CN110988060A - Nano porous carbide material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a nano porous carbide material and a preparation method and application thereof, belonging to the technical field of nano materials. The preparation method comprises the following steps: adding organic carbide containing nitrogen heterocycle, metal ammonium salt and silicon dioxide into water, stirring to prepare gel, drying, and then putting into inert gas for carbonization heating reaction to obtain an initial product; and (3) placing the initial product in hydrofluoric acid water solution for etching, centrifuging to obtain a precipitate, and freeze-drying the precipitate to obtain the nano porous carbide material. The electrochemical sensor prepared by taking the nano porous carbide material as the raw material has good biocompatibility, excellent selectivity, short response time, wide detection range and extremely high reaction sensitivity, shows extremely high sensitivity and selectivity when detecting hydrogen peroxide released by cells in situ in real time compared with the sensor prepared by the traditional material, and has the advantages of stable electrochemical performance, long cycle service life, simple preparation process operation of the material, low cost of raw materials and great industrial application value.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nano porous carbide material as well as a preparation method and application thereof.
Background
Hydrogen peroxide is a major active oxygen in the organism, mainly produced by most oxidases in the mitochondria, and can diffuse freely over the cell membrane. The toxicity of hydrogen peroxide is low, but excessive hydrogen peroxide can cause irreversible damage to biological processes such as nucleic acid, unsaturated fatty acid, cell membrane lipid, etc., and can also cause aging and diseases, including cardiovascular diseases, Alzheimer's disease, and even cancer.
The hydrogen peroxide is widely applied to the fields of chemical industry, food, medicine, environmental protection and the like. Therefore, the method has important significance for quickly, accurately and reliably measuring the trace hydrogen peroxide. The method for measuring the hydrogen peroxide mainly comprises an enzymatic electrochemical sensor detection method and a non-enzymatic electrochemical sensor detection method, and the enzymatic electrochemical sensor detection method is widely applied to various fields due to high sensitivity and good selectivity. Compared with an enzyme method, the non-enzyme method electrochemical sensor has the obvious advantages of low cost, simple operation, good stability and the like. However, most non-enzymatic electrochemical sensors contain precious metals. Therefore, the development of a non-noble metal enzyme-free electrochemical sensor with simple operation, high sensitivity and low price is the key point of research and is also a difficult point.
The hydrogen evolution process of the non-enzymatic electrochemical sensor is mainly to obtain electrons from a catalyst. It is well known that platinum-based materials are highly active electrocatalysts that catalyze the evolution of hydrogen, and that platinum-based materials also exhibit excellent performance in detecting hydrogen peroxide. However, platinum-based catalysts are costly, have low reserves, and are not as inexpensive, abundant, and sustainable as transition metals such as molybdenum, tungsten, cobalt, and the like.
The introduction of carbon in the early transition metal lattice results in an expansion of the lattice constant. Through the calculation of a Density Functional Theory (DFT), the hybridization of a metal d orbit, a carbon s orbit and a p orbit widens the structure of a d band, and the d band has the characteristic similar to platinum d.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a nanoporous carbide material; the second purpose is to provide a nano porous carbide material; the third purpose is to apply the nano porous carbide material.
In order to achieve the above purpose, the inventor of the present invention has made a long-term study and a great deal of practice to propose a technical scheme of the present invention, and the specific implementation process is as follows:
1. a preparation method of a nano-porous carbide material comprises the following steps:
s1, adding organic carbide containing nitrogen heterocycle, metal ammonium salt and silicon dioxide into water according to the mass ratio of 10-5: 5-4: 10-5, stirring to prepare gel, drying, and then placing in inert gas for carbonization and heating reaction at 700-1100 ℃ to obtain an initial product;
and S2, placing the initial product in hydrofluoric acid water solution for etching, centrifuging to obtain a precipitate, and freeze-drying the precipitate to obtain the nano porous carbide material.
Preferably, in S1, the organic carbide of the nitrogen-containing heterocycle is melamine, and the metal ammonium salt is ammonium molybdate.
Preferably, the mass ratio of the melamine to the ammonium molybdate to the silicon dioxide is 2:1: 2.
Preferably, in the step S1, the water is deionized water, and the added volume is one fiftieth of the added mass of the silicon dioxide.
Preferably, in the step S1, the gel is dried by a drying method, wherein the drying temperature is 50-120 ℃, and the drying time is 2-8 hours.
Preferably, in the step S1, the carbonization heating reaction time is 2 to 8 hours.
More preferably, in the step S1, the temperature of the carbonization heating reaction is 900 ℃ and the time is 2-3 h.
Preferably, in S1, the carbonization heating reaction is performed in a high-temperature tube furnace.
Preferably, in S2, the volume ratio of hydrofluoric acid to water in the hydrofluoric acid aqueous solution is 1: 1.
Preferably, in the step S2, the etching time is 2 to 8 hours.
Preferably, in S2, the rotation speed of centrifugation is 500-1000 r/min, and the time is 3-10 min.
More preferably, the rotation speed of the centrifugation is 1000r/min, and the time is 3 min.
Preferably, in S2, the temperature of freeze drying is-20 to-80 ℃ and the time is 8 to 18 hours.
More preferably, the temperature of the freeze-drying is-30 ℃.
2. The nanoporous carbide material prepared by the method.
3. The application of the nano porous carbide material in preparing the hydrogen peroxide electrochemical sensor.
4. A hydrogen peroxide electrochemical sensor prepared from a nano porous carbide material.
Preferably, the hydrogen peroxide electrochemical sensor comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and electrolyte, and the preparation method of the working electrode comprises the following steps: dispersing the nano porous carbide material in water according to the proportion concentration of 1-10 mg/mL to obtain an electrode modification solution, then dropwise adding or coating the electrode modification solution on a working electrode, and drying to obtain the nano porous carbide material.
Preferably, the working electrode is a glassy carbon electrode with a diameter of 3 mm.
Preferably, the drying temperature of the working electrode is 20-100 ℃, and the drying time is 20-60 min.
Wherein, the counter electrode is a platinum wire electrode, the reference electrode is an Ag/AgCl electrode, and the electrolyte in the electrolytic cell is phosphate buffer solution with the concentration of 0.01mol/L and the pH value of 7.4.
5. Application of a hydrogen peroxide electrochemical sensor in real-time in-situ detection of hydrogen peroxide released in a biological system.
The invention has the beneficial effects that:
1) the invention provides a nano porous carbide material and a preparation method and application thereof, when the nano porous carbide material is prepared, the quality proportion of organic carbide containing nitrogen heterocycle, metal ammonium salt and silicon dioxide is reasonably set, and the type of the metal ammonium salt is reasonably selected, so that an electrochemical sensor prepared by taking the finally prepared nano porous metal carbide material as a raw material not only has good biocompatibility, excellent selectivity, very short response time and a wider detection range, but also has extremely high sensitivity;
2) compared with the sensor prepared by the traditional material, the electrochemical sensor prepared by the nano porous carbide material has the advantages of high sensitivity and selectivity when the hydrogen peroxide released by cells is detected in situ in real time, stable electrochemical performance, long cycle service life, simple preparation process operation, low raw material cost and great industrial application value.
Drawings
FIG. 1 is a comparison of a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), and a High Resolution Transmission Electron Microscope (HRTEM) of the nanoporous carbide material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the nanoporous carbide material prepared in example 1;
FIG. 3 is a Raman plot of the nanoporous carbide material prepared in example 1;
FIG. 4 is a graph showing the results of a cyclic voltammetry response test of the electrochemical sensor constructed in example 1 to hydrogen peroxide at a voltage range of-0.9-0.6V;
FIG. 5 is a graph of the i-t response of a working electrode constructed in example 1 with respect to an Ag/AgCl reference electrode with successive additions of different concentrations of hydrogen peroxide to the electrolyte at a fixed potential of-0.65V;
FIG. 6 is a graph of the linear relationship between the steady-state current and the hydrogen peroxide concentration detected by the electrochemical sensor constructed in example 1, with successive additions of different concentrations of hydrogen peroxide to the electrolyte at a fixed potential of-0.65V;
FIG. 7 is a graph showing the results of a test for selectivity of hydrogen peroxide electrochemical sensors constructed in example 1 for different interfering components;
FIG. 8 is a graph showing the results of a stability test of the hydrogen peroxide electrochemical sensor constructed in example 1 after being stored for 25 days;
fig. 9 is a graph showing the results of real-time in-situ detection of cells by the electrochemical hydrogen peroxide sensor constructed in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples so that those skilled in the art can better understand the present invention and can practice it, but the examples are not intended to limit the present invention.
Example 1
The preparation method of the nano-porous carbide material comprises the following steps:
s1, adding 1g of melamine, 0.5g of ammonium molybdate and 1g of silicon dioxide into 20mL of deionized water, uniformly mixing, stirring to prepare gel, placing the gel in an oven at 80 ℃ for drying for 10 hours, then placing the gel in argon, and heating and reacting for 2 hours at 900 ℃ to obtain an initial product;
s2, placing the initial product in hydrofluoric acid water solution of 5mL of hydrofluoric acid and 5mL of deionized water for etching for 10h, centrifuging for 6min at the rotating speed of 1000r/min, taking the precipitate, and freeze-drying the precipitate at the temperature of-30 ℃ for 10h to obtain the nano porous metal carbide material, namely the nano porous molybdenum carbide material.
The nanoporous molybdenum carbide material prepared in the embodiment 1 is subjected to SEM detection, TEM detection and HRTEM detection, respectively. Wherein, the parameter of SEM detection is set to be 500 nm; the parameter of TEM detection is set to be 50 nm; the parameters for HRTEM detection were set to 2 nm. The results are shown in FIG. 1.
In FIG. 1, FIG. 1-a is an SEM image, FIG. 1-b is a TEM image, FIG. 1-c is an HRTEM image, and it can be seen from the observation and analysis in FIG. 1-a that: the surface of the prepared nano porous molybdenum carbide material is distributed in a uniform honeycomb structure; from the observation and analysis in FIG. 1-b, it can be seen that: the prepared nanoporous molybdenum carbide material, consisting of uniform molybdenum carbide nanoparticles with an average diameter of about 2nm, encapsulated in a layered carbon matrix, further confirmed the encapsulation of the molybdenum carbide nanoparticles in the nitrogen-doped carbon foam from the observation and analysis in fig. 1-c.
The nanoporous molybdenum carbide material prepared in this example 1 was subjected to X-ray diffraction analysis, and the results are shown in fig. 2.
From the diffraction peaks 39.4 °, 52.1 °, 61.5 °, and 75.5 ° in fig. 2, it can be seen that Mo exists in the material2And C, the composite nano material also contains graphitized carbon as shown by a diffraction peak of 26 degrees, and other miscellaneous peaks are not detected.
The nanoporous molybdenum carbide material prepared in this example 1 was subjected to raman spectroscopy, and the results are shown in fig. 3.
Analysis from FIG. 3 shows that the nano-porous composite material Mo2Fingerprint band of C is 654. 810 and 981cm-1. At 1300 to 1600cm-1The characteristic peaks D and G of the graphene are arranged between the two peaks.
Example 2
An electrochemical sensor made from the nanoporous molybdenum carbide material prepared in example 1, comprising the steps of:
1) dispersing the nano porous molybdenum carbide material in water according to the proportioning concentration of 1-10 mg/mL to obtain an electrode modification solution, coating the electrode modification solution on a glassy carbon electrode, and drying at 30 ℃ for 0.5h to obtain a working electrode coated with the nano porous molybdenum carbide material on the surface;
2) the working electrode coated with the nano-porous molybdenum carbide material on the surface, an electrochemical workstation, a counter electrode (platinum wire electrode), a reference electrode (Ag/AgCl electrode), an electrolytic cell and an electrolyte (phosphate buffer solution with the concentration of 0.01mol/L and the pH value of 7.4) are assembled into the hydrogen peroxide electrochemical sensor.
A solution containing 3mmol/L hydrogen peroxide was added to the electrolyte of the hydrogen peroxide electrochemical sensor assembled in example 2, and the cyclic voltammetric response of the sensor to hydrogen peroxide was tested at a voltage ranging from-0.9 to 0.6V, while the cyclic voltammetric response of the sensor to a phosphate buffer solution was used as a blank. The results are shown in FIG. 4.
From the analysis in FIG. 4, it can be seen that the current of the reduction peak in PBS solution containing 3mmol/L (phosphate buffer solution) is significantly increased compared with that in PBS solution without hydrogen peroxide, indicating that the sensor has significant electrochemical catalytic oxidation capability to hydrogen peroxide.
The electrochemical sensor constructed in example 2 was tested for chronoamperometric response to hydrogen peroxide at a fixed potential of-0.65V (optimum potential) by successively adding hydrogen peroxide solutions at concentrations of 50 μ M, 150 μ M,300 μ M,500 μ M for a time interval of 50s to the electrolyte of the electrochemical sensor constructed in example 2. The i-t response of the working electrode constructed in example 2 against the Ag/AgCl reference electrode is shown in fig. 5, and it can be seen from the analysis of the graph that the response of the sensor is very rapid after the hydrogen peroxide solution is added and a steady state is formed in a very short timeThe current, in response to the overall current, decreases as the concentration of hydrogen peroxide increases. The result of the linear relationship between the steady-state current and the hydrogen peroxide concentration detected by the electrochemical sensor constructed in example 2 is shown in fig. 6, and from the analysis in the figure, the linear equation of the response current and the hydrogen peroxide concentration can be expressed as: i (μ a) ═ 0.0404 × C (μ M) -21.8012(50 μ M)<C(μM)<4500 μ M), sensitivity was 577.14 μ AmM-1cm-2The detection limit was 0.22. mu.M.
Solutions of different substances were sequentially added to the electrolyte of the electrochemical sensor constructed in example 2, the chronoamperometric response of the sensor to different interfering components was tested, the test voltage was-0.65V, and 1mM hydrogen peroxide, 0.15mM ascorbic acid AA, 0.5mM uric acid UA, 5mM Glucose and 1mM hydrogen peroxide were sequentially and sequentially added to the electrolyte of the sensor every 50s, respectively, to obtain an amperometric response curve of the sensor to the selective test of different interfering components, with the results shown in fig. 7. As can be seen from the figure, the addition of AA, UA and Glucose does not cause interference to the detection of hydrogen peroxide by the sensor, which shows that the electrochemical sensor has good selectivity to hydrogen peroxide.
The electrochemical sensor constructed in example 2 was stored in 25d, and the stability of the electrochemical sensor was tested in 1d, 6d, 12d, 18d and 25d, respectively, and the results are shown in fig. 8. From the analysis in the figure, the electrochemical sensor shows good stability.
The electrochemical sensor constructed in the example 2 is used for real-time in-situ detection of liver cancer cells (HPEG2), and the number of the cells is 1 multiplied by 106Specifically, the results of real-time detection of hydrogen peroxide release of hepatoma cells under the stimulation of phorbol 12-myristate 13-acetate (PMA) by a chronoamperometry method in HPEG2 cells at a fixed potential of-0.65V are shown in FIG. 9, i.e., 100. mu. MPMA was injected into the cells. As can be seen from the analysis in FIG. 9, the stimulation of hepatoma cells with PMA to produce hydrogen peroxide can detect a significant change in current, whereas the stimulation of PMA with blank PBS did not detect a significant change in current. Thus, it can be confirmed that the hydrogen peroxide released by hepatoma cells under PMA stimulation is significantly changed by the molybdenum carbide material on the working electrode in the sensorCaptured and subjected to a reduction reaction at the surface thereof. Meanwhile, the electrochemical sensor prepared by using the nano-porous molybdenum carbide of the embodiment 1 as the raw material has good biocompatibility, and can detect hydrogen peroxide in cells in situ in real time.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (9)
1. A preparation method of a nano-porous carbide material is characterized by comprising the following steps:
s1, adding organic carbide containing nitrogen heterocycle, metal ammonium salt and silicon dioxide into water according to the mass ratio of 10-5: 5-4: 10-5, stirring to prepare gel, drying, and then placing in inert gas for carbonization and heating reaction at 700-1100 ℃ to obtain an initial product;
and S2, placing the initial product in hydrofluoric acid water solution for etching, centrifuging to obtain a precipitate, and freeze-drying the precipitate to obtain the nano porous carbide material.
2. The method according to claim 1, wherein in the S1, the nitrogen-containing heterocyclic organic carbide is melamine, and the metal ammonium salt is ammonium molybdate.
3. The method for preparing a nanoporous carbide material according to claim 2, wherein the mass ratio of melamine, ammonium molybdate and silicon dioxide is 2:1: 2.
4. The method according to claim 1, wherein in the step S2, the volume ratio of hydrofluoric acid to water in the hydrofluoric acid aqueous solution is 1: 1.
5. A nanoporous carbon material prepared by the method of any one of claims 1 to 4.
6. Use of the nanoporous carbide material produced by the method of claim 5 in the production of hydrogen peroxide electrochemical sensors.
7. A hydrogen peroxide electrochemical sensor made of the nanoporous carbide material produced by the method of claim 5.
8. The electrochemical hydrogen peroxide sensor according to claim 7, comprising an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, wherein the working electrode is prepared by: dispersing the nano porous carbide material in water according to the proportion concentration of 1-10 mg/mL to obtain an electrode modification solution, then dropwise adding or coating the electrode modification solution on a working electrode, and drying to obtain the nano porous carbide material.
9. Use of the electrochemical sensor of hydrogen peroxide according to claim 8 for real-time in situ detection of hydrogen peroxide release in a biological system.
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| CN111569881A (en) * | 2020-05-29 | 2020-08-25 | 西南大学 | Preparation method of monatomic biomimetic enzyme, and product and application thereof |
| CN112194136A (en) * | 2020-10-22 | 2021-01-08 | 哈尔滨工业大学 | Preparation method of three-dimensional bouquet structure alpha-molybdenum carbide @ carbon with efficient photo-thermal conversion characteristic |
| CN112748169A (en) * | 2020-12-24 | 2021-05-04 | 西南大学 | Preparation method of nano-particle bionic enzyme sensitive element, product and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569881A (en) * | 2020-05-29 | 2020-08-25 | 西南大学 | Preparation method of monatomic biomimetic enzyme, and product and application thereof |
| CN111569881B (en) * | 2020-05-29 | 2021-11-02 | 西南大学 | Preparation method of monatomic biomimetic enzyme, and product and application thereof |
| CN112194136A (en) * | 2020-10-22 | 2021-01-08 | 哈尔滨工业大学 | Preparation method of three-dimensional bouquet structure alpha-molybdenum carbide @ carbon with efficient photo-thermal conversion characteristic |
| CN112748169A (en) * | 2020-12-24 | 2021-05-04 | 西南大学 | Preparation method of nano-particle bionic enzyme sensitive element, product and application thereof |
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