CN113735884B - Porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material and preparation and application thereof - Google Patents
Porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material and preparation and application thereof. According to the invention, molybdenum disulfide is stripped into a few layers through butyl lithium, aminopyridine is covalently connected to the surface of layered molybdenum disulfide through diazonium reaction, porphyrin with metal zinc coordinated at the center is connected to the surface of the molybdenum disulfide modified by the aminopyridine through axial coordination, so that a porphyrin-molybdenum disulfide hybrid material is obtained, the covalent connection enhances the energy transmission between the molybdenum disulfide and the porphyrin, and therefore, the hybrid material shows enhanced nonlinear optical performance under nanosecond 532 nm.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic functional composite materials, and relates to a porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material, and preparation and application thereof.
Background
Molybdenum disulfide, a member of the transition metal disulfide, has an interlayer structure of S — Mo — S. The molybdenum disulfide layers are connected through chemical bonds with higher strength, and the layers are connected through Van der Waals force only, so that the massive molybdenum disulfide can be stripped into few layers or even a single layer. Due to quantum confinement effect, the band gap of the molybdenum disulfide changes along with the change of the layer number of the molybdenum disulfide. Liquid phase stripping of molybdenum disulfide is a relatively convenient method, but stripped molybdenum disulfide nanosheets are very easy to reaggregate. Modifying molybdenum disulfide by organic molecules can greatly improve the reaggregation of stripped molybdenum disulfide nanosheets in an organic solvent. Meanwhile, organic molecules are introduced to modify the molybdenum disulfide, so that electrons or energy transfer can occur in a hybrid system, and the photoelectric property of the material is changed.
Currently, the modification of molybdenum disulfide by organic molecules mainly comprises the following modes:
1. physical doping
The organic molecules and the molybdenum disulfide are mechanically mixed, the organic molecules are adsorbed on the surface of the molybdenum disulfide under the action of pi-pi accumulation, and only van der Waals force exists between the organic molecules and the molybdenum disulfide.
2. Sulfur vacancy filling
S-H bonds in organic molecules with mercaptan bonds are broken, and exposed sulfur atoms fill defect sulfur vacancies on a molybdenum disulfide plane.
3. Dithiolane ring opening
Under a certain condition, the dithiolane of the organic molecule with the dithiolane is subjected to ring opening and then is combined with sulfur atoms at the edge of the molybdenum disulfide nanosheet.
However, in the above method, the effect between the physical doping system and the molybdenum disulfide is relatively small, and the stability is not good; the sulfur vacancy filling and the dithiolane ring-opening mode are basically based on the defects with higher reaction activity, such as the sulfur vacancy of molybdenum disulfide, the edge of a nano sheet and the like. There is therefore a need for a modification that is relatively stable and not limited to sulfur vacancies or edges, and that is capable of modifying molybdenum disulfide across the entire molybdenum disulfide plane.
The present invention has been made in view of the above background.
Disclosure of Invention
The invention aims to provide a porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material, and preparation and application thereof. The hybrid material combines the characteristics of porphyrin and molybdenum disulfide in the aspects of structure and performance, enhances the energy transmission between the porphyrin and the molybdenum disulfide, and improves the nonlinear optical performance 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 a preparation method of porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material, which comprises the steps of taking aminopyridine as bridging, preparing aminopyridine into diazonium salt, anchoring and covalently connecting an amino end to the surface of molybdenum disulfide through diazonium salt reaction, and connecting a pyridine end of the aminopyridine to a pyridine end of the molybdenum disulfideThe nitrogen atom is axially coordinated with the central metal of the metalloporphyrin, so that the porphyrin and the molybdenum disulfide are bridged to obtain the covalently connected MoS2-4AP-Por nano hybrid material. The metalloporphyrin is preferably 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin, 5, 15-bis (3, 5-di-tert-butyl benzene) porphyrin is prepared by reacting 3, 5-di-tert-butylbenzaldehyde with dipyrromethane, and the 5, 15-bis (3, 5-di-tert-butyl benzene) porphyrin is metallized to obtain 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin.
Specifically, the preparation method comprises the following steps:
(1) mixing blocky molybdenum disulfide and n-butyl lithium, ultrasonically stirring, separating, washing and drying the obtained product to obtain few-layer molybdenum disulfide;
(2) under the ice bath condition, adding the aminopyridine into the tetrafluoroboric acid, stirring and dissolving, then dropwise adding a sodium nitrate solution, and stirring and reacting to obtain aminopyridine diazonium salt;
(3) dispersing a few layers of molybdenum disulfide in DMF (dimethyl formamide), dropwise adding a p-aminopyridine diazonium salt solution under an ice bath condition, stirring for reaction, filtering and washing an obtained product to obtain MoS2-4AP；
(4) Dissolving 5, 15-di (3, 5-di-tert-butyl benzene) porphyrin in anhydrous dichloromethane, adding zinc acetate dissolved in methanol for reaction, stirring overnight at room temperature in a dark place, and separating the obtained reaction product to obtain 5, 15-di (3, 5-di-tert-butyl benzene) zinc porphyrin;
(5) 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin dissolved in DCM is added with MoS dispersed in DMF24AP, stirring, filtering and washing to obtain the target product.
Further, in the step (1), the adding amount of the molybdenum disulfide and the n-butyl lithium is 1.3 g: (8-12) mL, preferably 1.3 g: 10 mL. Meanwhile, in this process, N is preferred2And (3) carrying out the reaction in the environment, quenching residual n-butyl lithium by adopting ultrapure water after stirring, separating out few layers of molybdenum disulfide by using a centrifugal machine, washing and drying.
Further, in the step (2), the ratio of the addition amounts of the aminopyridine, the tetrafluoroboric acid and the sodium nitrate is 21 mmol: (18-22) mL: (1.5-2) g, preferably 21 mmol: 20mL of: 1.725 g.
Further, in the step (2), the stirring reaction time is 30-90 min, preferably 1 h.
Further, in the step (3), the mass ratio of the few-layer molybdenum disulfide to the aminopyridine diazonium salt is 30 mg: 10-15 mmol, preferably 30 mg: 12.6 mmol. And dispersing a few layers of molybdenum disulfide in DMF, and carrying out nitrogen bubbling treatment for about 15 min.
Further, in the step (3), the stirring reaction process specifically comprises: stirring is carried out first for 2-4h, preferably 3h, at 0 ℃ and then overnight at room temperature.
Further, in the step (4), the mass ratio of 5, 15-di (3, 5-di-tert-butyl benzene) porphyrin to zinc acetate is (60-70): (75-80), preferably 63.7: 78.
Further, in the step (5), 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin and MoS2-the mass ratio of 4AP is 20 mg: 20 mg.
Further, in the step (5), the stirring reaction time is 12-24 h.
The second technical scheme of the invention provides a porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material which is prepared by adopting the preparation method.
The third technical scheme of the invention provides application of porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material in the field of nonlinear optics.
Compared with the prior art, the invention has the following advantages:
(1) the modification of the molybdenum disulfide by the organic molecules is based on the whole plane of the molybdenum disulfide, and the loading capacity of the organic molecules has larger regulation and control space;
(2) hybrid material MoS2The-4 AP-Por has MoS higher than that of the parent material under the irradiation of 532nm nanosecond laser2And reference material MoS2+ Por enhanced saturation absorption;
(3) hybrid material MoS2The-4 AP-Por enables MoS due to the surface grafting of organic molecules2The nano sheets are not easy to re-aggregate, so that the dispersibility of the nano sheets in the solution is enhancedAnd (4) stability.
Drawings
FIG. 1 shows a precursor material MoS of the present invention2-4AP and Por.
FIG. 2 is a MoS prepared according to the present invention2A preparation route of the 4AP-Por nano hybrid material.
FIG. 3 is a MoS prepared according to the present invention2-infrared (left) and ultraviolet (right) spectra of 4AP nano-hybrid.
FIG. 4 is a MoS prepared according to the present invention2An X-ray photoelectron spectrum (left one) and an ultraviolet spectrum (left two) and a fluorescence spectrum (right one) of the 4AP-Por nano hybrid material.
FIG. 5 is a MoS prepared according to the present invention2Nonlinear optical absorption spectra of 4AP-Por nano hybrid material and parent material and reference material under 532nm,12ns laser.
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 used are available from research platforms, Annage, Bailingwei, etc., wherein the synthesis of 5, 15-bis (3, 5-di-tert-butyl-phenyl) porphyrin is described in the literature (Odobel F, etc. Synthesis of oligomeric-branched bisporphyrins and study of the linking dependency of the electronic coupling.chemistry.2002 Jul 2; 8(13):3027-46.)
The rest of the raw materials or processing techniques are conventional commercial products or conventional techniques in the field if not specifically mentioned.
Example 1:
referring to fig. 1 and fig. 2, this example provides a preparation method of porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material:
the first step is as follows:
a50 mL schlenk bottle was charged with 1.3g of dried MoS2In N at210mL of n-butyllithium were added to the reaction mixture. After 2h of sonication, stirring was carried out for 2 days. After standing for 30min, the supernatant was removed, and then 20mL of ultrapure water was added to quench the residual n-butyllithium. Adding equal volume of ethanol, and performing ultrasonic treatment for 30 min. Centrifuging at 12000rpm for 20min, and collecting precipitate. The resulting precipitate was re-partitioned into ethanol and the above operation was repeated to wash off the organics. The precipitate was dispersed in ultrapure water and centrifuged at 4000rpm for 30min to remove unstripped MoS2. Taking the supernatant, centrifuging at 12000rpm for 20min, and collecting the precipitate. Re-dispersing the precipitate in ultrapure water, and centrifuging at 12000rpm for 20min to remove lithium salt to obtain single-layer or few-layer MoS precipitate2。
The second step is that:
at 0 deg.C, p-aminopyridine (1.976g 21mmol) was added to 20mL of HBF4And stirring until the solid is dissolved. Adding NaNO3(1.725g, 25mmol) was dissolved in 4mL of water, and the solution was added dropwise to the solution obtained in the above step while maintaining 0 ℃ and stirred for 1 hour to obtain a p-aminopyridine diazonium salt.
Mixing MoS2(30mg) was added to 30mL of DMF and dispersed homogeneously by sonication for 2 h. Then dispersing the mixture into a dispersion liquid N2Bubbling for 15min, p-aminopyridine diazonium salt (12.6mmol) was added dropwise (added as a solution) at 0 ℃, maintained at 0 ℃, stirred for 3h, then stirred at room temperature overnight. Filtering with PTFE membrane, washing with ultrapure water, isopropanol and DMF respectively to obtain MoS2-4AP。
The third step:
in a 1000mL dry two-necked flask, 850mL DCM and N were added2Bubbling for 10 min. Then, dipyrromethane (0.73g, 5mmol), 3, 5-di-t-butylbenzaldehyde (1.09g, 5mmol) and N were added2Bubbling for 0.5 h. TFA (0.37mL) was added dropwise and the solution turned orange-yellow. Stirred at room temperature for 15 h. DDQ (i.e., dichlorodicyanobenzoquinone, 1.62g, 7.11mmol) was added and stirred at room temperature for 5 h. Et was added3The reaction was quenched with N (4 mL). Polymer impurities were removed by flash column chromatography on silica gel followed by column chromatography on silica gel (PE: DCM ═ 5:1 to 1:1 gradient elution). And (3) adding 1% triethylamine to reduce the adsorption of the product in a silica gel column during column chromatography to obtain 5, 15-di (3, 5-di-tert-butyl benzene) porphyrin.
1H NMR(600MHz,CHCl3-d,TMS,δ/ppm):-2.99(s,2H),1.58(s,36H),7.85(t,2H；J＝1.8Hz),8.16(d,4H,3J＝1.8Hz),9.14(d,3J＝4.7Hz,4 H),9.40(d,3J＝4.7Hz,4H),10.31(s,2H).
The fourth step:
5, 15-bis (3, 5-di-tert-butylphenyl) porphyrin (63.7mg, 0.085mmol) was dissolved in anhydrous DCM (10 mL). And then Zn (OAc)2(78mg, 0.42mmol) in MeOH (5mL) was added to the reaction. Stir overnight at room temperature in the dark. Spin-drying on silica gel column to obtain 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin.
The fifth step:
mixing MoS2-4AP (20mg) was added to 20mL DMF and sonicated for 15 min. Zinc porphyrin (20mg) was dissolved in DCM and MoS was added24AP in DMF and stirred for 18 h. Filtering with PTFE membrane, washing with DMF and DCM respectively to obtain MoS2-4AP-Por。
The MoS prepared in this example is described below24AP-Por nanometer hybrid material for analysis.
FIG. 3a shows a precursor material MoS according to the present invention2-4AP and a matrix material MoS2An infrared spectrum of (1). Molybdenum disulfide had no significant absorption peak. MoS2-4AP at 1651cm-1An absorption peak corresponding to stretching vibration of-C ═ N bond, indicating the presence of 4 AP; at the same time, the length of the groove is 695cm-1The stretching vibration at which the absorption peak was S-C bond confirmed that 4AP was covalently linked to MoS2A surface. FIG. 3b shows a precursor material MoS according to the present invention2-4AP and a matrix material MoS2Ultraviolet spectrogram of (MoS)24AP with MoS at the same time2And 4AP characteristic peaks.
FIG. 4a shows the prepared hybrid material MoS2-an X-ray photoelectron spectrum of Por. MoS2And (4) carrying out peak separation and fitting on an S2 p orbit of the-4 AP-Por hybrid material to obtain three groups of double peaks. Binding energies at 162.34eV and 161.14eV correspond to 2H MoS2S2 p 1/2 and S2 p 3/2; the lower binding energy group of 161.38eV and 160.21eV corresponds to 1T MoS2. The generation of the group at 163.57eV and 162.34eV, in which the binding energy is higher, can be attributed to the generation of C-S bondsIt is true that 4AP is attached to the surface of the molybdenum disulfide via a C-S bond.
FIG. 4b shows the prepared hybrid material MoS2-4AP-Por and the parent MoS2Ultraviolet spectrum of (2). In general, porphyrin has a Soret band absorption peak at 420nm and four Q band absorption peaks at 500 to 700 nm. In the figure, the absorption peak of the zinc porphyrin at 415nm corresponds to the Soret band absorption peak of the porphyrin, and because the metal zinc is coordinated at the center, the Q band absorption peaks of the zinc porphyrin are only two and are respectively positioned at 546nm and 583 nm. MoS24AP-Por exhibits both MoS2The characteristic of broadband absorption at 350nm to 650nm also has a characteristic peak of porphyrin, and the Soret band absorption peak is red-shifted from 415nm to 417nm, so that an electronic or energy interaction exists between molybdenum disulfide and porphyrin, which indicates that zinc porphyrin is successfully coordinated to MoS24 AP. FIG. 4c shows the prepared hybrid material MoS2-4AP-Por and reference material MoS2Fluorescence spectrum of + Por. And MoS2+ Por phase ratio, MoS2The significant quenching of-4 AP-Por occurred at 591nm and 639nm, attributable to MoS2The molybdenum disulfide and the porphyrin in the-4 AP-Por hybrid material are connected through covalent bonds, and the porphyrin and the molybdenum disulfide are in specific physical doping to prepare the MoS2+ Por is more efficient for electron or energy transfer.
FIG. 5 shows the hybrid material MoS prepared by the invention2-4AP-Por and the results of Z-scan testing of the parent and reference materials at 532nm,12ns laser. MoS2The transmittance is maximum at the focal point and increases with increasing incident energy, characterizing saturated absorption. In contrast, porphyrins exhibit reverse saturable absorption characteristics. MoS2-4AP-Por exhibits MoS over the parent material2And reference material MoS2+ Por stronger saturable absorption response. From the above nonlinear optical absorption spectrum, it can be concluded that MoS obtained by chemically modifying molybdenum disulfide with porphyrin2The-4 AP-Por hybrid material has better third-order nonlinear performance, and the method provides a new idea for designing and preparing more, more flexible and better nonlinear optical materials and devices in the future.
The raw material reagents and their addition amounts, and the process parameters and conditions of the reaction, etc. used in the above examples may be arbitrarily adjusted within the following ranges (i.e., arbitrarily adjusted to their end values, or any intermediate value) as required:
the addition amount ratio of molybdenum disulfide to n-butyllithium is 1.3 g: (8-12) mL; the addition ratio of the aminopyridine, the tetrafluoroboric acid and the sodium nitrate is 21 mmol: (18-22) mL: (1.5-2) g; after the aminopyridine diazonium salt is added, stirring for 2-4h at 0 ℃, and then stirring overnight at room temperature; the mass ratio of the 5, 15-di (3, 5-di-tert-butyl benzene) porphyrin to the zinc acetate is (60-70): (75-80).
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.
Claims (10)
1. A preparation method of porphyrin covalent connection molybdenum disulfide nonlinear nano hybrid material is characterized by comprising the following steps:
(1) mixing blocky molybdenum disulfide and n-butyl lithium, ultrasonically stirring, separating, washing and drying the obtained product to obtain few-layer molybdenum disulfide;
(2) under the ice bath condition, adding the aminopyridine into the tetrafluoroboric acid, stirring and dissolving, then dropwise adding a sodium nitrate solution, and stirring and reacting to obtain aminopyridine diazonium salt;
(3) dispersing a few layers of molybdenum disulfide in DMF (dimethyl formamide), dropwise adding a p-aminopyridine diazonium salt solution under an ice bath condition, stirring overnight, filtering and washing an obtained product to obtain MoS2-4AP；
(4) Dissolving 5, 15-di (3, 5-di-tert-butyl benzene) porphyrin in anhydrous dichloromethane, adding zinc acetate dissolved in methanol for reaction, stirring overnight at room temperature in a dark place, and separating the obtained reaction product to obtain 5, 15-di (3, 5-di-tert-butyl benzene) zinc porphyrin;
(5) 5, 15-bis (3, 5-di-tert-butyl benzene) zinc porphyrin dissolved in DCM is added with MoS dispersed in DMF24AP, stirring, filtering and washing to obtain the target product.
2. The preparation method of the porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material as claimed in claim 1, wherein in the step (1), the addition amount ratio of molybdenum disulfide to n-butyllithium is 1.3 g: (8-12) mL.
3. The preparation method of the porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material as claimed in claim 1, wherein in the step (2), the addition amount ratio of aminopyridine, tetrafluoroboric acid and sodium nitrate is 21 mmol: (18-22) mL: (1.5-2) g.
4. The method for preparing the porphyrin covalent-connection molybdenum disulfide nonlinear nano hybrid material according to claim 1, wherein in the step (3), the stirring reaction process specifically comprises the following steps: stirring was first carried out at 0 ℃ for 2-4h and then at room temperature overnight.
5. The method for preparing the porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material according to claim 1, wherein in the step (3), the mass ratio of the few layers of molybdenum disulfide to the aminopyridine diazonium salt is 30 mg: 12.6 mmol.
6. The preparation method of the porphyrin covalent-connection molybdenum disulfide nonlinear nano hybrid material as claimed in claim 1, wherein in the step (4), the mass ratio of 5, 15-bis (3, 5-di-tert-butyl phenyl) porphyrin to zinc acetate is (60-70): (75-80).
7. The method of claim 1, wherein the porphyrin is covalently linked with the molybdenum disulfide nonlinear nano hybrid materialThe preparation method is characterized in that in the step (5), 5, 15-di (3, 5-di-tert-butyl benzene) zinc porphyrin and MoS2The mass ratio of-4 AP is 1: 1.
8. The preparation method of the porphyrin covalent-connection molybdenum disulfide nonlinear nano hybrid material as claimed in claim 1, wherein in the step (5), the stirring reaction time is 12-24 h.
9. Porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material prepared by the preparation method of any one of claims 1 to 8.
10. The use of a porphyrin covalent-bonded molybdenum disulfide nonlinear nano hybrid material as defined in claim 9 in the field of nonlinear optics.
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