CN113831350B - Porphyrin covalent functionalization Ti 3 C 2 T x Nanometer sheet nonlinear nanometer hybrid material, preparation and application thereof - Google Patents
Porphyrin covalent functionalization Ti 3 C 2 T x Nanometer sheet nonlinear nanometer hybrid material, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin covalent functionalization Ti 3 C 2 T x Nanometer sheet nonlinear nanometer hybrid material, preparation and application thereof, wherein the nonlinear nanometer hybrid material is formed by covalently bonding tetraphenylporphyrin TPP to Ti 3 C 2 T x Is formed on the surface of the substrate. Compared with the prior art, the invention covalently bonds TPP to Ti through diazotization reaction 3 C 2 T x The surface is used for preparing the organic-inorganic covalent functionalized nano functional material, rather than simply and physically mixing the two different optical functional materials, and compared with the traditional material, the prepared material has enhanced nonlinear optical performance in the nanosecond visible light and near infrared fields, and has very wide application prospect.
Description
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 Ti 3 C 2 T x The nanometer sheet nonlinear nanometer hybridized material and its preparation and application.
Background
Since 1960 strong light source invention based on the laser principle, the strong laser technology has been widely applied to civil, military and scientific fields as an important means of modern high technology; with the development and practical application of such strong laser equipment, research on strong laser sensitive materials by means of nonlinear optics has attracted great attention. There are many materials that can be used as nonlinear optical applications, such as organic materials, high molecular materials, inorganic crystals, two-dimensional materials, and the like. In recent years, two-dimensional (2D) materials have attracted extensive attention in the field of nonlinear optics (NLO), such as graphene, molybdenum disulfide, antimony, phosphorus, and the like. Ti (Ti) 3 C 2 T x Nanoplatelets are a new star in two-dimensional materials due to their unique electronic and optical properties. Research groupTeam discovery of Ti 3 C 2 T x Nanoplatelets exhibit a broadband saturable absorption nonlinear optical response in the fs range of 800nm to 1800nm and a Reverse Saturated Absorption (RSA) NLO response under nanosecond laser radiation at 475nm to 700 nm.
The large conjugated chromophore functionalized two-dimensional material nonlinear optical absorption material has important scientific significance and practical value in research and creation because the synergistic nanosecond optical limiting effect is considered as one of important materials for nanosecond strong laser protection. Porphyrins and phthalocyanines are a class of dye molecules having a macrocyclic, planar conjugate that exhibit significant reverse saturation absorption under nanosecond laser irradiation due to their excited state absorption cross-section values greater than their ground state absorption cross-section values. As an outstanding class of nonlinear optical materials, they are often combined with some two-dimensional materials in covalent or non-covalent form to produce better performing composite nonlinear optical materials.
In the past studies, porphyrin or phthalocyanine has been attached to the surface of two-dimensional materials, such as graphene, carbon nanotubes, molybdenum disulfide, etc., by various means, and the resulting composite materials have superior nonlinear optical properties to single components because of the combination of the advantages of the two. Ti (Ti) 3 C 2 T x The surface of the nanoplatelets during etching will form surface groups such as-OH, -F, -O-etc. which are specific to Ti 3 C 2 T x Has a very important influence on the photoelectric properties of (a). And at Ti 3 C 2 T x The 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 very well explored. To date, no porphyrin or phthalocyanine has been introduced into Ti 3 C 2 T x In the nanoplatelets and research on their extended photophysical properties, the present invention has been made based on the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a porphyrin covalent functionalized Ti 3 C 2 T x Nanometer sheet nonlinear nanometer hybrid material and preparation and application thereofApplication. The prepared organic-inorganic covalent nanometer hybrid material combines TPP and Ti at the same time 3 C 2 T x The characteristics of the nano-sheets in the aspects of electronic structure and chemical structure improve the nonlinear optical absorption performance of the material and widen the nonlinear application range of the material.
The aim of the invention can be achieved by the following technical scheme:
one of the technical proposal of the invention provides a porphyrin covalent functionalized Ti 3 C 2 T x The nanometer sheet nonlinear nanometer hybridized material is formed by covalently bonding tetraphenylporphyrin TPP to Ti 3 C 2 T x The surface of the nanoplatelets is formed. The third-order nonlinear coefficient of the organic-inorganic hybrid material is enhanced by the enhanced electron coupling and transmission effect between the two.
The second technical proposal of the invention provides a porphyrin covalent functionalized Ti 3 C 2 T x Preparation method of nano-sheet nonlinear nano-hybrid material for preparing porphyrin covalent functionalized Ti 3 C 2 T x The nonlinear nanometer hybridized nanometer sheet material is first prepared into diazonium salt of porphyrin. In the first step, tetraphenylporphyrin is prepared in large quantity by catalyzing pyrrole condensation reaction through propionic acid. In order to prepare the porphyrin diazonium salt, a nitro group needs to be introduced into porphyrin by using concentrated nitric acid as a nitrifying reagent. Then pass through SnCl 2 Reduction of nitro groups to amino groups, and finally conversion of amino groups to diazo groups by the action of isopentyl nitrite and tetrafluoroboric acid, without further purification, is direct to Ti due to the instability of the porphyrin diazonium salt 3 C 2 T x The target hybrid material TPP-Ti is successfully prepared by reaction 3 C 2 T x 。
Specifically, the preparation method can comprise the following steps:
(1) Dissolving tetraphenylporphyrin in dichloromethane, dropwise adding concentrated nitric acid under ice bath for reaction, and separating the 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 under the protection of nitrogen for reaction, and separating the products to obtain 5- (4-aminophenyl) -10,15, 20-phenylporphyrin;
(3) Dissolving 5- (4-aminophenyl) -10,15, 20-phenylporphyrin in acetic acid, adding tetrafluoroboric acid water solution, then dropwise adding acetic acid solution of isoamyl nitrite, reacting, and separating to obtain tetraphenylporphyrin tetrafluoroborate;
(4) Taking Ti 3 C 2 T x Adding the nano-sheet into N, N-dimethylformamide for ultrasonic treatment, adding tetraphenylporphyrin tetrafluoroborate, and reacting overnight to obtain the target product tetraphenylporphyrin covalent functionalized Ti 3 C 2 T x Nanoplatelet nonlinear nanohybrid materials (i.e., TPP-Ti 3 C 2 T x )。
Further, in the step (1), the ratio of the addition amount of tetraphenylporphyrin to concentrated nitric acid is 1g: (1.5-3) mL, and the mass fraction of the concentrated nitric acid is 65%. Meanwhile, after adding concentrated nitric acid as a nitrifying reagent, TLC reaction tracking is needed to be carried out on a reaction system to determine the proceeding degree of the reaction, and after the raw material tetraphenylporphyrin is completely reacted, sodium bicarbonate is added to neutralize the excessive nitric acid.
Further, in the step (1), the pH is neutralized to 8 with sodium bicarbonate after the completion of the reaction.
Further, in the step (2), the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1:1.5-2.
Further, in the step (2), the temperature of the heating reaction is 60 to 70 ℃.
Further, in the step (3), the ratio of the addition amount of the aqueous solution of 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, tetrafluoroboric acid and isoamyl nitrite was 100mg: (0.08-0.12) mL: (0.08-0.12) mL, wherein the concentration of the tetrafluoroboric acid aqueous solution is 40-60% (herein, refer to mass fraction, the same applies below).
Further, in the step (4), ti 3 C 2 T x The mass ratio of the nano-sheet to the tetraphenylporphyrin tetrafluoroborate is 15: (150-200). The porphyrin is in a large amount more than Ti 3 C 2 T x The nano-sheet is preferably added in multiple portionsTo ensure Ti 3 C 2 T x The nano-sheet surface is bonded with TPP as much as possible, the reaction is carried out under nitrogen atmosphere, and the solvent is also subjected to bubbling treatment to prevent Ti 3 C 2 T x The nanoplatelets oxidize during the reaction.
Further, the 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 ℃.
Further, the Ti is 3 C 2 T x The preparation process of the nano-sheet comprises the following steps:
taking Ti 3 AlC 2 Placing the mixture in hydrofluoric acid solution for reaction, washing the obtained reaction product, dispersing the reaction product in deionized water again, performing ultrasonic treatment, centrifugally extracting supernatant, and drying to obtain fluffy black solid Ti 3 C 2 T x A nano-sheet.
Further, ti 3 AlC 2 After adding the solution of hydrofluoric acid, the reaction solution is subjected to nitrogen bubbling treatment to remove oxygen and prevent Ti 3 C 2 T x Oxidation occurs during etching, and the deionized water used during washing is required to be treated to remove 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 a porphyrin covalent functionalized Ti 3 C 2 T x The application of the nano-sheet nonlinear nano-hybrid material in the nanosecond visible light field. Covalent bonding in the material enhances porphyrin and Ti 3 C 2 T x The conjugated degree, the electron coupling and the transmission are adopted, 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 nano hybrid material has broadband linear absorption at 375-800nm, and fluorescence quenching efficiency reaches 90%.
Compared with the prior art, the invention has the following advantages:
(1) The hybrid material has strong broadband linear absorption at 375-800nm, spans the whole visible light field, rather than showing obvious absorption purely at the characteristic soret band and Q band positions of porphyrin.
(2)TPP-Ti 3 C 2 T x The ultraviolet absorption peak and the fluorescence emission peak of (C) are obviously red-shifted compared with physical mixing, which proves that the TPP-Ti is covalently connected 3 C 2 T x More efficient electron transfer and transport between.
(3) TPP-Ti prepared by the invention 3 C 2 T x The nanometer hybrid material has the characteristics that under 532nm and 1064nm nanosecond laser irradiation, the nanometer hybrid material has the characteristics that the ratio of porphyrin to Ti is higher than that of the parent material 3 C 2 T x The nano-sheet has stronger nonlinear absorption performance and widens Ti 3 C 2 T x Application in the field of nonlinear optics.
Drawings
FIG. 1 shows TPP-Ti prepared according to the present invention 3 C 2 T x A preparation route of the nano hybrid material;
FIG. 2 shows TPP-Ti prepared according to the present invention 3 C 2 T x Nano hybrid material, precursor material thereof and Ti 3 C 2 T x Is a red spectrum of (c);
FIG. 3 shows TPP-Ti prepared according to the present invention 3 C 2 T x An X-ray diffraction pattern (XRD) of the nano-hybrid material and its precursor material;
FIG. 4 shows TPP-Ti prepared according to the present invention 3 C 2 T x X-ray photoelectron spectroscopy of the nano hybrid material;
FIG. 5 shows TPP-Ti prepared according to the present invention 3 C 2 T x Nano hybrid material and precursor material Ti thereof 3 C 2 T x Transmission electron microscopy images of (2);
FIG. 6 shows TPP-Ti prepared according to the present invention 3 C 2 T x Ultraviolet absorption spectrum of the nanometer hybrid material and the precursor material;
FIG. 7 shows TPP-Ti prepared according to the present invention 3 C 2 T x Fluorescence emission spectrum of the nano hybrid material and the precursor material;
FIG. 8 shows TPP-Ti prepared according to the present invention 3 C 2 T x Z-scan spectra of the nanohybrid material and the precursor material at wavelengths of 532nm and 1064 nm.
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.
The raw materials in the examples below were all from reagent companies such as exploration platform, an Naiji, carbofuran, etc., wherein synthetic methods for tetraphenylporphyrin were referred to in the literature (Ostrowski, S., grzyb, S. (2012). Directβ -amination reaction in porphyrin systems-a simple route to compounds containing two nitrogen substituents at both β -positions of the same pyrrole unit.tetrahedron Letters,53 (47), 6355-6357.)
The remainder, unless specifically stated, is indicated as being conventional commercial products or conventional processing techniques in the art.
Example 1:
covalent functionalization of Ti based on porphyrin 3 C 2 T x Preparation of the nanoplatelet nonlinear nano hybrid material, as shown in fig. 1:
the first step:
Ti 3 C 2 T x reference synthesis of nanoplates. In general, 1g of Ti 3 AlC 2 Carefully add to 20mL of hydrofluoric acid solution and then stir at 40 ℃ for 24h. Ti (Ti) 3 C 2 T x The product was washed with deionized water and centrifuged at 8000rpm for 5 minutes. This process requires several times until the pH of the supernatant becomes 6. Re-dispersing the precipitate obtained by centrifugation in deoxidized deionized water, then carrying out ultrasonic treatment on the suspension for one hour, centrifuging at 3500 r for 45min, removing supernatant, and freeze-drying to obtain black fluffy Ti 3 C 2 T x Nanosheets(350mg)。
And a second step of:
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). Directβ -amination reaction in porphyrin systems-a simple route to compounds containing two nitrogen substituents at both β -positions of the same pyrrole unit. Tetrahedron Letters,53 (47), 6355-6357.)), 250mL of methylene chloride and 3.5mL of 65% -68% nitric acid. After the temperature of the reaction system was controlled to be lower than 0 ℃, the reaction was vigorously stirred and monitored by TLC. After the reaction reached the end point, a large amount of sodium bicarbonate was added to adjust ph=8 to terminate the reaction. Extraction with dichloromethane (6 x 50 ml), washing the organic phase with distilled water, collecting the organic phase, adding anhydrous MgSO 4 Drying, filtering the drying agent, and removing the solvent under reduced pressure to obtain crude 5- (4-nitrophenyl) -10,15, 20-triphenylporphyrin (1.95 g, 95%).
1 H NMR(CDCl 3 ,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)。
And a third step of:
the preparation of 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin comprises the following specific steps: 1.9g of dry 5- (4-nitrophenyl) -10,15, 20-triphenylporphyrin was added to a 500mL three-necked flask, and 190mL of concentrated hydrochloric acid was added. Magnetic stirring and nitrogen protection, adding 3.1g SnCl into the reaction system 2 ·6H 2 O is heated to 70 ℃ for continuous reaction for 4 hours, the reaction solution is poured into ice water, ammonia water is used for neutralization until the reaction mixture becomes alkaline, the liquid is poured into a separating funnel, floccules are separated out, and anhydrous MgSO is added 4 Drying to precipitate all solids in the floc. After separating the precipitate, dichloromethane was added for extraction, the organic phases were collected, the solvent was dried under reduced pressure, and purified by silica gel column chromatography (dichloromethane: petroleum ether=2:1) to give 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin (1.8 g, 92%).
1 H NMR(500MHz,CDCl 3 )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).
Fourth step:
0.1mL HBF 4 aqueous solution (50 wt%,1.59 mmol) was added to 10mL of acetic acid solution containing 150mg (0.24 mmol) of 5- (4-aminophenyl) -10,15, 20-triphenylporphyrin. Subsequently, a solution of 0.1mL of isoamyl nitrite (i.e., 0.75 mmol) dissolved in 5mL of acetic acid was slowly dropped into the porphyrin solution. After 10 minutes, the reaction mixture was quenched with 20mL of diethyl ether, and then stored in a refrigerator for 6 hours. Filtration through 0.2 μm pore size filter paper gave a blue-green solid which was washed with diethyl ether to give 98% (171 mg) of porphyrin diazonium salt.
IR(cm -1 )2355,2280(N 2+ group),MS(MALDI-TOF,CHCl 3 ,no matrix):m/z 614 [TPP+H] .+ ,629[TPP-NH 2 ] .+ ,673[TPP-CH 3 COOH] .+ .
Fifth step:
freeze-drying Ti 3 C 2 T x (15 mg) sonicated in 20mL of N, N-dimethylformamide solvent for 1 hour, and TPP-N dissolved in 10mL of N, N-dimethylformamide was added to the suspension after completion of the sonication 2 + BF 4 - (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 in the dark. After the reaction was completed, the reaction system was diluted with 10ml of DMF, filtered with a polytetrafluoroethylene film (0.22 mm), and washed with N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, methylene chloride, 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 repeated multiple times to remove the physisorbed TPP. Finally, the final product was collected by filtration on a polytetrafluoroethylene film and dried in a vacuum oven at 80℃for 10 hours to give Ti as a black powder 3 C 2 T x 17.4mg of nano hybrid material is the target product.
The invention successfully designs the preparation method by firstly preparing tetrafluoroborate of porphyrin and diazotizingTPP is covalently bonded to Ti 3 C 2 T x Surface formed nano hybrid material TPP-Ti 3 C 2 T x . In addition, the present invention systematically investigated TPP-Ti by using the Z-scan technique 3 C 2 T x TPP and Ti 3 C 2 T x Nonlinear optical properties, it was found that all materials showed anti-saturation absorption characteristics at 532nm and 1064nm,4ns laser pulses, compared to the parent materials TPP, ti 3 C 2 T x In contrast, TPP-Ti 3 C 2 T x The nanohybrid materials exhibit significantly enhanced nonlinear optical absorption properties, primarily due to charge and energy transfer that occurs between the two. Therefore, the invention has wider laser wavelength and pulse application range, and provides a new idea for designing and developing more general nonlinear optical materials.
FIG. 2 shows the covalent functionalization of Ti with porphyrin prepared according to the present invention 3 C 2 T x Nanosheet nonlinear nano hybrid material TPP-Ti 3 C 2 T x And infrared spectra of the precursor materials. It can be seen that in TPP-Ti 3 C 2 T x In 863-1010 cm -1 And 1300-1431cm -1 There are some characteristic peaks belonging to porphyrin, which are in Ti, despite the lower intensity 3 C 2 T x Strong evidence of diazonium functionalization of the surface. And N is 2+ Stretching vibration is 2270cm -1 The absorption peak at this point had completely disappeared, indicating that no physical adsorption of diazonium salts had occurred.
FIG. 3 shows a non-linear nano-hybrid material TPP-Ti 3 C 2 T x And the X-ray diffraction pattern of the precursor material show that Ti 3 C 2 T x The nanoplatelets were successfully etched from the MAX phase due to the original Ti 3 AlC 2 (104) The diffraction peak at the plane of about 39 deg. disappeared. And compared with pure Ti3C2Tx, the hybrid material TPP-Ti 3 C 2 T x The (002) peak 2 theta angle of (2) was shifted lower, indicating Ti after covalent grafting of porphyrin 3 C 2 T x The interlayer distance increases.
X-ray photoelectron Spectroscopy (XPS) of FIG. 4 shows the presence of N-element signals, indicating porphyrin and Ti 3 C 2 T x The nanoplatelets react. To obtain more details about porphyrins and Ti 3 C 2 T x The bonding condition between the two materials was tested for a high resolution O1s map. Ti (Ti) 3 C 2 T x And TPP-Ti 3 C 2 T x Both Ti-OH bonds located at 531.1eV and Ti-O bonds around 529.8eV are shown. However, TPP-Ti 3 C 2 T x An additional peak appears at 529.4eV, which is a porphyrin and Ti 3 C 2 T x The formation of the Ti-O-C bond between the two proves that the porphyrin group is covalently bonded to the Ti3C2Tx surface.
FIG. 5 shows Ti 3 C 2 T x Transmission Electron Microscope (TEM) images of (c) clearly show the lamellar structure of the few layers. Furthermore, it can be seen that the hybrid material TPP-Ti 3 C 2 T x The surface roughness of (c) increased significantly, demonstrating that porphyrin reacted with it.
FIG. 6 shows Tetraphenylporphyrin (TPP), ti 3 C 2 T x 、TPP-Ti 3 C 2 T x Is to physically blend Tetraphenylporphyrin (TPP) and Ti 3 C 2 T x Control samples in DMF. The spectrum of the TPP solution shows characteristic Soret absorbance at 417nm, and several weak peaks appear at 513, 549, 590 and 648nm, which are derived from the Q-band absorbance of TPP. Ti (Ti) 3 C 2 T x Because of its special near zero band gap structure, it absorbs in both the visible and near infrared regions, compared to control samples (physical mixture) and mono-porphyrins, TPP-Ti 3 C 2 T x The Soret band of the hybridized product broadens significantly and red shifts to 426nm, and the Q band is also approximately red shifted by 4-6 nm. These observations indicate that TPP-Ti is covalently linked 3 C 2 T x There is a stronger ground state charge and energy transfer between them, and this charge exchange plays a very important role in enhancing the nonlinear performance.
FIG. 7 exploration of impuritiesTPP and Ti in chemical materials 2 C 3 T x To the excited state interaction of TPP-Ti 3 C 2 T x Fluorescence spectroscopy studies were performed on mono-porphyrin and control samples. For convenience, the absorbance of the three samples at the excitation wavelength (417 nm) was uniformly adjusted to 0.8. At an excitation wavelength of 417nm, the porphyrin solution showed two typical emission peaks at 650nm and 715nm, respectively. Control samples (physical mix) and TPP-Ti 3 C 2 T x The hybrid materials all showed significant fluorescence quenching with quenching efficiencies of 91% and 93%, respectively. TPP-Ti compared to the Monoporphyrin and control samples 3 C 2 T x The main fluorescence emission peak (650 nm) of the hybrid material red shifted to 652nm, indicating that the porphyrin was covalently grafted to Ti 3 C 2 T x The surface, rather than the non-covalent interactions, also demonstrate more efficient charge transfer behavior between the two components of the hybrid material.
FIG. 8 shows TPP, ti 3 C 2 T x ，TPP-Ti 3 C 2 T x Is provided. At 532nm and 1064nm, ti was explored under a 12ns laser pulse condition 3 C 2 T x Porphyrin, and TPP-Ti 3 C 2 T x Non-linear (NLO) performance of (a) is provided. It was found that the nano-hybrid material was thicker than the precursor material Ti, both at 532nm and 1064nm laser irradiation 3 C 2 T x Or 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 the result of the synergistic effect of different nonlinear response mechanisms of precursor materials, mainly Ti 3 C 2 T x Nonlinear scattering and small amount of two-photon absorption, anti-saturation absorption of TPP, and porphyrin to Ti 3 C 2 T x Electron/energy transfer of (c). TPP-Ti according to the results of the above Z-scan test 3 C 2 T x The nanometer hybrid material has better third-order nonlinear performance, shows broadband NLO characteristics, greatly widens the application range of the material, and is designed laterThe preparation of more, more flexible and better-performance nonlinear optical materials and devices provides new ideas.
Example 2:
in comparison with example 1, the same operation was carried out except that the ratio of the amount of 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous tetrafluoroboric acid solution and the amount of isoamyl nitrite added was adjusted to 100mg:0.08mL:0.08mL.
Example 3:
in comparison with example 1, the same operation was carried out in the same manner as in example 1 except that the ratio of the amount of 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous tetrafluoroboric acid solution and the amount of isoamyl nitrite added was 100mg:0.12mL:0.12mL.
Example 4:
the vast majority of the same is compared to example 1, except that the mass ratio of 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1:1.5.
Example 5:
the vast majority of the same is compared to example 1, except that the mass ratio of 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1:2.
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 (5)
1. Porphyrin covalent functionalization Ti 3 C 2 T x The nano-sheet nonlinear nano-hybrid material is characterized in that tetraphenylporphyrin TPP is covalently bonded to Ti 3 C 2 T x The surface of the nano-sheet is formed;
the nano hybrid material is prepared by the following method:
(1) Dissolving tetraphenylporphyrin in dichloromethane, dropwise adding concentrated nitric acid under ice bath for reaction, and separating the 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 under the protection of nitrogen for reaction, and separating the products to obtain 5- (4-aminophenyl) -10,15, 20-phenylporphyrin;
(3) Dissolving 5- (4-aminophenyl) -10,15, 20-phenylporphyrin in acetic acid, adding tetrafluoroboric acid water solution, then dropwise adding acetic acid solution of isoamyl nitrite, reacting, and separating to obtain tetraphenylporphyrin tetrafluoroborate;
(4) Taking Ti 3 C 2 T x Adding the nanosheets into N, N-dimethylformamide for ultrasonic treatment, adding tetraphenylporphyrin tetrafluoroborate, and reacting overnight to obtain a target product;
in the step (1), the ratio of the adding amount of tetraphenylporphyrin to concentrated nitric acid is 1g: (1.5-3) mL, and the mass fraction of the concentrated nitric acid is 65%;
after the reaction is finished, sodium bicarbonate is adopted to neutralize the pH to 8;
in the step (2), the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1:1.5-2;
the temperature of the heating reaction is 60-70 ℃;
in the step (3), the ratio of the addition amount of the 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous solution of tetrafluoroboric acid and the isoamyl nitrite is 100mg: (0.08-0.12) mL: (0.08-0.12) mL, wherein the mass concentration of the tetrafluoroboric acid aqueous solution is 40-60%;
in step (4), ti 3 C 2 T x The mass ratio of the nano-sheet to the tetraphenylporphyrin tetrafluoroborate is 15: (150-200);
the 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 ℃.
2. A porphyrin covalent functionalized Ti according to claim 1 3 C 2 T x Nanoplatelet nonlinearityThe preparation method of the nano hybrid material is characterized by comprising the following steps:
(1) Dissolving tetraphenylporphyrin in dichloromethane, dropwise adding concentrated nitric acid under ice bath for reaction, and separating the 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 under the protection of nitrogen for reaction, and separating the products to obtain 5- (4-aminophenyl) -10,15, 20-phenylporphyrin;
(3) Dissolving 5- (4-aminophenyl) -10,15, 20-phenylporphyrin in acetic acid, adding tetrafluoroboric acid water solution, then dropwise adding acetic acid solution of isoamyl nitrite, reacting, and separating to obtain tetraphenylporphyrin tetrafluoroborate;
(4) Taking Ti 3 C 2 T x Adding the nanosheets into N, N-dimethylformamide for ultrasonic treatment, adding tetraphenylporphyrin tetrafluoroborate, and reacting overnight to obtain a target product;
in the step (1), the ratio of the adding amount of tetraphenylporphyrin to concentrated nitric acid is 1g: (1.5-3) mL, and the mass fraction of the concentrated nitric acid is 65%;
after the reaction is finished, sodium bicarbonate is adopted to neutralize the pH to 8;
in the step (2), the mass ratio of the 5- (4-nitrophenyl) -10,15, 20-phenylporphyrin to stannous chloride is 1:1.5-2;
the temperature of the heating reaction is 60-70 ℃;
in the step (3), the ratio of the addition amount of the 5- (4-aminophenyl) -10,15, 20-phenylporphyrin, the aqueous solution of tetrafluoroboric acid and the isoamyl nitrite is 100mg: (0.08-0.12) mL: (0.08-0.12) mL, wherein the mass concentration of the tetrafluoroboric acid aqueous solution is 40-60%;
in step (4), ti 3 C 2 T x The mass ratio of the nano-sheet to the tetraphenylporphyrin tetrafluoroborate is 15: (150-200);
the 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 ℃.
3. A porphyrin covalent functionalized Ti according to claim 2 3 C 2 T x The preparation method of the nano-sheet nonlinear nano-hybrid material is characterized in that the Ti 3 C 2 T x The preparation process of the nano-sheet comprises the following steps:
taking Ti 3 AlC 2 Placing the mixture in hydrofluoric acid solution for reaction, washing the obtained reaction product, dispersing the reaction product in deionized water again, performing ultrasonic treatment, centrifugally extracting supernatant, and drying to obtain fluffy black solid Ti 3 C 2 T x A nano-sheet.
4. A porphyrin covalent functionalized Ti according to claim 3 3 C 2 T x The preparation method of the nano-sheet nonlinear nano-hybrid material is characterized by comprising the following steps of 3 AlC 2 Adding the solution into hydrofluoric acid solution, and then carrying out nitrogen bubbling treatment on the reaction solution;
the reaction temperature is 30-50 ℃ and the reaction time is 18-36 h.
5. A porphyrin covalent functionalized Ti of claim 1 3 C 2 T x The application of the nano-sheet nonlinear nano-hybrid material in the nanosecond visible light field.
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