Copper-samarium bimetallic layered hydroxide nano material and preparation method and application thereof

Abstract

The invention relates to a copper-samarium double-metal layered hydroxide nano material and a preparation method and application thereof, samarium salt, copper salt and NH4F are dissolved in water, a mixed aqueous solution of NaOH and Na2CO3 is added, standing is performed, precipitates are collected, and the copper-samarium double-metal layered hydroxide nano material is obtained after drying. The copper-samarium bimetallic layered hydroxide nano material is of a two-dimensional sheet structure, the atomic mass of the element O is 75.05%, the atomic mass of the element Cu is 15.47%, and the atomic mass of the element Sm is 9.47%. Compared with the prior art, the prepared CuSm-LDH shows good water solubility, the problem that traditional bimetal layered hydroxides such as MgAl-LDH and NiFe-LDH are poor in water solubility is solved, and the advantages that the traditional bimetal layered hydroxides are good in adhesion and high in adsorbability are reserved; therefore, the method has huge potential application value in the field of biosensors.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterials, and in particular to a copper-samarium double-metal layered hydroxide nanomaterial, a preparation method thereof, and an application thereof. Background Art

[0002] Due to the advantages of good biocompatibility and strong adhesion, double-metal layered hydroxides are widely used in the construction of aptasensors. For example, CN113512418A discloses a layered double-metal hydroxide composite material, a preparation method thereof, and an application thereof. The double metal includes divalent metal cations and trivalent metal cations, where the divalent metal cations include any one or more of zinc ions, magnesium ions, ferrous ions, nickel ions, calcium ions, barium ions, and copper ions, and the trivalent metal cations include any one or more of aluminum ions, cobalt ions, cerium ions, iron ions, manganese ions, chromium ions, and vanadium ions. The layered double-metal hydroxide composite material can effectively coordinate and bind rare earth elements and exhibits good fluorescence properties.

[0003] However, traditional double-metal layered hydroxides, such as magnesium-aluminum layered hydroxide (MgAl-LDH) and nickel-iron layered hydroxide (NiFe-LDH), all have the problem of being insoluble in water, which greatly limits their applications.

[0004] The present invention aims to explore a double-metal layered hydroxide that not only has good water solubility but also retains the original adhesion properties of layered hydroxides, which is crucial for the field of biosensing detection. Summary of the Invention

[0005] The purpose of the present invention is to provide a copper-samarium double-metal layered hydroxide nanomaterial, a preparation method thereof, and an application thereof to overcome the defects existing in the above-mentioned prior art.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the technical solutions of the present invention is to provide a copper-samarium double-metal layered hydroxide nanomaterial. The copper-samarium double-metal layered hydroxide nanomaterial has a two-dimensional sheet structure. In the copper-samarium double-metal layered hydroxide nanomaterial, the atomic mass of the O element is (75-76)%, the atomic mass of the Cu element is (15-16)%, and the atomic mass of the Sm element is (9-10)%.

[0008] In some specific embodiments, in the copper-samarium double-metal layered hydroxide nanomaterial, the atomic mass of the O element is 75.05%, the atomic mass of the Cu element is 15.47%, and the atomic mass of the Sm element is 9.47%.

[0009] The second technical solution of the present invention is to provide a preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial as described in one of the above technical solutions, comprising the following steps:

[0010] Dissolve samarium salt, copper salt, and NH4F in water, add a mixed aqueous solution of NaOH and Na2CO3, let it stand, collect the precipitate, and obtain the copper-samarium bimetallic layered hydroxide nanomaterial after drying.

[0011] In some specific embodiments, the molar ratio of samarium salt, copper salt, and NH4F is 3:(7 - 8):(8 - 9).

[0012] In some specific embodiments, the samarium salt is selected from any one of SmCl3·6H2O, SmCl3, and Sm(NO3)3.

[0013] In some specific embodiments, the copper salt is selected from any one of CuCl2 and Cu(NO3)2.

[0014] In some specific embodiments, the molar ratio of NaOH, Na2CO3 to samarium salt is (1.5 - 2):(4.5 - 5):1.

[0015] In some specific embodiments, the standing conditions are: standing in the dark, the standing time is 22 - 25 h, and the standing temperature is 22 - 30 °C.

[0016] In some specific embodiments, the drying conditions are: vacuum drying at 60 °C for 22 - 25 h.

[0017] The third technical solution of the present invention is to provide a copper-samarium bimetallic layered hydroxide nanomaterial as described in one of the above technical solutions for preparing a biosensor.

[0018] In practical applications, the copper-samarium bimetallic layered hydroxide nanomaterial can be more uniformly modified on the surface of the biosensor. Especially for electrochemical biosensors, it can also increase the stability of the sensor.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The copper-samarium bimetallic layered hydroxide nanomaterial (CuSm-LDH) prepared by the present invention exhibits good water solubility, overcomes the problem of poor water solubility of traditional bimetallic layered hydroxides such as magnesium-aluminum layered hydroxide (MgAl-LDH) and nickel-iron layered hydroxide (NiFe-LDH), and retains the advantages of good adhesion and strong adsorption of traditional bimetallic layered hydroxides, which makes it have great potential application value in the field of biosensors.

[0021] (2) The CuSm-LDH of the present invention also has the advantages of simple preparation method and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 FIGURES are the scanning electron microscope characterization and elemental distribution maps of CuSm-LDH, where FIGURES A and B are the scanning electron microscope morphology maps of CuSm-LDH, and FIGURES C and D are the scanning electron microscope surface scans (SEM Mapping) of CuSm-LDH.

[0023] Figure 2 is the X-ray diffraction pattern of CuSm-LDHs.

[0024] Figure 3 is the XPS spectrum of CuSm-LDH, where FIGURE A is the total spectrum of CuSm-LDH, FIGURE B is the Cd3d spectrum, FIGURE C is the Sm 3d spectrum, and FIGURE D is the O1s spectrum.

[0025] Figure 4 is the Fourier transform infrared spectrum of CuSm-LDHs.

[0026] Figure 5 is the schematic diagram of the preparation process of CuSm-LDH.

[0027] Figure 6 is the comparison chart of the water solubility of CuSm-LDH, MgAl-LDH and NiFe-LDH. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be described in detail below with reference to the drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and the detailed implementation manner and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0029] In the following embodiments, unless otherwise specified, the raw materials or processing techniques are all conventional commercially available raw material products or conventional processing techniques in the art.

[0030] Example 1

[0031] This example provides a copper-samarium double metal layered hydroxide nanomaterial (CuSm-LDH), and its preparation method includes the following steps, as Figure 5 shown:

[0032] Dissolve 0.6023 g of SmCl3·6H2O, 0.5540 g of CuCl2, and 0.1667 g of NH4F in 13 mL of deionized water. While stirring continuously, slowly drip 15 mL of a mixed aqueous solution containing 0.12 g of NaOH and 0.795 g of Na2CO3 into the above-mentioned mixed solution. After stirring at room temperature for 30 minutes, let it stand in the dark for 24 hours. Then, centrifuge and wash it with deionized water 2 - 3 times. Finally, vacuum dry the collected precipitate at 60 °C for 24 hours to obtain CuSm-LDH.

[0033] The prepared CuSm-LDH was tested as follows:

[0034] (1) SEM and elemental analysis

[0035] Use a scanning electron microscope (SEM) to study the morphology and structural characteristics of the synthesized CuSm-LDH.

[0036] As shown in A - B of Figure 1 , according to the scanning electron microscope image of CuSm-LDH, it shows a two-dimensional sheet-like structure morphology.

[0037] As shown in C - D of Figure 1 , verify the elemental composition of CuSm-LDH through elemental mapping. According to the scanning electron microscope surface scan image of CuSm-LDH, the presence and distribution of elements such as Cu, Sm, and O prove the successful synthesis of the CuSm-LDH nanomaterial. Among them, the atomic mass of the O element is 75.05%, the atomic mass of the Cu element is 15.47%, and the atomic mass of the Sm element is 9.47%.

[0038] (2) XRD characterization

[0039] Use X-ray diffraction (XRD) to detect the crystallinity of CuSm-LDH, thereby determining the synthesis of CuSm-LDH.

[0040] As shown in Figure 2 , the diffraction peaks at approximately 17.67° and 25.75° are the (020) and (021) lattice planes of Cu(OH)2. Among them, the diffraction peaks at 2θ = 16.0°, 29.2°, 32.4°, 39.8°, 45.2°, and 52.2° respectively represent the characteristic peaks of (100), (101), (200), (201), (210), and (102) of Sm(OH)3. Especially, a sharp peak is shown at (101), indicating that CuSm-LDH has good crystallinity.

[0041] (3) XPS characterization

[0042] Use X-ray photoelectron spectroscopy (XPS) to show the elemental composition and electronic state of CuSm-LDH.

[0043] As shown in Figure 3 A of Figure

[0044] As shown in Figure 3 B of Figure 2+ state. According to the Cd3d spectrogram, the binding energies of Cu 2p 3 / 2 and Cu 2p 1 / 2 are determined to be 934.57 eV and 954.28 eV respectively, indicating the existence of Cu

[0045] As shown in Figure 3 C of Figure 3+ state. According to the Sm 3d spectrogram, two obvious peaks can be seen at 1084.72 V and 1111.28 eV, which are related to the Sm 3d 5 / 2 and Sm 3d 3 / 2 states respectively, indicating the existence of Sm

[0046] As shown in Figure 3 D of Figure

[0047] (4) FT-IR Characterization

[0048] The structural characteristics of the CuSm-LDH nanomaterial were determined using Fourier transform infrared spectroscopy (FTIR).

[0049] As shown in Figure 4 Figure -1 , the absorption peak of CuSm-LDH at 1498 cm -1 is mainly caused by the characteristic vibration of the chloride salt (Cl -1 ). The absorption peaks of the hydroxyl group (-OH) are mainly caused by the stretching vibration and bending vibration of the O-H at 1636 cm -1 and 3440 cm -1 . The broadband around 3346.7 cm -1 originates from the stretching and bending of H-O-H. The absorption peaks at 851.7 cm -1 and 1407.7 cm

[0050] (5) Water Solubility

[0051] 1 mg of CuSm-LDH, MgAl-LDH (the preparation method refers to the reference: Wu M, Liu S, Qi F, et al. AI label-free electrochemical immunosensor for CA125 detection based on CMK-3(Au / Fc@MgAl-LDH)n multilayer nanocomposites modification[J]. Talanta, 2022, 241:123254.), and NiFe-LDH (purchased from Xianfeng Nano Materials Technology Co., Ltd.) were respectively dissolved in 1 mL of deionized water to investigate the dispersion performance of the three layered double hydroxides in water.

[0052] The results are as Figure 6 shown in A-D of Figure 6 B), there is no phenomenon of solid aggregation in water for CuSm-LDH, indicating that CuSm-LDH has good dispersion performance. While for NiFe-LDH Figure 6 shown in C) and MgAl-LDH Figure 6 shown in D), there are precipitate aggregations at the bottom of the centrifuge tube, indicating that MgAl-LDH and NiFe-LDH have poor water solubility.

[0053] The above results prove that the prepared CuSm-LDH of the present invention has better water solubility compared with traditional MgAl-LDH and NiFe-LDH.

[0054] The above description of the embodiments is to enable those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and all improvements and modifications made by those skilled in the art without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. A copper-samarium double-metal layered hydroxide nanomaterial, characterized in that, The copper-samarium bimetallic layered hydroxide nanomaterial is a two-dimensional sheet structure, and the atomic mass of element O in the copper-samarium bimetallic layered hydroxide nanomaterial is (75-76)%, the atomic mass of element Cu is (15-16)%, and the atomic mass of element Sm is (9-10)%.

2. The copper-samarium double-metal layered hydroxide nanomaterial according to claim 1, wherein In the copper-samarium bimetallic layered hydroxide nanomaterial, the atomic mass of element O is 75.05%, the atomic mass of element Cu is 15.47%, and the atomic mass of element Sm is 9.47%.

3. A preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial as described in any one of claims 1 or 2, characterized in that, It includes the following steps: Dissolve samarium salt, copper salt, and NH4F in water, add a mixed aqueous solution of NaOH and Na2CO3, let it stand, collect the precipitate, and obtain the copper-samarium bimetallic layered hydroxide nanomaterial after drying.

4. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 3, characterized in that, The molar ratio of samarium salt, copper salt, and NH4F is 3:(7-8):(8-9).

5. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 4, wherein, The samarium salt is selected from any one of SmCl3·6H2O, SmCl3, and Sm(NO3)3.

6. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 4, characterized in that, The copper salt is selected from any one of CuCl2 and Cu(NO3)2.

7. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 3, characterized in that, The molar ratio of NaOH, Na2CO3 to samarium salt is (1.5-2):(4.5-5):

1.

8. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 3, characterized in that, The conditions for standing are: standing in the dark, the standing time is 22-25 h, and the standing temperature is 22-30 °C.

9. The preparation method of the copper-samarium bimetallic layered hydroxide nanomaterial according to claim 3, characterized in that, The conditions for drying are: vacuum drying at 60 °C for 22-25 h.

10. Use of a copper-samarium bimetallic layered hydroxide nanomaterial as described in any one of claims 1 or 2, characterized in that, The copper-samarium bimetallic layered hydroxide nanomaterial is used for preparing a biosensor.

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