A layered Ti3C2T x FeCo nanoparticle composite material loaded on MXene, preparation method and application

Abstract

The application relates to the material field and provides a layered Ti3C2T x / MXene loaded FeCo nanoparticle composite material, a preparation method and application, FeCo nanoparticles prepared by a hydrothermal method and Ti3C2T x / MXene are combined by an electrostatic self-assembly method, so that a layered composite material is obtained, FeCo nanoparticles with soft magnetic properties are loaded between layers and on the surface of the Ti3C2T x / MXene material, and the FeCo nanoparticles can adjust the dielectric property of the composite material, so that the composite material can be widely applied in the wave absorption field. The application has the advantages of simple equipment, low production cost, high production efficiency and green pollution-free. The composite material is a high-reflection and low-absorption material in a 170-220 GHz frequency band, and the absorption rate is 10-30%. In a 0.2-3 THz range, the product prepared by the method also has a wave absorption effect, and the absorption coefficient is 100-150 cm ‑1 .

Description

Technical Field

[0001] This invention belongs to the field of materials, and specifically provides a layered Ti3C2T x / MXene-supported FeCo nanoparticle composite materials, preparation methods and applications. Background Technology

[0002] Terahertz waves, with frequencies ranging from 0.1 to 10 THz, are widely used in medical imaging, wireless communication, and security inspection due to their ultra-wideband spectrum, low electron energy, and spectral fingerprint characteristics. While terahertz technology brings convenience, electromagnetic pollution also has a significant impact on human health, environmental development, and information security. Therefore, researchers are increasingly focusing on the field of electromagnetic wave absorption, as ideal absorbing materials can effectively absorb excess electromagnetic waves. Developing a high-performance terahertz absorbing material that is lightweight, thin, has low reflection, and a wide effective absorption bandwidth is therefore of paramount importance.

[0003] MXene is a two-dimensional material composed of transition metal elements and carbides or nitrides, with the chemical formula M. n+1 X n T x (n = 1, 2, 3), where M represents an early transition metal element (Ti, Mo, or Zr, etc.), X represents a carbide or nitride, and T represents a nitride. x It has surface groups (-OH, -F, or -O, etc.). Ti3C2T x As one of the earliest synthesized MXenes, it has attracted widespread attention. It is obtained by etching Al layers into Ti3AlC2. x / MXene, with its unique layered structure, excellent dielectric properties, and abundant surface functional groups, has been regarded as an ideal alternative material for TEMW interactions, especially given its abundant surface functional groups for Fe. 2+ and Co 2+ Metal ions provide the most suitable ligands. Ti3C2T x MXene is one of the most widely studied MXene materials due to its excellent electrical conductivity and good terahertz absorption performance. FeCo alloy is an excellent soft magnetic material with low coercivity and high saturation magnetic susceptibility. Introducing FeCo nanoparticles can reduce the coercivity of Ti3C2T... x The extremely high conductivity of MXene itself also facilitates the adjustment of electromagnetic parameters and optimization of impedance matching. (This is achieved by incorporating Ti3C2T...) x Combining MXene with other magnetic materials to form magnetic-dielectric composite materials is an effective way to achieve electromagnetic wave absorption. Currently, there are no related reports.

[0004] Patent CN117362856A discloses an electromagnetic shielding composite material and its preparation method. Polymer core-shell microspheres are prepared by copolymerizing maleic anhydride with styrene and divinylbenzene, respectively. The microsphere template core is then eluted with acetone to obtain hollow microspheres. The hollow microspheres are dispersed in water and then mixed with an MXene aqueous dispersion and filtered to incorporate the hollow microspheres into the MXene layers, forming a multi-level structure beneficial for electromagnetic shielding. However, it does not address applications related to electromagnetic absorption.

[0005] Patent CN114454573A discloses a Ti3C2T x / MXene / GO heterostructure film, its preparation method and application: The heterostructure film consists of a GO layer and a Ti3C2T layer. x The Ti3C2T film is a three-layer structure thin film with microscopic heterogeneous interfaces formed by the sequential stacking of MXene layers. x The / MXene / GO heterostructure not only has good electromagnetic shielding performance, but GO can also protect Ti3C2T. x MXene does not oxidize, giving it long-lasting properties and making it suitable for electromagnetic shielding applications. However, it is not applicable to microwave absorption. Summary of the Invention

[0006] The synthesized layered Ti3C2Tx / MXene-supported FeCo nanoparticle composite material has great application potential in microwave absorption and urgently needs to be developed and studied.

[0007] This invention employs an electrostatic self-assembly method to combine FeCo nanoparticles prepared by a hydrothermal method and Ti3C2T nanoparticles prepared by an in-situ etching method. x By combining with MXene, a layered composite material was obtained. Due to the flexible, controllable, safe, and reliable reaction conditions, nanocomposites with unique structures and tunable dielectric properties that do not require subsequent processing can be prepared in large quantities and are environmentally stable, suitable for terahertz electromagnetic wave absorption.

[0008] The purpose of this invention is to provide a composite material of layered Ti3C2Tx / MXene loaded with FeCo nanoparticles and its application, namely, the preparation of FeCo nanoparticles and Ti3C2Tx / MXene composite material by hydrothermal method, in-situ etching method and electrostatic self-assembly method. x A composite material combining FeCo nanoparticles and Ti3C2T is provided, in which FeCo nanoparticles are successfully loaded onto Ti3C2T. x The surface and interlayer of MXene material do not require further processing and have excellent microwave absorption properties.

[0009] The technical solution of this invention is as follows:

[0010] The layered Ti3C2Tx / MXene-supported FeCo nanoparticle composite material has a structure consisting of magnetic nanoparticles and wrinkled Ti3C2Tx nanoparticles. x The composite material contains a layered structure composed of MXene and FeCo magnetic nanoparticles, which are loaded onto Ti3C2T. x The interlayer and surface of the MXene material allow the magnetic particles to disperse among themselves.

[0011] The FeCo loading percentage in the composite material structure is 10–30 wt.%.

[0012] The interlayer spacing in the composite material structure is 150–190 nm; the diameter of the FeCo magnetic nanoparticles is 15–20 nm.

[0013] The present invention also provides the aforementioned combination of magnetic nanoparticles with a two-dimensional layered structure Ti3C2T x The preparation method of the composite material combining / MXene involves first preparing FeCo spherical nanoparticles by hydrothermal method using Fe sulfate and Co chloride salts; secondly, using Ti3AlC2MAX material as a precursor, preparing layered Ti3C2T material by in-situ etching method with HCl+LiF. x / MXene material; finally, an electrostatic self-assembly method was used to combine magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The composite material is obtained by combining MXene with MXene.

[0014] Solved Ti3C2T x The technical challenges in preparing MXene composite materials have been overcome, resulting in a simple, convenient, low-cost, safe, and reliable preparation process.

[0015] FeCo nanoparticles were obtained via a hydrothermal method with a mass ratio of Fe sulfate and Co chloride of 1:4.

[0016] The HCl + LiF mixed solution was stirred in a stirrer for 0–1 h, preferably 0–0.5 h. After adding the Ti3AlC2MAX precursor, the three solutions were stirred in a water bath for 24–48 h, preferably 24–36 h, to obtain Ti3C2T. x / MXene material; subsequently, FeCo nanoparticles were combined with Ti3C2T via electrostatic self-assembly. x Combined with / MXene.

[0017] The sulfate and chloride salts of Fe and Co are FeSO4·7H2O and CoCl2·6H2O, respectively, and m FeSO4·7H2O: m CoCl2·6H2O=1:4; the raw materials used are Ti3AlC2 precursor and FeSO4·7H2O and CoCl2·6H2O of analytical grade; the solvent is preferably deionized water; a stirrer and a water bath are used for heating and stirring, and the stirring speed of the stirrer and water bath is 300-500 r / min.

[0018] The beneficial effects of this invention are as follows:

[0019] 1. This invention employs an electrostatic self-assembly method to combine FeCo nanoparticles and Ti3C2T x The combination of MXene and other materials yields a layered composite material with simple equipment, low production cost, high production efficiency, and is green and pollution-free.

[0020] 2. Scanning electron microscopy and Raman spectroscopy showed that the product prepared by the method was a layered composite material, with its Ti3C2T... x The interlayer spacing of the MXene material was 170 nm, and the FeCo nanoparticles were 15–20 nm. The successful preparation of the composite material was further confirmed by X-ray diffraction (XRD) spectroscopy.

[0021] 3. The prepared FeCo nanoparticles and Ti3C2T x The composite material samples with layered structures obtained by combining / MXene do not require further processing.

[0022] 4. In the 170-220 GHz range, the product prepared by the method described in this invention is a high-reflection, low-absorption material in the 170-220 GHz frequency band, with an absorption rate of 10-30%, due to the introduction of FeCo nanoparticles which is beneficial to the multiple reflection and scattering of terahertz waves.

[0023] 5. Within the 0.2–3 THz range, the product prepared by the method also exhibits microwave absorption effects, with an absorption coefficient of 100–150 cm⁻¹. -1 . Attached Figure Description

[0024] Figure 1 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x X-ray diffraction pattern of composite materials combining / MXene;

[0025] Figure 2 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x Raman spectra of composite materials combining MXene;

[0026] Figure 3 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2Tx X-ray photoelectron spectroscopy of composite materials combining MXene;

[0027] Figure 4 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x Magnetic property spectrum of composite material combining / MXene;

[0028] Figure 5 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x Scanning electron microscope image of the composite material combined with MXene;

[0029] Figure 6 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x The relationship between frequency and transmittance of the composite material combined with MXene in the 170–220 GHz band;

[0030] Figure 7 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x The relationship between frequency and reflectivity of the composite material combined with MXene in the 170-220 GHz band;

[0031] Figure 8 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x The graph shows the relationship between frequency and absorption rate of the composite material combined with MXene in the 170–220 GHz band;

[0032] Figure 9 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x The relationship between frequency and transmittance of the composite material combined with MXene in the 0.2–3 THz frequency band;

[0033] Figure 10 In Example 1, magnetic nanoparticles were combined with a two-dimensional layered structure Ti3C2T x The relationship between frequency and absorption coefficient of the composite material combined with MXene in the 0.2–3 THz frequency band;

[0034] Figure 11 Ti3AlC2 and Ti3C2T x X-ray diffraction pattern of the MXene hybrid material. Detailed Implementation

[0035] The example uses m FeSO4·7H2O: m CoCl2·6H2OFeCo nanoparticles and Ti3C2T were prepared at a ratio of 1:4. x Composite materials with MXene combined with layered structures

[0036] In the following examples, unless otherwise specified, m1 represents the mass of Fe sulfate and m2 represents the mass of Co chloride. FeCo nanoparticles were prepared via a hydrothermal method using analytically pure FeSO4·7H2O and CoCl2·6H2O. Ti3C2T nanoparticles were obtained by in-situ etching of Ti3AlC2 precursor in a mixed solution of HCl and LiF. x / MXene material; FeCo nanoparticles and Ti3C2T were combined using an electrostatic self-assembly method. x The composite material is obtained by combining MXene.

[0037] Example 1

[0038] First, a certain mass of polyethylene glycol is dissolved in 10-30 mL of deionized water and stirred to obtain a solution. Then, a certain mass of cyclohexane and FeSO4·7H2O (Fe 3+ ) and CoCl2·6H2O (Co 2+ The product was added to the above mixed solution (m1:m2 = 1:4) and dissolved. The solution was then preheated at 60–90°C for 3–6 minutes. After preheating, a certain mass of sodium hydroxide and a certain volume of hydrazine hydrate were added to obtain a homogeneous mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and heated at 100–130°C for 2–4 hours. After hydrothermal treatment, the lower layer product was washed with anhydrous ethanol and then with deionized water. The product was collected and then placed in an oven and dried under vacuum for 10–14 hours to finally obtain spherical FeCo nanoparticles.

[0039] Ti3C2T was obtained by etching the Al layer elements in the Ti3AlC2 precursor using an in-situ HF production method. x For the / MXene material, a certain mass of LiF was dissolved in a certain volume of hydrochloric acid and stirred thoroughly. After the LiF was completely dissolved, Ti3AlC2 powder was added in small amounts several times. Then, the mixture was placed in a water bath and stirred at 30-45℃ for 24-48 hours. After the reaction was complete, the mixture was repeatedly washed with deionized water after centrifugation at 4000-6000 rpm for 5-8 minutes until the pH value was around 5-6. Finally, the supernatant was retained to obtain the layered structure of Ti3C2T. x / MXene solution.

[0040] The composite material is made by electrostatic self-assembly of spherical FeCo nanoparticles and Ti3C2T. x / MXene combination. First, a certain volume of polydienedimethylammonium chloride solution was measured, and then a certain mass of FeCo nanoparticles were ultrasonically dispersed in PDDA solution to carry a positive charge. Next, the FeCo mixed solution was poured into Ti3C2T x The mixture was then filtered using a vacuum filtration device to obtain FeCo-Ti3C2T from the MXene supernatant. x / MXene composite material.

[0041] Comparative Example 1

[0042] Ti3C2T was obtained by etching the Al layer elements in the Ti3AlC2 precursor using an in-situ HF production method. x For the / MXene material, a certain mass of LiF was dissolved in a certain volume of hydrochloric acid and stirred thoroughly. After the LiF was completely dissolved, Ti3AlC2 powder was added in small amounts several times. Then, the mixture was placed in a water bath and stirred at 30-45℃ for 24-48 hours. After the reaction was complete, the mixture was repeatedly washed with deionized water after centrifugation at 4000-6000 rpm for 5-8 minutes until the pH value was around 3-4. Ti3C2T could not be obtained. x / MXene materials can only yield Ti3AlC2 and Ti3C2T x / MXene mixed materials.

[0043] Figure 1 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The X-ray diffraction pattern of the composite material combined with MXene not only reveals Ti3C2T x Typical diffraction peaks of MXene materials were observed, as well as diffraction peaks of FeCo.

[0044] Figure 2 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x Raman spectra of the composite material combined with / MXene show that the composite material not only possesses Ti3C2T x The MXene material exhibits typical Raman peaks, as well as FeCo Raman peaks.

[0045] Figure 3 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The X-ray photoelectron spectrum of the composite material combined with / MXene shows that, apart from Ti3C2T, the composite material contains... x In addition to C, Ti, and O, MXene materials also contain Fe and Co elements.

[0046] Figure 4 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The magnetic spectrum of the composite material combined with MXene shows that the composite material has soft magnetic characteristics.

[0047] Figure 5 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x Scanning electron microscopy of the composite material combined with MXene reveals that the composite material also exhibits a layered structure, particularly in the Ti3C2T layer. x The / MXene surface and interlayer exhibit distinct FeCo nanoparticles, which are nanoscale spherical and uniformly distributed, indicating that the prepared FeCo particles successfully bonded with Ti3C2T. x Combined with / MXene.

[0048] Figure 6 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The relationship between frequency and transmittance of the composite material combined with MXene in the 170-220 GHz band shows that the average transmittance of the composite material is 20%, so the incident terahertz wave exhibits either reflection or absorption after interacting with the material.

[0049] Figure 7 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The relationship between frequency and reflectivity of the composite material combined with MXene in the 170-220 GHz band shows that the reflectivity of the composite material in this band first decreases and then increases, with the lowest reflectivity being 50%.

[0050] Figure 8 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The relationship between frequency and absorptivity of the composite material combined with MXene in the 170-220 GHz band shows that the absorptivity of the composite material in this band first increases and then decreases, with the highest absorptivity being 30%.

[0051] Figure 9 The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The relationship between frequency and transmittance of the composite material combined with MXene in the 0.2–3 THz frequency band can be observed. The transmittance is 0.5 in the two frequency bands of 0.2–0.5 THz and 0.5–0.8 THz, while the transmittance is almost zero in other ranges.

[0052] Figure 10The invention presents a method for combining magnetic nanoparticles with a two-dimensional layered structure Ti3C2T. x The relationship between frequency and absorption coefficient of the MXene-bonded composite material in the 0.2–3 THz frequency band is shown, with the absorption coefficient of the composite material ranging from 100 to 150 cm⁻¹. -1 This indicates that in Ti3C2T x Loading FeCo particles onto MXene materials enhances the material's absorption of terahertz waves.

[0053] Figure 11 Ti3AlC2 and Ti3C2T are given. x The X-ray diffraction pattern of the / MXene hybrid material shows that not only Ti3C2T... x The diffraction peaks of / MXene and Ti3AlC2 were also observed, indicating that Ti3C2T was not successfully prepared. x / MXene material.

[0054] Matters not covered in this invention are common knowledge.

[0055] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A two-dimensional layered Ti3C2T x The MXene-supported FeCo magnetic nanoparticle composite material is characterized by: The two-dimensional layered Ti3C2T x The structure of the / MXene-supported FeCo magnetic nanoparticle composite material is composed of magnetic nanoparticles and Ti3C2T with wrinkled features. x The composite material has a layered structure composed of MXene, and FeCo magnetic nanoparticles are loaded onto Ti3C2T. x The interlayer and surface of the / MXene material, the interlayer spacing of the composite material structure is 150~190nm, and the diameter of the FeCo magnetic nanoparticles is 15~20nm.

2. The two-dimensional layered Ti3C2T according to claim 1 x The MXene-supported FeCo magnetic nanoparticle composite material is characterized by: The FeCo loading percentage in the composite material structure is 10~30 wt.%.

3. A two-dimensional layered Ti3C2T as described in claim 1 x The method for preparing MXene-supported FeCo magnetic nanoparticle composite materials is characterized by: First, FeCo spherical nanoparticles were prepared by hydrothermal synthesis using Fe sulfates and Co chlorides. Second, layered Ti3C2T nanoparticles were prepared using Ti3AlC2 as a precursor via in-situ etching with HCl + LiF. x / MXene material; finally, magnetic nanoparticles and two-dimensional layered structures of Ti3C2T were prepared by electrostatic self-assembly. x Composite materials combining MXene.

4. The two-dimensional layered Ti3C2T according to claim 3 x The method for preparing MXene-supported FeCo magnetic nanoparticle composite materials is characterized by: FeCo nanoparticles were obtained by solvothermal synthesis using a 1:4 mass ratio of Fe sulfate and Co chloride. A mixed solution of HCl and LiF was stirred in a stirrer for 0–1 h, and then a Ti3AlC2 precursor was added. The three solutions were then stirred in a water bath for 24–48 h to obtain Ti3C2T. x / MXene material; subsequently, FeCo nanoparticles were combined with Ti3C2T via electrostatic self-assembly. x Combined with / MXene.

5. The two-dimensional layered Ti3C2T according to claim 4 x The method for preparing MXene-supported FeCo magnetic nanoparticle composite materials is characterized by: The HCl+LiF mixed solution was stirred in a stirrer for 0~0.5 h, and after the Ti3AlC2 precursor was added, the three were stirred in a water bath for 24~36 h.

6. The two-dimensional layered Ti3C2T according to claim 4 x The method for preparing MXene-supported FeCo magnetic nanoparticle composite materials is characterized by: The sulfate and chloride salts of Fe and Co are FeSO4·7H2O and CoCl2·6H2O, respectively, and m FeSO4·7H2O: m CoCl2·6H2O =1:4; the raw materials used are Ti3AlC2 precursor and FeSO4·7H2O and CoCl2·6H2O of analytical grade; the solvent is deionized water; the stirring is carried out by a stirrer and a water bath, and the stirring speed is 300~500 r / min.

7. A two-dimensional layered Ti3C2T according to claim 1 x Application of MXene-loaded FeCo magnetic nanoparticle composite materials in the frequency bands of 170~220 GHz and 0.2~3 THz.

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