peak current value was about 40. mu.A, and the peak current was increased by 27. mu.A. This shows that the modified electrode Co-TCPP/GCE has better catalytic oxidation effect on nitrite in the presence of Co-TCPP MOF nanomaterial than the bare electrode GCE. FIG. 7 reflects CV curves of Co-TCPP/GCE for different concentrations of nitrite (a to i: 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5 mM). As can be seen, the NaNO reaction proceeds with2The concentration is continuously increased, the oxidation peak current of Co-TCPP/GCE is also continuously increased, and the peak current value and NaNO are2The concentration relationship is shown in FIG. 7, the two show good linear relationship, and the value of the correlation coefficient R2 reaches 0.9991.
The detection limit and the linear range of the modified electrode for detecting nitrite are determined by an amperometric current (I-t curve) method commonly used in the experiment. As can be seen from the CV experiments described above, the oxidation peak potential of Co-TCPP/GCE catalyzed nitrite was between 0.9 and 1.0V (0.9V for a scan range of 0-1.0V and 1.0V for a scan range of 0-1.2V). However, at such a higher positive potential, oxygen, among other factors, can interfere with the I-t curve. Therefore, the optimum catalytic potential was selected by chronoamperometry prior to the experiment. The results of the experiment are shown in FIG. 9 (a-e:0.7V, 0.8V, 0.85V, 0.9V, 1.0V) with the addition of nitrite to Phosphate Buffered Saline (PBS) base solution every 50s for four times starting from 100s at different potentials. As can be seen from the figure, when the catalytic potential is 0.7V, the obtained I-t curve is the smoothest, but the step is lower, which indicates that the experimental interference at the potential is small, but the current response of the modified electrode to nitrite is also lower. On the contrary, when the catalytic potential is 0.9 or 1.0V, the step current is large, but the curve is not smooth, which means that the experiment, modification, is carried out at the potentialThe current response to nitrite is greater for the electrode, but the interference is also more pronounced. In comprehensive comparison, when the catalytic potential is 0.8 or 0.85V, the interference is low, and the current response of the modified electrode to nitrite is also large, considering that the I-t curve obtained under 0.8V is smoother, and the step current is close to that under 0.85V, therefore, 0.8V is selected as the optimal catalytic potential for subsequent I-t experiments, and the experimental result is shown in fig. 5. When the addition of 1 μ M nitrite started, the curve had a distinct current step, and the step current value increased continuously as the nitrite concentration added increased, as shown in fig. 9. It can be found by analysis that the step response current value and the nitrite concentration have a good linear relationship as shown in FIG. 10, and the correlation coefficient R thereof20.9956 is reached, the linear equation is I (mu A) ═ 0.0435C (mM) +0.8009, the linear range is 1 mu m-1.388 mM, the detection limit is 0.617 mu m (signal to noise ratio is 3). Compared with the reported performance of the nitrite electrochemical sensor, the main performance of the sensor is wider in linear range and lower in detection limit.
An interference test of the sensor was also performed, and the test result is shown in fig. 11, in which sodium carbonate (Na)2CO3) Sodium sulfate (Na)2SO4) Potassium nitrate (KNO)3) Potassium carbonate (K)2CO3) Sodium chloride (NaCl), a common substance, may interfere with the sensor detection, and 1.0mM NaNO was added to the base solution at an operating potential of 0.8V2A distinct response step was observed, whereas 1.0mM Na was added sequentially at 50s intervals2CO3、Na2SO4、KNO3、K2CO3And the response current after NaCl does not change, which shows that the sensor has good anti-interference performance on the common interference substances. In addition, the reproducibility and stability of the sensor were also investigated. The Relative Standard Deviation (RSD) of the current response values obtained with 5 identical Co-TCPP/GCE measurements of equivalent nitrite, respectively, was about 3%, indicating a better reproducibility of the sensor. In order to research the stability of the sensor, the same Co-TCPP/GCE modified electrode is used for detecting nitrite, the current response value is recorded, the nitrite with the same concentration is tested again after 21 days,the current response signal is 89% of the original current response signal, which indicates that the stability is better.
Milk samples were processed according to GB 5009.33-2010. 53.5g of zinc sulfate (ZnSO4 & 7H2O) were dissolved in water and diluted to 100 mL. 50mL of skim milk was diluted with 20mL of distilled water, and various doses of NaNO2 (20. mu.M, 50. mu.M, 100. mu.M) were added, followed by 15mL of ZnSO4 solution and 15mL of PBS solution at pH 7. And standing for 1h after stirring, and filtering supernatant to obtain filtrate to be detected. The measurement results are shown in table 4, the recovery rate is 99.45% -102.6%, and the sensor can be used for quantitative detection of nitrite in actual samples.
Claims (7)
1. A2D porphyrin MOF nanometer material for an electrochemical sensor is characterized by comprising the following components: the volume ratio of the N, N-dimethylformamide to the ethanol is 1:3, the cobalt nitrate hexahydrate is 15mg, the polyvinylpyrrolidone is 20mg, and the 4-carboxyphenylporphyrin is 12 mg.
2. The method for preparing the nano-material according to claim 1, which is characterized by comprising the following specific steps of:
step 1: prefabricated building block
Respectively adding N, N-dimethylformamide and ethanol in a volume ratio of 1:3 into a beaker by adopting a hydrothermal method, uniformly mixing to obtain a mixed solution, and then weighing 15mg of cobalt nitrate hexahydrate and 20mg of polyvinylpyrrolidone to dissolve in the mixed solution to obtain a prefabricated solution;
step 2: reaction of
Slowly adding 12mg of 4-carboxyphenylporphyrin in the step 1 into the prefabricated liquid under the condition of magnetic stirring, fully and uniformly mixing under the ultrasonic condition, further transferring the mixture into a reaction kettle, and placing the reaction kettle into an oven for primary drying;
and step 3: treatment of
And taking out the reaction kettle after the reaction is finished, naturally cooling to room temperature, centrifuging, washing, and drying for the second time to obtain the 2D porphyrin MOF nano material expressed as Co-TCPP MOF.
3. The method for preparing nano-materials according to claim 2, wherein the beaker in the step 1 is 25 ml.
4. The method for preparing nano-materials according to claim 3, wherein the ultrasonic condition of the step 2 is 80 KHz/100W.
5. The method for preparing nano-materials according to claim 4, wherein the condition of primary drying in the step 2 is reaction at 80 ℃ for 24 h.
6. The method for preparing nano-materials according to claim 5, wherein the conditions of the centrifugation in the step 3 are as follows: centrifuging for 10min under the condition of 10000 revolutions per minute of the centrifuge, wherein the washing condition is as follows: washing with ethanol for 3 times, wherein the conditions of secondary drying are as follows: drying for 6h at 50 ℃.
7. A method for coating an electrode of an electrochemical sensor by using the nanomaterial of claim 1, which comprises the following specific steps:
step 1: pretreatment of glassy carbon electrodes
Before modification, polishing and grinding the glassy carbon electrode by using 1.0 mu m and 0.3 mu m alumina powder respectively until the surface is a mirror surface, then ultrasonically cleaning the surface in ethanol and water respectively, then washing the surface by using distilled water for 3 times, and drying the surface by using nitrogen to obtain a standby glassy carbon electrode;
step 2: preparation of the Mixed solution
Weighing 1.0mg of 2D porphyrin MOF nano material, fusing the 2D porphyrin MOF nano material in 1mL of 5% chitosan, and thoroughly dispersing the 2D porphyrin MOF nano material under the ultrasonic treatment condition to obtain a mixed solution;
and step 3: dispensing
And transferring 7 mu L of the mixed solution, dripping the mixed solution on the surface of the standby glassy carbon electrode, and naturally drying at room temperature for 12h to obtain the modified glassy carbon electrode, which is expressed as Co-TCPP/GCE.
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