CN116462198B - Fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, synthesis and application thereof - Google Patents
Fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, synthesis and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 91
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 63
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 49
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 229910052719 titanium Inorganic materials 0.000 description 2
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y35/00—Methods or apparatus for measurement or analysis of nanostructures
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, synthesis and application thereof, which are obtained by respectively carrying out 1, 3-dipole cycloaddition reaction on fullerene C 60、C70 and 4-benzaldehyde pre-modified titanium carbide Ti 3C2Tx, and are the first examples of covalent bond formation on fullerene and MXene nano sheets at present. Compared with the simple physical mixing of the two optical functional components, the nano hybrid materials C 60 -MXene and C 70 -MXene obtained through covalent bond connection show a remarkably enhanced optical limiting effect under both nanosecond pulse light of 532nm and femtosecond pulse light of 800 nm. The invention develops a surface chemical modification strategy of titanium carbide MXene, and the obtained nano hybrid material shows the optical amplitude limiting performance of the cross-time domain and the spectral domain and has the potential of being applied to modern photon or photoelectron devices.
Description
Technical Field
The invention belongs to the technical field of three-order nonlinear optical materials, and relates to a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, and synthesis and application thereof.
Background
Nonlinear optics is a branch optical discipline that explores the interaction of a medium with light under strong coherent light. In recent years, high performance nonlinear optical materials are increasingly being used in advanced photonic or optoelectronic devices. Reverse saturation absorption is a very important third-order nonlinear optical effect, which means that as the laser energy increases, the light absorption capacity of the medium shows a strong incident light intensity dependence, resulting in a gradual suppression of transmitted light intensity. The material with the anti-saturation absorption effect can well reduce the injury or damage risk of human eyes or photosensitive devices exposed to strong light environment, and plays a role of optical clipping.
Since the preparation of single-layer graphene is successfully realized by mechanically peeling graphite powder, the three-order nonlinear optical property of the two-dimensional layered material has attracted research interests of a plurality of scholars. Following graphene, nonlinear saturation or reverse saturation absorption behavior of various two-dimensional layered materials such as hexagonal boron nitride, topological insulators, black phosphazenes, transition metal chalcogenides, perovskite, graphite alkyne, MXenes, and the like has been reported by multiple research groups. Mxnes is a generic name for a class of transition metal carbo/nitrides that was first reported in 2011. The chemical structural general formula of the material can be represented as M n+1XnTx (n=1, 2 or 3), wherein M represents front transition metal, X represents carbon or nitrogen atom, and T is a functional group (such as-OH, =O and-F) generated on the surface of the material in the etching process. Ti 3C2Tx is an MXene that is currently widely studied and exhibits broadband anti-saturation absorption optical response under pulsed light in different time domains. Some non-covalent modification strategies for Ti 3C2Tx (e.g., fe 3O4 nanoparticles, ag nanoparticles, black phosphanes) have been demonstrated to enhance the nonlinear optical properties of Ti 3C2Tx -based nanocomposites. However, these examples are synthesized by non-covalent functionalization of the preparation, i.e., assembly of the complex between the components is achieved by weak attractive forces such as van der Waals forces, electrostatic attraction or hydrogen bonding. Such preparation strategies tend to reduce the photo and thermal stability of the material; and, the larger spacing between the components is detrimental to achieving efficient inter-component electron and/or energy transfer behavior—the latter is an important factor for the overall nonlinear optical performance of the nanohybrid material over simple addition of the single components. However, no study on the influence of covalent functionalized Ti 3C2Tx on the third-order nonlinear optical properties of the nano-sheet is reported.
Disclosure of Invention
The invention aims to provide a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material and synthesis and application thereof, wherein covalent bonding between components is realized through 1, 3-dipole cycloaddition reaction between fullerene C 60, fullerene C 70 and the like and surface aldehyde group pre-modified MXene nano sheets, the obtained binary nano hybrid material combines optical characteristics of the two components, the electronic coupling effect between the two components is maximized, and the optical limiting performance of the material across a time domain and a spectral domain is improved. Unlike synthetic methods of non-covalent surface modification, covalent functionalization relies on the formation of strong covalent bonds between components to achieve assembly of the hybrid system. The modification strategy can promote tight connection among optical functional units, ensures maximization of a hybridization interface, and is beneficial to realizing more efficient coupling effect among components.
The aim of the invention can be achieved by the following technical scheme:
One of the technical schemes of the invention provides a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, which is prepared by using a bond between fullerene and a naked entity on the surface of titanium carbide Ti 3C2Tx through a pyrrolidine ring. Specifically, the nano-sized titanium dioxide nano-particles are prepared by 1, 3-dipolar cycloaddition reaction between fullerene such as C 60 and C 70 and a 4-benzaldehyde pre-modified Ti 3C2Tx nano-plate.
According to the preparation method of the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, after the prior art (taking lithium fluoride/hydrochloric acid as an etchant to etch and strip MAX phase Ti 3AlC2) is adopted to obtain few-layer titanium carbide Ti 3C2Tx, 4-benzaldehyde tetrafluoroboric acid diazonium salt is used to treat MXene nano sheets to load aldehyde groups, and then covalent bonding environment between zero-dimensional fullerene and two-dimensional Ti 3C2Tx nano sheets is constructed by utilizing 1, 3-dipole cycloaddition reaction of the aldehyde groups and fullerene carbon-carbon double bonds in the presence of excessive sarcosine, so that target products of fullerene-MXene such as C 60 -MXene and C 70 -MXene are obtained.
The method specifically comprises the following steps:
(1) Dispersing a few-layer titanium carbide Ti 3C2Tx nano-sheets in deionized water, adding 4-benzaldehyde tetrafluoroboric acid diazonium salt and potassium iodide under ice bath, and separating to obtain 4-benzaldehyde surface-modified Ti 3C2Tx nano-sheets, which are marked as f-Mxene;
(2) And (3) dispersing the f-MXene obtained in the step (1) in a mixed solvent of anhydrous N, N-dimethylformamide and anhydrous toluene, adding fullerene and sarcosine, heating and refluxing, and separating to obtain the fullerene covalent modified Ti 3C2Tx nano-sheet, namely the target product.
Further, in the step (1), the addition amount ratio of the few-layer titanium carbide Ti 3C2Tx nano-sheets, 4-benzaldehyde tetrafluoroboric acid diazonium salt and potassium iodide is 144mg:4mmol:4mmol.
Further, in the step (1), the time of the ice bath reaction is 20min.
Further, in the step (2), the dosage ratio of f-Mxene, fullerene and sarcosine is 50mg:0.17mmol:0.67mmol.
Further, in the step (2), the volume ratio of anhydrous N, N-dimethylformamide to anhydrous toluene is 2:1.
Further, in the step (2), the fullerene is C 60 or C 70.
Further, in the step (2), the temperature during the heating and refluxing process is 120 ℃ for 24 hours.
Further, in the step (2), the heat refluxing is performed under a nitrogen atmosphere.
The third technical scheme of the invention provides application of the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, and the nano hybrid material is used as a third-order nonlinear optical material in modern photon or photoelectron devices.
The ultraviolet-visible light-near infrared spectrum test results of the nano hybrid materials C 60 -MXene and C 70 -MXene prepared by the invention show that the transverse surface plasmon resonance absorption peak of the Ti 3C2Tx MXene component has obvious red shift after surface covalent functionalization is implemented, and no peak shift phenomenon is observed in a physical mixed sample of the fullerene material and the nano sheet, thus proving the important influence of obvious electronic interaction and covalent bonding environment in the C 60 -MXene and C 70 -MXene nano hybrid materials on the interaction between lifting components.
The nano hybrid materials C 60 -MXene and C 70 -MXene prepared by the invention show obviously enhanced anti-saturation absorption phenomenon under 532nm nanosecond pulse light and 800nm femtosecond pulse, namely, compared with a precursor material, the nano hybrid materials have more obvious light limiting effect. At 532nm of incident light, the nonlinear absorption coefficient β and the third order polarization imaginary value Im χ (3) of C 60 -MXene are 74.9cm GW -1 and 2.63×10 -11 esu, respectively, and β and Im χ (3) of C 70 -MXene are 70.0 and 2.46×10 -11 esu, respectively, when the incident energy is 105 μj. Beta and Im chi (3) of C 60 -MXene are 3.26X10 -3cm GW-1 and 1.85X10 -15esu,C70 -MXene, respectively, and Im chi (3) are 2.80X10 -3cm GW-1 and 1.59X10 -15 esu, respectively, when the incident light is 800nm and the energy is 136 nJ. Compared with pure titanium carbide Ti 3C2Tx nano-sheets, the three-order nonlinear optical performance of the nano-hybrid material is obviously improved. For example, under 532nm nanosecond pulsed light excitation, the beta value of C 60 -MXene is 2.1 times that of pure MXene nanoplatelets; when the excitation condition is 800nm of femtosecond pulse light, the beta value of the C 60 -MXene is 1.9 times of that of the pure MXene nano-sheet.
Compared with the prior art, the invention has the following advantages:
1. The invention utilizes the free radical addition reaction of diazonium salt to Ti 3X2Tx MXene material and the 1, 3-dipolar cycloaddition reaction of aldehyde group and carbon-carbon double bond in the presence of amino acid to realize covalent bond connection by taking fullerene C 60、C70 and Ti 3X2Tx MXene as bridging groups through pyrrolidine ring for the first time. The invention expands the surface chemistry of the titanium carbide MXene and enriches the design and preparation strategy of the binary nano hybrid material based on the titanium carbide MXene.
2. The nanometer hybridized materials C 60 -MXene and C 70 -MXene prepared by the invention have obvious red shift on the transverse surface plasma resonance signals from the MXene component in the ultraviolet-visible light-near infrared absorption spectrum, and prove that strong electronic interaction exists between the two components of the zero-dimensional fullerene and the two-dimensional nanometer sheet.
3. The C 60 -MXene and C 70 -MXene nano hybrid materials prepared by the invention show remarkably enhanced optical limiting effect under 532nm nanosecond excitation light and 800nm femtosecond excitation light compared with single-component C 60、C70, pure nano-sheets and physical mixed samples. Particularly, under the condition of 800nm light excitation, although C 60 and C 70 do not show nonlinear light absorption signals, the anti-saturation absorption of the C 60 -MXene and C 70 -MXene nano hybrid materials is enhanced, so that the coupling effect between fullerene and titanium carbide MXene nano sheets plays an important role in improving the overall nonlinear optical performance of the materials, and the design idea of a donor-acceptor hybrid system is reference to the future synthesis and preparation of more Ti 3C2Tx -based binary nonlinear optical functional materials.
Drawings
FIG. 1 is a schematic illustration of the preparation routes of the nano-hybrid materials C 60 -MXene and C 70 -MXene prepared by the present invention;
FIG. 2 shows X-ray diffraction (XRD) test results of samples, wherein a) C 60 -MXene and C 70 -MXene nano-hybrid materials prepared by the invention, MAX phase Ti 3AlC2 powder, pure nanosheets (MXene) and 4-benzaldehyde modified MXene (f-MXene) XRD spectra, b) C 60 -MXene and C 70 -MXene nano-hybrid materials, are subjected to small angle XRD test results;
FIG. 3 shows the results of Raman spectrum testing of samples, wherein a) the C 60 -MXene and C 70 -MXene nanohybrid materials prepared according to the invention and the Raman spectra of pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene), b) the results of Raman testing of C 60 and C 70;
FIG. 4 shows the results of IR spectrum tests of samples, wherein a) the C 60 -MXene and C 70 -MXene nano-hybrid materials prepared by the invention, and the IR spectra of pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene), b) the IR spectra of 4-benzaldehyde tetrafluoroborate diazonium salt, C 60 and C 70;
FIG. 5 is a thermogravimetric analysis (TGA) curve of C 60 -MXene and C 70 -MXene nanohybrid materials and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene) prepared according to the invention;
FIG. 6 is an ultraviolet-visible-near infrared absorption spectrum of each sample, wherein a) the absorption spectrum of the prepared C 60 -MXene and C 70 -MXene nanohybrid material and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene), b) the absorption spectrum of ph-CHO/MXene (physical mixing of titanium carbide MXene and benzaldehyde according to the TGA test results of f-MXene), ph-CHO/C 60/MXene (physical mixing of titanium carbide MXene, C 60 and benzaldehyde according to the TGA test results of f-MXene and C 60 -MXene) and ph-CHO/C 70/MXene (physical mixing of titanium carbide MXene, C 70 and benzaldehyde according to the TGA test results of f-MXene and C 70 -MXene);
FIG. 7 is a graph of three-order nonlinear optical performance test results for each sample at 532nm under 12ns excitation light, wherein a) the pure titanium carbide MXene was tested for Z-scan at different energies, b) the C 60 -MXene was tested for Z-scan at different energies, C) the C 70 -MXene was tested for Z-scan at different energies, d) the MXene, f-MXene, C 60、C70, the nano-hybrid materials C 60 -MXene and C 70 -MXene, and the physical hybrid materials C 60/MXene and C 70/MXene (the MXene samples were physically mixed with C 60、C70 according to the TGA test results, respectively) were tested for Z-scan at 105 μJ;
FIG. 8 shows the results of three-order nonlinear optical performance tests of samples under 800nm,34fs excitation light, wherein a) the results of Z-scan test of pure titanium carbide MXene at different energies, b) the results of Z-scan test of C 60 -MXene at different energies, C) the results of Z-scan test of C 70 -MXene at different energies, d) the results of Z-scan test of MXene, f-MXene, C 60、C70, nano-hybrid materials C 60 -MXene and C 70 -MXene, and the results of Z-scan test of physical hybrid materials C 60/MXene and C 70/MXene at 136 nJ.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the raw materials or treatment techniques are all conventional commercially available raw materials or conventional treatment techniques in the art, for example, raw materials are all from reagent companies such as exploration platform, annaiji, national drug group chemical reagent, etc.
Example 1:
Referring to the process flow shown in fig. 1, the embodiment provides a preparation method of a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material, which comprises the following steps:
the first step:
Synthesis preparation of few-layer titanium carbide MXene based on previous report (Michael Naguib,Murat Kurtoglu,Volker Presser,Jun Lu,Junjie Niu,Min Heon,Lars Hultman,Yury Gogotsi,Michel W.Barsoum,Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2,Advanced Materials,2011,23,4248-4253). MAX phase precursor Ti 3AlC2 was added multiple times to a polytetrafluoroethylene reaction vessel containing lithium fluoride (1 g) and hydrochloric acid (9M, 20 mL) and nitrogen was bubbled into it for 5 minutes after the addition was completed. Then, the reaction vessel was closed and stirred at 35℃for 24 hours. After the reaction was completed, the mixture was centrifuged (6000 rpm,5 minutes) and the supernatant was poured off, deionized water was then added, and the mixture was centrifuged again (6000 rpm,5 minutes) after shaking. This step was repeated until the pH of the supernatant was approximately 7. The lower layer was sonicated in a water bath at 0 ℃ for 1 hour under nitrogen bubbling followed by centrifugation (3500 rpm,30 minutes) to separate the unpeeled and multilayered Ti 3C2Tx nanoplatelets. Sucking 2/3 of the liquid in the centrifuge tube by using a suction tube, and freeze-drying in a freeze dryer to remove water, thus obtaining a few-layer titanium carbide MXene solid;
and a second step of:
the synthesis of 4-benzaldehyde tetrafluoroborate diazonium salt is one example of a classical reaction (Long-Li Lai,Chia-Husan Ho,Yu-Jen Lin,Eshin Wang,Synthesis and Study of an N,N-Disubstituted4-[(4-Aminophenyl)diazenyl]benzaldehyde,Helvetica Chimica Acta,2002,85,108-114). reported previously in which 4-aminobenzaldehyde (5 mmol,605 mg) was dissolved in aqueous tetrafluoroboric acid (48%, mass fraction, 4 mL) and diluted with deionized water (3.5 mL). Sodium nitrite (6 mmol,414 mg) was added in portions to the reaction solution in an ice bath under vigorous stirring, and the temperature of the reaction system was controlled so as not to exceed 10℃during the addition. After 20 minutes, the orange insoluble matter obtained by filtration was washed with diethyl ether and left to stand at room temperature to volatilize the diethyl ether, to obtain 4-benzaldehyde tetrafluoroboric acid diazonium salt (674 mg, yield 75%). Next, 4-benzaldehyde tetrafluoroborate diazonium salt (4 mmol, 284 mg) was added to an aqueous dispersion of few-layer Ti 3C2Tx nanoplatelets (1.2 mg mL -1, 120 mL). At the same time, an equivalent amount of potassium iodide (4 mmol,664 mg) was added to activate diazonium salt to increase the loading. After 20 minutes, the reaction solution was filtered, and the filtrate was repeatedly washed with deionized water, N-dimethylformamide and ethanol. Drying the filtrate in a vacuum drying oven for 24 hours after washing is completed, thus obtaining the titanium carbide MXene nanosheet solid (f-MXene, 141 mg) with the surface modified by 4-benzaldehyde;
And a third step of:
to a mixed solvent of anhydrous N, N-dimethylformamide (50 mL) and anhydrous toluene (25 mL) under nitrogen, f-MXene (50 mg) was added, and C 60 powder (0.17 mmol,120 mg) and sarcosine (0.67 mmol,90 mg) were added. After all reactants were added, the mixture was stirred under nitrogen at 120 ℃ for 24 hours. After the completion of the reaction, the cooled reaction solution was filtered, and the filtrate was washed with N, N-dimethylformamide and toluene. After washing, the filtrate was thoroughly dispersed in a mixed solvent of N, N-dimethylformamide and toluene (2:1, volume ratio), and filtered again. The above operation is repeated several times to thoroughly remove the physically adsorbed and unreacted fullerenes and other organics. Finally, the filtrate was washed with ethanol and dried overnight in a vacuum oven to give a black solid, which was C 60 -MXene nanohybrid (48 mg).
The preparation process of C 70 -MXene is the same as that of C 60 -MXene except for the difference of fullerene raw materials. To a mixed solvent of anhydrous N, N-dimethylformamide (50 mL) and anhydrous toluene (25 mL) under nitrogen protection was added f-MXene (50 mg), and C 70 powder (0.17 mmol,140 mg) and sarcosine (0.67 mmol,90 mg) were added. After all reactants were added, the mixture was stirred under nitrogen at 120 ℃ for 24 hours. After the completion of the reaction, the cooled reaction solution was filtered, and the filtrate was washed with N, N-dimethylformamide and toluene. After washing, the filtrate was thoroughly dispersed in a mixed solvent of N, N-dimethylformamide and toluene (2:1, volume ratio), and filtered again. The above operation is repeated several times to thoroughly remove the physically adsorbed and unreacted fullerenes and other organics. Finally, the filtrate was washed with ethanol and dried overnight in a vacuum oven to give a black solid, which was C 70 -MXene nanohybrid (46 mg).
Figure 2 shows the XRD test results of each sample. Wherein figure a) is the XRD spectra of the C 60 -MXene and C 70 -MXene nano-hybrid materials prepared according to the invention, MAX phase Ti 3AlC2 powder, pure nanosheets (MXene) and 4-benzaldehyde modified MXene (f-MXene). Panel b) is the result of a small angle XRD test of C 60 -MXene and C 70 -MXene nanohybrid materials. From fig. a) it can be found that the strongest crystal plane peak at 39.2 ° in Ti 3AlC2 after the etching and stripping process was completed disappears in the MXene sample and the (002) crystal plane peak has shifted to 6.1 °. The phenomenon shows that the aluminum atomic layer is successfully etched and removed, and the Ti 3C2Tx nano-sheets with a small layer are successfully prepared. In the pattern of f-MXene, it can be seen that the surface modification of 4-benzaldehyde resulted in a further shift of the (002) crystal plane peak representing the interlayer spacing to a small angle of 5.5℃proving that the interlayer spacing was widenedFrom panel b), it was found that (002) peaks of the nano-hybrid materials C 60 -MXene and C 70 -MXene were located at 4.7℃and 4.1℃respectively, despite the strong background signal, demonstrating that covalent functionalization of fullerenes further resulted in an expansion of the nano-platelet spacing. In addition, the black straight line in fig. a) represents the theoretical diffraction peaks of the anatase and rutile phases of TiO 2, and it can be found that no significant signal from TiO 2 is found in all MXene-based materials, demonstrating a low or negligible degree of oxidation of the nanoplatelets during etching, exfoliation and functionalization.
Fig. 3 shows the raman spectrum test results of each sample. Wherein FIG. a) is a Raman spectrum of the C 60 -MXene and C 70 -MXene nanohybrid materials and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene) prepared according to the present invention. Panel b) shows the Raman test results of C 60 and C 70. A 1g out-of-plane vibration peak from titanium, oxygen, carbon atoms was seen on the Raman spectrum of the MXene sample at 200cm -1. 286. Signals of 400 and 611cm -1 are derived from the E g in-plane vibrational modes of the titanium atom, carbon atom and surface oxygen/fluorine containing functional groups, respectively. In all of f-MXene, C 60 -MXene and C 70 -MXene, significant decreases in the intensity of these signals were observed, demonstrating successful surface modification of the nanoplatelets. Notably, no characteristic signal of pure C 60 or C 70 (Panel b)) appears in the Raman spectra of the nanohybrid materials C 60 -MXene and C 70 -MXene, probably because the chemical derivatization of fullerenes results in their symmetrical vibrational modes being strongly suppressed. D and G peaks of-1375 cm -1 and-1580 cm -1 can be observed in the nanohybrid material. The D and G peaks of the carbon material correspond to molecular defects and sp 2 conjugated regions, respectively. Since the MXene and f-MXene samples do not have significant raman signals in the high wavenumber region, the occurrence of D and G peaks is closely related to the covalent modification of C 60、C70, demonstrating the loading of fullerenes on the nanoplatelet surface.
FIG. 4 shows the results of the IR spectrum test for each sample. Wherein figure a) is the infrared spectrum of the C 60 -MXene and C 70 -MXene nano-hybrid materials and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene) prepared by the invention. Panel b) is the IR spectrum of diazonium 4-benzaldehyde tetrafluoroborate, C 60 and C 70. As can be seen from fig. a), the MXene sample shows several characteristic peaks. The signals at 3423 and 1444cm -1 can be attributed to the stretching and bending vibrations of O-H. The broad absorption peak of the c=o bond, which is located in the 1642cm -1.500-800cm-1 region, is derived from Ti-OH, ti-O and Ti-C. The low signal between 1900-2250cm -1 comes from the instrument. For the f-MXene samples, a decrease in the intensity of the absorption peak in the high wavenumber region was seen, demonstrating that the hydroxyl groups had been consumed during diazotization. Correspondingly, the flexural vibration signal intensity of the hydroxyl group is also reduced, and the absorption peak shifted to 1463cm -1.1664cm-1 is derived from c=o, and should be contributed from the aldehyde group on the aromatic ring. Vibration signals of residual carbon-carbon double bonds of benzene rings are located at 853 and 1161cm -1, and the successful surface modification of Ti 3C2Tx nano-sheets by 4-benzaldehyde tetrafluoroboric acid diazonium salt is proved. It is worth mentioning that the characteristic peak of N 2 + at 2298cm -1 on diazonium salt (panel b)) completely disappeared on the spectral plot of f-MXene, demonstrating that the post-treatment of f-MXene has completely removed the physically adsorbed diazonium salt. The infrared spectra of pure C 60 and C 70 show several characteristic peaks (panel b)), whereas the infrared spectra of C 60 -MXene and C 70 -MXene show a broadband absorption similar to the characteristic peak of a poly-fullerene in the 600-1200cm -1 band, similar to those reported in the literature. In addition, a small peak at 535cm -1 can be observed in C 60 -MXene, which can be attributed to the characteristic signal at 523cm -1 in C 60. The movement of the signal may be due to chemical derivatization or aggregation of the fullerene material.
FIG. 5 is a TGA thermogravimetric plot of C 60 -MXene and C 70 -MXene nanohybrid materials and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene) prepared according to the invention. TGA tests the weight loss behavior of the materials during the temperature rise of the different samples from room temperature to 800 ℃ under nitrogen atmosphere. For pure nanoplatelets, the sample loses weight 7.1% when the temperature reaches 420 ℃, and then shows good thermal stability until the end of the test. The 7.1% weight loss can be divided into two stages, namely desorption of the material crystal water and bound water at room temperature to 200 ℃ and thermal dissociation of the surface functional groups at 200-420 ℃. The almost unchanged weight loss curve of the MXene sample at the temperature rise stage of 420-800 ℃ indicates that all the surface functional groups of the MXene sample have been removed (transition from Ti 3C2Tx to Ti 3C2). Whereas for 4-benzaldehyde functionalized f-MXene, it has a weight loss of 4.8% in the 500-800℃interval, it is evident that this part of the weight loss should be attributed to the surface-loaded 4-benzaldehyde molecules. Based on this loss ratio, it can be calculated that the loading rate of 4-benzaldehyde is about 1 4-benzaldehyde molecule per 12 Ti 3C2 units. Whereas for C 60 -MXene and C 70 -MXene, 18.2% and 15.5% of the weight were lost between 370-800℃and 400-800℃respectively. The former studies on the thermal weight loss behavior of fullerene-graphene nanohybrid materials bonded with pyrrolidine ring, it is believed that the weight loss between 300 and 600 ℃ is due to thermal dissociation of benzene ring on pyrrolidine ring, and after the temperature exceeds 600 ℃, fullerene starts to decompose. According to the results of this study, 18.2% and 15.5% of the weight loss of the C 60 -MXene and C 70 -MXene nanohybrid materials, respectively, in the TGA test of the invention should contain benzene rings on the pyrrolidine ring, covalently bonded fullerenes, and unreacted 4-benzaldehyde molecules on the nanoplatelet surface. Based on this assumption, we calculated a loading rate of C 60 of about 1C 60 molecule per 43 Ti 3C2 units; the loading of C 70 was about 1C 70 molecule per 76 Ti 3C2 units. The higher loading of C 60 was due to the higher reactivity in the dipolar cycloaddition relative to C 70,C60.
Fig. 6 shows the uv-visible-near infrared absorption spectrum of each sample. Wherein FIG. a) is the absorption spectrum of C 60 -MXene and C 70 -MXene nanohybrid materials and pure nanoplatelets (MXene) and 4-benzaldehyde modified MXene (f-MXene) prepared according to the invention. Panel b) shows the absorption spectra of ph-CHO/MXene (physical mixing of titanium carbide MXene and benzaldehyde according to the TGA test results of f-MXene), ph-CHO/C 60/MXene (physical mixing of titanium carbide MXene, C 60 and benzaldehyde according to the TGA test results of f-MXene and C 60 -MXene) and ph-CHO/C 70/MXene (physical mixing of titanium carbide MXene, C 70 and benzaldehyde according to the TGA test results of f-MXene and C 70 -MXene). A mixed solvent of N, N-dimethylformamide/toluene (2:1, volume ratio) was used to disperse each sample. MXene samples exhibit characteristic peaks at 321 and 759nm, which can be attributed to interband transitions and lateral surface plasmon (TSP) resonances, respectively. After diazonium salt functionalization of titanium carbide MXene, the characteristic peak of 4-benzaldehyde modified f-MXene in the ultraviolet region is not significantly changed, while the TSP mode is red shifted to 776nm. Since the peak position of the characteristic peak is not dependent on the thickness and the size of the nano-sheet, the occurrence of the red shift phenomenon indicates that the surface environment of the nano-sheet is changed. This is clearly associated with the modification of the 4-benzaldehyde molecule. Some studies indicate that when the electron density of the Ti 3C2Tx nanoplatelets surface is reduced, the TSP peak appears to be red shifted; when electrons are injected into the nanoplatelets, the TSP signal will shift blue in the absorption spectrum. Thus, the present invention believes that the red shift of the TSP formants in f-MXene is due to the covalent modification of 4-benzaldehyde which reduces the electron density of the nanoplatelets themselves. Whereas in C 60 -MXene and C 70 -MXene the TSP signal is further red shifted to 801 and 792nm. This red shift should be attributed to the electron transfer behavior from the nanoplatelets to the fullerenes, taking into account the strong electron withdrawing properties of the fullerenes. Despite the fact that C 70 is a stronger electron absorber than C 60, TSP in the absorption spectrum of C 60 -MXene exhibits a more pronounced red shift. This may be due to the higher loading of C 60 as described above for analysis of TGA results. In addition, it was found that the characteristic peak of the interband transition of MXene in the ultraviolet region of the nanohybrid materials C 60 -MXene and C 70 -MXene disappeared. This is probably due to the strong electron withdrawing properties of fullerenes leading to depletion of electrons in the subsurface energy levels of Ti 3C2Tx nanoplatelets, where the interband transitions occur. As can be seen in panel b), three samples physically mixed according to TGA results, with TSP characteristic peaks at 759nm, consistent with pure nanoplatelets, demonstrate negligible interactions between the components, demonstrating the important role played by the covalent bonding environment between fullerenes and titanium carbide MXene in promoting electron flow between the components.
FIG. 7 shows the results of a third order nonlinear optical property test of the material at 532nm,12ns excitation light. Figures a), b) and C) are Z-scan test results of titanium carbide MXene, C 60 -MXene and C 70 -MXene, respectively, at different energies. Panel d) is the Z scan test results at 105 μJ for MXene, f-MXene, C 60、C70, nano-hybrid materials C 60 -MXene and C 70 -MXene, and physical hybrid materials C 60/MXene and C 70/MXene. In the Z scan test, the incident light is focused by the lens, and the focal point is zero (z=0). As the sample moves along the Z-axis parallel to the optical path, before and after the focal point, its transmitted light intensity, which is position dependent, is recorded. The normalized transmittance is obtained by dividing the linear transmittance. All samples were tested by dispersing in a mixed solvent N, N-dimethylformamide/toluene (2:1, volume ratio) and the transmittance at 532nm was uniformly adjusted to 60%. From figures a), b) and c) it can be seen that all three samples show the lowest normalized transmittance at zero, i.e. the reverse saturation absorption phenomenon. And, as the energy increases (from 37 muj to 105 muj), the trough of the reverse saturation absorption gradually deepens, showing the dependency between the optical clipping effect of the material and the intensity of the incident light. To better compare the optical limiting performance of each sample, graph d) gives the Z-scan test results at the same incident optical energy. The minimum normalized transmittance at zero T 0 was used to quantify the nonlinear optical properties of the different samples. C 60 -MXene and C 70 -MXene give minimum T 0 of 0.59 and 0.60, respectively, significantly less than single component materials. In addition, the T 0 of the physical mixed samples, namely the non-covalent composite material, C 60/MXene and C 70/MXene (the fullerene material and the MXene nano-sheet are physically mixed according to the loading rate obtained by a TGA test) are respectively 0.72 and 0.69, which are similar to the T 0 of the pure MXene, and the important effect of the covalent functionalization strategy on the whole improvement of the optical limiting performance of the material under 532nm nanosecond pulse light is proved. Considering the strong electron transfer behavior between fullerenes and titanium carbide MXene, the present invention recognizes that this behavior may lead to enhanced absorption of excited states in fullerenes. Whereas delocalization of excited electrons on the MXene component to fullerenes can induce MXene itself to produce more pronounced two-photon absorption. These two nonlinear absorption processes act synergistically and ultimately result in an enhancement of the overall optical clipping performance.
FIG. 8 shows the results of a three-order nonlinear optical property test of the material at 800nm and 34fs excitation light. Figures a), b) and C) are Z-scan test results of titanium carbide MXene, C 60 -MXene and C 70 -MXene, respectively, at different energies. Panel d) is the Z scan test results at 136nJ for MXene, f-MXene, C 60、C70, nano-hybrid materials C 60 -MXene and C 70 -MXene, and physical hybrid materials C 60/MXene and C 70/MXene. It can be seen that MXene, C 60 -MXene and C 70 -MXene all exhibit significant anti-saturation absorption under the irradiation of femtosecond pulsed light. Whereas in panel d) MXene has a T 0 of 0.953, neither fullerene showed a significant Z-scan signal. The distance of the excitation light from its main absorption band (ultraviolet and visible region) may be a major cause of the phenomenon of no light absorption of fullerenes under 800nm femtosecond light excitation. Even though fullerenes can achieve light absorption at 800nm, since the main mechanism that leads to material reverse saturation absorption is excited state absorption, their lifetime is typically in the nanosecond or picosecond domain, much slower than the ultrafast femtosecond lasers used in the present invention. Therefore, the excited state absorption cannot be observed under excitation of the femtosecond pulse light. Although no nonlinear optical activity was observed in C 60 and C 70, the reverse saturation absorption of C 60 -MXene and C 70 -MXene was still enhanced, and T 0 reached 0.934 and 0.938, respectively, which were significantly stronger than the monocomponent MXene and C 60/MXene and C 70/MXene. The electron transfer behavior between the components should play a critical role in the enhancement of the nanohybrid material. Because the fullerene material cannot be excited, a large number of empty orbitals are vacated on the excited state of the fullerene material, which is favorable for the relaxation of excited electrons on the MXene component to the fullerene. The rapid electron delocalization can lead to the reduction of the electron quantity on the MXene conduction band, is beneficial to enhancing the two-photon absorption of the nano-sheet, and finally realizes the enhancement of the optical limiting performance of C 60 -MXene and C 70 -MXene under ultra-fast near infrared pulse. The difference of the nonlinear optical properties of the covalently bonded C 60-MXene、C70 -MXene and the physically mixed sample (i.e., non-covalently modified, fullerene and Ti 3C2Tx MXene mixed according to TGA results) has been compared in the Z-scan test, which proves that the covalently functionalized C 60-MXene、C70 -MXene has more excellent optical limiting properties, as shown in FIGS. 7 and 8.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material is characterized in that the fullerene is bonded with the exposed primordial on the surface of titanium carbide Ti 3C2Tx through a pyrrolidine ring;
The nano hybrid material is prepared by the following method:
(1) Dispersing a few-layer titanium carbide Ti 3C2Tx nano-sheets in deionized water, adding 4-benzaldehyde tetrafluoroboric acid diazonium salt and potassium iodide under ice bath, and separating to obtain 4-benzaldehyde surface-modified Ti 3C2Tx nano-sheets, which are marked as f-Mxene;
(2) And (3) dispersing the f-MXene obtained in the step (1) in a mixed solvent of anhydrous N, N-dimethylformamide and anhydrous toluene, adding fullerene and sarcosine, heating and refluxing, and separating to obtain the fullerene covalent modified Ti 3C2Tx nano-sheet.
2. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 1, which is characterized by comprising the following steps:
(1) Dispersing a few-layer titanium carbide Ti 3C2Tx nano-sheets in deionized water, adding 4-benzaldehyde tetrafluoroboric acid diazonium salt and potassium iodide under ice bath, and separating to obtain 4-benzaldehyde surface-modified Ti 3C2Tx nano-sheets, which are marked as f-Mxene;
(2) And (3) dispersing the f-MXene obtained in the step (1) in a mixed solvent of anhydrous N, N-dimethylformamide and anhydrous toluene, adding fullerene and sarcosine, heating and refluxing, and separating to obtain the fullerene covalent modified Ti 3C2Tx nano-sheet, namely the target product.
3. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (1), the addition amount ratio of the few-layer titanium carbide Ti 3C2Tx nano-sheets, 4-benzaldehyde tetrafluoroboric acid diazonium salt and potassium iodide is 144mg:4mmol:4mmol.
4. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (1), the time of the ice bath reaction is 20min.
5. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (2), the dosage ratio of f-Mxene, fullerene and sarcosine is 50mg:0.17mmol:0.67mmol.
6. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (2), the volume ratio of anhydrous N, N-dimethylformamide to anhydrous toluene is 2:1.
7. The method for preparing a fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (2), the fullerene is C 60 or C 70.
8. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (2), the temperature in the heating reflux process is 120 ℃ and the time is 24 hours.
9. The method for preparing the fullerene covalent functionalized few-layer titanium carbide MXene nonlinear optical nano hybrid material according to claim 2, wherein in the step (2), heating reflux is performed under a nitrogen atmosphere.
10. The use of fullerene covalently functionalized few-layer titanium carbide MXene non-linear optical nano-hybrid material according to claim 1, characterized in that it is used as a third-order non-linear optical material in modern photonic or optoelectronic devices.
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