CN117779203A - N-benzyl-2-methyl-4-nitroaniline monocrystal and preparation method and application thereof - Google Patents
N-benzyl-2-methyl-4-nitroaniline monocrystal and preparation method and application thereof Download PDFInfo
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- WPJTZCLHFWRBBC-UHFFFAOYSA-N n-benzyl-2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1NCC1=CC=CC=C1 WPJTZCLHFWRBBC-UHFFFAOYSA-N 0.000 title claims abstract description 70
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Abstract
The invention discloses an N-benzyl-2-methyl-4-nitroaniline monocrystal and a preparation method and application thereof, and relates to the technical field of organic crystals. Dispersing N-benzyl-2-methyl-4-nitroaniline polycrystal materials in absolute ethyl alcohol to obtain polycrystal solution; preserving the temperature of the polycrystalline solution at 45-60 ℃ for 12-24 hours to obtain a saturated solution; and (3) placing the saturated solution in a water bath furnace, setting the initial temperature of the water bath furnace to be 55-60 ℃, firstly cooling the solution from 55-60 ℃ to 50-52 ℃ at a cooling rate of 0.2 ℃/h, and then cooling the solution to room temperature at a speed of 0.05-0.1 ℃/h to obtain the N-benzyl-2-methyl-4-nitroaniline monocrystal. The BNA monocrystal is prepared by changing the temperature to regulate the supersaturation degree of the solution and adopting a spontaneous nucleation mode, the requirement of crystal growth equipment is low, the process is simple, the crystal growth interval is large, and seed crystals are not required to be introduced.
Description
Technical Field
The invention relates to the technical field of organic crystals, in particular to an N-benzyl-2-methyl-4-nitroaniline monocrystal and a preparation method and application thereof.
Background
In recent years, application prospects of terahertz (THz) technology in many fields are attracting attention, but the development of THz technology is hindered by the lack of high-performance THz source devices. The organic crystal material has the advantages of large second-order nonlinear coefficient, stable dispersion curve, small absorption coefficient, easy realization of molecular design and the like in the application of the THz radiation source device. The molecular organic crystal BNA (N-benzyl-2-methyl-4-nitroaniline) has higher nonlinear coefficient, is not easy to deliquesce, has higher working stability, solves the problems of low THz wave energy output by the ionic crystal in a low-frequency THz wave band range, uneven spectral line, poor environmental stability and the like, and has wide application prospect. The crystal quality has great influence on the output of THz waves, improves the crystal quality of the crystals, and is beneficial to obtaining THz output spectral lines with higher intensity, wider bandwidth and higher signal-to-noise ratio. At the same time, increasing the crystal size also contributes to the further application of the crystal in THz wave imaging.
The BNA crystal growth method is various and mainly adopts a melt method and a solution method. Since the crystallinity of the organic crystal is poor and the vapor pressure is relatively high, and the melting point of the BNA crystal is low (about 104 ℃), the requirement for crystal growth equipment is high when the BNA single crystal is prepared by a melt method, and the prepared crystal often has lattice defects caused by mechanical stress and thermal stress. Meanwhile, BNA crystals grown by a melt method have the problems of poor crystallization uniformity and quality, need of subsequent directional cutting processing to be applied to THz wave generation and the like. Therefore, the melt method is not suitable for preparing high quality BNA single crystals.
The BNA crystal is prepared by the disclosed solution method, seed crystals are obtained from the BNA ethanol high-temperature solution by cooling, and then the seed crystals are subjected to epitaxial growth of BNA in the low-temperature solution (15-0 ℃). Supersaturation of the solution to grow crystals is achieved by increasing the solute concentration by reducing the solvent mass in the solution by evaporating the solvent at a constant temperature. The solvent evaporation rate is affected by various process factors, such as concentration, temperature, liquid level area, gas flow condition above the solution, and the like, so that quantitative control of the solvent evaporation rate is difficult, namely control of the supersaturation degree change of the solution is difficult to realize, particularly, the solvent evaporation rate is changed drastically in the later stage of crystal growth, the supersaturation degree change of the solution is extremely unstable, and preparation of BNA crystals with high quality and large size is difficult to realize. The supersaturation degree of crystal growth is obtained by reducing the temperature of the solution, but in the process of introducing the seed crystal into the low-temperature solution, on one hand, crystal defects of the seed crystal can be further expanded along with epitaxial growth, on the other hand, accurate temperature reduction at low temperature is realized, higher requirements are also put on crystal growth equipment, and after the crystal growth is completed, a part of the crystal, which is defective due to the fixed seed crystal, needs to be processed and removed. The technology is relatively complex in process, high in equipment requirement, small in size of the prepared BNA crystals and poor in crystal quality due to the existence of more defects. The BNA crystal bicrystal X-ray rocking curve prepared by the solution method is not less than 30arcsec, the crystallization quality is poor, and the crystal size is smaller and is below 10 mm.
Therefore, in order to improve the quality and size of BNA crystals and realize the wider application of the BNA crystals in THz wave technology, it is necessary to develop a process method for preparing BNA crystals with high quality and large size.
Disclosure of Invention
Aiming at the defects in the background technology, the invention mainly solves the problems of low crystallization quality, small crystal size, complex process, high requirement on crystal growth equipment and the like in the existing BNA crystal growth process. The invention provides an N-benzyl-2-methyl-4-nitroaniline monocrystal, a preparation method and application thereof. The method realizes the regulation and control of the supersaturation degree of the solution by changing the temperature, prepares BNA monocrystal by a spontaneous nucleation mode, has low requirement on crystal growth equipment, simple process and large crystal growth interval, and does not need to introduce seed crystals.
The first object of the invention is to provide a preparation method of N-benzyl-2-methyl-4-nitroaniline monocrystal, which comprises the following steps:
dispersing N-benzyl-2-methyl-4-nitroaniline polycrystal materials in absolute ethyl alcohol to obtain polycrystal solution;
preserving the temperature of the polycrystalline solution at 45-60 ℃ for 12-24 hours, and filtering after the heat preservation is finished to obtain a saturated solution;
placing the saturated solution into a water bath furnace, setting the initial temperature of the water bath furnace to be 55-60 ℃, firstly cooling the solution from 55-60 ℃ to 50-52 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to be 0.05-0.1 ℃/h until the temperature is reduced to room temperature, thus obtaining N-benzyl-2-methyl-4-nitroaniline single crystal;
the dosage ratio of the N-benzyl-2-methyl-4-nitroaniline polycrystalline material to the absolute ethyl alcohol is (0.016-0.091) mol (20-50) mL.
Preferably, the dispersing of the N-benzyl-2-methyl-4-nitroaniline polycrystal material in absolute ethyl alcohol is carried out in a closed container, and the temperature is set to 45-60 ℃.
Preferably, the filtering after the heat preservation is finished is performed by combining an organic filter tip with a syringe booster.
Preferably, the N-benzyl-2-methyl-4-nitroaniline polycrystalline material is obtained by purifying the N-benzyl-2-methyl-4-nitroaniline powder raw material for a plurality of times, wherein each purification process comprises: dissolving 0.11-0.63 mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 100-300 mL of absolute ethyl alcohol at 50-70 ℃, completely dissolving the raw material by magnetic stirring, and filtering and drying the raw material; wherein the purity of the N-benzyl-2-methyl-4-nitroaniline powder raw material is more than or equal to 97 percent.
Preferably, the purity of the absolute ethyl alcohol is more than or equal to 99.5 percent.
Preferably, the N-benzyl-2-methyl-4-nitroaniline powder raw material is purified for 3-5 times to obtain N-benzyl-2-methyl-4-nitroaniline polycrystal material.
The second object of the present invention is to provide a single crystal of N-benzyl-2-methyl-4-nitroaniline, characterized in that the single crystal is produced by the above-mentioned method.
Preferably, the crystal size of the single crystal is equal to or larger than 3×3×1 mm 3 The half-peak width value of the bicrystal X-ray rocking curve of the (020) plane is less than or equal to 20 arcsec.
The third object of the invention is to provide an application of N-benzyl-2-methyl-4-nitroaniline monocrystal in a terahertz radiation source device.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an N-benzyl-2-methyl-4-nitroaniline monocrystal and a preparation method and application thereof, wherein the supersaturation degree of a solution is regulated and controlled by changing the temperature, the solution is subjected to stage cooling, and a faster cooling rate is set in the early stage of cooling, so that the solution enters a supersaturation zone as soon as possible to reach a nucleation condition; after the crystal nucleus is obtained, the cooling rate is adjusted to a smaller value, so that the solution enters the growth area, the residence time of the solution in the supersaturation area is further reduced, the nucleation rate is reduced, and the crystal quality deterioration caused by the excessively high growth rate is avoided. Finally, the spontaneous nucleation and further growth of the crystal in the solution are realized, and the crystal defects and the subsequent machining process caused by using seed crystals are avoided. And simultaneously, the temperature range of BNA crystal growth is enlarged, and more solutes are provided for the crystal growth process so as to obtain BNA crystals with larger size. Compared with the prior art, the invention has relatively lower requirement on crystal growth equipment and simpler crystal growth process. Finally, BNA single crystals with higher crystallization quality and larger size are prepared, and the BNA single crystals have excellent THz wave output effect at 1300 and nm.
According to the ultraviolet-visible-near infrared transmission spectrum (figure 4) of the BNA crystal, the BNA has higher transmittance near 1300nm, the BNA crystal is an orthorhombic system, has a non-central symmetry space point group and higher second-order nonlinear coefficient, and THz radiation can be generated through the light rectification effect under 1300nm femtosecond pulse laser pumping.
Drawings
Fig. 1 shows a solubility curve and a supersaturation curve of BNA in an ethanol solution, wherein the lower part of the solubility curve is an undersaturation region for crystal growth, the upper part of the supersaturation curve is a supersaturation region, and a crystal growth region is arranged between the two curves.
Fig. 2 is a schematic diagram of the water bath furnace used in the fourth step.
FIG. 3 is a photograph of a single crystal of BNA provided in examples 1-3 and a photograph of a polycrystalline BNA provided in comparative examples 1-5.
Fig. 4 shows an X-ray diffraction pattern of the BNA single crystal provided in example 1, and a bi-crystal X-ray rocking curve of the BNA single crystal (020) plane provided in examples 1 to 3.
Fig. 5 is an ultraviolet-visible-near infrared transmission spectrum of the BNA single crystal provided in example 1.
Fig. 6 shows THz wave output spectra of BNA single crystals provided in examples 1 to 3 and frequency domain spectra obtained by fourier transforming the time domain spectra.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The invention aims to provide an N-benzyl-2-methyl-4-nitroaniline monocrystal, a preparation method and application thereof, so as to solve the problems of low crystal quality, small crystal size, complex process, high requirement on crystal growth equipment and the like in the existing BNA crystal growth process, prepare the BNA monocrystal with high quality and large size, and realize the output of terahertz waves under the pumping of a femtosecond laser with the center wavelength of 1300nm based on the prepared BNA monocrystal.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an N-benzyl-2-methyl-4-nitroaniline single crystal, comprising the steps of:
dispersing N-benzyl-2-methyl-4-nitroaniline polycrystal materials in absolute ethyl alcohol to obtain polycrystal solution;
preserving the temperature of the polycrystalline solution at 45-60 ℃ for 12-24 hours, and filtering after the heat preservation is finished to obtain a saturated solution;
placing the saturated solution into a water bath furnace, setting the initial temperature of the water bath furnace to be 55-60 ℃, firstly cooling the solution from 55-60 ℃ to 50-52 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to be 0.05-0.1 ℃/h until the temperature is reduced to room temperature, thus obtaining N-benzyl-2-methyl-4-nitroaniline single crystal;
the dosage ratio of the N-benzyl-2-methyl-4-nitroaniline polycrystalline material to the absolute ethyl alcohol is (0.016-0.091) mol (20-50) mL.
Wherein, when the N-benzyl-2-methyl-4-nitroaniline polycrystal material is dispersed in absolute ethyl alcohol, the dispersion is carried out in a closed container, and the temperature is set to be 45-60 ℃.
And the filtering after the heat preservation is finished is performed by combining an organic filter tip with a syringe booster.
According to the invention, the N-benzyl-2-methyl-4-nitroaniline polycrystalline material is obtained by purifying the N-benzyl-2-methyl-4-nitroaniline powder raw material for a plurality of times, wherein each purifying process comprises the following steps: dissolving 0.11-0.63 mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 100-300 mL of absolute ethyl alcohol at 50-70 ℃, completely dissolving the raw material by magnetic stirring, and filtering and drying the raw material; wherein the purity of the N-benzyl-2-methyl-4-nitroaniline powder raw material is more than or equal to 97%; and purifying the N-benzyl-2-methyl-4-nitroaniline powder raw material for 3-5 times to obtain N-benzyl-2-methyl-4-nitroaniline polycrystal material. Specifically, the purity of the absolute ethyl alcohol is more than or equal to 99.5 percent.
In one embodiment, a method for preparing a single crystal of BNA comprises the steps of:
step one: purifying raw materials; completely dissolving 0.11-0.63 mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 100-300 mL of absolute ethyl alcohol at 50-70 ℃, putting magnetons into the absolute ethyl alcohol, stirring magnetically to accelerate the dissolution, cooling the solution to room temperature, filtering out precipitated BNA polycrystal material, and drying the BNA polycrystal material in a vacuum drying oven to remove residual ethyl alcohol; repeating the steps for 3-5 times, and purifying the N-benzyl-2-methyl-4-nitroaniline powder raw material;
step two: preparing a solution; a saturated solution of BNA in absolute ethanol was formulated. And (3) respectively adding the 0.016~0.091 mol BNA polycrystal material obtained in the step (I) and 20-50 mL of absolute ethyl alcohol into a conical flask, putting the conical flask into a magnet, and accelerating dissolution at 45-60 ℃ through magnetic stirring. In order to avoid adverse effect of solvent diffusion to the external environment on crystal growth, the process needs to seal the conical flask by using a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 45-60 ℃ for 12-24 hours to fully dissolve the solute and stabilize the solution, filtering out particles possibly separated out in the heat preservation process by using an organic filter tip after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; referring to fig. 2, the clarified solution obtained in the third step is placed into a water bath furnace, the initial temperature of the water bath furnace is set to 55-60 ℃, the temperature of the solution is firstly reduced to 50-52 ℃ from 55-60 ℃ at a temperature reduction rate of 0.2 ℃/h, then the temperature reduction rate is adjusted to 0.05-0.1 ℃/h until the temperature is reduced to room temperature, the supersaturation degree of the solution is changed along with the gradual reduction of the temperature, the solution enters a supersaturation zone from a growth zone, after a crystal nucleus is formed in the supersaturation zone, the supersaturation degree of the solution is reduced to enter the growth zone, the crystal nucleus grows in the growth zone until the temperature is reduced to room temperature, and the BNA single crystal is obtained.
Referring to fig. 1, according to the solubility curve and supersaturation curve of BNA in ethanol, the supersaturation degree of the solution is regulated and controlled through continuous cooling and control of cooling rate, so that the driving force of crystal nucleation and growth is obtained, and the crystals are further grown in a growth area after spontaneous nucleation in the supersaturation area, and finally the BNA single crystal is obtained.
Referring to fig. 2, the positions of the thermometer and the heating rod in the water bath furnace are in a diagonal relationship, the position of the conical flask in the water bath furnace is as central as possible in the cavity, and the circulating water pump is positioned near the heating rod, so that the temperature around the conical flask is heated uniformly.
Step five: and (5) drying. And (3) taking the crystal in the step four out of the conical flask, sucking the residual solution on the surface of the crystal by using absorbent paper, and transferring the crystal into a vacuum drying oven for drying to obtain the BNA single crystal.
In order to adjust the supersaturation degree change of the solution, the crystal enters a growth zone to further grow after less nucleation in the supersaturation zone as much as possible, different cooling rates are adopted in different growth stages of BNA single crystals, and the cooling rate in each stage is not higher than 0.2 ℃/h.
In a second aspect, the present invention provides a single crystal of N-benzyl-2-methyl-4-nitroaniline, the single crystal being prepared by the method described above. The crystal size of the single crystal is more than or equal to 3 multiplied by 1 mm 3 The half-peak width value of the bicrystal X-ray rocking curve of the (020) plane is less than or equal to 20 arcsec.
In a third aspect, the invention provides the use of a single crystal of N-benzyl-2-methyl-4-nitroaniline in a THz radiation source device.
In the application process, the N-benzyl-2-methyl-4-nitroaniline monocrystal is arranged in a wide spectrum THz time domain spectrum system, a pumping source is a femtosecond laser with the center wavelength of 1300nm, the output power of 200 mW is the (020) plane of the BNA crystal, and the test is carried out under the condition that the ambient humidity is less than 5%, so that the THz wave output spectrum of the BNA monocrystal is obtained.
It should be noted that, the experimental methods adopted in the invention are all conventional methods unless otherwise specified; the reagents and materials employed, unless otherwise specified, are commercially available.
Example 1
The specific process for preparing BNA single crystal in this example is:
step one: purifying raw materials; dissolving 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 300mL of absolute ethyl alcohol at 50 ℃, adding magnetons, accelerating the dissolution through magnetic stirring, filtering out precipitated BNA polycrystal materials after the solution is cooled to room temperature, and drying in a vacuum drying oven to remove residual ethanol; this step was repeated 3 times to purify the N-benzyl-2-methyl-4-nitroaniline powder starting material.
Step two: preparing a solution; adding BNA polycrystal material of 0.072mol and absolute ethyl alcohol of 50mL into a conical flask respectively, putting a magnet, and accelerating dissolution by magnetic stirring at 55 ℃, wherein the conical flask is required to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 55 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 55 ℃, firstly cooling the solution from 55 ℃ to 50 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to 0.05 ℃/h until the temperature is cooled to room temperature. During this process, the BNA single crystal precipitates and grows gradually in the flask.
Step five: drying; and (3) taking the crystal in the step four out of the conical flask, sucking the residual solution on the surface of the crystal by using absorbent paper, and transferring the crystal into a vacuum drying oven to obtain the BNA single crystal.
The BNA crystals prepared in step five had a size of 17X 4X 1.9 mm 3 Referring to fig. 3 (a), the half-width of the bi-crystal X-ray rocking curve of the (020) plane was measured to be 8.10arcsec, referring to fig. 4 (b).
The specific process for preparing BNA single crystal and applying the BNA single crystal to THz radiation source device in the embodiment is as follows:
step six: and (3) installing the BNA single crystal obtained in the step (V) in a broad-spectrum terahertz time-domain spectroscopy system, wherein a pumping source is a femtosecond laser with the center wavelength of 1300 and nm, the output power is 200 and mW, the femtosecond laser is perpendicularly incident to the (020) surface of the BNA crystal, and the test is performed under the condition that the ambient humidity is less than 5%, so that the terahertz wave output spectrum of the BNA single crystal is obtained, and referring to FIG. 6.
Example 2
The specific process for preparing BNA single crystal in this example is:
step one: purifying raw materials; dissolving 0.54mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 300mL of absolute ethyl alcohol at 60 ℃, adding magnetons, accelerating the dissolution through magnetic stirring, filtering out precipitated BNA polycrystal materials after the solution is cooled to room temperature, and drying in a vacuum drying oven to remove residual ethanol; this step was repeated 4 times to purify the N-benzyl-2-methyl-4-nitroaniline powder starting material.
Step two: preparing a solution; 0.043 mol BNA polycrystal material and 30mL absolute ethyl alcohol are respectively added into a conical flask, a magnet is placed into the conical flask, and the dissolution is accelerated by magnetic stirring at 55 ℃, and the conical flask is sealed by using a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 55 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 55 ℃, firstly cooling the solution from 55 ℃ to 50 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to 0.1 ℃/h until the temperature is cooled to room temperature. During this process, the BNA single crystal precipitates and grows gradually in the flask.
Step five: drying; and (3) taking the crystal in the step four out of the conical flask, sucking the residual solution on the surface of the crystal by using absorbent paper, transferring the crystal into a vacuum drying oven, and drying to obtain the BNA single crystal.
The BNA crystals prepared in step five had a size of 8.3X1.5 mm 3 Referring to fig. 3 (b), the half-width of the bicrystal X-ray rocking curve of the (020) plane was measured to be 9.12arcsec, referring to fig. 4 (c).
The specific process for preparing BNA single crystal and applying the BNA single crystal to THz radiation source device in the embodiment is as follows:
step six: and (3) installing the BNA single crystal obtained in the step (V) in a broad spectrum THz time domain spectrum system, wherein the pumping source is a femtosecond laser with the center wavelength of 1300 and nm, the output power is 200 and mW, the femtosecond laser is perpendicularly incident to the (020) plane of the BNA crystal, and the test is performed under the condition that the ambient humidity is less than 5%, so that the THz wave output spectrum of the BNA single crystal is obtained, and referring to FIG. 6.
Example 3
The specific process for preparing BNA single crystal in this example is:
step one: purifying raw materials; dissolving 0.63mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 300mL of absolute ethyl alcohol at 70 ℃, adding magnetons, accelerating the dissolution through magnetic stirring, filtering out precipitated BNA polycrystal materials after the solution is cooled to room temperature, and drying the BNA polycrystal materials in a vacuum drying oven for 24 and h to remove residual ethanol; this step was repeated 5 times to purify the N-benzyl-2-methyl-4-nitroaniline powder starting material.
Step two: preparing a solution; adding 0.055 mol BNA polycrystal material and 30mL absolute ethyl alcohol into a conical flask, putting a magnet, and accelerating dissolution by magnetic stirring at 60 ℃, wherein the conical flask needs to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 60 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 60 ℃, firstly cooling the solution from 60 ℃ to 52 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to 0.1 ℃/h until the temperature is cooled to room temperature. During this process, the BNA single crystal precipitates and grows gradually in the flask.
Step five: drying; and (3) taking the crystal in the step four out of the conical flask, sucking the residual solution on the surface of the crystal by using absorbent paper, and transferring the crystal into a vacuum drying oven for drying to obtain the BNA single crystal.
The BNA crystals prepared in step five had a size of 16X 9.5X2.4 mm 3 Referring to fig. 3 (c), the half-width of the bicrystal X-ray rocking curve of the (020) plane was measured to be 12.17arcsec, referring to fig. 4 (d).
The specific process for preparing BNA single crystal and applying the BNA single crystal to THz radiation source device in the embodiment is as follows:
step six: and (3) installing the BNA single crystal obtained in the step (V) in a broad spectrum THz time domain spectrum system, wherein the pumping source is a femtosecond laser with the center wavelength of 1300 and nm, the output power is 200 and mW, the femtosecond laser is perpendicularly incident to the (020) plane of the BNA crystal, and the test is performed under the condition that the ambient humidity is less than 5%, so that the THz wave output spectrum of the BNA single crystal is obtained, and referring to FIG. 6.
Comparative example 1
The specific process for preparing BNA crystals in this comparative example is as follows:
step one: purifying raw materials; 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material is completely dissolved in 300mL of absolute ethyl alcohol at 50 ℃, magnetons are added to accelerate dissolution through magnetic stirring, the solution is cooled to room temperature, precipitated BNA polycrystal materials are filtered out, and the BNA polycrystal materials are placed in a vacuum drying oven to be dried for 24 and h to remove residual ethanol.
Step two: preparing a solution; adding 0.083 mol BNA polycrystal material and 30mL absolute ethyl alcohol into a conical flask, putting a magnet, and accelerating dissolution by magnetic stirring at 70 ℃, wherein the conical flask needs to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 70 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 70 ℃, and cooling the solution to room temperature at a cooling rate of 0.3 ℃/h. During this process, BNA precipitates and aggregates into a polycrystal in the conical flask, see fig. 3 (d).
The reason why the crystal growth result of the fourth step occurs is that the nucleation rate of the crystal is improved by the higher temperature, and the initial temperature of 70 ℃ is close to the boiling point (about 78 ℃) of the pure solvent of ethanol, and the unstable state of the solution at the temperature also affects the precipitation of the crystal.
Comparative example 2
The specific process for preparing BNA crystals in this comparative example is as follows:
step one: purifying raw materials; 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material is completely dissolved in 300mL of absolute ethyl alcohol at 50 ℃, magnetons are added to accelerate dissolution through magnetic stirring, the solution is cooled to room temperature, precipitated BNA polycrystal materials are filtered out, and the BNA polycrystal materials are placed in a vacuum drying oven to be dried for 24 and h to remove residual ethanol.
Step two: preparing a solution; adding 0.083 mol BNA polycrystal material and 30mL absolute ethyl alcohol into a conical flask, putting a magnet, and accelerating dissolution by magnetic stirring at 70 ℃, wherein the conical flask needs to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 70 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 70 ℃, and cooling the solution to room temperature at a cooling rate of 0.05 ℃/h. During this process, BNA precipitates and aggregates into a polycrystal in the conical flask, see fig. 3 (e).
Similar to comparative example 1, the high temperature increases the nucleation rate of the crystal, and the manner of decreasing the cooling rate does not effectively improve the nucleation rate.
Comparative example 3
The specific process for preparing BNA crystals in this comparative example is as follows:
step one: purifying raw materials; 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material is completely dissolved in 300mL of absolute ethyl alcohol at 50 ℃, magnetons are added to accelerate dissolution through magnetic stirring, the solution is cooled to room temperature, precipitated BNA polycrystal materials are filtered out, and the BNA polycrystal materials are placed in a vacuum drying oven to be dried for 24 and h to remove residual ethanol.
Step two: preparing a solution; adding BNA polycrystal material of 0.020 mol and 30mL absolute ethyl alcohol into a conical flask, putting a magnet, and accelerating dissolution by magnetic stirring at 40 ℃, wherein the conical flask needs to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 40 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 40 ℃, and cooling the solution to room temperature at a cooling rate of 0.05 ℃/h. During this process, the solution remained clear at all times with no crystals present, as shown in fig. 3 (f).
Referring to fig. 1, BNA solutions have a broader growth zone and when saturated solutions cool at a slower rate from 40 c, the solution needs to be cooled to a lower temperature to enter the supersaturation zone to reach nucleation conditions. When the temperature is reduced to room temperature, the solution still does not enter the supersaturation zone, so that nucleation and growth of crystals are not generated.
Comparative example 4
The specific process for preparing BNA crystals in this comparative example is as follows:
step one: purifying raw materials; 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material is completely dissolved in 300mL of absolute ethyl alcohol at 50 ℃, magnetons are added to accelerate dissolution through magnetic stirring, the solution is cooled to room temperature, precipitated BNA polycrystal materials are filtered out, and the BNA polycrystal materials are placed in a vacuum drying oven to be dried for 24 and h to remove residual ethanol.
Step two: preparing a solution; adding BNA polycrystal material of 0.020 mol and 30mL absolute ethyl alcohol into a conical flask, putting a magnet, and accelerating dissolution by magnetic stirring at 40 ℃, wherein the conical flask needs to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 40 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 40 ℃, reducing the temperature to 30.6 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to 0.1 ℃/h until the temperature is reduced to room temperature. During this process, BNA precipitates in the flask, but the crystals adhere, aggregate into polycrystals, see fig. 3 (g).
The reason why the step four crystal growth results is that at a lower temperature, solute transport during crystal growth is insufficient, and the difference in local solute concentration in the solution is obvious, so that more crystal nuclei and adhesion and aggregation of the crystal nuclei occur.
Comparative example 5
The specific process for preparing BNA crystals in this comparative example is as follows:
step one: purifying raw materials; dissolving 0.33mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 300mL of absolute ethyl alcohol at 50 ℃, adding magnetons, accelerating the dissolution through magnetic stirring, filtering out precipitated BNA polycrystal materials after the solution is cooled to room temperature, and drying in a vacuum drying oven to remove residual ethanol; this step was repeated 3 times to purify the N-benzyl-2-methyl-4-nitroaniline powder starting material.
Step two: preparing a solution; adding BNA polycrystal material of 0.072mol and absolute ethyl alcohol of 50mL into a conical flask respectively, putting a magnet, and accelerating dissolution by magnetic stirring at 55 ℃, wherein the conical flask is required to be sealed by a rubber plug, a preservative film, a rubber band and the like.
Step three: preserving heat and filtering; and (3) preserving the temperature of the solution prepared in the second step at 55 ℃ for 24 hours, filtering by using an organic filter tip combined with a syringe booster after the heat preservation process is finished, obtaining a clear saturated solution, and sealing the clear saturated solution in an conical flask.
Step four: growing crystals; and (3) placing the clarified solution obtained in the step (III) into a water bath furnace, setting the initial temperature of the water bath furnace to 55 ℃, and cooling the solution to room temperature at a cooling rate of 0.2 ℃/h. During this process, the BNA single crystal precipitates and grows gradually in the flask.
Step five: drying; the crystals in the fourth step were taken out of the conical flask, and after the residual solution on the surface of the crystals was sucked out using a water-absorbing paper, the crystals were transferred to a vacuum drying oven to obtain BNA crystals, see FIG. 3 (h).
The BNA crystals prepared in the comparative example have obvious macroscopic defects, poor crystal permeability and incomplete shape, which indicates that the crystal quality is low. This is because the crystal quality is greatly affected by the crystal growth rate, and when BNA crystals are grown by the solution method, the excessively fast cooling rate accelerates the crystal growth rate, greatly reducing the crystal quality.
In order to illustrate the relevant properties of the BNA single crystal provided by the invention, the invention is described with reference to the accompanying drawings.
FIG. 1 is a graph showing the solubility curve and supersaturation curve of BNA in ethanol, wherein the solubility curve is below the undersaturation region of crystal growth, and the solution state is very stable in the undersaturation region without nucleation and growth of crystals; the supersaturation zone is above the supersaturation curve, where crystal nucleation occurs; the growth area of the crystal is arranged between the two curves, and if crystal nucleus or seed crystal exists in the solution, the crystal can further grow. In the preparation of BNA crystals, it is first necessary to bring the solution state into the supersaturation zone to form nuclei. In order to reduce the nucleation rate and avoid the occurrence of conditions unfavorable for single crystal growth such as polycrystal aggregation, the solution should rapidly enter the growth area after forming crystal nuclei in the supersaturation area so as to realize the growth of the crystal nuclei. In addition, proper cooling interval and cooling rate should be selected, the nucleation rate of the crystal is improved by a higher initial temperature, which is unfavorable for single crystal preparation, and the initial temperature should not be close to the boiling point of the solvent, and the initial temperature should not be too low to ensure that the solute is sufficiently transported. The excessively fast cooling rate can reduce the crystallization quality of crystals, even cause crystal aggregation and adhesion to form polycrystal, and the cooling rate should not be excessively slow in order to make the solution reach the nucleation condition as soon as possible.
Fig. 2 is a schematic diagram of the water bath furnace used in the fourth step. Wherein, fig. 2 comprises a thermometer 1, a conical flask 2, a circulating water pump 3, a heating rod 4 and a temperature control module 5; charging a large amount of water into the furnace chamber as a heat transfer medium; heating water in the furnace chamber through the heating rod to enable the furnace chamber to reach a target temperature; the heating rod and the thermometer are connected to a temperature control module, and the target temperature and the cooling rate are set through the temperature control module, and the water bath temperature is fed back in real time; the water in the furnace chamber is kept in a flowing state to a certain extent by the circulating water pump so as to ensure the uniformity of a temperature field.
FIG. 3 is a photograph of a single crystal of BNA provided in examples 1-3, and a photograph of a crystal of BNA provided in comparative examples 1-5; wherein (a), (b) and (c) in fig. 3 are BNA single crystals prepared in example 1, example 2 and example 3, respectively; in FIG. 3, (d), (e), (f), (g) and (h) are photographs of BNA prepared in comparative examples 1, 2, 3, 4 and 5, respectively. In order to illustrate the beneficial effects of the process parameters for preparing BNA single crystals, the invention also compares other process parameters, the starting temperature and the cooling rate are set to other process parameters in comparative examples 1-5, and the crystal growth results are shown in (d) - (h) of fig. 3. Compared with BNA single crystals with complete morphology, good light transmittance and large size shown in (a), (b) and (c) in fig. 3, the nucleation rate of crystals is high, crystals are aggregated and adhered in (d), (e) and (g) in fig. 3, and finally polycrystal is formed, no crystals are precipitated in (f) in fig. 3, macroscopic defects of crystals are obvious in (h) in fig. 3, the crystal permeability is poor and the shape is incomplete.
FIG. 4 is an X-ray diffraction pattern of the BNA single crystal provided in example 1, and a (020) plane bicrystal X-ray rocking curve of the BNA single crystal provided in examples 1 to 3; in fig. 4 (a), the powder X-ray diffraction pattern of the BNA single crystal provided in example 1 shows that the diffraction peaks are identical to those of the simulation calculation X-ray diffraction pattern of the orthorhombic BNA crystal structure, indicating that the produced orthorhombic BNA single crystal. FIGS. 4 (b), (c) and (d) are bicrystal X-ray rocking curves of the (020) plane of the BNA single crystal provided in example 1, example 2 and example 3, respectively; wherein, the narrower the half height peak width of the bicrystal X-ray rocking curve is, the better the crystallization quality of the crystal is.
FIG. 5 is an ultraviolet-visible-near infrared transmission spectrum of the BNA single crystal provided in example 1; as is clear from fig. 5, the transmittance of the BNA single crystal at 1300 and nm is 79%.
FIG. 6 is a frequency domain spectrum obtained by performing Fourier transform on the THz wave output spectrum of BNA single crystal provided in examples 1-3; in fig. 6, (a) shows a time domain spectrum of THz wave generated by the measured BNA single crystal under 1300nm femtosecond pulse laser pumping, and (b) shows a frequency domain spectrum obtained by fourier transforming the time domain spectrum. As can be seen from the graph (b) in FIG. 6, the BNA single crystal prepared by the invention can generate THz wave output of 0.1-5.0 THz frequency band under 1300nm femtosecond pulse laser pumping.
In summary, the embodiment of the invention provides a preparation process of organic single crystal BNA and application of the organic single crystal BNA in a terahertz radiation source device. The invention adopts a solution method, realizes the regulation and control of the supersaturation degree of the solution by changing the temperature, and prepares BNA crystals by a spontaneous nucleation mode. Compared with the prior art, the method has the advantages that the requirement on crystal growth equipment is low, the process is simple, the crystal growth interval is large, seed crystals are not required to be introduced, and the prepared large-size BNA crystal has a lower half-peak width value and THz wave output performance under 1300nm femtosecond laser pumping, so that the further application of the BNA single crystal in the terahertz technology is facilitated.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the N-benzyl-2-methyl-4-nitroaniline monocrystal is characterized by comprising the following steps of:
dispersing N-benzyl-2-methyl-4-nitroaniline polycrystal materials in absolute ethyl alcohol to obtain polycrystal solution;
preserving the temperature of the polycrystalline solution at 45-60 ℃ for 12-24 hours, and filtering after the heat preservation is finished to obtain a saturated solution;
placing the saturated solution into a water bath furnace, setting the initial temperature of the water bath furnace to be 55-60 ℃, firstly cooling the solution from 55-60 ℃ to 50-52 ℃ at a cooling rate of 0.2 ℃/h, and then adjusting the cooling rate to be 0.05-0.1 ℃/h until the temperature is reduced to room temperature, thus obtaining N-benzyl-2-methyl-4-nitroaniline single crystal;
the dosage ratio of the N-benzyl-2-methyl-4-nitroaniline polycrystalline material to the absolute ethyl alcohol is (0.016-0.091) mol (20-50) mL.
2. The method for producing an N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 1, wherein the process of dispersing the N-benzyl-2-methyl-4-nitroaniline polycrystal material in absolute ethanol is performed in a closed container, and the temperature is set to 45-60 ℃.
3. The method for producing an N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 1, wherein the filtering after the end of the heat preservation is performed by combining an organic filter with a syringe booster.
4. The method for preparing an N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 1, wherein the N-benzyl-2-methyl-4-nitroaniline polycrystal material is obtained by purifying an N-benzyl-2-methyl-4-nitroaniline powder raw material a plurality of times, wherein each purification process comprises: dissolving 0.11-0.63 mol of N-benzyl-2-methyl-4-nitroaniline powder raw material in 100-300 mL of absolute ethyl alcohol at 50-70 ℃, completely dissolving the raw material by magnetic stirring, and filtering and drying the raw material; wherein the purity of the N-benzyl-2-methyl-4-nitroaniline powder raw material is more than or equal to 97 percent.
5. The method for producing an N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 4, wherein the purity of the absolute ethyl alcohol is not less than 99.5%.
6. The method for preparing an N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 5, wherein the N-benzyl-2-methyl-4-nitroaniline powder raw material is purified 3-5 times to obtain an N-benzyl-2-methyl-4-nitroaniline polycrystal material.
7. An N-benzyl-2-methyl-4-nitroaniline single crystal, characterized in that the single crystal is produced by the method of any one of claims 1 to 6.
8. The N-benzyl-2-methyl-4-nitroaniline single crystal according to claim 7, wherein the crystal size of the single crystal is equal to or larger than 3X 1 mm 3 Bicrystal X-ray of (020) faceThe half-peak width value of the rocking curve is less than or equal to 20 arcsec.
9. Use of an N-benzyl-2-methyl-4-nitroaniline single crystal of claim 7 in a terahertz radiation source device.
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