CN113773232B - Compound dihydroxy-difluoro-guanidine triborate, dihydroxy-difluoro-guanidine triborate nonlinear optical crystal, preparation method and application - Google Patents

Compound dihydroxy-difluoro-guanidine triborate, dihydroxy-difluoro-guanidine triborate nonlinear optical crystal, preparation method and application Download PDF

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CN113773232B
CN113773232B CN202111067525.3A CN202111067525A CN113773232B CN 113773232 B CN113773232 B CN 113773232B CN 202111067525 A CN202111067525 A CN 202111067525A CN 113773232 B CN113773232 B CN 113773232B
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潘世烈
金聪聪
米日丁·穆太力普
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a compound dihydroxy-difluoro-guanidine triborate, a preparation method and application thereof, wherein the chemical formula of the compound is [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The molecular weight is 212.53, and the preparation method adopts an evaporation method, a hydrothermal method or a room-temperature solution method; the chemical formula of the crystal is [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Molecular weight of 212.53, crystal belongs to triclinic system, space groupP1, unit cell parameters a =4.8288 (7), b =6.8455 (10) A, c =7.3212 (11) A,α=114.308(5)，β=90.258(5)，γ=102.865(5)，Z=1，V=213.75(6)Å 3 . [ C (NH) obtained by the method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal has the advantages of wider light-transmitting wave band, stable physical and chemical properties, moderate mechanical hardness, difficult fragmentation, easy cutting, polishing processing and storage and the like.

Description

Compound dihydroxy-difluoro-guanidine triborate, dihydroxy-difluoro-guanidine triborate nonlinear optical crystal, preparation method and application
Technical Field
The invention relates to a compound dihydroxy difluoro guanidine tribasic and a dihydroxy difluoro guanidine tribasic nonlinear optical crystal, a preparation method and application thereof.
Background
The development of all-solid-state deep ultraviolet laser light sources along with the strong demand of 193nm lithography, micro-nano fine laser processing, ultra-high energy resolution photoelectron spectrometers, photoelectron emission microscopes and other modern instruments on deep ultraviolet laser sources (generally, the wavelength is shorter than 200 nm) has become a hot spot of recent research in the international laser science community. The development of all-solid-state deep ultraviolet laser light sources, and the deep ultraviolet nonlinear optical crystal is a very critical element.
The ultraviolet and deep ultraviolet nonlinear optical crystal applied in the industry at present mainly comprises LiB 3 O 5 (LBO)、CsB 3 O 5 (CBO)、CsLiB 6 O 10 (CLBO)、BaB 2 O 4 (BBO) and KBe 2 BO 3 F 2 (KBBF) crystal. The LBO crystal has wide light transmission range, high optical uniformity, large effective frequency doubling coefficient (3 KDP) and high damage threshold (18.9 GW/cm) 2 ). But due to its relatively small birefringence (Δ n = 0.04-0.05), it cannot achieve phase matching in the deep ultraviolet region, the shortest doubling wavelength being 276nm. Like LBO crystals, CBO and CLBO crystals are limited in application in the deep ultraviolet region due to their relatively small birefringence. Although the BBO crystal has larger frequency multiplication coefficient and birefringence, the BBO crystal has the shortest frequency multiplication wavelength of 204.8nm due to the relatively higher ultraviolet absorption cut-off edge (189 nm), thereby limiting the application of the BBO crystal in the deep ultraviolet region. KBBF can realize direct six-frequency-multiplication output of 1064nm fundamental frequency light, but because KBBF has a layered growth habit, large-size crystal growth difficulty is high, and the application of KBBF is limited to a certain extent. Therefore, the development of a novel deep ultraviolet nonlinear optical crystal with excellent comprehensive performance is urgently needed.
Disclosure of Invention
The invention aims to provide a compound dihydroxy difluoro guanidine triboronate, wherein the chemical formula of the compound is [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The molecular weight is 212.53, and the preparation method adopts an evaporation method, a hydrothermal method or a room-temperature solution method.
Another object of the present invention is to provide dihydroxydifluorotriguanidinium [ C (NH) borate 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal having a chemical formula of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Molecular weight of 212The crystal belongs to the triclinic system, space group P1, and the unit cell parameter is
Figure BDA0003259086410000011
α＝114.308(5)，β＝90.258(5)，γ＝102.865(5)，Z＝1，
Figure BDA0003259086410000012
The invention also aims to provide a preparation method of the dihydroxyl difluorinated guanidine triborate nonlinear optical crystal, which adopts an evaporation method, a hydrothermal method or a room-temperature solution method to grow the crystal.
It is a further object of the present invention to provide dihydroxydifluorotriguanidinium [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Use of a nonlinear optical crystal.
The compound dihydroxy difluoro guanidine triboronate has the chemical formula of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The molecular weight is 212.53, and the preparation method adopts an evaporation method, a hydrothermal method or a room-temperature solution method.
The preparation method of the compound dihydroxy-difluoro guanidine triborate adopts an evaporation method, a hydrothermal method or a room-temperature solution method to prepare: the evaporation method is used for preparing the compound dihydroxy-difluoro-guanidine triborate, and the specific operation is carried out according to the following steps:
a. will contain [ C (NH) 2 ) 3 ]The compound of group, the compound containing B and the compound containing F according to the molar ratio [ C (NH) 2 ) 3 ]B to F = 0.5-2: 1.5-6: 0.5-2, adding 0-50mL deionized water to fully mix and dissolve to obtain a mixed solution containing [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 50-300mL, and heating at the speed of 10-30 ℃/h until the temperature is raisedStanding at 40-60 deg.C for 2-5 days, quickly washing the product with deionized water after the solvent is volatilized, and air drying at room temperature to obtain compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]；
The preparation method of the compound dihydroxy-difluoro-guanidine triborate by the hydrothermal method comprises the following specific steps:
a. will contain [ C (NH) 2 ) 3 ]The compound of group, the compound containing B and the compound containing F according to the molar ratio [ C (NH) 2 ) 3 ]B and F = 0.5-2: 1.5-6: 0.5-2, adding 0-50mL deionized water to fully mix and dissolve to obtain a mixed solution containing [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 23-100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 150-220 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 1-3 days, and cooling to room temperature at the cooling speed of 1-10 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]；
The room-temperature solution method for preparing the compound dihydroxy-difluoro-guanidine triborate comprises the following specific operations:
a. will contain [ C (NH) 2 ) 3 ]The compound of group, the compound containing B and the compound containing F according to the molar ratio [ C (NH) 2 ) 3 ]B and F = 0.5-2: 1.5-6: 0.5-2, adding 0-50mL deionized water to fully mix and dissolve to obtain a mixed solution containing [ C (NH) 2 ) 3 ]The radical compound being difluoroGuanidine hydride, guanidine carbonate, guanidine chloride or guanidine nitrate, wherein the compound B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 50-300mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
A dihydroxyl difluorinated guanidine triborate nonlinear optical crystal has a chemical formula of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Molecular weight of 212.53, crystal belongs to triclinic system, space group P1, and unit cell parameter is
Figure BDA0003259086410000021
Figure BDA0003259086410000022
α＝114.308(5)，β＝90.258(5)，γ＝102.865(5)，Z＝1，
Figure BDA0003259086410000023
Figure BDA0003259086410000024
The preparation method of the dihydroxyl guanidine difluoride nonlinear optical crystal adopts an evaporation method, a hydrothermal method or a room-temperature solution method to grow the crystal:
the evaporation method is used for growing the dihydroxy-difluorinated guanidine triborate nonlinear optical crystal, and the specific operation is carried out according to the following steps:
a. will contain [ C (NH) 2 ) 3 ]Compound of group, compound containing B, compound containing FAdding the mixture into a polytetrafluoroethylene beaker with the volume of 300mL, uniformly mixing, adding 5-20mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst containing [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to enable the mixed solution to be fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. b, placing the mixed solution in the step b in a resistance furnace, heating to 45-50 ℃ at the speed of 10 ℃/h, standing at the constant temperature for 15 days, volatilizing the solvent, and obtaining the dihydroxy-difluorinated guanidine triboronate nonlinear optical crystal after the crystal growth is finished;
the method for growing the dihydroxy-difluoro guanidine triborate nonlinear optical crystal by the hydrothermal method comprises the following specific steps:
a. will contain [ C (NH) 2 ) 3 ]Adding the group compound, the compound containing B and the compound containing F into a polytetrafluoroethylene beaker with the volume of 100mL, uniformly mixing, adding 1-2mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst contains [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 23-100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 150-220 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 2-5 days, and cooling to room temperature at the cooling speed of 1-3 ℃/h;
d. opening the high-pressure reaction kettle, and obtaining a dihydroxy-difluorinated guanidine triborate nonlinear optical crystal in a colorless clear solution;
the room temperature solution method for growing the dihydroxy-difluorinated guanidine triborate nonlinear optical crystal comprises the following specific steps:
a. will contain [ C (NH) 2 ) 3 ]Adding a group compound, a compound containing B and a compound containing F into a polytetrafluoroethylene beaker with the volume of 100mL, uniformly mixing, adding 5mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst contains [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. and (b) performing ultrasonic treatment on the mixed solution in the step a to fully mix and dissolve the mixed solution, filtering the mixed solution by using qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, placing the clear solution in a static environment without shaking, pollution or air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, then precipitating crystals in the solution and gradually growing the crystals, and obtaining the centimeter-sized dihydroxy-difluoro-guanidine triboronate nonlinear optical crystal after the growth is finished.
The application of the dihydroxy-difluoro-guanidine triborate nonlinear optical crystal in preparing multiband frequency doubling devices or optical elements.
The dihydroxyl guanidine difluoride nonlinear optical crystal is used for 2-frequency or 3-frequency or 4-frequency or 5-frequency harmonic light output of 1064nm fundamental frequency light output by a Nd-YAG laser.
Use of the dihydroxydifluoroguanidine triborate nonlinear optical crystal in the preparation of a compound that produces a deep ultraviolet multiplied light output of less than 200 nm.
The application of the dihydroxy-difluoro-guanidine triborate nonlinear optical crystal in preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The compound dihydroxy-difluoro-guanidine triboronate, the dihydroxy-difluoro-guanidine triboronate nonlinear optical crystal and the preparation method and the application thereof are disclosed, wherein in the method, a container is a polytetrafluoroethylene beaker, and the lining is a polytetrafluoroethylene lining or a stainless steel lined hydrothermal kettle provided with a platinum sleeve. Before using the container, the container is cleaned with acid, rinsed with deionized water and dried.
The resistance furnace is a muffle furnace or a drying box.
The preparation method of the dihydroxyl difluorinated guanidine triborate nonlinear optical crystal obtains the [ C (NH) with the size of centimeter level 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal has no obvious lamellar growth habit, uses a large-size container, and prolongs the growth period of the crystal, so that the nonlinear optical crystal [ C (NH) with corresponding large size can be obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]In the [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is easy to grow, transparent and free of package in the growth of the nonlinear optical crystal, and has the advantages of high growth speed, low cost, easy obtainment of large-size crystals and the like.
Large size [ C (NH) ] obtainable by the process according to the invention 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal is prepared by orienting a crystal blank according to crystallographic data of the crystal, cutting the crystal according to required angle, thickness and cross-sectional dimension, and polishing the light-passing surface of the crystal, wherein the [ C (NH) can be used as a nonlinear optical device 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal has the advantages of wider light-transmitting wave band, stable physical and chemical properties, moderate mechanical hardness, difficult fragmentation, easy cutting, polishing processing and storage and the like.
Drawings
FIG. 1 shows a compound of the present invention [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The powder XRD spectrum of the compound is consistent with the theoretical XRD spectrum, and the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Presence of (a);
FIG. 2 shows [ C (NH) of the present invention 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A structural drawing of the crystal;
FIG. 3 shows [ C (NH) according to the present invention 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Crystal, 4 is emergent light beam, and 5 is filter.
Detailed Description
Example 1
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, synthesizing compound [ C (NH) by evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]HF 2 、H 3 BO 3 Uniformly mixing according to the molar ratio of 1: 3 to obtain a mixture;
b. b, transferring the mixture obtained in the step a into a polytetrafluoroethylene beaker with the volume of 50mL, heating to 40 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 2
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Synthesis of Compound [ C (NH) by Evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 10mL of deionized water to fully mix and dissolve to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 100mL, heating to 50 ℃ at the speed of 20 ℃/h, keeping the temperature for 3 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 3
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 The compound [ C (NH) ] is synthesized by evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 15mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 150mL, heating to 45 ℃ at the speed of 15 ℃/h, standing for 4 days at constant temperature, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 4
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 × (C) and (NH) are synthesized by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 30mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 200mL, heating to 60 ℃ at the speed of 30 ℃/h, keeping the temperature for 5 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 5
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, synthesizing compound [ C (NH) by evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing the components according to the mol ratio of 1: 3, adding 5mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 50mL, heating to 40 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 6
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 The compound [ C (NH) ] is synthesized by evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 15mL of deionized water to fully mix and dissolve the mixture to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 80mL, heating to 50 ℃ at the speed of 25 ℃/h, standing for 3 days at constant temperature, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 7
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Synthesis of Compound [ C (NH) by Evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 30mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 100mL, heating to 55 ℃ at the speed of 25 ℃/h, keeping the temperature for 4 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 8
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 ↓ [ C (NH) synthesized by evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 40mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 200mL, heating to 60 ℃ at the speed of 30 ℃/h, keeping the temperature for 5 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after the solvent is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 9
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, and synthesizing a compound [ C (NH) by an evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 50mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 300mL, heating to 40 ℃ at the speed of 30 ℃/h, standing for 2 days at constant temperature, and quickly cleaning the polytetrafluoroethylene with deionized water after water is volatilizedDrying the product in the ethylene lining at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 10
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, and synthesizing the compound [ C (NH) by an evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 45mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 150mL, heating to 45 ℃ at the speed of 28 ℃/h, keeping the temperature for 3 days, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 11
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, and synthesizing a compound [ C (NH) by an evaporation method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 10mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. transferring the mixed solution in the step a into a bodyHeating to 60 ℃ at the speed of 10 ℃/h in a polytetrafluoroethylene beaker with the volume of 50mL, standing for 5 days at constant temperature, quickly cleaning a product in a polytetrafluoroethylene lining by deionized water after water is volatilized, and airing at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 12
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, synthesizing compound [ C (NH) ] by adopting a hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]HF 2 、H 3 BO 3 Uniformly mixing the components according to the molar ratio of 1: 3 to obtain a mixture,
b. b, transferring the mixture obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 23mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 150 ℃ at the speed of 10 ℃/h, keeping the temperature for 1 day, and then cooling to room temperature at the speed of 1 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 13
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Synthesizing compound [ C (NH) ] by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 1mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 28mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 170 ℃ at a speed of 15 ℃/h, keeping the temperature for 2 days, and cooling to room temperature at a cooling speed of 5 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 14
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 Synthesis of compound [ C (NH) ] by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 5mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 50mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 200 ℃ at the speed of 20 ℃/h, keeping the temperature for 3 days, and then cooling to room temperature at the cooling speed of 6 ℃/h;
d. opening the hydrothermal reaction kettle, and rapidly cleaning the poly-tetra-ethyl acetate with deionized waterDrying the product in the vinyl fluoride lining at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 15
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 × [ C (NH) synthesized by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 20mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 80mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 25 ℃/h, keeping the temperature for 1 day, and then cooling to room temperature at the speed of 9 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 16
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, and synthesizing a compound [ C (NH) by adopting a hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 30mL of deionized water to fully mix and dissolve the mixture to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 200 ℃ at the speed of 30 ℃/h, keeping the temperature for 3 days, and then cooling to room temperature at the cooling speed of 8 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 17
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, and synthesizing compound [ C (NH) by adopting a hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 35mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 60mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 165 ℃ at the speed of 18 ℃/h, keeping the temperature for 1 day, and then cooling to room temperature at the speed of 2 ℃/h;
d. opening the hydrothermal reaction kettle, quickly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperatureTo obtain a compound [ C (NH) ] 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]；
Example 18
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, and synthesizing a compound [ C (NH) ] by adopting a hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 50mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 50mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 220 ℃ at the speed of 20 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 7 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 19
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, synthesizing compound [ C (NH) by a hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
Said [ C (NH) 2 ) 3 ]HF 2 The solvent can be evaporated by reacting guanidine carbonate with excessive hydrofluoric acidAnd (4) preparation.
a. Will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing the components according to the mol ratio of 1: 3, and adding 8mL of deionized water to fully mix and dissolve the components to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 40mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 155 ℃ at the speed of 12 ℃/h, keeping the temperature for 3 days, and cooling to room temperature at the cooling speed of 10 ℃/h;
d. opening the hydrothermal reaction kettle, rapidly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 20
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 Synthesizing compound [ C (NH) ] by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 12mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 23mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 160 ℃ at a speed of 25 ℃/h, keeping the temperature for 2 days, and cooling to room temperature at a cooling speed of 3 ℃/h;
d. opening the hydrothermal reaction kettle, quickly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperatureTo obtain a compound [ C (NH) ] 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 21
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Synthesizing compound [ C (NH) ] by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 45mL of deionized water to fully mix and dissolve the mixture to obtain mixed solution,
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 60mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 175 ℃ at a speed of 28 ℃/h, keeping the temperature for 3 days, and cooling to room temperature at a cooling speed of 10 ℃/h;
d. opening the hydrothermal reaction kettle, quickly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 22
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 × [ C (NH) synthesized by hydrothermal method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 50mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the hydrothermal reaction kettle in the step b in a constant temperature box, heating to 220 ℃ at the speed of 30 ℃/h, keeping the temperature for 1 day, and cooling to room temperature at the cooling speed of 4 ℃/h;
d. opening the hydrothermal reaction kettle, quickly cleaning the product in the polytetrafluoroethylene lining by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]；
Example 23
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, adopting a room temperature solution method to synthesize a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]HF 2 、H 3 BO 3 Uniformly mixing according to the molar ratio of 1: 3 to obtain a mixture;
b. b, transferring the mixture obtained in the step a into a polytetrafluoroethylene beaker with the volume of 50mL, carrying out ultrasonic treatment to fully mix and dissolve the mixture, sealing the mixture by using a polyvinyl chloride film, placing the sealed mixture in a static environment without shaking, pollution and air convection, standing the sealed mixture at room temperature, gradually precipitating crystals in the solution, quickly cleaning the product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 24
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Synthesizing compound [ C (NH) by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 5mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 100mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the mouth with a polyvinyl chloride film, placing the sealed mouth in a static environment without shaking, pollution and air convection, standing at room temperature, gradually precipitating crystals in the solution, quickly cleaning the product in the polytetrafluoroethylene beaker with deionized water after the reaction is finished, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 25
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 Synthesizing compound [ C (NH) by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 10mL of deionized water to fully mix and dissolve to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 150mL, and performing ultrasonic treatmentFully mixing and dissolving the raw materials, sealing the mixture by using a polyvinyl chloride film, placing the mixture in a static environment without shaking, pollution and air convection, standing the mixture at room temperature, gradually precipitating crystals in the solution, quickly cleaning the product in a polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain the compound [ C (NH) C 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 26
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 ↓ [ C (NH) synthesized by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 15mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 200mL, performing ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the sealed polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the sealed polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 27
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, adopting a room temperature solution method to synthesize a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
Said [ C (NH) 2 ) 3 ]HF 2 Can be prepared by evaporating the solvent by reacting guanidine carbonate with an excess of hydrofluoric acid.
a. Will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing the components according to the mol ratio of 1: 3, adding 20mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 200mL, performing ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the sealed polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the sealed polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 28
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 Synthesizing compound [ C (NH) by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing according to the mol ratio of 1: 3: 1, adding 30mL of deionized water to fully mix and dissolve the mixture to obtain mixed solution,
b. transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 250mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the mouth with a polyvinyl chloride film, placing the mouth in a static environment without shaking, pollution and air convection, standing at room temperature, and then standing the solutionGradually precipitating crystals, after the reaction is finished, rapidly cleaning the product in a polytetrafluoroethylene beaker by deionized water, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 29
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Synthesizing compound [ C (NH) by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 40mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 300mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 30
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 ↓ [ C (NH) synthesized by room temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a、Will [ C (NH) 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 6: 4, adding 50mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 300mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 31
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, and synthesizing the compound [ C (NH) by a room-temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 12mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 60mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the mouth with a polyvinyl chloride film, placing the sealed mouth in a static environment without shaking, pollution and air convection, standing at room temperature, gradually precipitating crystals in the solution, quickly cleaning the product in the polytetrafluoroethylene beaker with deionized water after the reaction is finished, and airing at room temperature to obtain the compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 32
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, and synthesizing a compound [ C (NH) by a room-temperature solution method 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will be [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 18mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 180mL, carrying out ultrasonic treatment to fully mix and dissolve the mixed solution, sealing the polytetrafluoroethylene beaker by using a polyvinyl chloride film, placing the polytetrafluoroethylene beaker in a static environment without shaking, pollution and air convection, standing the polytetrafluoroethylene beaker at room temperature, gradually precipitating crystals in the solution, quickly cleaning a product in the polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 33
Preparation of the compound:
according to the reaction formula: [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, and adopting a room-temperature solution method to synthesize a compound [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]：
a. Will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the components according to the mol ratio of 1: 3: 1, adding 28mL of deionized water to fully mix and dissolve the components to obtain mixed solution,
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene beaker with the volume of 22mL, and performing ultrasonic treatmentFully mixing and dissolving the raw materials, sealing the mixture by using a polyvinyl chloride film, placing the mixture in a static environment without shaking, pollution and air convection, standing the mixture at room temperature, gradually precipitating crystals in the solution, quickly cleaning the product in a polytetrafluoroethylene beaker by using deionized water after the reaction is finished, and airing the product at room temperature to obtain the compound [ C (NH) C 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]。
Example 34
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, will [ C (NH) 2 ) 3 ]HF 2 And H 3 BO 3 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3, adding 10mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with the size of phi 6mm multiplied by 5mm multiplied by 3mm after the crystal growth is finished 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 35
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 50 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows, and after the crystal growth is finished, the [ C (NH) with the size of phi 1.8mm multiplied by 1.1mm multiplied by 0.8mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 36
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 50 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of 1.3mm × 1.2mm × 0.7mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 37
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 × [ C (NH) ×, [ C [ (. Sup. 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 6: 4, adding 8mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with the size of phi 0.9mm × 0.6mm × 0.3mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 38
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3, adding 20mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of 1.8mm × 1.4mm × 0.5mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 39
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 15mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of phi 2mm × 1.4mm × 0.3mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 40
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 8mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of 1.5mm × 1.3mm × 0.4mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
EXAMPLE 41
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 ↓ [ C (NH) 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 In mole ratioUniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the ratio of 1: 6: 4, adding 15mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of 1mm × 1mm × 0.6mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 42
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 10mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of phi 2mm × 1.5mm × 0.7mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 43
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, and [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows, and after the crystal growth is finished, the [ C (NH) with the size of phi 2.1mm multiplied by 1.3mm multiplied by 0.6mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 44
Growth of [ C (NH) by evaporation 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 300mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. placing the mixed solution in the step b into a resistance furnace, heating to 45 ℃ at the speed of 10 ℃/h, keeping the temperature for 15 days, standing, volatilizing the solvent, [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Separating out crystal and gradually growing up to obtain [ C (NH) with size of 1.7mm × 1.6mm × 1.1mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 45
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, will [ C (NH) 2 ) 3 ]HF 2 And H 3 BO 3 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3, adding 1mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened and [ C (NH) of 12 mm. Times.11 mm. Times.6 mm was obtained in solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 46
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemistryThe reaction equation is shown in the specification [ C (NH) 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened and [ C (NH) of phi 3.1 mm. Times.2.4 mm. Times.1 mm was obtained in the solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 47
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) having a particle size of 1.8 mm. Times.1.5 mm. Times.0.4 mm was obtained in the solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 48
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 ↓ [ C (NH) 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 6: 4, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened to obtain [ C (NH) of 0.8 mm. Times.0.7 mm. Times.0.2 mm in solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 49
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) (2 mm. Times.1.4 mm. Times.1.1 mm) was obtained from the solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 50
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, and [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) of 0.7 mm. Times.0.4 mm in solution was obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 51
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) of phi 0.9 mm. Times.0.4 mm. Times.0.3 mm was obtained in the solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 52
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. c, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) (1.3 mm. Times.1.1 mm. Times.1 mm) was obtained in solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 53
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened, and [ C (NH) of 1.1 mm. Times.1 mm. Times.0.7 mm in solution was obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 54
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemistryThe reaction equation is shown in the specification [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened to obtain [ C (NH) of 0.5 mm. Times.0.3 mm in solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 55
Hydrothermal growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 × [ C (NH) ×, [ C [ (. Sup. 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 6: 4, adding 2mL of water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 100mL, and screwing and sealing the opening of the hydrothermal reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 190 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, and then cooling to room temperature at the cooling speed of 1 ℃/h;
d. the autoclave was opened to obtain [ C (NH) of 0.3 mm. Times.0.3 mm. Times.0.2 mm in solution 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 56
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3H 3 BO 3 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O, will [ C (NH) 2 ) 3 ]HF 2 And H 3 BO 3 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 9mm multiplied by 8mm multiplied by 4mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 57
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 2.1mm multiplied by 1.4mm multiplied by 1.1mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 58
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、H 3 BO 3 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, treating the mixed solution in the step a by ultrasonic waves to fully mix and dissolve the mixed solution, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by a polyvinyl chloride film, placing the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of the solvent in the solution, and standing the solution at room temperature to obtain [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 1.6mm multiplied by 1.5mm multiplied by 1.2mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 59
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ] 2 CO 3 +6H 3 BO 3 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+9H 2 O+4NH 4 F+CO 2 × [ C (NH) ×, [ C [ (. Sup. 2 ) 3 ] 2 CO 3 、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 6: 4, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 1.3mm multiplied by 0.8mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 60
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]HF 2 +3HBO 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O, will [ C (NH) 2 ) 3 ]HF 2 、HBO 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 1mm multiplied by 0.7mm multiplied by 0.5mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 61
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]NO 3 +3HBO 2 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+RbNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Crystals precipitate and grow graduallyLarge, when the growth is finished, [ C (NH) with the size of phi 1.7mm multiplied by 1.4mm multiplied by 0.4mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 62
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ]NO 3 +3HBO 2 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+H 2 O+CsNO 3 Is prepared from [ C (NH) 2 ) 3 ]NO 3 、HBO 2 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 2mm multiplied by 1.4mm multiplied by 0.7mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 63
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation [ C (NH) 2 ) 3 ] 2 CO 3 +6HBO 2 +4NH 4 HF 2 →2[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+3H 2 O+4NH 4 F+CO 2 × (C: ×) (×)NH 2 ) 3 ] 2 CO 3 、HBO 2 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 6: 4, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, treating the mixed solution in the step a by ultrasonic waves to fully mix and dissolve the mixed solution, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by a polyvinyl chloride film, placing the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of the solvent in the solution, and standing the solution at room temperature to obtain [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 0.4mm multiplied by 0.3mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 64
Room temperature solution method for growing [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +RbHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + RbCl, [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、RbHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grown up, and the growth is finished to obtain the crystalTo [ C (NH) of size phi 2.7mm by 2.5mm by 1.6mm 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 65
Room temperature solution method for growing [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +CsHF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O + CsCl, [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、CsHF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, performing ultrasonic treatment on the mixed solution in the step a to ensure that the mixed solution is fully mixed and dissolved, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by using a polyvinyl chloride film, putting the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the solution at room temperature, and obtaining the product [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 1.9mm multiplied by 1.4mm multiplied by 1.1mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 66
Room temperature solution growth of [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Nonlinear optical crystal:
a. according to the chemical reaction equation, [ C (NH ] 2 ) 3 ]Cl+3H 3 BO 3 +NH 4 HF 2 →[C(NH 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]+4H 2 O+NH 4 Cl, will [ C (NH) 2 ) 3 ]Cl、H 3 BO 3 、NH 4 HF 2 Uniformly mixing the materials in a polytetrafluoroethylene beaker with the volume of 100mL according to the mol ratio of 1: 3: 1, adding 5mL of water, and uniformly stirring to obtain a mixed solution;
b. b, treating the mixed solution in the step a by ultrasonic waves to fully mix and dissolve the mixed solution, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by a polyvinyl chloride film, placing the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of the solvent in the solution, and standing the solution at room temperature to obtain [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The crystal is precipitated and gradually grows up, and after the growth is finished, the [ C (NH) with the size of phi 2.7mm multiplied by 2.2mm multiplied by 1.8mm is obtained 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]A nonlinear optical crystal.
Example 67
Any of [ C (NH) obtained in examples 34 to 66 was reacted 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal is processed in matching direction, arranged at the position 3 shown in figure 3, and irradiated with infrared beam 2 with wavelength of 1064nm emitted from a Q-switched Nd-YAG laser with incident wavelength of 1064nm at room temperature by a Q-switched QNd YAG laser 1 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]And (3) a single crystal which generates green frequency doubling light with the wavelength of 532nm and has the output intensity which is about 1 time of KDP under the same condition.
Example 68
Any of [ C (NH) obtained in examples 34 to 66 was reacted 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]The nonlinear optical crystal is processed in matching directions, and is arranged at the position 3 as shown in FIG. 3, at room temperature, a Q-switched Nd: YAG laser is used as light source, the incident wavelength is 532nm, and an infrared beam 2 with the wavelength of 532nm is emitted from the Q-switched Nd: YAG laser 1 to inject [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Single crystal 3, which produces light of 266nm wavelength doubled, has an output intensity of about 0.3 times that of BBO under the same conditions.

Claims (5)

1. A dihydroxy-difluoro guanidine triborate nonlinear optical crystal is characterized in that the chemical formula of the crystal is [ C (NH) 2 ) 3 ][B 3 O 3 F 2 (OH) 2 ]Molecular weight of 212.53, crystal belongs to triclinic system, space groupP1, unit cell parameters a =4.8288 (7), b =6.8455 (10) A, c =7.3212 (11) A,α = 114.308(5)，β = 90.258(5)，γ= 102.865(5)，Z = 1，V = 213.75(6) Å 3 。
2. the method for preparing a dihydroxy-difluoroguanidine triborate nonlinear optical crystal according to claim 1, wherein the crystal is grown by an evaporation method, a hydrothermal method or a room-temperature solution method:
the evaporation method is used for growing the dihydroxy-difluorinated guanidine triborate nonlinear optical crystal, and the specific operation is carried out according to the following steps:
a. will contain [ C (NH) 2 ) 3 ]Adding the group compound, the compound containing B and the compound containing F into a polytetrafluoroethylene beaker with the volume of 300mL, uniformly mixing, adding 5-20mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst containing [ C (NH) 2 ) 3 ]The group compound is guanidine hydrogen difluoride, guanidine carbonate, guanidine chloride or guanidine nitrate, the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, carrying out ultrasonic treatment on the mixed solution in the step a to enable the mixed solution to be fully mixed and dissolved, and filtering the mixed solution by using qualitative filter paper to obtain a clear solution;
c. b, placing the mixed solution in the step b in a resistance furnace, heating to 45-50 ℃ at the speed of 10 ℃/h, standing at the constant temperature for 15 days, volatilizing the solvent, and obtaining the dihydroxy-difluorinated guanidine triboronate nonlinear optical crystal after the crystal growth is finished;
the method for growing the dihydroxy-difluoro guanidine triborate nonlinear optical crystal by the hydrothermal method comprises the following specific steps:
a. will contain [ C (NH) 2 ) 3 ]Radical ofAdding the compound (A), the compound (B) and the compound (F) into a polytetrafluoroethylene beaker with the volume of 100mL, uniformly mixing, adding 1-2mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst contains [ C (NH) 2 ) 3 ]The group compound is guanidine hydrogen difluoride, guanidine carbonate, guanidine chloride or guanidine nitrate, the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. b, transferring the mixed solution in the step a into a polytetrafluoroethylene lining of a hydrothermal reaction kettle with the volume of 23-100mL, and screwing and sealing the opening of the reaction kettle;
c. b, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 150-220 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 2-5 days, and cooling to room temperature at the cooling speed of 1-3 ℃/h;
d. opening the high-pressure reaction kettle, and obtaining a dihydroxy-difluorinated guanidine triborate nonlinear optical crystal in a colorless clear solution;
the room temperature solution method for growing the dihydroxy-difluorinated guanidine triborate nonlinear optical crystal comprises the following specific steps:
a. will contain [ C (NH) 2 ) 3 ]Adding the group compound, the compound containing B and the compound containing F into a polytetrafluoroethylene beaker with the volume of 100mL, uniformly mixing, adding 5mL of water, and uniformly stirring and mixing to obtain a mixed solution; said catalyst contains [ C (NH) 2 ) 3 ]The radical compound is hydrogen difluoride guanidine, guanidine carbonate, guanidine chloride or guanidine nitrate, and the compound containing B is H 3 BO 3 Or HBO 2 The F-containing compound is guanidine bifluoride, rubidium hydrofluoride, cesium hydrofluoride or ammonium hydrofluoride;
b. and (b) treating the mixed solution in the step a by ultrasonic waves to fully mix and dissolve the mixed solution, filtering the mixed solution by qualitative filter paper to obtain a clear solution, sealing the clear solution by a polyvinyl chloride film, placing the clear solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the clear solution at room temperature, then precipitating crystals in the solution and gradually growing the crystals, and obtaining the dihydroxyl guanidine difluoride nonlinear optical crystal with the size of centimeter grade after the growth is finished.
3. Use of the dihydroxydifluorotribasic guanidine borate nonlinear optical crystal according to claim 1 in the preparation of multiband frequency doubling devices or optical elements.
4. The use of the dihydroxy-difluoroguanidine triborate nonlinear optical crystal of claim 1 in the preparation of 2-frequency or 3-frequency or 4-frequency doubled harmonic light output of 1064nm fundamental frequency light output by Nd: YAG laser.
5. Use of the dihydroxy-difluoroguanidine triborate nonlinear optical crystal of claim 1 in the preparation of a frequency doubling generator, an upper or lower frequency converter, or an optical parametric oscillator.
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