CN114479144B - Preparation method of composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matched - Google Patents

Preparation method of composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matched Download PDF

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CN114479144B
CN114479144B CN202210227565.8A CN202210227565A CN114479144B CN 114479144 B CN114479144 B CN 114479144B CN 202210227565 A CN202210227565 A CN 202210227565A CN 114479144 B CN114479144 B CN 114479144B
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赵丽娜
高旭
李玉鑫
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Heilongjiang University
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Abstract

A preparation method of a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matching belongs to the technical field of MOF material preparation. The invention aims to solve the problem that the existing rare earth MOF cannot be applied to electromagnetic absorption due to low conductivity and non-magnetism, and solve the problem that the MXene material has too high intrinsic conductivity and extremely poor matching impedance, so that the MXene material can only be directly applied to electromagnetic shielding materials and cannot be directly applied to electromagnetic absorption. The preparation method comprises the following steps: 1. two-dimensional Ti 3 C 2 T x Is synthesized by (1); 2. synthesizing a two-dimensional Tb-MOF; 3. synthesis of dimension matched MXene/Tb-MOF. The method is used for preparing the composite material with the dimension matching of the two-dimensional MXene and the two-dimensional Tb-MOF.

Description

Preparation method of composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matched
Technical Field
The invention belongs to the technical field of MOF material preparation.
Background
The widespread use of wireless communications in the military and civilian fields has led to the potential threat of Electromagnetic (EM) wave pollution, and high performance microwave absorbers are an effective approach to solving the electromagnetic pollution problem. Generally, electromagnetic wave absorbing materials capable of being widely used should have strong absorbing ability and meet practical requirements, such as light weight, wide frequency range, etc. So far, efficient electromagnetic absorbers mainly comprise carbon-based materials, magnetic materials and conductive polymers and mixtures of the above materials, but they are still limited by narrow absorption bandwidths, low dispersibility and corrosion risks.
Metal-organic frameworks (MOFs) are a class of organic-inorganic hybrids that show high potential in various applications such as electrocatalysis, photocatalysis, etc. Due to its unique structure, MOFs are ideal precursors for nanostructured metal/carbon hybrid materials that can be prepared by simple pyrolysis methods and exhibit strong electromagnetic absorption properties. However, the currently known MOF materials are usually MOFs synthesized by magnetic metal ions (Co, ni, fe, etc.) and organic ligands as electromagnetic absorbing materials, and are generally represented by N 2 Or Ar 2 Calcination is carried out under atmosphere to increase dielectric lossFurther improving electromagnetic absorption capacity. However, the MOF is subjected to high-temperature calcination to destroy the original structural framework of the MOF, the obtained MOF is mainly metal oxide and nano porous carbon material, the morphology of the MOF is lost, the calcination process is irreversible, and the MOF after calcination is called as a MOF derivative (even metal/carbon hybrid) and has a substantial difference in structure and performance from the MOF. There are few reports of directly using the MOF as an electromagnetic shielding/absorbing material in the true sense, but no report of directly using the rare earth MOF as an electromagnetic shielding/absorbing material in the true sense exists at present, and the non-magnetism and low conductivity of the rare earth MOF are main reasons that the rare earth MOF cannot be directly applied to electromagnetic shielding/absorbing.
The calcined MXene of the 2D transition metal carbide/titanium compound material has high microwave absorption performance due to the two-dimensional multilayer microstructure, large specific surface area, abundant functional groups, metallic property and good chemical mechanical property. However, the high dielectric loss of the original MXene reduces the absorption capacity. Oxidation at room temperature from Ti 3 C 2 T x Derived TiO 2 Improved dielectric loss and impedance matching, enhanced electromagnetic absorption capability, university of Drexel, derex, U.S. and professor YuryGogotsi, entitled "parent of Mxene", found MXene (Ti 3 C 2 T x ) (this paper was published in 2011 on Advanced Materials, DOI: 10.1002/adma.201102306), it was found in later studies that electromagnetic interference shielding values (EMISE) can be up to 92dB (2016, published in Science, DOI: 10.1126/science.aag2421); thereafter Korean et al, from Ti by heat treatment 3 C 2 T x Production of 2D laminated disordered C/TiO 2 Nanoparticles, minimized in Return Loss (RL) to-36 dB at 15.5GHz, 1.6mm thick (2017, publication ACS APPLIED MATERIALS)&INTERFACES, DOI: 10.1021/acsami.7b04602). However, due to the excessively high intrinsic conductivity of the MXene material, there is a very poor matching impedance, which results in a direct application to electromagnetic shielding materials, but not to electromagnetic absorption.
Disclosure of Invention
The invention aims to solve the problem that the conventional rare earth MOF cannot be applied to electromagnetic absorption due to low conductivity and non-magnetism, solve the problem that the conventional rare earth MOF can only be directly applied to an electromagnetic shielding material and cannot be directly applied to electromagnetic absorption due to extremely poor matching impedance caused by the fact that the intrinsic conductivity of an MXene material is too high, and further provide a preparation method of a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matching.
A preparation method of a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matching is carried out according to the following steps:
1. two-dimensional Ti 3 C 2 T x Is synthesized by the following steps:
mixing LiF and concentrated hydrochloric acid at 25-35 deg.c and stirring to react for 15-30 min, and adding Ti 3 AlC 2 Stirring for 12-48 h at 35-40 ℃ to obtain a colloid solution, centrifugally washing the colloid solution, and taking supernatant to obtain a two-dimensional MXene colloid solution;
the volume ratio of the LiF to the concentrated hydrochloric acid is 1g (9-12.5) mL; said LiF and Ti 3 AlC 2 The mass ratio of (1) (0.3-0.7); the concentration of the two-dimensional MXene colloidal solution is 2 mg/mL-8 mg/mL;
2. synthesis of two-dimensional Tb-MOF:
tb (NO) 3 ) 2 ·6H 2 Adding O and 2,6 pyridine dicarboxylic acid into deionized water, stirring and dissolving, then heating to 120-150 ℃, carrying out hydrothermal reaction for 72-120 h under the condition that the temperature is 120-150 ℃ to obtain a precipitate, washing and drying the precipitate to obtain the two-dimensional Tb-MOF;
said Tb (NO) 3 ) 2 ·6H 2 The mol ratio of O to 2,6 pyridine dicarboxylic acid is 1 (2-4);
3. synthesis of dimension matched MXene/Tb-MOF:
adding a two-dimensional Tb-MOF into a two-dimensional MXene colloidal solution, diluting with distilled water, performing ultrasonic treatment for 30-60 min to obtain a mixed solution, performing vacuum assisted suction filtration on the mixed solution to obtain a black film, and drying at room temperature to obtain a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimensions matched;
the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF is (0.55-1): 1; the volume ratio of the two-dimensional MXene colloidal solution to distilled water is 1 (1-3).
The beneficial effects of the invention are as follows:
the invention provides a method for vacuum assisted suction filtration, which uses MXene (Ti 3 C 2 T x ) As a matrix, a 2D Tb-MOF was doped therein in a proportion to prepare a MXene/Tb-MOF. Tb-MOF and MXene are two-dimensional structures, and in the ultrasonic process, the Tb-MOF and the MXene are mutually overlapped and mutually mixed, so that the MXene nano-sheets are prevented from being aggregated, and the electromagnetic wave absorption capacity is enhanced. Multiple loss mechanisms, including multiple reflection losses, magnetic losses, and dielectric losses, enhance electromagnetic wave attenuation. Reflection loss RL min Can reach-26dB and EAB can reach 1.8GHz. Meanwhile, the conversion from the electromagnetic shielding material to the electromagnetic absorbing material can be realized according to the proportion of the doped paraffin. Thus, MXene/Tb-MOF hybrids with novel structures can be a new guideline for the planning and manufacture of electromagnetic absorbing materials and can be explored as ideal candidates for microwave absorbing materials.
The invention is used for preparing the composite material with the dimension matching of the two-dimensional MXene and the two-dimensional Tb-MOF.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matching according to the invention;
FIG. 2 is an XRD pattern, 1 is MAX as described in example one step, 2 is two-dimensional MXene colloidal solution prepared in example one step, 3 is two-dimensional Tb-MOF prepared in example one step, and 4 is MXene/Tb-MOF prepared in example one step;
FIG. 3 is a two-dimensional Tb-MOF scanning electron microscope image prepared in step two of the example;
FIG. 4 is a scanning electron microscope image of a two-dimensional MXene colloidal solution prepared in step one of the examples;
FIG. 5 is a scanning electron microscope image of an MXene/Tb-MOF prepared in accordance with example I, with area A being the upper surface and area B being the cross-section;
FIG. 6 is XPS spectrum of MXene/Tb-MOF prepared in example one;
FIG. 7 is a Tb element distribution energy spectrum of the MXene/Tb-MOF prepared in example one;
FIG. 8 is a graph of the conductivity of MXene/Tb-MOFe measured at room temperature for different Tb-MOF contents in example one and comparative experiments one to three;
FIG. 9 is a pore size distribution plot of a two-dimensional MXene self-supporting membrane;
FIG. 10 is an N of a two-dimensional MXene self-supporting film 2 Adsorption-desorption drawing, 1 is N 2 Desorption curve, 2 is N 2 Adsorption curve;
FIG. 11 is a graph of the real and imaginary parts of the dielectric constant of 40wt% MXene/Tb-MOF paraffin wax composite, 1 being ε',2 being ε ",3 being tan delta ε ；
FIG. 12 is a graph of the real and imaginary parts of complex permeability of 40wt% MXene/Tb-MOF paraffin composite, 1 is μ',2 is μ ",3 is tan δ μ ；
FIG. 13 is a RL 3D plot of a 60wt% MXene/Tb-MOF paraffin composite;
FIG. 14 is a graph of electromagnetic shielding of 60wt% MXene/Tb-MOF paraffin composite, 1 is SE T 2 is SE A 3 is SE R ；
FIG. 15 is a RL 3D plot of a 40wt% MXene/Tb-MOF paraffin composite;
FIG. 16 is a graph of electromagnetic shielding of 40wt% MXene/Tb-MOF paraffin composite, 1 is SE T 2 is SE A 3 is SE R ；
FIG. 17 is a graph of decay constants for 40wt% MXene/Tb-MOF paraffin composite;
FIG. 18 is a graph of electromagnetic coefficients for 40wt% MXene/Tb-MOF paraffin wax composite, 1 for T,2 for R, and 3 for A;
FIG. 19 is a mechanical drawing of an EM absorption of a composite material with two dimensions of two-dimensional MXene and two dimensions of Tb-MOF in the example, a is a schematic diagram of a sample of 40wt% of the MXene/Tb-MOF paraffin composite material for testing by a vector network analyzer, b is a schematic diagram of disordered dispersion of ground and crushed MXene/Tb-MOF in the sample of FIG. a, and c is a schematic diagram of electromagnetic absorption of 40wt% of the MXene/Tb-MOF paraffin composite material.
Detailed Description
The first embodiment is as follows: the preparation method of the composite material with the dimension matching of the two-dimensional MXene and the two-dimensional Tb-MOF comprises the following steps:
1. two-dimensional Ti 3 C 2 T x Is synthesized by the following steps:
mixing LiF and concentrated hydrochloric acid at 25-35 deg.c and stirring to react for 15-30 min, and adding Ti 3 AlC 2 Stirring for 12-48 h at 35-40 ℃ to obtain a colloid solution, centrifugally washing the colloid solution, and taking supernatant to obtain a two-dimensional MXene colloid solution;
the volume ratio of the LiF to the concentrated hydrochloric acid is 1g (9-12.5) mL; said LiF and Ti 3 AlC 2 The mass ratio of (1) (0.3-0.7); the concentration of the two-dimensional MXene colloidal solution is 2 mg/mL-8 mg/mL;
2. synthesis of two-dimensional Tb-MOF:
tb (NO) 3 ) 2 ·6H 2 Adding O and 2,6 pyridine dicarboxylic acid into deionized water, stirring and dissolving, then heating to 120-150 ℃, carrying out hydrothermal reaction for 72-120 h under the condition that the temperature is 120-150 ℃ to obtain a precipitate, washing and drying the precipitate to obtain the two-dimensional Tb-MOF;
said Tb (NO) 3 ) 2 ·6H 2 The mol ratio of O to 2,6 pyridine dicarboxylic acid is 1 (2-4);
3. synthesis of dimension matched MXene/Tb-MOF:
adding a two-dimensional Tb-MOF into a two-dimensional MXene colloidal solution, diluting with distilled water, performing ultrasonic treatment for 30-60 min to obtain a mixed solution, performing vacuum assisted suction filtration on the mixed solution to obtain a black film, and drying at room temperature to obtain a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimensions matched;
the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF is (0.55-1): 1; the volume ratio of the two-dimensional MXene colloidal solution to distilled water is 1 (1-3).
The embodiment of the inventionMode Ti 3 AlC 2 Powder (98%), tb (NO) 3 ) 2 ·6H 2 O (98%), 2, 6-pyridinedicarboxylic acid (98%), concentrated hydrochloric acid, liF, deionized water and distilled water were used without further purification.
As specifically described in connection with FIG. 1, the present embodiment is to selectively etch Ti by LiF and HCl 3 AlC 2 An Al layer in (MAX) to obtain an accordion-like multi-layer Ti 3 C 2 T x (MXene), washing with distilled water for several times, centrifuging, separating the MXene into single-layer or few-layer nano-sheets, adding Tb-MOF into the MXene colloid solution after the colloid solution of the MXene is successfully prepared, diluting with distilled water, and performing sufficient ultrasonic treatment to fully mix two-dimensional MXene with two-dimensional Tb-MOF so as to achieve the mutual overlapping of the MXene sheets and the Tb-MOF sheets, wherein the ultrasonic mixing method is adopted in the process, and the arrangement sequence of the Tb-MOF nano-sheets and the MXene nano-sheets has some possibility: with MXene a /Tb-MOF b /MXene c /Tb-MOF d /MXene e For example, a, b, c, d, e represents the number of layers of MXene nanoplatelets and Tb-MOF nanoplatelets, respectively, a, b, c, d and e are each not less than 1, and merely by way of example, the stacking of MXene and Tb-MOF in the preparation of a composite is explained, and the number of stacking cycles of MXene and Tb-MOF inside the composite is not constant. Finally, the mixed solution is prepared into a black film with an MXene and Tb-MOF interlayer under vacuum auxiliary suction filtration, thus obtaining the self-supporting film formed by stacking MXene and Tb-MOF sheets, and the self-supporting film is dried at room temperature, so that a part of MXene inevitably faces TiO 2 And (3) transformation.
In view of the weak dielectric loss of pure MOF carbon-based composite materials to electromagnetic wave absorption, MXene with strong dielectric loss can be reasonably used to adjust the complex dielectric constant of MOF-derived carbon absorbers. Whereas the non-magnetic rare earth MOF can effectively reduce the problem of impedance mismatch due to the high conductivity of MXene. In addition, due to multiple reflections and prolonged electromagnetic wave transmission paths, the two-dimensional rare earth MOF and the two-dimensional MXene (Ti 3 C 2 T x ) The dimensionally matched layered microstructure further enhances electromagnetic attenuation. More importantly, MXene can be tightly adhered to MOFAnd the high electron flow on the surface of the MXene is reduced, so that electromagnetic waves fully enter the material and are converted into heat energy or other forms of energy to be dissipated, and the electromagnetic waves can be reflected and refracted repeatedly between the two materials, so that the possibility of full absorption is provided.
The preparation of the electromagnetic shielding/absorbing performance material by using MXene/Tb-MOF (ligand: 2,6 pyridine diacid) is tried for the first time, and based on simple suction filtration treatment, the porous two-dimensional structure MXene of layered and high-conductivity carbon-titanium has better structural stability and electromagnetic loss. Tb-MOF nano-sheets are fixed by MXene, so that charges between Tb-MOF and MXene are quickly transferred, the problem of poor conductivity of Tb-MOF is solved, and meanwhile, agglomeration of the MXene nano-sheets is avoided. Furthermore, the two-dimensional matching of the organic ligands of Tb-MOF to MXene plays a key role: it reduces the exposure of surface groups of MXene, limits oxidation of MXene, and increases its interlayer spacing, thereby promoting rapid ion transport. RL of MXene/Tb-MOF min The value reaches-26.8 dB (< -10 dB), which is a value that can satisfy most commercial applications. The RL value is smaller than-10 dB, the material can absorb 90% of electromagnetic waves, and the EAB (absorption broadband) can reach 1.8GHz, so that the MXene low-absorption broadband is expanded to a certain extent.
The beneficial effects of this embodiment are:
the embodiment provides a method for vacuum assisted suction filtration using MXene (Ti 3 C 2 T x ) As a matrix, a 2D Tb-MOF was doped therein in a proportion to prepare a MXene/Tb-MOF. Tb-MOF and MXene are two-dimensional structures, and in the ultrasonic process, the Tb-MOF and the MXene are mutually overlapped and mutually mixed, so that the MXene nano-sheets are prevented from being aggregated, and the electromagnetic wave absorption capacity is enhanced. Multiple loss mechanisms, including multiple reflection losses, magnetic losses, and dielectric losses, enhance electromagnetic wave attenuation. Reflection loss RL min Can reach-26dB and EAB can reach 1.8GHz. Meanwhile, the conversion from the electromagnetic shielding material to the electromagnetic absorbing material can be realized according to the proportion of the doped paraffin. Thus, the MXene/Tb-MOF hybrids with novel structures can be a new guideline for the planning and manufacture of electromagnetic absorbing materials and as microwave absorbing materialsThe ideal candidate is explored.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the concentration of the concentrated hydrochloric acid in the first step is 8 mol/L-12 mol/L. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: in the first step, ti is added at an adding speed of 0.2 g/min-1 g/min 3 AlC 2 . The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: step one, mixing LiF and concentrated hydrochloric acid and stirring for reaction for 15 to 30 minutes at the temperature of between 25 and 35 ℃ and at the rotating speed of between 400 and 600 revolutions per minute; in the first step, stirring is carried out for 12-48 h under the conditions that the temperature is 35-40 ℃ and the rotating speed is 400-600 rpm. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and in the first step, the colloid solution is washed by centrifugal distilled water for a plurality of times until the pH value is 6-7. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: tb (NO) 3 ) 2 ·6H 2 The volume ratio of the mol of O to the deionized water is 1mmol (5-10) mL. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the washing and drying in the second step is specifically carried out by washing with deionized water for multiple times, and then drying for 12-24 hours under the condition of 60-80 ℃. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: in the second step, the temperature is raised to 120-150 ℃ under the condition that the temperature raising speed is 2-5 ℃/min. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the vacuum auxiliary suction filtration in the third step is specifically that the air pressure in the closed suction filtration bottle is reduced to 0.09MPa by a vacuum pump, the atmospheric pressure pumps water into the suction filtration bottle, and the nano sheets are stacked on a Buchner funnel to form a film. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step three, under the condition that the power is 400-600 w, carrying out ultrasonic treatment for 30-60 min. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one:
a preparation method of a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimension matching is carried out according to the following steps:
1. two-dimensional Ti 3 C 2 T x Is synthesized by the following steps:
mixing 1.6g LiF with 20mL concentrated hydrochloric acid at 25deg.C and 600 rpm, stirring for 30min, and adding 1g Ti at a rate of 0.2g/min 3 AlC 2 Stirring for 24 hours at 35 ℃ and 600 rpm to obtain a colloid solution, washing the colloid solution with centrifugal distilled water for many times until the pH value is 6, and taking supernatant to obtain a two-dimensional MXene colloid solution;
the concentration of the two-dimensional MXene colloidal solution is 8mg/mL;
2. synthesis of two-dimensional Tb-MOF:
1mmol of Tb (NO) 3 ) 2 ·6H 2 Adding O and 2mmol of 2,6 pyridine dicarboxylic acid into 5mL of deionized water, stirring for 30min for dissolution, then heating to 120 ℃ at a heating rate of 5 ℃/min, performing hydrothermal reaction for 72h at the temperature of 120 ℃ to obtain precipitate, washing and drying the precipitate to obtain the two-dimensional Tb-MOF;
3. synthesis of dimension matched MXene/Tb-MOF:
adding a two-dimensional Tb-MOF into a two-dimensional MXene colloidal solution, diluting with distilled water, performing ultrasonic treatment for 30min under the condition of 400w of power to obtain a mixed solution, performing vacuum-assisted suction filtration on the mixed solution to obtain a black film, and drying at room temperature to obtain a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimensions matched;
the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF is 1:1; the volume ratio of the two-dimensional MXene colloidal solution to distilled water is 1:3.
The concentration of the concentrated hydrochloric acid in the first step is 12mol/L.
The washing and drying in the second step is specifically carried out by washing with deionized water for multiple times, and then drying for 12 hours under the condition of 80 ℃.
The vacuum auxiliary suction filtration in the third step is specifically that the air pressure in the closed suction filtration bottle is reduced to 0.09MPa by a vacuum pump, so that the atmospheric pressure pumps the water in the mixed solution into the suction filtration bottle, and then the nano sheets are stacked on a Buchner funnel to form a film.
Ti as described in example one step one 3 AlC 2 Marked MAX; the composite material of the two-dimensional MXene prepared in example one, which matches the two-dimensional Tb-MOF dimension, was labeled MXene/Tb-MOF.
Comparative experiment one: the first difference between this comparative experiment and the example is: in the third step, two-dimensional Tb-MOF is not added. The other is the same as in the first embodiment.
Comparison experiment II: the first difference between this comparative experiment and the example is: the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF in the third step is 34:66. The other is the same as in the first embodiment.
Comparison experiment three: the first difference between this comparative experiment and the example is: the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF in the step three is 25:75. The other is the same as in the first embodiment.
XRD test: the sample crystal structure was characterized on a Smart Lab X-ray diffractometer (XRD, rigaku) with Cu Ka radiation at 2θ=5° to 80 °.
FIG. 2 shows an XRD pattern, 1 is MAX as described in example one step one, 2 is two-dimensional MXe as prepared in example one step oneThe ne colloid solution, 3 is the two-dimensional Tb-MOF prepared in example one step two, and 4 is the MXene/Tb-MOF prepared in example one. As can be seen from the figure, ti 3 C 2 T x (MXene) shows no response Ti at 39 DEG 3 AlC 2 The peak of the (104) plane of (b) indicates successful removal of the Al layer after etching. Importantly, due to HF stripping and Li + The peak of the (002) plane moves to a lower angle and is opposite to the original Ti 3 AlC 2 The peak phase of the powder is broadened. XRD patterns of MXene/Tb-MOF also showed peaks of Tb-MOF. Since Tb-MOF is wrapped in MXene, the characteristic peak of Tb-MOF cannot be well developed, but notably, the (002) peak in XRD of MXene/Tb-MOF has a larger low degree of migration than the (002) peak of MXene, which can indicate that two-dimensional Tb-MOF is inserted between MXene nano-sheets, resulting in an increase of the distance between MXene nano-sheets, and more possibility is provided for multiple reflection of electromagnetic waves in the MXene nano-sheets.
Scanning electron microscope test: the morphology and structure of the gold-plated samples were observed under a FEI aspect F50 Scanning Electron Microscope (SEM).
FIG. 3 is a two-dimensional Tb-MOF scanning electron microscope image prepared in step two of the example; FIG. 4 is a scanning electron microscope image of a two-dimensional MXene colloidal solution prepared in step one of the examples; FIG. 5 is a scanning electron microscope image of an MXene/Tb-MOF prepared in example one, with area A being the upper surface and area B being the cross-section. From the graph, it can be seen that by Ti 3 AlC 2 Multilayer Ti prepared by powder etching 3 C 2 T x The colloidal solution showed a typical morphology of flexible two-dimensional lamellar (fig. 4); SEM images of Tb-MOF showed a well-defined two-dimensional morphology of the sheet stack (fig. 3), which was dimension matched to MXene, but exhibited significant stiffness characteristics compared to flexible MXene nanoplatelets. In the stacking process of Tb-MOF and MXene, the Tb-MOF and the MXene can be tightly combined in dimension to form the MXene a /Tb-MOF b /MXene c /Tb-MOF d /MXene e (a, b, c, d, e represents the number of layers of the corresponding nanoplatelets and is not less than 1, by way of example only, the form of stacks of MXene and Tb-MOF in the composite material being prepared, the number of stacking cycles of MXene and Tb-MOF inside the composite material being not constant), but due to the pure Tb-MOFThe self-supporting film prepared by the MXene/Tb-MOF is a conclusion that the MXene is taken as an upper surface and a lower surface as a supporting structure, and the upper surface (A area) of the MXene/Tb-MOF self-supporting film can see a plurality of white spots, namely the micro-tilted MXene nano-sheet in FIG. 4, and the surface of the MXene/Tb-MOF can also be proved to be the MXene nano-sheet. And the self-supporting film is seen to be a laminate film stack from the cross section (B region) of the MXene/Tb-MOF/MXene self-supporting film. By simple vacuum assisted suction filtration, the MXene nanoplatelets and Tb-MOF are stacked layer by layer into a self-supporting film (FIG. 5), which is not different in appearance from the self-supporting film of MXene due to dimensional matching, which is also matched with the (002) peak of MXene/Tb-MOF in the XRD pattern of FIG. 2 by lower phase shift than that of MXene, demonstrating that non-magnetic, non-conductive Tb-MOF is inserted into MXene, and that Tb-MOF nanoplatelets are between MXene nanoplatelets, which are stacked layer by layer, but as part of FIG. 1 there is uncertainty in the respective layers of the two, but the spacing between MXene is increased, which facilitates electromagnetic absorption.
XPS test: x-ray photoelectron spectrometer (XPS), spot size 650 μm, pass energy 30.0eV.
FIG. 6 is XPS spectrum of MXene/Tb-MOF prepared in example one; FIG. 7 is a Tb element distribution energy spectrum of the MXene/Tb-MOF prepared in example one. From the figure, it can be seen that Tb in the composite material 3+ Is present but is present in minor amounts, which may be due to the fact that a large amount of water is used as solvent during the preparation process, so that a part of the Tb-MOF is dissolved in the water, resulting in a material in which the Tb-MOF is only a small part. It can be demonstrated that Tb-MOF was successfully incorporated into MXene nanomaterials.
FIG. 8 is a graph of the conductivity of MXene/Tb-MOFe measured at room temperature for different Tb-MOF contents in example one and comparative experiments one to three; as can be seen from the graph, the maximum conductivity of pure MXene obtained by vacuum-assisted suction filtration of the two-dimensional MXene colloidal solution prepared in the first step of the embodiment can reach 2169.90Scm -1 This is mainly due to the framework of carbon and titanium in the structure of the MXene material, and the presence of functional groups such as-F, -OH, etc., which are abundant on the surface of the MXene material.The conductivity of the MXene/Tb-MOF is improved by 10% compared with that of the MXene after the Tb-MOF with the mass percentage of 50% is introduced, the Tb-MOF is possibly matched with the dimension of the MXene, the MXene nano sheets with high conductivity are intercalated between the MXene nano sheets to isolate the MXene nano sheets, the aggregation of the MXene nano sheets is prevented, the transfer of electrons from the MXene to the Tb-MOF is promoted, and the pore canal on the surface of the MOF provides a path for the transfer of electrons and the reflection of electromagnetic waves. This may be the main reason for the increased conductivity of MXene/Tb-MOF. Matching of the two dimensions may be critical for conductivity enhancement. The conductivity of the MXene/Tb-MOF incorporating a Tb-MOF of 66 mass percent was substantially the same as that of pure MXene, but the conductivity decreased with further increases in Tb-MOF content.
Carrying out vacuum auxiliary suction filtration treatment on the two-dimensional MXene colloidal solution prepared in the first step of the embodiment, thereby obtaining a two-dimensional MXene self-supporting film, and carrying out the following test: FIG. 9 is a pore size distribution plot of a two-dimensional MXene self-supporting membrane; FIG. 10 is an N of a two-dimensional MXene self-supporting film 2 Adsorption-desorption drawing, 1 is N 2 Desorption curve, 2 is N 2 Adsorption curve. Using the BET method, MXene samples showed typical type IV isotherms with pore sizes centered between 1.8nm and 3.4 nm. This may be caused by a mixture of microporous and mesoporous structures. SBET value of MXene of 84.457m 2 And/g, its average pore size can reach 2.6nm. This is due to the defect caused by the Ti on the MXene surface drying to titanium oxide at room temperature. Such microporous and mesoporous structures can provide multiple sites for multiple reflections and scattering of electromagnetic waves within the material.
Electromagnetic wave absorption characteristics: electromagnetic parameters of the samples were measured using an Agilent PNA N5224A vector network analyzer in the range of 2GHz to 18 GHz. The MXene/Tb-MOF prepared in example I was ground, pulverized into powder, mixed with paraffin to prepare a sample/paraffin mixed sample, and pressed into a ring shape (outer diameter 7.00 mm; inner diameter 3.04 mm); the mass percent based on the incorporated MXene/Tb-MOF was designated 40wt% MXene/Tb-MOF paraffin composite and 60wt% MXene/Tb-MOF paraffin composite.
To evaluate the electromagnetic wave absorption characteristics of MXene/Tb-MOF, the complex dielectric constant (. Epsilon.) at frequencies of 2GHz to 18GHz was studied r ＝ε′-jε″) And complex permeability (mu) r =μ' -jμ "). Generally, ε ' and ε "(or μ ' and μ ') represent the storage and loss of electrical (or magnetic) energy in a material, respectively. tan delta ε =ε "/ε' and tan δ μ =μ "/μ' is the power loss used to detect the electromagnetic absorption in the material.
The 40wt% MXene/Tb-MOF paraffin composite was tested for frequency dependence of electromagnetic index. FIG. 11 is a graph of the real and imaginary parts of the dielectric constant of 40wt% MXene/Tb-MOF paraffin wax composite, 1 being ε',2 being ε ",3 being tan delta ε .40wt% of MXene/Tb-MOF paraffin wax composite material can reach 10 in real part epsilon' of dielectric constant. And epsilon' has a small value, but has a very gentle trend in the whole frequency range, and has small amplitude along with the frequency change, so that the material has stable electromagnetic loss capability in a frequency band. tan delta ε The dielectric loss power index, commonly used, varies similarly to ε '/ε'.
The conduction loss depends on the conductivity, which can be determined from the degree of graphitization. The MXene is formed by stacking layered carbon and Ti, and in the drying process at room temperature, ti is oxidized into titanium oxide, a carbon framework exists, and Tb-MOF takes inorganic 2,6 pyridine dicarboxylic acid as a framework, and C, N is taken as the framework, so that the conductivity is improved. On the basis of the free electron theory, both the conductivity and the complex permittivity will thus be improved. In the microwave frequency range, the interface and dipole polarization effects may cause polarization losses. Although the dimension matching MXene/Tb-MOF is closely attached by two-dimensional structure, multi-interface polarization can occur on the surface of the interconnected MXene and Tb-MOF, tiO 2 Interfaces with carbon backbones or paraffin, interfaces of Tb-MOF with paraffin. In this case, dipole polarization may generally be caused by dipole redirection and electromagnetic wave interaction.
FIG. 12 is a graph of the real and imaginary parts of complex permeability of 40wt% MXene/Tb-MOF paraffin composite, 1 is μ',2 is μ ",3 is tan δ μ . As can be seen from the graph, both the actual permeability (μ ') and the virtual permeability (μ') slightly fluctuate with increasing frequency, tan δ μ =μ "/μ' was also calculated and plottedAs a function of frequency. tan delta μ The variation of (c) is similar to the dispersion of μ ". And the three materials are at very low values, which shows that the two non-magnetic materials of MXene and Tb-MOF are simply compounded together through vacuum assisted suction filtration, and the material has almost no magnetic loss. Therefore, the absorption shielding mechanism of the composite material is mainly due to electromagnetic loss caused by high conductivity of the C-Ti structure of (1) MXene; (2) The MXene nano-sheets can be separated by introducing Tb-MOF, so that impedance matching is optimized; (3) In the MXene drying process, part of Ti is oxidized into TiO 2 This is advantageous for matching the impedance; (4) In the process of oxidizing MXene, the defect polarization of the surface layer and the micropore structure of the MOF surface are beneficial to the defect polarization; (5) MXene, MOF, tiO 2 Multiple interfacial polarizations with carbon layers, etc.; (6) the-OH, -F, etc. functional groups on the MXene surface, especially-F, are critical for dipole polarization.
The Return Loss (RL) is calculated using transmission line theory: the absorption capacity of each absorber was evaluated using Return Loss (RL) using ε according to transmission line theory r Sum mu r And (3) calculating:
Z in ＝Z 0 (μ r /ε r ) 1/2 tanh[j(2πfd/c)(μ r ε r ) 1/2 ] (1)
wherein Z is in Is the input impedance of the absorbent, mu r Is the dielectric constant epsilon r Is complex permeability, d is MXene/Tb-MOF thickness (nm), Z 0 Is the impedance of the free space, f is the frequency of the microwaves (GHz), c is the electromagnetic wave velocity in the free space (m/s). Typically, the RL of the electromagnetic absorbing material should be below-10 dB (90% microwave absorption), i.e., satisfactory for commercial use.
R+A+T＝1 (3)
R＝|S 11 | 2 ＝|S 22 | 2 (4)
T＝|S 12 | 2 ＝|S 21 | 2 (5)
SE T ＝SE R +SE A (6)
R: reflection coefficient, a: absorption coefficient, T: a transmission coefficient; the letter "S" indicates the port of the network analyzer (electromagnetic shielding/absorption data measuring device) that receives electromagnetic interference radiation, the letters "11, 22, 12, 21" indicate the ports that send incident energy, and the vector network analyzer directly gives four scattering parameters (S11, S12, S21, S22); SE (SE) T Is the total electromagnetic shielding value, SE R Representing electromagnetic reflectance value, SE A Representing the electromagnetic absorption value.
FIG. 13 is a RL 3D plot of a 60wt% MXene/Tb-MOF paraffin composite; FIG. 14 is a graph of electromagnetic shielding of 60wt% MXene/Tb-MOF paraffin composite, 1 is SE T 2 is SE A 3 is SE R The method comprises the steps of carrying out a first treatment on the surface of the FIG. 15 is a RL 3D plot of a 40wt% MXene/Tb-MOF paraffin composite; FIG. 16 is a graph of electromagnetic shielding of 40wt% MXene/Tb-MOF paraffin composite, 1 is SE T 2 is SE A 3 is SE R The method comprises the steps of carrying out a first treatment on the surface of the As can be seen, the RL of the samples with mass loading of 40wt% and 60wt% at different thicknesses and frequencies of 2-18 GHz. 60wt% of MXene/Tb-MOF Paraffin composite shows a poor RL with MXene/Tb-MOF (FIG. 13), but SE T Above 10dB (fig. 14), which is advantageous for electromagnetic shielding rather than electromagnetic absorption, this suggests that the MXene/Tb-MOF of 60wt% MXene/Tb-MOF paraffin composite is suitable for electromagnetic shielding rather than electromagnetic absorption, which is mainly due to the large loading of MXene/Tb-MOF, the electrical conductivity being too high, resulting in a material with a relatively large difference in impedance compared to electromagnetic waves in air, but due to the good electrical conductivity of the material itself, a large number of carriers are present on the surface, which is able to shield electromagnetic waves. While at 40wt% loading, the MXene/Tb-MOF exhibits relatively excellent electromagnetic absorption properties, RL min The effective absorption bandwidth is 1.8GHz, the MXene/Tb-MOF thickness is 4.5mm (figure 15), the electromagnetic shielding performance is weaker, and obviously 40wt% of the load material of the MXene/Tb-MOF paraffin wax composite material is an electromagnetic absorption material, and the conversion from electromagnetic shielding to electromagnetic absorption can be realized by reducing the load of the material, which is not basically known in the prior report, and the conversion from electromagnetic shielding to electromagnetic absorption can be realized by changing the load.
Analysis of decay constant: from epsilon r Sum mu r The calculated attenuation constant α for 40wt% MXene/Tb-MOF paraffin wax composite is given by the formula:
where α is the attenuation constant, f is the frequency of the microwave (GHz), c is the electromagnetic wave velocity in free space (m/s), μ ', "represents the real and imaginary parts of the permeability, respectively, ε', ε" represents the real and imaginary parts of the permittivity, respectively.
FIG. 17 is a graph of decay constants for 40wt% MXene/Tb-MOF paraffin composite; FIG. 18 is a graph of electromagnetic coefficients for 40wt% MXene/Tb-MOF paraffin wax composite, 1 for T,2 for R, and 3 for A; from this figure it can be seen that a is higher, which is advantageous for electromagnetic absorption. And further analysis was performed by (fig. 18) electromagnetic coefficients, T (transmission coefficient) +r (reflection coefficient) +a (absorption coefficient) =1 (equation 3), the reflection coefficient still dominates, mainly due to the high conductivity of MXene, whereas with increasing frequency, the absorption coefficient increases, corresponding to the RL exhibiting better return loss at high frequencies. Such a phenomenon may be caused by multiple reflections of electromagnetic waves between layers of material.
FIG. 19 is a mechanical drawing of an EM absorption of a composite material with two dimensions of two-dimensional MXene and two dimensions of Tb-MOF in the example, a is a schematic diagram of a sample of 40wt% of the MXene/Tb-MOF paraffin composite material for testing by a vector network analyzer, b is a schematic diagram of disordered dispersion of ground and crushed MXene/Tb-MOF in the sample of FIG. a, and c is a schematic diagram of electromagnetic absorption of 40wt% of the MXene/Tb-MOF paraffin composite material. The incident electromagnetic wave contacts the material surface, and due to the large number of high conductivity MXene nanoplatelets on the material surface, a part of the electromagnetic wave is reflected back into the original environment, and due to the better RL (< -10 dB) of 40wt% of the MXene/Tb-MOF paraffin composite material, a part of the electromagnetic wave is left to enter the inside of the material and is dissipated by converting the electromagnetic wave into heat energy or other forms of energy. First, the insertion of a 2D Tb-MOF in an MXene nanoplatelet creates more interfaces and rich interface polarization, thereby greatly exacerbating dielectric loss. Second, when electromagnetic waves enter the medium, the laminated structure causes multiple reflections between the multilayer microstructures, resulting in effective electromagnetic attenuation. Third, defect polarization relaxation and electron polarization caused by residual groups on the surface of MXene, oxidation of the surface of MXene, and pore channels on the surface of Tb-MOF contribute to electromagnetic attenuation. Fourth, the 2D Tb-MOF insertion provides more conductive paths between MXene nanoplatelets, thereby exacerbating conduction losses. The interface between the MXene layer and the Tb-MOF attached to the MXene surface can be considered a resistive-capacitive circuit model. Capacitor-like structures may attenuate the power of incident electromagnetic waves as charge carriers move to the MXene layer or cross non-uniform interfaces.

Claims (1)

1. The preparation method of the composite material with the dimension matching of the two-dimensional MXene and the two-dimensional Tb-MOF is characterized by comprising the following steps of:
1. two-dimensional Ti 3 C 2 T x Is synthesized by the following steps:
mixing 1.6g LiF with 20mL concentrated hydrochloric acid at 25deg.C and 600 rpm, stirring for 30min, and adding 1g Ti at a rate of 0.2g/min 3 AlC 2 Stirring for 24 hours at 35 ℃ and 600 rpm to obtain a colloid solution, washing the colloid solution with centrifugal distilled water for many times until the pH value is 6, and taking supernatant to obtain a two-dimensional MXene colloid solution;
the concentration of the two-dimensional MXene colloidal solution is 8mg/mL;
2. synthesis of two-dimensional Tb-MOF:
will be 1mmolTb (NO) 3 ) 2 ·6H 2 Adding O and 2mmol of 2,6 pyridine dicarboxylic acid into 5mL of deionized water, stirring for 30min for dissolution, then heating to 120 ℃ at a heating rate of 5 ℃/min, performing hydrothermal reaction for 72h at the temperature of 120 ℃ to obtain precipitate, washing and drying the precipitate to obtain the two-dimensional Tb-MOF;
3. synthesis of dimension matched MXene/Tb-MOF:
adding a two-dimensional Tb-MOF into a two-dimensional MXene colloidal solution, diluting with distilled water, performing ultrasonic treatment for 30min under the condition of 400w of power to obtain a mixed solution, performing vacuum-assisted suction filtration on the mixed solution to obtain a black film, and drying at room temperature to obtain a composite material with two-dimensional MXene and two-dimensional Tb-MOF dimensions matched;
the mass ratio of the two-dimensional MXene colloidal solution to the two-dimensional Tb-MOF is 1:1; the volume ratio of the two-dimensional MXene colloidal solution to distilled water is 1:3;
the concentration of the concentrated hydrochloric acid in the first step is 12mol/L;
the washing and drying in the second step is specifically carried out by washing with deionized water for a plurality of times, and then drying for 12 hours under the condition that the temperature is 80 ℃;
the vacuum auxiliary suction filtration in the third step is specifically that the air pressure in a closed suction filtration bottle is reduced to 0.09MPa by a vacuum pump, so that the atmospheric pressure pumps the water in the mixed solution into the suction filtration bottle, and then the nano-sheets are stacked on a Buchner funnel to form a film;
in the composite material with the dimension matching between the two-dimensional MXene and the two-dimensional Tb-MOF, MXene nano sheets and the two-dimensional Tb-MOF are stacked layer by layer to form a self-supporting film with an intercalation structure, and the surface of the composite material is MXene nano sheets.
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CN113174751A (en) * 2021-04-09 2021-07-27 安徽大学 Multi-stage heterostructure composite material, preparation method thereof and electromagnetic microwave absorption application
CN113896900A (en) * 2021-10-19 2022-01-07 黑龙江希光科技有限公司 Lanthanide series metal organic framework Ln-MOF material and preparation method thereof

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CN113174751A (en) * 2021-04-09 2021-07-27 安徽大学 Multi-stage heterostructure composite material, preparation method thereof and electromagnetic microwave absorption application
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