Dual-performance molybdenum selenide nano material and application thereof in detection of small molecular substances

Abstract

The invention provides a dual-performance molybdenum selenide nano-material and application thereof in small molecular substance detection, and belongs to the field of fluorescent and catalytic nano-materials, bulk molybdenum selenide, melamine and boric acid are used as raw materials, dual-element doping is achieved through ultrasonic mixing, stripping and high-temperature calcination, and the dual-performance molybdenum selenide nano-material is obtained. The molybdenum selenide nano material with fluorescence and catalytic performance is successfully prepared. The prepared material has the advantages of being high in fluorescence intensity, high in catalytic performance, high in stability, easy to store and the like, the application prospects of molybdenum selenide in the aspects of optics, catalytic materials and the like are widened, and a new thought is provided for performance regulation and control and preparation of more inorganic nanometer materials.

Description

Technical Field

[0001] The invention belongs to the field of fluorescent and catalytic nanomaterials, and specifically relates to a dual-performance molybdenum selenide nanomaterial and its application in the detection of small molecule substances. Background Art

[0002] Two-dimensional materials are one of the most widely studied material classes. They have developed rapidly in recent years and have attracted great attention from thousands of scientists in the fields of materials science, physics, chemistry, engineering and medicine. Since the successful separation of a single sheet of graphene in 2004, it has been shown that two-dimensional (2D) materials in the strict sense can exist at a limited temperature. Since then, the preparation method of graphene has been explored by many researchers. At the same time, due to its excellent properties in terms of carrier concentration, mobility, thermal conductivity, etc., graphene has been widely used. However, with the continuous development of science and technology, the requirements in various fields are getting higher and higher. The defect of zero band gap of graphene limits its application and cannot meet the increasingly high requirements.

[0003] With the discovery of graphene, other two-dimensional materials have gradually come into people's view. Among them, two-dimensional layered materials - transition metal halides have caused a huge sensation, with molybdenum sulfide (MoS 2 ), Molybdenum selenide (MoSe 2 ) is the representative. Among them, monolayer MoSe has been widely used in the fields of nanoelectronics, photons, sensors, catalysis, transistors, etc. However, although monolayer MoSe has excellent performance in many aspects, the preparation conditions and process of monolayer MoSe are harsh and complicated, resulting in extremely low yield.

[0004] Molybdenum selenide has a similar structure to graphene, but has its own unique photoelectric properties. Molybdenum selenide has an adjustable band gap, and its performance changes significantly with the change of its band gap. For this reason, researchers have developed many methods to adjust the properties of materials. Among them, chemical doping is a relatively effective method to adjust the properties of materials. Generally, doping elements are divided into two categories: metals and non-metals, such as metal copper, nickel, iron, etc., and non-metallic elements include boron, sulfur, phosphorus, etc. Element doping is used to adjust the physical and chemical properties of materials in order to enhance and change their properties. Although the existing technology can adjust the properties of materials by doping two elements, the properties are single. Summary of the invention

[0005] In view of this, the present application provides a dual-performance molybdenum selenide nanomaterial and its application in the detection of small molecule substances, which solves the technical problems in the prior art that the preparation conditions and processes of single-layer molybdenum selenide are harsh, complex, and low in yield, and that the properties are single after doping with two elements.

[0006] According to the first aspect of the present invention, the present application provides a method for preparing a dual-performance molybdenum selenide nanomaterial, the preparation method comprising the following steps: 2 ) powder, melamine (C 3 N 3 (NH 2 ) 3 ) powder and boric acid (H 3 BO 3 ) powders are mixed to obtain a mixture, the mixture is added into an organic solvent for ultrasonic treatment to obtain a black mixed solution, and the black mixed solution is dried to obtain a black powder; the black powder is placed in an inert gas condition for high-temperature calcination, and cooled to room temperature to obtain a crude product; the crude product is repeatedly washed and dried to obtain a boron and nitrogen doped dual-performance molybdenum selenide nanomaterial.

[0007] In one embodiment, the mass ratio of the molybdenum selenide powder, melamine, and boric acid is 1:(4-5):(4-5).

[0008] In one embodiment, the organic solvent is anhydrous ethanol.

[0009] In one embodiment, the mixture is sonicated for 1 h to 2 h at a power of 200 W to 300 W at room temperature.

[0010] In one embodiment, the black mixed solution is placed in a forced air drying oven for drying at a drying temperature of 80° C.-90° C.

[0011] In one embodiment, the inert gas is nitrogen. Under nitrogen conditions, the black powder is placed in a quartz tube furnace for high-temperature calcination. The heating rate of the quartz tube furnace is 10°C / min. After the calcination temperature of the quartz tube furnace reaches 400°C, the calcination time is maintained for 4-5 hours.

[0012] In one embodiment, the crude product is repeatedly washed with ethanol and distilled water for 3-5 times.

[0013] In one embodiment, the washed crude product is placed in an oven for drying at a drying temperature of 80°C-90°C.

[0014] According to the second aspect of the present application, the present application provides a dual-performance molybdenum selenide nanomaterial prepared by the above-mentioned method for preparing the dual-performance molybdenum selenide nanomaterial, characterized in that the prepared dual-performance molybdenum selenide nanomaterial has a layered structure.

[0015] According to the third aspect of the present application, the present application provides the use of the above-mentioned dual-performance molybdenum selenide nanomaterial with a layered structure in the detection of mercury ions and glucose at different concentrations.

[0016] The present invention provides a method for preparing a dual-performance molybdenum selenide nanomaterial, comprising the following steps: 2 ), melamine powder (C 3 N 3 (NH 2 ) 3 ) and boric acid (H 3 BO 3 ) powders are mixed to obtain a mixture, the mixture is added to an organic solvent, placed in an ultrasonic instrument for ultrasonic treatment to obtain a black mixed solution, and then the black mixed solution is dried to obtain a black powder; the black powder is placed under inert gas conditions for high-temperature calcination, and cooled to room temperature to obtain a crude product; the crude product is repeatedly washed and dried to obtain a boron-nitrogen dual-performance molybdenum selenide nanomaterial. The present application prepares a molybdenum selenide nanomaterial with dual performance by adopting an ultrasound-high-temperature doping method, and adopts a simple and green material preparation method. This aspect has the characteristics of cheap raw material price, simple operation, mild reaction conditions, and environmental friendliness, and the obtained product has a high yield and strong repeatability. The prepared molybdenum selenide nanomaterial with dual performance has a typical layered structure, strong fluorescence intensity, and high catalytic performance, and has good application prospects in fluorescent materials, optoelectronic materials, nanozymes, etc. The prepared dual-performance nanomaterial with fluorescence and catalytic properties can be used as a probe for the analysis and detection of small molecules. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Shown is a scanning electron microscope image of the dual-performance molybdenum selenide nanomaterial prepared in Example 1 of the present application;

[0018] Figure 2 Shown is the XRD pattern of the dual-performance molybdenum selenide nanomaterial in Experimental Example 2 of the present application;

[0019] Figure 3 Shown is the XPS graph of the dual-performance molybdenum selenide nanomaterial in Experimental Example 2 of the present application;

[0020] Figure 4 Shown is the fluorescence image of the dual-performance molybdenum selenide nanomaterial in Experimental Example 3 of this application;

[0021] Figure 5 The figure shows the catalytic performance verification diagram of the dual-performance molybdenum selenide nanomaterial in Experimental Example 4 of the present application;

[0022] Figure 6 Shown is a fluorescence image of the dual-performance molybdenum selenide nanomaterial detecting mercury ions of different concentrations in Experimental Example 5 of the present application;

[0023] Figure 7Shown is the fluorescence image of the dual-performance molybdenum selenide nanomaterial detecting different concentrations of glucose in Experimental Example 6 of the present application. DETAILED DESCRIPTION

[0024] To further illustrate the present invention, the present invention is now described in detail through specific implementation examples. Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples are analytically pure unless otherwise specified.

[0025] Molybdenum selenide (MoSe 2 ) was purchased from Shanghai MacLean Biochemical Co., Ltd.;

[0026] Melamine (C 3 N 3 (NH 2 ) 3 ) was purchased from Shanghai Baoman Biotechnology Co., Ltd.;

[0027] Boric acid (H 3 BO 3 ) was purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0028] Anhydrous ethanol (C 2 H 5 OH) was purchased from Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd.;

[0029] Hydrogen peroxide (H 2 O 2 ) was purchased from Shanghai Wokai Biotechnology Co., Ltd.;

[0030] Tetramethylbenzidine (TMB) was purchased from Shanghai Jinsui Biotechnology Co., Ltd.

[0031] Embodiment 1:

[0032] Preparation of dual-performance molybdenum selenide nanomaterials: Step (1), using an analytical balance to accurately weigh 4g of melamine powder, 4g of boric acid powder and 1g of bulk molybdenum selenide powder (bulk molybdenum selenide is a trade name), mix them and place them in a beaker with 100mL of anhydrous ethanol. Next, place the beaker in an ultrasonic cleaner for ultrasonic treatment for 1h, the ultrasonic power is 200W, and the three substances are ultrasonically mixed at room temperature to obtain a black mixed solution. The water in the ultrasonic cleaner is replaced every half an hour to prevent the water temperature in the ultrasonic cleaner from being too high, and then the obtained black mixed solution is placed in a blast drying oven at 80°C for 3h for drying treatment to completely volatilize the anhydrous ethanol to obtain a black powder.

[0033] Step (2), the black powder obtained in step (1) is spread flat on a ceramic boat, and placed in a quartz tube furnace under nitrogen protection for high-temperature calcination, after the temperature is raised to 400° C., calcination is performed for 4 hours.

[0034] Step (3), after the temperature in the quartz tube furnace is naturally cooled to room temperature, the porcelain boat is taken out, the crude product is collected, washed and dried, and the crude product is repeatedly washed with ethanol and distilled water for 3-5 times, and then placed in an oven at 80°C for drying to obtain a powdered boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ).

[0035] Experimental Example 1

[0036] The prepared boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ) was placed under a scanning electron microscope (JSM-6610LV) to characterize the morphology of the dual-performance MoSe material. Figure 1 This is a scanning electron microscope image of the dual-performance molybdenum selenide nanomaterial prepared in Example 1 of this application. Figure 1 As shown, the boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ) has a layered structure, similar to multiple sheets of paper stacked together. Therefore, the dual-performance molybdenum selenide material prepared by the method of the present invention has a layered structure and an adjustable band gap.

[0037] Experimental Example 2

[0038] The prepared boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ) was placed in an X-ray diffractometer to measure the B,N-MoSe 2 The structure and composition of nanomaterials were characterized by X-ray diffraction (XRD). Figure 2 This is the XRD diagram of the dual-performance molybdenum selenide nanomaterial in Experimental Example 2 of this application, as shown in Figure 2 As shown, B,N-MoSe 2 The nanomaterial has 8 significant diffraction peaks, corresponding to the crystal planes

[002] ,

[004] ,

[100] ,

[103] ,

[006] ,

[105] ,

[110] , and

[008] , which are consistent with the crystal planes of standard molybdenum selenide (XRD theoretical diffraction peak database PDF-#: 29-0914). 2 and doped MoSe 2 With bulk MoSe 2 Compared with the previous studies, the MoSe 2 and calcined MoSe 2The changes are not the same, indicating that the atomic doping has changed the diffraction peak. 2 The

[002] interplanar spacing of the nanostructured carbon nanotubes decreases from 0.64635 to 0.64307 nm. This is due to the change caused by element doping.

[0039] The prepared boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ) was placed in an X-ray photoelectron instrument to measure the B,N-MoSe 2 The structure and composition of nanomaterials were characterized by X-ray photoelectron spectroscopy (XPS). Figure 3 This is the XPS graph of the dual-performance molybdenum selenide nanomaterial in Experimental Example 2 of this application, as shown Figure 3 As shown, the boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ), and B1s and N1s peaks appeared in the energy spectrum of the nanostructured carbon nanotubes, and the B1s and N1s peaks were obvious, indicating that boron and nitrogen atoms were successfully doped into molybdenum selenide, and the doping effect was obvious.

[0040] Experimental Example 3

[0041] In order to illustrate the preparation of nanomaterials B, N-MoSe 2 First, the prepared boron and nitrogen doped dual-performance molybdenum selenide nanomaterial (B,N-MoSe 2 ) was put into a mortar for grinding, and then 200 mg of the powder was weighed and ultrasonicated in 20 mL of pure water for 30 min. After the ultrasonication, the solution was allowed to stand. Then the supernatant (i.e., B, N-MoSe 2 Fluorescence spectrum test of fluorescent probe solution Figure 4 This is the fluorescence image of the dual-performance molybdenum selenide nanomaterial in Experimental Example 3 of this application, such as Figure 4 The fluorescence spectra shown in the figure show that the doped (B,N-MoSe 2 ) nanomaterials have strong fluorescence, with the best excitation emission wavelengths at 270nm and 370nm, while undoped MoSe 2 and calcined MoSe 2 It does not have fluorescent properties.

[0042] Experimental Example 4

[0043] In order to illustrate the catalytic performance of the nanomaterial, we investigated whether the material could catalyze the color reaction of the substrate TMB (tetramethylbenzidine) in the presence of hydrogen peroxide. First, 100 μL of 8 mM TMB and 40 μL of 0.04 g / mL B,N-MoSe 2 Fluorescent probe solution and 50 μL of HO 2 O 2Add to 840 μL of 0.2 mol / L sodium dihydrogen phosphate solution and mix evenly. Place the mixed solution in a constant temperature shaking incubator at 37°C for 10 min, remove the solution and add 100 μL of sulfuric acid stop solution to the solution, and add 0.2M sodium dihydrogen phosphate solution to 2 mL when the solution color changes from blue to yellow, and use a UV spectrophotometer to test the absorbance. Figure 5 This is a diagram for verifying the catalytic performance of the dual-performance molybdenum selenide nanomaterial in Experimental Example 4 of this application, as shown in FIG. Figure 5 As shown, where a represents B,N-MoSe 2 +TMB+H 2 O 2 ,b represents B,N-MoSe 2 +TMB; c represents TMB+H 2 O 2 ; The B,N-MoSe 2 The material can catalyze hydrogen peroxide to oxidize TMB to develop color.

[0044] Experimental Example 5

[0045] The prepared dual-performance MoSe nanomaterials were used to detect mercury ions at different concentrations. 2 The relationship between the fluorescence intensity of the fluorescent probe solution was investigated. Mercury ion solutions of different concentrations (0-33 μM) were mixed with B,N-MoSe 2 The fluorescent probe solution was mixed in equal volumes and the sample was tested after sufficient reaction. Figure 6 The figure shows the fluorescence image of the dual-performance molybdenum selenide nanomaterial detecting mercury ions of different concentrations in Experimental Example 5 of the present application; Figure 6 As shown in a, the fluorescence intensity gradually decreases with the increase of mercury ion concentration, and the fluorescence intensity almost completely disappears when the mercury ion concentration is 33 μM. Figure 6 As shown in b, Figure 6 b shows the dot diagram corresponding to the fluorescence spectrum curve, from which Hg 2+ There is a good linear relationship between the concentration and the degree of fluorescence quenching in the range of 0.05-10 μM (R 2 =0.99678), with a detection limit (LOD) of 2.9 nM.

[0046] Experimental Example 6

[0047] Preparation of nanozyme solution: Weigh 0.4 g B,N-MoSe using an analytical balance 2 The powder was added into ultrapure water and ultrasonically treated for 2 h to prepare B,N-MoSe with a concentration of 0.04 g / mL. 2 The solution was used for subsequent experiments.

[0048] 100 μL of 2 mg / mL glucose oxidase was mixed with 300 μL of 10 mM phosphate buffer solution at pH 7 containing different concentrations of glucose (0-5 mM) and incubated in a water bath for 30 min. Then, 200 μL of 8 mM TMB, 80 μL of 0.04 g / mL N-MoSe 2 The nanozyme solution and 1380 μL of 0.2M sodium dihydrogen phosphate solution were added to the above solution and mixed evenly. After 10 minutes of reaction in the dark, 100 μL of sulfuric acid stop solution was added. The resulting system was then added with phosphate buffer to 2 mL and detected with a UV spectrophotometer. Figure 7 The fluorescence image of the dual-performance molybdenum selenide nanomaterials detecting different concentrations of glucose in Experimental Example 6 of this application is shown as follows: Figure 7 As shown in a, the detection range of glucose is 0 to 5 mM. The linear range of glucose concentration is 0.3-2.6 mM, the linear equation is y=0.09365x+0.0906, and the detection limit of glucose (3σ) is 0.06 mM.

[0049] The present invention adopts an ultrasonic-high temperature doping method to prepare a molybdenum selenide nanomaterial with dual properties. The raw material molybdenum selenide powder (MoSe 2 ), melamine powder (C 3 N 3 (NH 2 ) 3 ) and boric acid (H 3 BO 3 ) powder is cheap. In the preparation process, an ultrasonic-high temperature doping method is used. The reaction is mild, and the product yield is high and the repeatability is strong. The preparation process obtains a molybdenum selenide nanomaterial with dual properties. It has a typical layered structure, strong fluorescence intensity, the best excitation emission wavelength is 270nm and 370nm, and high catalytic performance. 2 The material can catalyze hydrogen peroxide to oxidize TMB to produce color, and has good application prospects in fluorescent materials, optoelectronic materials, nanozymes, etc. 2 The material has both fluorescent and catalytic properties, B,N-MoSe 2 The material can be used as a probe for the analysis and detection of glucose and mercury ions.

[0050] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a dual-performance molybdenum selenide nanomaterial, characterized in that: The following steps are involved: A certain amount of molybdenum selenide (MoSe2) powder, melamine (C3N3(NH2)3) powder and boric acid (H3BO3) powder are mixed to obtain a mixture, the mixture is added into an organic solvent, placed in an ultrasonic instrument for ultrasonic stripping to obtain a black mixed solution, and then the black mixed solution is dried to obtain a black powder; The black powder is placed in an inert gas environment for high temperature calcination, and then cooled to room temperature to obtain a crude product; The crude product is repeatedly washed and dried to obtain boron and nitrogen doped dual-performance molybdenum selenide nanomaterials.

2. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 1, characterized in that: The mass ratio of the molybdenum selenide powder, melamine, and boric acid is 1:(4-5):(4-5).

3. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 2, characterized in that: The organic solvent is anhydrous ethanol.

4. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 3, characterized in that: The mixture is ultrasonicated for 1 h to 2 h, with an ultrasonic power of 200 W to 300 W, at room temperature.

5. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 4, characterized in that: The black mixed solution is placed in a forced air drying oven for drying at a temperature of 80° C.-90° C. for a drying time of 3 h-4 h.

6. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 5, characterized in that: The inert gas is nitrogen. Under nitrogen conditions, the black powder is placed in a quartz tube furnace for high-temperature calcination. The heating rate of the quartz tube furnace is 10°C / min. After the calcination temperature of the quartz tube furnace reaches 400°C, the calcination time is maintained for 4-5h.

7. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 1, characterized in that: The crude product was washed repeatedly with ethanol and distilled water for 3-5 times.

8. The method for preparing the dual-performance molybdenum selenide nanomaterial according to claim 1, characterized in that: The washed crude product is placed in an oven for drying at a drying temperature of 80°C-90°C.

9. A dual-performance molybdenum selenide nanomaterial prepared by the method for preparing a nanomaterial according to any one of claims 1 to 8, characterized in that: The prepared dual-performance molybdenum selenide nanomaterial has a layered structure.

10. Use of the dual-performance molybdenum selenide nanomaterial with a layered structure according to claim 9 in the detection of small molecule substances.

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