阅读说明：本技术 一种卟啉共价功能化Ti3C2Tx纳米片非线性纳米杂化材料及其制备与应用 (Porphyrin covalent functionalized Ti3C2TxNano-sheet nonlinear nano hybrid material and preparation and application thereof ) 是由 张弛 赵洋 伏露露 于 2021-09-22 设计创作，主要内容包括：本发明涉及一种卟啉共价功能化Ti-(3)C-(2)T-(x)纳米片非线性纳米杂化材料及其制备与应用,该非线性纳米杂化材料由四苯基卟啉TPP共价键连在Ti-(3)C-(2)T-(x)的表面形成。与现有技术相比,本发明通过重氮化反应将TPP共价键连在Ti-(3)C-(2)T-(x)表面,制备有机-无机共价功能化纳米功能材料,而不是将这两类不同光学功能材料简单的物理混杂,所制得材料相对传统材料而言,在纳秒可见光及近红外领域具备增强的非线性光学性能,具有非常广泛的应用前景。(The invention relates to porphyrin covalent functionalized Ti 3 C 2 T x The nanometer sheet non-linear nanometer hybrid material is prepared with tetraphenylporphyrin TPP covalently bonded to Ti 3 C 2 T x Is formed. Compared with the prior art, the invention connects TPP covalent bond to Ti through diazotization reaction 3 C 2 T x Preparing organic-inorganic covalent functionalized nano functional material on the surface, rather than using the two different lightsThe material with the optical function is simple in physical mixing, and compared with the traditional material, the prepared material has enhanced nonlinear optical performance in the field of nanosecond visible light and near infrared, and has a very wide application prospect.)

1. Porphyrin covalent functionalized Ti₃C₂T_xThe nano-sheet nonlinear nano hybrid material is characterized in that tetraphenylporphyrin TPP is covalently bonded with Ti₃C₂T_xThe surface of the nanosheet is formed.

2. The porphyrin covalently functionalized Ti of claim 1₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized by comprising the following steps:

(1) dissolving tetraphenylporphyrin in dichloromethane, dropwise adding concentrated nitric acid in an ice bath for reaction, and separating a product to obtain 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin;

(2) dissolving 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin in concentrated hydrochloric acid, adding stannous chloride, heating to react under the protection of nitrogen, and separating a product to obtain 5- (4-aminophenyl) -10,15, 20-phenylporphyrin;

(3) dissolving 5- (4-aminophenyl) -10,15, 20-phenylporphyrin in acetic acid, adding a tetrafluoroboric acid aqueous solution, dropwise adding an acetic acid solution of isoamyl nitrite, reacting, and separating to obtain tetraphenylporphyrin tetrafluoroborate;

(4) taking Ti₃C₂T_xAdding the nanosheets into N, N-dimethylformamide for ultrasonic treatment, adding tetraphenylporphyrin tetrafluoroborate, and reacting overnight to obtain the target product.

3. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xNanoplate nonlinear nanoThe preparation method of the hybrid material is characterized in that in the step (1), the addition amount ratio of the tetraphenylporphyrin to the concentrated nitric acid is 1 g: (1.5-3) mL, wherein the mass fraction of the concentrated nitric acid is 65%;

after the reaction was completed, the pH was neutralized to 8 with sodium hydrogencarbonate.

4. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that in the step (2), the mass ratio of 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1: 1.5-2;

the heating reaction temperature is 60-70 ℃.

5. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that in the step (3), the adding amount ratio of 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, tetrafluoroboric acid aqueous solution and isoamyl nitrite is 100 mg: (0.08-0.12) mL: (0.08-0.12) mL, wherein the mass concentration of the tetrafluoroboric acid aqueous solution is 40-60%.

6. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that in the step (4), Ti₃C₂T_xThe adding mass ratio of the nano-sheets to the tetraphenylporphyrin tetrafluoroborate is 15: (150-200).

7. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that tetraphenylporphyrin is obtained by reacting pyrrole and benzaldehyde in a propionic acid solvent, wherein the molar ratio of the pyrrole to the benzaldehyde is 1 (1.00-1.05), and the reaction temperature is 140 ℃.

8. The porphyrin covalently functionalized Ti of claim 2₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that the Ti is₃C₂T_xThe preparation process of the nanosheet specifically comprises the following steps:

taking Ti₃AlC₂Placing the mixture into hydrofluoric acid solution for reaction, washing the obtained reaction product, dispersing the reaction product into deionized water again, performing ultrasonic treatment, centrifugally extracting supernatant, and drying to obtain fluffy black solid Ti₃C₂T_xNanosheets.

9. The porphyrin covalently functionalized Ti of claim 8₃C₂T_xThe preparation method of the nano-sheet nonlinear nano hybrid material is characterized in that Ti₃AlC₂After adding into hydrofluoric acid solution, carrying out nitrogen bubbling treatment on the reaction solution;

the reaction temperature is 30-50 ℃, and the reaction time is 18-36 h.

10. The porphyrin covalently functionalized Ti of claim 1₃C₂T_xThe application of the nano-sheet nonlinear nano-hybrid material in the field of nanosecond visible light.

Technical Field

The invention belongs to the technical field of organic-inorganic functional composite materials and military strong laser protection materials, and relates to porphyrin covalent functionalized Ti₃C₂T_xA nano-sheet nonlinear nano hybrid material and preparation and application thereof.

Background

Since the invention of a strong light source based on the laser principle in 1960, the strong laser technology is widely applied to the fields of civil use, military use and science and technology as an important means of modern high technology; with the development and practical application of such intense laser equipment, the research of intense laser sensitive materials by means of nonlinear optics has attracted great attention. There are many materials that can be used for nonlinear optical applications, such as organic materials, polymer materials, inorganic crystals, two-dimensional materials, and the like. In recent years, two-dimensional (2D) materials have attracted a wide range of attention in the field of nonlinear optics (NLO), such as graphene, molybdenum disulfide, antimony, phosphorus, and the like. Ti₃C₂T_xThe nano-sheet becomes a new star in two-dimensional materials due to the unique electronic and optical properties of the nano-sheet. Discovery of Ti by research team₃C₂T_xThe nanoplatelets exhibit a broadband saturable absorption nonlinear optical response in the fs range of 800nm to 1800nm and a Reverse Saturable Absorption (RSA) NLO response under nanosecond laser radiation of 475nm to 700 nm.

The nonlinear optical absorption material of the large conjugated chromophore functionalized two-dimensional material is considered as one of important materials for nanosecond strong laser protection due to the synergistic enhancement of the nanosecond optical limiting effect, and the research and creation of the nonlinear optical absorption material have important scientific significance and practical value. Porphyrins and phthalocyanines are dye molecules with large ring and plane conjugation, and because the excited state absorption cross section value of the dye molecules is larger than the ground state absorption cross section value of the dye molecules, the dye molecules can show an obvious reverse saturable absorption phenomenon under nanosecond laser irradiation. As an outstanding class of nonlinear optical materials, they are often combined with some two-dimensional materials in a covalent or non-covalent manner to produce composite nonlinear optical materials with better performance.

In past researches, porphyrin or phthalocyanine is connected to the surface of a two-dimensional material, such as graphene, carbon nanotubes, molybdenum disulfide and the like, through various ways, and the formed composite material combines the advantages of the two materials, so that the performance of nonlinear optical performance is superior to that of a single component。Ti₃C₂T_xThe surface of the nano-sheet can form some surface groups such as-OH, -F, -O-and the like during the etching process, and the surface groups can be used for Ti₃C₂T_xHas a very important influence on the optoelectronic properties of the light-emitting diode. In addition to Ti₃C₂T_xThe surface of the nano-sheet is connected with some nonlinear functional dye molecules through surface groups, so that the nonlinear optical properties of the nano-sheet can be influenced significantly, and the nano-sheet is worthy of being researched. To date, no porphyrin or phthalocyanine has been introduced into Ti₃C₂T_xThe present invention has been made in view of the above problems, and has been made in view of the research on the photophysical properties of the nanosheets.

Disclosure of Invention

The invention aims to provide porphyrin covalent functionalized Ti₃C₂T_xA nano-sheet nonlinear nano hybrid material and preparation and application thereof. The prepared organic-inorganic covalent nano hybrid material combines TPP and Ti simultaneously₃C₂T_xThe characteristics of the nanosheets in terms of electronic structures and chemical structures improve the nonlinear optical absorption performance of the material and widen the nonlinear application range of the material.

The purpose of the invention can be realized by the following technical scheme:

one of the technical schemes of the invention provides porphyrin covalent functionalized Ti₃C₂T_xThe nano-sheet nonlinear nano hybrid material is formed by connecting tetraphenylporphyrin TPP (thermoplastic polyporphyrin) with Ti through covalent bonds₃C₂T_xThe surface of the nanosheet is formed. And enhancing the third-order nonlinear coefficient of the organic-inorganic hybrid material through the enhanced electronic coupling and transmission effect between the organic-inorganic hybrid material and the organic-inorganic hybrid material.

The second technical proposal of the invention provides porphyrin covalent functionalized Ti₃C₂T_xPreparation method of nano-sheet nonlinear nano-hybrid material for preparing porphyrin covalent functionalized Ti₃C₂T_xFirstly, preparing diazonium salt of porphyrin from the nano-sheet nonlinear nano-hybrid material. First step mass preparation of tetraphenylporphyrins by propionic acid catalyzed pyrrole condensationAnd (3) an alkyl group. To prepare the porphyrin diazonium salt, it is necessary to first introduce the nitro group into the porphyrin by means of concentrated nitric acid as nitrating agent. Then passing through SnCl₂Reducing nitro group into amino group, and finally converting the amino group into diazonium group under the action of isoamyl nitrite and tetrafluoroboric acid, wherein the diazonium salt of porphyrin is unstable, so that the diazonium salt of porphyrin can be directly mixed with Ti without further purification₃C₂T_xThe target hybrid material TPP-Ti is successfully prepared by reaction₃C₂T_x。

Specifically, the preparation method can comprise the following steps:

(1) dissolving tetraphenylporphyrin in dichloromethane, dropwise adding concentrated nitric acid in an ice bath for reaction, and separating a product to obtain 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin;

(2) dissolving 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin in concentrated hydrochloric acid, adding stannous chloride, heating to react under the protection of nitrogen, and separating a product to obtain 5- (4-aminophenyl) -10,15, 20-phenylporphyrin;

(3) dissolving 5- (4-aminophenyl) -10,15, 20-phenylporphyrin in acetic acid, adding a tetrafluoroboric acid aqueous solution, dropwise adding an acetic acid solution of isoamyl nitrite, reacting, and separating to obtain tetraphenylporphyrin tetrafluoroborate;

(4) taking Ti₃C₂T_xAdding the nano sheet into N, N-dimethylformamide for ultrasonic treatment, adding tetraphenylporphyrin tetrafluoroborate, and reacting overnight to obtain the target product tetraphenylporphyrin covalent functionalized Ti₃C₂T_xNano-sheet nonlinear nano hybrid material (namely TPP-Ti)₃C₂T_x)。

Further, in the step (1), the adding amount ratio of the tetraphenylporphyrin to the concentrated nitric acid is 1 g: (1.5-3) mL, and the mass fraction of the concentrated nitric acid is 65%. Meanwhile, after adding concentrated nitric acid as a nitration reagent, TLC reaction tracing needs to be carried out on a reaction system to determine the degree of reaction progress, and after the reaction of the raw material tetraphenylporphyrin is completed, sodium bicarbonate is added to neutralize redundant nitric acid.

Further, in the step (1), after the reaction is finished, the pH value is neutralized to 8 by using sodium bicarbonate.

Further, in the step (2), the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to the stannous chloride is 1: 1.5-2.

Further, in the step (2), the temperature of the heating reaction is 60-70 ℃.

Further, in the step (3), the ratio of the addition amounts of the 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous tetrafluoroborate solution and isoamylnitrite is 100 mg: (0.08-0.12) mL: (0.08-0.12) mL, wherein the concentration of the tetrafluoroboric acid aqueous solution is 40-60% (mass fraction, the same applies below).

Further, in the step (4), Ti₃C₂T_xThe adding mass ratio of the nano-sheets to the tetraphenylporphyrin tetrafluoroborate is 15: (150-200). The amount of porphyrin is much greater than that of Ti₃C₂T_xThe nanosheets are preferably added in batches and a plurality of times to ensure Ti₃C₂T_xTPP is bonded on the surface of the nano sheet as much as possible, the reaction needs to be carried out in a nitrogen atmosphere, and the solvent also needs to be subjected to bubbling treatment to prevent Ti₃C₂T_xThe nanosheets are oxidized during the reaction.

Further, the tetraphenylporphyrin is obtained by reacting pyrrole with benzaldehyde in a propionic acid solvent, wherein the molar ratio of the pyrrole to the benzaldehyde is 1 (1.00-1.05), and the reaction temperature is 140 ℃.

Further, said Ti₃C₂T_xThe preparation process of the nanosheet specifically comprises the following steps:

taking Ti₃AlC₂Placing the mixture into hydrofluoric acid solution for reaction, washing the obtained reaction product, dispersing the reaction product into deionized water again, performing ultrasonic treatment, centrifugally extracting supernatant, and drying to obtain fluffy black solid Ti₃C₂T_xNanosheets.

Further, Ti₃AlC₂After adding into hydrofluoric acid solution, nitrogen bubbling treatment is carried out on the reaction solution to remove oxygen and prevent Ti₃C₂T_xOxidation occurs during etching, and stripping is used during washingThe sub-water is required to be treated by removing oxygen. Meanwhile, in the preparation process, the reaction temperature is 30-50 ℃ and the reaction time is 18-36 h.

The third technical proposal of the invention provides porphyrin covalent functionalized Ti₃C₂T_xThe application of the nano-sheet nonlinear nano-hybrid material in the field of nanosecond visible light. The covalent bond connection in the material enhances porphyrin and Ti₃C₂T_xThe conjugated degree, the electronic coupling and the transmission between the two materials are realized, so that the prepared material has more enhanced nonlinear optical performance in the nanosecond visible light field compared with the traditional material, and has very strong reference significance. The nanometer hybrid material has broadband linear absorption at 375-800nm, and the fluorescence quenching efficiency reaches 90%.

Compared with the prior art, the invention has the following advantages:

(1) the hybrid material has stronger broadband linear absorption at 375-800nm, spans the whole visible light field, and does not show obvious absorption at the positions of the characteristic soret band and Q band of porphyrin.

(2)TPP-Ti₃C₂T_xThe ultraviolet absorption peak and the fluorescence emission peak are obviously red-shifted compared with the physical mixture, and the TPP-Ti through covalent linkage is proved₃C₂T_xMore efficient electron transfer and transport efficiency.

(3) TPP-Ti prepared by the invention₃C₂T_xThe nano hybrid material has porphyrin and Ti which are parent materials under the irradiation of nanosecond laser at 532nm and 1064nm₃C₂T_xThe nano-sheet has stronger non-linear absorption performance, and widens Ti₃C₂T_xThe application range in the field of nonlinear optics.

Drawings

FIG. 1 shows TPP-Ti prepared by the present invention₃C₂T_xA preparation route of the nano hybrid material;

FIG. 2 shows TPP-Ti prepared by the present invention₃C₂T_xNano hybrid material, precursor material thereof and Ti₃C₂T_x(ii) infrared spectroscopy;

FIG. 3 shows TPP-Ti prepared by the present invention₃C₂T_xX-ray diffraction patterns (XRD) of the nano hybrid material and precursor materials thereof;

FIG. 4 shows TPP-Ti prepared by the present invention₃C₂T_xX-ray photoelectron spectroscopy of the nano-hybrid material;

FIG. 5 shows TPP-Ti prepared by the present invention₃C₂T_xNano hybrid material and precursor material Ti thereof₃C₂T_xTransmission electron microscopy images of (a);

FIG. 6 shows TPP-Ti prepared by the present invention₃C₂T_xUltraviolet absorption spectra of the nano hybrid material and the precursor material;

FIG. 7 shows TPP-Ti prepared by the present invention₃C₂T_xFluorescence emission spectra of the nano hybrid material and the precursor material;

FIG. 8 shows TPP-Ti prepared by the present invention₃C₂T_xZ-scan spectra of the nano-hybrid material and the precursor material at wavelengths of 532nm and 1064 nm.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

In the following examples, the starting materials are from research platform, Annaige, Bailingwei and other reagents, among which the synthetic method of tetraphenylporphyrin is referred to in the literature (Ostrowski, S., Grzyb, S. (2012), Direct β -amino reaction in pore systems-a simple route to a complex control of two nucleotides, each of which is shown in FIGS. 53, 6355-

The rest of the raw material products or processing techniques, if not specifically mentioned, are all conventional commercial products or conventional processing techniques in the art.

Example 1:

porphyrin-based covalent functionalization of Ti₃C₂T_xThe preparation of the nano-sheet nonlinear nano-hybrid material is shown in figure 1:

the first step is as follows:

Ti₃C₂T_xreference synthesis of nanoplatelets. In general, 1g of Ti₃AlC₂Carefully add to 20mL of hydrofluoric acid solution and stir at 40 ℃ for 24 h. Ti₃C₂T_xThe product was washed with deionized water and centrifuged at 8000rpm for 5 minutes. This process was repeated several times until the pH of the supernatant became 6. Dispersing the precipitate obtained by centrifugation in de-ionized water with oxygen removed again, then carrying out ultrasonic treatment on the suspension for one hour, centrifuging the suspension for 45min at 3500 revolutions, removing the supernatant, and carrying out freeze drying to obtain black and fluffy Ti₃C₂T_xNanoplatelets (350 mg).

The second step is that:

5- (4-Nitrophenyl) -10,15, 20-triphenylporphyrin was prepared by literature methods. The method comprises the following specific steps: to a 500mL three-necked flask was added 1.7g of tetraphenylporphyrin (synthesized according to literature methods, (Ostrowski, S., Grzyb, S. (2012.) Direct β -amino reaction in pore systems-a simple route to a complex contacting two nitro reagent groups β -sites of the same saline unit. Tetrahedron Letters,53(47), 6355-. After the temperature of the reaction system was controlled to fall below 0 ℃, the reaction was vigorously stirred and monitored by TLC. When the reaction is finished, a large amount of sodium bicarbonate is added to adjust the pH to 8 to terminate the reaction. Extracting with dichloromethane (6 × 50mL), washing the organic phase with distilled water, collecting the organic phase, adding anhydrous MgSO₄Drying, filtering off the drying agent, and removing the solvent under reduced pressure to obtain crude 5- (4-nitrophenyl) -10,15, 20-triphenylporphyrin (1.95g, 95%).

¹H NMR(CDCl₃,300MHz):δ8.90(m,6H),8.74(d,2H,J＝4.8Hz),8.63(m, 2H),8.40(m,2H),8.22(m,6H),7.78(m,9H),-2.79(s,2H,pyrrole NH)。

The third step:

the preparation method of 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin comprises the following specific steps: 1.9g of dried 5- (4-nitrophenyl) -10,15, 20-triphenylporphyrin was added to a 500mL three-necked flask, and 190mL of concentrated hydrochloric acid was added. Stirring by magnetic force and protecting by nitrogen, adding 3.1g SnCl into the reaction system₂·6H₂Heating to 70 deg.C, reacting for 4 hr, pouring the reaction solution into ice water, neutralizing with ammonia water until the reaction mixture is alkaline, pouring the solution into separating funnel, separating out floccule, adding anhydrous MgSO₄Drying to precipitate all solids in the floccule. After separating the precipitate, dichloromethane was added for extraction, the organic phases were combined and collected, the solvent was dried under reduced pressure, and purification was performed by silica gel column chromatography (dichloromethane: petroleum ether ═ 2: 1) to obtain 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin (1.8g, 92%).

¹H NMR(500MHz,CDCl₃)δ8.93(d,J＝4.7Hz,2H),8.83(d,J＝2.6Hz,6H), 8.21(m,6H),7.98(d,J ＝8.3Hz,2H),7.77–7.73(m,9H),7.03(d,2H),3.98(s, 2H),-2.75(s,2H).

The fourth step:

0.1mL HBF₄the aqueous solution (50 wt%, 1.59mmol) was added to 10mL of an acetic acid solution containing 150mg (0.24mmol) of 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin. Subsequently, 5mL of an acetic acid solution in which 0.1mL of isoamyl nitrite (i.e., 0.75mmol) was dissolved was slowly dropped into the porphyrin solution. After 10 minutes, the reaction solution was quenched with 20mL of diethyl ether and stored in a refrigerator for 6 hours. Filtration through a 0.2 μm pore size filter paper gave a blue-green solid which was washed with diethyl ether to give 98% (171mg) of the porphyrin diazonium salt.

IR(cm^-1)2355,2280(N²⁺group),MS(MALDI-TOF,CHCl₃,no matrix):m/z 614 [TPP+H]^.+,629[TPP-NH₂]^.+,673[TPP-CH₃COOH]^.+.

The fifth step:

freeze-drying Ti₃C₂T_x(15mg) in 20mL of N, N-dimethylformamide as a solvent for 1 hour, and after completion of the sonication, TPP-N dissolved in 10mL of N, N-dimethylformamide was added to the suspension₂ ⁺BF₄ ^-(200 mg). The reaction mixture was transferred to a reaction tube and bubbled with nitrogen for 20 minutes, after which the mixture was reacted under nitrogen atmosphere at 25 ℃ for 24 hours with exclusion of light. After the reaction was completed, the reaction system was diluted with 10ml of DMF, and filtered with a polytetrafluoroethylene membrane (0.22mm), and washed with N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dichloromethane, deionized water and ethanol in this order. The resulting solid was repeatedly sonicated in N, N-dimethylformamide and tetrahydrofuran, redispersed and filtered, and the process was repeated several times to remove physisorbed TPP. Finally, the final product was collected by filtration on a Teflon film and dried in a vacuum oven at 80 ℃ for 10h to obtain Ti as a black powder₃C₂T_x17.4mg of nano hybrid material is the target product.

The invention successfully designs TPP covalent bond connected with Ti by preparing tetrafluoroborate of porphyrin and diazotizing₃C₂T_xSurface formed nano hybrid material TPP-Ti₃C₂T_x. In addition, the present invention systematically studied TPP-Ti by using Z-scan technique₃C₂T_xTPP and Ti₃C₂T_xNonlinear optical properties, it was found that all materials show reverse saturable absorption characteristics with the parent material TPP, Ti under 532nm and 1064nm, 4ns laser pulses₃C₂T_xIn contrast, TPP-Ti₃C₂T_xNanohybrids exhibit significantly enhanced nonlinear optical absorption properties, primarily due to charge and energy transfer effects that occur between the two. Therefore, the invention has wider application range of laser wavelength and pulse, and provides a new idea for designing and developing more general nonlinear optical materials.

FIG. 2 shows porphyrin covalent functionalized Ti prepared by the present invention₃C₂T_xNano-sheet nonlinear nano hybrid material TPP-Ti₃C₂T_xAnd infrared spectroscopy of the precursor material. It can be seen that in TPP-Ti₃C₂T_xIn 863-^-1And 1300-1431cm^-1There are some characteristic peaks attributed to porphyrins, which, although of lower intensity, are porphyrins at Ti₃C₂T_xStrong evidence of diazo functionalization of the surface. And N is²⁺The stretching vibration is 2270cm^-1The absorption peak at (a) has disappeared completely, indicating that no physical adsorption of the diazonium salt has taken place.

Nonlinear nano hybrid material TPP-Ti of figure 3₃C₂T_xAnd the X-ray diffraction pattern of the precursor material shows that Ti₃C₂T_xThe nanoplatelets were successfully etched out of the MAX phase due to the original Ti₃AlC₂(104) The diffraction peak at about 39 ° of the face disappeared. Compared with pure Ti3C2Tx, the hybrid material TPP-Ti₃C₂T_xThe (002) peak 2 theta of (A) is angularly shifted lower, indicating Ti after covalent grafting of porphyrin₃C₂T_xThe interlayer distance increases.

The X-ray photoelectron spectroscopy (XPS) of FIG. 4 shows the appearance of N, indicating that porphyrin and Ti are present₃C₂T_xThe nanosheets have reacted. To obtain more details about porphyrins and Ti₃C₂T_xThe high resolution O1s plot of the two materials was tested. Ti₃C₂T_xAnd TPP-Ti₃C₂T_xBoth show a Ti-OH bond with Ti-OH at 531.1eV and a Ti-O bond around 529.8 eV. However, TPP-Ti₃C₂T_xAn additional peak at 529.4eV is attributed to porphyrin and Ti₃C₂T_xThe formation of Ti-O-C bond between the two proves that the porphyrin group is connected to the surface of Ti3C2Tx by covalent bond.

Ti shown in FIG. 5₃C₂T_xThe Transmission Electron Microscope (TEM) image of (a) clearly shows a few-layered lamellar structure. Furthermore, it can be seen that the hybrid material TPP-Ti₃C₂T_xThe surface roughness of the porphyrin was significantly increased, demonstrating the reaction of the porphyrin therewith.

FIG. 6 shows Tetraphenylporphyrin (TPP), Ti₃C₂T_x、TPP-Ti₃C₂T_xUltraviolet absorption, and physical blending of Tetraphenylporphyrin (TPP) and Ti₃C₂T_xControl sample in DMF. The spectrum of the TPP solution shows a characteristic Soret absorption at 417nm and several weak peaks at 513, 549, 590 and 648nm, which arise from the Q-band absorption of TPP. Ti₃C₂T_xDue to its special near-zero band gap structure, it absorbs in both the visible and near-infrared regions, and compared to the control sample (physical mixture) and the monoporphyrin, TPP-Ti₃C₂T_xThe Soret band of the hybrid product is obviously widened and red-shifted to 426nm, and the Q band is also approximately red-shifted by 4-6 nm. These observations indicate that TPP-Ti is covalently linked₃C₂T_xThere is stronger ground state charge and energy transfer, and this charge exchange plays a very important role in enhancing the nonlinear performance.

FIG. 7 explores TPP and Ti in hybrid materials₂C₃T_xFor TPP-Ti₃C₂T_xFluorescence spectroscopy studies were performed with the monoporphyrin and control samples. For comparison, the absorbance at the excitation wavelength (417nm) of the three samples was uniformly adjusted to 0.8. At an excitation wavelength of 417nm, two typical emission peaks appear at 650nm and 715nm in porphyrin solution, respectively. Control sample (physical mixing) and TPP-Ti₃C₂T_xThe hybrid materials all showed significant fluorescence quenching with quenching efficiencies of 91% and 93%, respectively. TPP-Ti compared to the monoporphyrins and control samples₃C₂T_xThe main fluorescence emission peak (650nm) of the hybrid material red-shifted to 652nm, indicating that the porphyrin was covalently grafted to Ti₃C₂T_xThe surface, rather than the non-covalent interaction, demonstrates the more efficient charge transfer behavior between the two components of the hybrid material.

FIG. 8 shows TPP, Ti₃C₂T_x，TPP-Ti₃C₂T_xZ-scan test results. Search for Ti at 532nm and 1064nm under the condition of 12ns laser pulse₃C₂T_xPorphyrin, and TPP-Ti₃C₂T_xNon-linear (NLO) performance of. It was found that the nano-hybrid material is better than the precursor material Ti under the laser irradiation of 532nm and 1064nm₃C₂T_xOr porphyrin monomer TPP shows better NLO response and shows nonlinear performance from visible light to near infrared broadband, which is an obvious characteristic of covalent functionalized connection and is a result of synergistic effect of different nonlinear response mechanisms of precursor materials, mainly Ti₃C₂T_xNon-linear scattering and small two-photon absorption, reverse saturation absorption of TPP, and porphyrin to Ti₃C₂T_xElectron/energy transfer of (1). TPP-Ti according to the results of the above Z-scan test₃C₂T_xThe nano hybrid material has better third-order nonlinear performance, shows broadband NLO (non-linear optical) characteristics, greatly widens the application range of the material, and provides a new idea for designing and preparing more, more flexible and better-performance nonlinear optical materials and devices in the future.

Example 2:

most of them were the same as in example 1 except that 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the ratio of the amount of the aqueous tetrafluoroborate solution to the amount of isoamylnitrite added was adjusted to 100 mg: 0.08 mL: 0.08 mL.

Example 3:

compared with example 1, the two samples were almost the same except that the ratio of the amounts of 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous tetrafluoroborate solution and isoamylnitrite added was 100 mg: 0.12 mL: 0.12 mL.

Example 4:

compared with example 1, the two parts are mostly the same, except that the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to the stannous chloride is 1: 1.5.

Example 5:

compared with example 1, the two-phase composite material is mostly the same except that the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to the stannous chloride is 1: 2.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.