CN109752433B - Nickel phosphate/Co-MOFs composite material and preparation method and application thereof - Google Patents
Nickel phosphate/Co-MOFs composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nickel phosphate/Co-MOFs composite material and a preparation method and application thereof, belonging to the technical field of electrocatalyst materials. Dissolving nickel salt and phosphate in water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle, filtering after the hydrothermal reaction is finished, taking precipitate, washing and drying the precipitate to obtain nano nickel phosphate; and then dispersing nano nickel phosphate into a solvent, adding cobalt salt, stirring for 1-5h, then adding a 2-methylimidazole solution to obtain a reaction solution, stirring the reaction solution for 0.5-5h, standing for 1-24h, centrifuging, and taking a precipitate to obtain the nickel phosphate/Co-MOFs composite material. The electrode modified by the composite material has high sensitivity and low detection limit on glucose sensing, and can be used for detecting glucose in human serum. The composite material has simple preparation process, no need of additives such as reducing agent, structure directing agent and the like, low requirement on equipment, low cost and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of electrocatalyst materials, and particularly relates to a nickel phosphate/Co-MOFs composite material as well as a preparation method and application thereof.
Background
The blood glucose content of normal human is 3.8-6.9mmol/L, and the blood glucose content exceeds the standard value, which indicates that the human body has pathological changes, wherein the diabetes caused by insufficient insulin secretion is an incurable disease. At present, diabetes threatens the health of 6 hundred million people worldwide, and diabetics need to monitor the blood sugar concentration in vivo in real time every day, so that the development of a portable and low-cost glucose sensor has important significance.
At present, high performance liquid chromatography, colorimetry, chemiluminescence, fluorescence, surface enhanced raman, mass spectrometry and electrochemical methods are all technologies for detecting glucose. Among them, the electrochemical method becomes the most potential glucose detection means with the advantages of simple operation, low equipment cost, easy integration, portability, etc., the core component of the electrochemical sensor in the method is the electrocatalyst of the sensor, and the current commercial glucose sensor generally uses noble metal nanoparticles. Noble metals are expensive and tend to deactivate preventing their widespread use.
The transition metal element has high electrochemical activity similar to that of noble metal, is rich in storage and low in price, and is an important electrocatalyst replacing the noble metal as a glucose sensor. In order to solve the problems of agglomeration and low specific surface area in the nickel phosphate electrocatalysis process, the invention designs a nickel phosphate composite catalyst supported by open-pore MOF, which is used for electrocatalysis oxidation of glucose.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing nickel phosphate/Co-MOFs composite material; the second purpose is a nickel phosphate/Co-MOFs composite material; it is a further object to provide an electrochemical sensor; the fourth purpose is to provide the application of the electrochemical sensor in the detection of glucose.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of nickel phosphate/Co-MOFs composite material comprises the following steps:
(1) dissolving nickel salt and phosphate in water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle, filtering after the hydrothermal reaction is finished, taking precipitate, and washing and drying the precipitate to obtain nano nickel phosphate;
(2) dispersing the nano nickel phosphate prepared in the step (1) in a solvent, adding cobalt salt, stirring for 1-5h, adding a 2-methylimidazole solution to obtain a reaction solution, stirring the reaction solution for 0.5-5h, standing for 1-24h, centrifuging, and taking a precipitate to obtain the nickel phosphate/Co-MOFs composite material.
Preferably, in the step (1), the molar ratio of nickel element in the nickel salt to phosphorus element in the phosphate to water to N, N-dimethylformamide is 40:20:5-35: 1-9; the hydrothermal reaction is carried out for 3-10h at the temperature of 100-180 ℃.
Preferably, in the step (1), the nickel salt is one of nickel nitrate, nickel chloride or nickel sulfate; the phosphate is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
Preferably, in the step (1), the drying is specifically drying at 60 ℃ for 10 h.
Preferably, in the step (2), the mass ratio of the nano nickel phosphate and the nano cobalt salt prepared in the step (1) to the 2-methylimidazole in the reaction solution is 100:14-742: 16-821.
Preferably, in the step (2), the solvent is one of methanol, N-dimethylformamide or ethanol; the 2-methylimidazole solution is one of a 2-methylimidazole methanol solution, a 2-methylimidazole N, N-dimethylformamide solution or a 2-methylimidazole ethanol solution.
Preferably, in the step (2), the cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt sulfate.
2. The nickel phosphate/Co-MOFs composite material prepared by the method.
3. An electrochemical sensor comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and electrolyte, wherein the surface of the working electrode is coated with the nickel phosphate/Co-MOFs composite material.
Preferably, the working electrode is prepared as follows:
dispersing the nickel phosphate/Co-MOFs composite material in N, N dimethyl formamide according to the proportioning concentration of 1-5mg/mL to obtain an electrode modification solution, coating the electrode modification solution on the electrode which is ground and cleaned, and airing.
Preferably, the electrode is one of a glassy carbon electrode, a graphite electrode, or a gold electrode.
4. The electrochemical sensor is applied to glucose detection.
The invention has the beneficial effects that: the invention provides a nickel phosphate/Co-MOFs composite material and a preparation method and application thereof, wherein nano nickel phosphate can be uniformly loaded on Co-MOFs through the exchange effect of cobalt ions and nickel ions, and the Co-MOFs can effectively prevent the nano nickel phosphate from agglomerating, so that the specific surface area of the nano nickel phosphate is increased, and the performance of the nano nickel phosphate for electrocatalytic oxidation of glucose is improved by 21 times. The sensitivity of the electrode modified by the composite material to glucose is up to 2783 muA/mM cm2The detection limit is as low as 0.7 mu mol/L, and the method can be used for detecting the glucose in the serum of a human body. The composite material has simple preparation process, no need of additives such as reducing agent, structure directing agent and the like, low requirement on equipment, low cost and suitability for industrial production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an SEM image of nano nickel phosphate prepared in example 1;
FIG. 2 is an SEM photograph of Co-MOFs formed during the preparation of nickel phosphate/Co-MOFs composite material in example 1;
FIG. 3 is an SEM photograph of nickel phosphate/Co-MOFs composite material prepared in example 1;
FIG. 4 is a graph showing the results of the current response test of glucose molecules on electrodes modified with different materials in example 4;
FIG. 5 is a graph of i-t curves for glucose solutions of different concentrations in example 5;
FIG. 6 is a linear plot of the current value on the i-t curve of FIG. 5 increasing linearly with increasing concentration of glucose solution;
FIG. 7 is a graph of the anti-interference test results of the working electrode modified by the nickel phosphate/Co-MOFs composite material prepared in example 1.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of nickel phosphate/Co-MOFs composite material
(1) Dissolving nickel nitrate and ammonium dihydrogen phosphate in deionized water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle at 100 ℃ for 5 hours, filtering after the hydrothermal reaction is finished, taking a precipitate, washing the precipitate, and drying at 60 ℃ for 10 hours to obtain nano nickel phosphate, wherein the molar ratio of nickel element in the nickel nitrate to phosphorus element in the ammonium dihydrogen phosphate to water to the N, N-dimethylformamide is 40:20:6: 9;
(2) dispersing the nano nickel phosphate prepared in the step (1) in methanol, adding cobalt nitrate, stirring for 2 hours, adding a 2-methylimidazole methanol solution to obtain a reaction solution, stirring the reaction solution for 2 hours, standing for 24 hours, centrifuging to obtain a precipitate, and preparing the nickel phosphate/Co-MOFs composite material, wherein the mass ratio of the nano nickel phosphate, the cobalt nitrate and the 2-methylimidazole prepared in the step (1) in the reaction solution is 100:145: 324.
Example 2
Preparation of nickel phosphate/Co-MOFs composite material
(1) Dissolving nickel sulfate and sodium dihydrogen phosphate in deionized water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle at 150 ℃ for 10 hours, filtering after the hydrothermal reaction is finished, taking a precipitate, washing the precipitate, and drying at 60 ℃ for 10 hours to obtain nano nickel phosphate, wherein the molar ratio of nickel element in nickel salt, phosphorus element in phosphate, water and N, N-dimethylformamide is 40:20:35: 1;
(2) dispersing the nano nickel phosphate prepared in the step (1) in ethanol, adding cobalt sulfate, stirring for 1h, adding a 2-methylimidazole ethanol solution to obtain a reaction solution, stirring the reaction solution for 0.5h, standing for 10h, centrifuging, and taking a precipitate to obtain the nickel phosphate/Co-MOFs composite material, wherein the mass ratio of the nano nickel phosphate and cobalt salt prepared in the step (1) to the 2-methylimidazole in the reaction solution is 100:14: 821.
Example 3
Preparation of nickel phosphate/Co-MOFs composite material
(1) Dissolving nickel chloride and diammonium hydrogen phosphate in deionized water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle at 180 ℃ for 3 hours, filtering after the hydrothermal reaction is finished, taking a precipitate, washing the precipitate, and drying at 60 ℃ for 10 hours to obtain nano nickel phosphate, wherein the molar ratio of nickel element in nickel salt, phosphorus element in phosphate, water and N, N-dimethylformamide is 40:20:18: 5;
(2) dispersing the nano nickel phosphate prepared in the step (1) in N, N-dimethylformamide, adding cobalt chloride, stirring for 5 hours, then adding a 2-methylimidazole N, N-dimethylformamide solution to obtain a reaction solution, stirring the reaction solution for 5 hours, standing for 18 hours, centrifuging, and taking a precipitate to prepare the nickel phosphate/Co-MOFs composite material, wherein the mass ratio of the nano nickel phosphate, the cobalt salt and the 2-methylimidazole prepared in the step (1) in the reaction solution is 100:742: 16.
Fig. 1 is an SEM image of the nano nickel phosphate prepared in example 1, and it can be seen from fig. 1 that the nano nickel phosphate is relatively serious in agglomeration phenomenon.
FIG. 2 is an SEM image of Co-MOFs formed in the process of preparing the nickel phosphate/Co-MOFs composite material in example 1, and it can be known from FIG. 2 that the Co-MOFs have regular rhombic dodecahedron shapes.
FIG. 3 is an SEM image of the nickel phosphate/Co-MOFs composite material prepared in example 1, and it can be seen from FIG. 3 that Co-MOFs are successfully loaded on nickel phosphate, the loading is relatively uniform, and compared with FIG. 1, the agglomeration phenomenon of nano nickel phosphate is obviously improved.
Example 4
Testing current response of glucose molecules on nickel phosphate/Co-MOFs composite material modified electrode
(1) Respectively dispersing nickel phosphate, Co-MOFs and a nickel phosphate/Co-MOFs composite material in N, N dimethyl formamide according to the proportion concentration of 3mg/mL to obtain 3 electrode modification solutions, respectively coating 5 mu L of each electrode modification solution on a glassy carbon electrode which is polished and alternately cleaned by absolute ethyl alcohol and deionized water, and airing to obtain 3 working electrodes (each working electrode is sequentially marked as Ni)3(PO4)2/GCE、Co-MOFs/GCE、Ni3(PO4)2and/Co-MOFs/GCE), respectively constructing 3 electrochemical sensors by using the 3 working electrodes, a saturated calomel electrode (reference electrode), a platinum wire (counter electrode), electrolyte (NaOH solution with the concentration of 0.1M) and an electrochemical workstation, and simultaneously using a glassy carbon electrode which is polished and alternately cleaned by absolute ethyl alcohol and deionized water as a working electrode (the working electrode is marked as GCE), and also using the electrochemical sensor together with the saturated calomel electrode (reference electrode), the platinum wire (counter electrode), the electrolyte (NaOH solution with the concentration of 0.1M) and the electrochemical workstation as a blank control.
(2) Adding a glucose standard solution with the concentration of 0.1M into the electrolyte in the 4 electrochemical sensors constructed in the step (1) respectively to enable the concentration of glucose in the electrolyte to be 1mmol/L, controlling the stirring speed of magnetons to be 500r/min, simultaneously loading a forward scanning voltage on the working electrode in each electrochemical sensor, wherein the scanning range is 0V to 0.8V, and the scanning amplitude is 50mV/s, recording the change situation of oxidation current-voltage by an electrochemical workstation in each electrochemical sensor, and obtaining a CV curve graph, as shown in FIG. 4, as can be seen from FIG. 4, the current response of the glucose molecule on the nickel phosphate/Co-MOFs composite material modified electrode prepared in the example 1 is the maximum, and the oxidation peaks around 0.26V and 0.52V are respectively attributed to the oxidation peak of nickel phosphate and the oxidation peak of glucose.
Example 5
Modified by the nickel phosphate/Co-MOFs composite prepared in example 1 and configured in example 4The electrochemical sensor of the working electrode is used as a testing device, glucose standard solutions with the concentrations of 0.001M, 0.01M and 0.1M are prepared, and 8mL of 0.1M NaOH solution is used as electrolyte. By using a chronoamperometry, an initial voltage of 0.4-0.6V was set, a running time was set to 1200s, glucose standard solution having a concentration of 0.001M was added every 30s after the start of the running for 200s in the amount of 8 μ L, 4 μ L, 8 μ L, 16 μ L, 40 μ L, and 16 μ L in this order, glucose standard solution having a concentration of 0.1M was added in the amount of 8 μ L, 16 μ L, 40 μ L, and 40 μ L in this order, while controlling a magneton stirring speed to be 500r/min, and an oxidation current corresponding to each glucose concentration was recorded to obtain an i-t graph, and as a result, as shown in fig. 5, a current value on the i-t graph linearly increased as the concentration of the glucose solution increased. The current value is plotted against the glucose concentration as shown in FIG. 6, and a linear equation is fitted according to FIG. 6. from FIG. 6, it can be seen that the response of the glucose current to its concentration ranges linearly from 0.001 mM to 4.0mM, and the fitted linear relationship is: y (μ a) ═ 196.6x (μmol/L) +19.2, correlation coefficient R2The detection sensitivity is 196.6 muA/. mu.M, the data is obtained based on nickel phosphate/Co-MOFs modified glassy carbon electrode with the diameter of 3mM, and therefore, the unit area sensitivity can be converted into 2783 muA/mM cm2The limit of detection of glucose by the sensor of the present invention (based on 3 times the noise) is 0.7X 10-6mol/L。
Example 6
Anti-interference test of working electrode modified by nickel phosphate/Co-MOFs composite material prepared in example 1
The electrochemical sensor configured with the working electrode modified by the nickel phosphate/Co-MOFs composite material prepared in example 1 in example 4 was used as a testing device, a chronoamperometry was used, an initial voltage was set to 0.5V, 80 μ L of a glucose standard solution with a concentration of 0.1mol/L was added after 100s of operation, a magneton stirring speed was controlled to 500r/min, the operation was continued, 8 μ L of a fructose solution with a concentration of 0.1mol/L, 8 μ L of a lactose solution with a concentration of 0.1mol/L, 8 μ L of a sucrose solution with a concentration of 0.1mol/L, 8 μ L of an ascorbic acid solution with a concentration of 0.1mol/L, 8 μ L of a dopamine solution with a concentration of 0.1mol/L, 8 μ L of a uric acid solution with a concentration of 0.1mol/L were sequentially added every 20s, and oxidation currents corresponding to the different solutions were recorded, as shown in fig. 7, the current values caused by fructose, lactose, sucrose, ascorbic acid, dopamine and uric acid with the concentrations of 0.1mM can be ignored and are far lower than the current value of glucose with the concentration of 1.0mM, so that the fructose, lactose, sucrose, ascorbic acid, dopamine and uric acid have little influence on the detection of glucose by the electrochemical sensor provided with the working electrode modified by the nickel phosphate/Co-MOFs composite material, and the electrochemical sensor has good anti-interference performance.
Example 7
Detection of glucose in human serum
Two human serum samples (numbered 1 and 2 respectively) were provided by the fourth national hospital of tribute city, the concentrations were measured by a full-automatic bioanalyzer, and 2 human serum samples were measured by the following method, using the electrochemical sensor equipped with the working electrode modified with the nickel phosphate/Co-MOFs composite material prepared in example 1 in example 4 as a test device: transferring 8 mu L of serum into 8mL of electrolyte with the concentration of 0.1mol/L NaOH, controlling the stirring speed of magnetons to be 500r/min, detecting the reliability of the electrochemical sensor by adopting a chronoamperometry method, operating for 100s, adding 16 mu L of glucose standard solution with the concentration of 0.1mol/L, and calculating the recovery rate of standard glucose. Three replicates were run at each concentration and the recovery was calculated for each concentration and the results of the spiked recoveries are shown in table 1.
TABLE 1
As can be seen from Table 1, the recovery rate is 92-109%, which shows that the electrochemical sensor provided with the working electrode modified by the nickel phosphate/Co-MOFs composite material has practical application value.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of nickel phosphate/Co-MOFs composite material is characterized by comprising the following steps:
(1) dissolving nickel salt and phosphate in water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle, filtering after the hydrothermal reaction is finished, taking precipitate, and washing and drying the precipitate to obtain nano nickel phosphate; the molar ratio of nickel element in the nickel salt to phosphorus element in the phosphate to water to N, N-dimethylformamide is 40:20:5-35: 1-9; the hydrothermal reaction is carried out for 3-10h at the temperature of 100-180 ℃;
(2) dispersing the nano nickel phosphate prepared in the step (1) in a solvent, adding cobalt salt, stirring for 1-5h, adding a 2-methylimidazole solution to obtain a reaction solution, stirring the reaction solution for 0.5-5h, standing for 1-24h, centrifuging, and taking a precipitate to obtain a nickel phosphate/Co-MOFs composite material; the mass ratio of the nano nickel phosphate and the cobalt salt prepared in the step (1) to the 2-methylimidazole in the reaction solution is 100:14-742: 16-821.
2. The method of claim 1, wherein in step (1), the nickel salt is one of nickel nitrate, nickel chloride or nickel sulfate; the phosphate is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
3. The method of claim 1, wherein in step (2), the solvent is one of methanol, N-dimethylformamide, or ethanol; the 2-methylimidazole solution is one of a 2-methylimidazole methanol solution, a 2-methylimidazole N, N-dimethylformamide solution or a 2-methylimidazole ethanol solution.
4. The method of claim 1, wherein in step (2), the cobalt salt is one of cobalt nitrate, cobalt chloride or cobalt sulfate.
5. Nickel phosphate/Co-MOFs composite material prepared by the process according to any one of claims 1 to 4.
6. An electrochemical sensor comprising an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, wherein the surface of the working electrode is coated with the nickel phosphate/Co-MOFs composite material according to claim 5.
7. An electrochemical sensor according to claim 6, wherein the working electrode is prepared by:
dispersing the nickel phosphate/Co-MOFs composite material in N, N dimethyl formamide according to the proportioning concentration of 1-5mg/mL to obtain an electrode modification solution, coating the electrode modification solution on the electrode which is ground and cleaned, and airing.
8. Use of an electrochemical sensor according to claim 6 for the detection of glucose.
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