Near-infrared emission zero-dimensional Sb-based metal halide material and preparation method thereof
阅读说明：本技术 一种近红外发射的零维Sb基金属卤化物材料及制备方法 (Near-infrared emission zero-dimensional Sb-based metal halide material and preparation method thereof ) 是由 夏志国 苏彬彬 于 2021-08-31 设计创作，主要内容包括：本发明公开了一种近红外发射的零维Sb基金属卤化物材料及制备方法；该卤化物材料化学组成式为(C-(13)H-(22)N)SbCl-(4)；其制备方法为：将有机配体和锑源加入到氯化氢水溶液中,加热溶解形成透明溶液A；将透明溶液A自然冷却到室温得到粉末样品,洗涤,干燥,得到卤化物粉末；或将步骤(1)透明溶液A以20-30℃/天的速率降至室温,得到无色透明的棒状晶体,洗涤,干燥,得到近红外发射的零维Sb基金属卤化物单晶。本发明制备方法的原料丰富且价格低廉,合成工艺简单,能够进行大规模生产；本发明合成的卤化物材料填补了零维金属卤化物材料在近红外研究领域的空白,极大地扩展了零维金属卤化物材料在近红外领域的应用。(The invention discloses a near-infrared emission zero-dimensional Sb-based metal halide material and a preparation method thereof; the chemical composition formula of the halide material is (C) 13 H 22 N)SbCl 4 (ii) a The preparation method comprises the following steps: adding an organic ligand and an antimony source into an aqueous solution of hydrogen chloride, and heating and dissolving to form a transparent solution A; naturally cooling the transparent solution A to room temperature to obtain a powder sample, washing and drying to obtain halide powder; or cooling the transparent solution A obtained in the step (1) to room temperature at the speed of 20-30 ℃/day to obtain a colorless and transparent rod-shaped crystal, washing and drying to obtain the near-infrared emission zero-dimensional Sb-based metal halide single crystal. The preparation method has the advantages of rich and cheap raw materials, simple synthesis process and capability of large-scale production; the halide material synthesized by the invention fills in zero-dimensional metal halogenationThe blank of the material in the near infrared research field greatly expands the application of the zero-dimensional metal halide material in the near infrared field.)
1. AThe near-infrared emission zero-dimensional Sb-based metal halide material is characterized by having a chemical composition formula of (C)13H22N)SbCl4Luminescence from Sb3+Ionic triplet self-trapped exciton emission.
2. The near-infrared emitting zero-dimensional Sb-based metal halide material of claim 1, wherein the near-infrared emitting zero-dimensional Sb-based metal halide material is a powder or a single crystal.
3. The method of preparing a near-infrared emitting zero-dimensional Sb-based metal halide material of claim 1 or 2, comprising the steps of:
(1) adding an organic ligand and an antimony source into an aqueous solution of hydrogen chloride, and heating and dissolving to form a transparent solution A; the organic ligand is at least one of benzyltriethylammonium chloride and a compound capable of being converted into benzyltriethylammonium chloride, and the antimony source is at least one of antimony trichloride and a compound capable of being converted into antimony trichloride;
(2) naturally cooling the transparent solution A obtained in the step (1) to room temperature to obtain a powder sample, washing and drying to obtain near-infrared emission zero-dimensional Sb-based metal halide powder; or
And (2) cooling the transparent solution A obtained in the step (1) to room temperature at the speed of 20-30 ℃/day to obtain a colorless and transparent rod-shaped crystal, washing and drying to obtain the near-infrared emission zero-dimensional Sb-based metal halide single crystal.
4. The production method according to claim 3, characterized in that the aqueous hydrogen chloride solution of step (1) has a mass concentration of 20 to 38%.
5. The preparation method according to claim 3, wherein the molar ratio of the organic ligand to the antimony source in step (1) is X:1, wherein 1. ltoreq. X.ltoreq.4.
6. The method of claim 5, wherein X is 1, 2, 3, 4.
7. The method according to claim 3, wherein the ratio of the molar amount of the organic ligand in step (1) to the volume of the aqueous solution of hydrogen chloride is Xmmol: Yml, wherein X is 1. ltoreq. X.ltoreq.4 and Y is 10. ltoreq. Y.ltoreq.25.
8. The method of claim 7, wherein X is 1, 2, 3, 4; and Y is 10, 15, 20 and 25.
9. The method according to claim 3, wherein the temperature for the heating dissolution in the step (1) is 90-120 ℃; washing with ethanol in the step (2).
10. The method according to claim 3, wherein the drying temperature in step (2) is 60-90 ℃ and the drying time is 6-24 h.
Technical Field
The invention belongs to the technical field of optical materials; in particular to a near-infrared emission zero-dimensional Sb-based metal halide material and a preparation method thereof.
Background
Near-infrared light sources have been widely studied in the fields of physical therapy, night vision, intelligent equipment, infrared spectrum detection and the like due to the advantages of low thermal effect, no damage, good penetrability and the like. Especially near infrared radiation at 700-1100nm, which has a significant penetration depth into biological tissue, can be easily used for harmless diagnosis of body functions of the human body. The traditional broadband near-infrared light source, such as halogen lamp, tungsten lamp, etc., has the disadvantages of large size, low efficiency, short service life, poor matching degree with an infrared detector, etc., so that the exploration of a novel near-infrared luminescent material is a point of research at present.
In recent years, zero-dimensional metal halide materials as perovskite halide derivatives show unprecedented application prospects in the field of visible light due to structural diversity and photoluminescence adjustability, particularly in the fields of broadband illumination and narrow-band display. By selecting suitable metal halides, highly efficient red, orange, yellow, green and blue light has been achieved. However, despite the great commercial potential of near-infrared light sources, no broadband near-infrared emitting zero-dimensional metal halide material with high luminous efficiency has been designed, and its application in the near-infrared field is expanded, for example: physical therapy, night vision, intelligent equipment, infrared spectrum detection, face recognition and the like. Designing a wide band near-infrared emitting zero-dimensional metal halide material is therefore a challenge for current metal halide systems. And secondly, the zero-dimensional metal halide is simple in synthesis process (liquid phase synthesis), rich in raw materials, low in price, capable of being produced in a large scale and has potential application advantages.
Several examples of near-infrared emitting zero-dimensional metal halides, such as hybridized Bmpip, have also been reported2SnI4And all-inorganic Cs2ZnCl4:Sb3+And Rb2InBr5·H2O:Sb3+(Adv.Optical Mater.2021,2100434，Tailoring the Broadband Emission in All-Inorganic Lead-Free 0D In-Based Halides through Sb3+Doping). However, the largest of them has an emission wavelength of 760nm, and a large part of its spectrum is in the visible region.Therefore, the design of the zero-dimensional metal halide material emitting near infrared in a long wave band is the focus of the current research, and has important significance for the development of a near infrared light source.
Disclosure of Invention
One of the purposes of the invention is to explore the zero-dimensional metal halide emitted by near infrared and fill the blank of the metal halide in the near infrared field.
The invention also aims to overcome the defects of the prior art and provide the zero-dimensional metal halide with the emission peak positioned at 880nm and capable of emitting near infrared in a broadband manner.
The invention also aims to provide a preparation method for preparing the near-infrared luminescent material. The preparation method is simple, easy to operate, low in equipment cost and free of pollution.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a near-infrared emitting zero-dimensional Sb-based metal halide material has a chemical composition formula of (C)13H22N)SbCl4Luminescence from Sb3+Ionic triplet self-trapped exciton emission.
Preferably, the near-infrared emitting zero-dimensional Sb-based metal halide material is a powder or a single crystal.
The preparation method of the near-infrared emission zero-dimensional Sb-based metal halide material comprises the following steps:
(1) adding an organic ligand and an antimony source into an aqueous solution of hydrogen chloride, and heating and dissolving to form a transparent solution A; the organic ligand is at least one of benzyltriethylammonium chloride and a compound capable of being converted into benzyltriethylammonium chloride, and the antimony source is at least one of antimony trichloride and a compound capable of being converted into antimony trichloride;
(2) naturally cooling the transparent solution A obtained in the step (1) to room temperature to obtain a powder sample, washing and drying to obtain near-infrared emission zero-dimensional Sb-based metal halide powder; or cooling the transparent solution A obtained in the step (1) to room temperature at the speed of 20-30 ℃/day to obtain a colorless and transparent rod-shaped crystal, washing and drying to obtain the near-infrared emission zero-dimensional Sb-based metal halide single crystal.
Preferably, the mass concentration of the aqueous hydrogen chloride solution in the step (1) is 20-38%.
Preferably, the molar ratio of the organic ligand to the antimony source in the step (1) is X:1, wherein X is more than or equal to 1 and less than or equal to 4.
More preferably, X is 1, 2, 3, 4.
Preferably, the volume ratio of the molar amount of the organic ligand in the step (1) to the aqueous solution of hydrogen chloride is Xmmol: y ml, wherein X is more than or equal to 1 and less than or equal to 4, and Y is more than or equal to 10 and less than or equal to 25.
Further preferably, X is 1, 2, 3, 4; and Y is 10, 15, 20 and 25.
Preferably, the temperature for heating and dissolving in the step (1) is 90-120 ℃; washing with ethanol in the step (2).
Preferably, the drying temperature in the step (2) is 60-90 ℃, and the drying time is 6-24 h.
The invention uses a certain proportion of benzyltriethylammonium chloride (C)13NH22Cl) and antimony trichloride (SbCl)3) Dissolving in 38% hydrogen chloride solution to form transparent solution A, naturally cooling to room temperature to obtain white powder sample, washing with ethanol, and drying in 60 deg.C oven for 24 hr. The single crystal sample is prepared by transferring the hot transparent solution A into a preheated 25ml polytetrafluoroethylene reaction kettle, transferring the reaction kettle into an oven at 100 ℃ for heat preservation for 60 minutes, then reducing the temperature to room temperature at the speed of 30 ℃/day to obtain white transparent flaky crystals, washing with ethanol, and drying in the oven at 60 ℃ for 24 hours for later use.
Compared with the prior art, the invention has the following advantages:
(1) the invention realizes the broadband near-infrared emission of zero-dimensional Sb-based metal halide for the first time, the emission spectrum is in the range of 500-1300 nm, the half-peak width is about 300nm, the Stokes shift is as high as 530nm, and the invention can be used in the fields of night vision monitoring, spectrum detection and the like.
(2) The preparation method is simple, easy to operate, low in equipment cost and free of pollution; can generate huge social benefit and economic benefit, and is suitable for being widely popularized and used.
(3) The invention realizes the broadband near-infrared emission of the zero-dimensional Sb-based metal halide for the first time, and more people will be encouraged to research the near-infrared emitted zero-dimensional metal halide.
Drawings
FIGS. 1a and 1b show a near-infrared luminescent material (C) prepared in example 113H22N)SbCl4X-ray diffraction spectrum and spectrogram of (1).
FIGS. 2a and 2b are views of a near-infrared luminescent material (C) prepared in example 213H22N)SbCl4X-ray diffraction spectrum and spectrogram of (1).
FIGS. 3a and 3b are views of a near-infrared luminescent material (C) prepared in example 313H22N)SbCl4X-ray diffraction spectrum and spectrogram of (1).
FIGS. 4a and 4b are views of a near-infrared luminescent material (C) prepared in example 413H22N)SbCl4X-ray diffraction spectrum and spectrogram of (1).
Detailed Description
The invention is further illustrated with reference to the following figures and examples, which are not intended to limit the invention in any way.
The design idea of the invention is that the zero-dimensional metal halide luminescent material shows potential application in the research field of optical functional materials and devices due to the adjustability of structure and luminescence. Although efficient light emission has been achieved in the visible region, zero-dimensional metal halides with emission bands in the near infrared region have not been widely studied, and the near infrared is relatively rarely studied even if extended to the entire metal halide system. Therefore, the search for metal halides with high near infrared emission efficiency is a research hotspot of the current metal halide system, and the practical application of the metal halides is expanded. And the metal halide has simple synthesis process, abundant raw materials and low price, can be produced in a large scale and is expected to replace the traditional near-infrared luminescent material.
The invention relates to a synthesis method of a near-infrared emission zero-dimensional metal halide material, which adopts 20-38% aqueous solution of hydrogen chloride as a solvent for dissolving reactants of benzyltriethylammonium chloride and antimony trichloride, the benzyltriethylammonium chloride and the antimony trichloride are dissolved in the 20-38% aqueous solution of the hydrogen chloride to form a transparent solution A, and a powder sample is obtained by directly cooling the hot transparent solution A to room temperature. The obtained powder sample is washed by ethanol and dried in an oven at 60-90 ℃ for 6-24 hours for later use.
Example 1
The chemical composition formula of the near-infrared emitting metal halide of this example is (C)13H22N)SbCl4Wherein the proportion of the benzyltriethylammonium chloride to the antimony trichloride is 1: 1. The mass concentration of the aqueous hydrogen chloride solution in which benzyltriethylammonium chloride and antimony trichloride were dissolved was 20% and the volume was 10 ml.
Step 1: washing 1 beaker and polytetrafluoroethylene reaction kettle with deionized water and ethanol, and drying in a drying oven for later use;
step 2: weighing high-purity powdery raw materials of benzyltriethylammonium chloride (1mmol) and antimony trichloride (1mmol) according to a specified proportion, adding the weighed raw materials into 10ml of 20% aqueous hydrogen chloride solution, and heating and dissolving at 90 ℃ to form a transparent solution A;
and step 3: the powder sample was obtained by directly cooling the hot clear solution a to room temperature. Washing the obtained powder sample with ethanol, and drying in an oven at 60 ℃ for 6 hours for later use;
and 4, step 4: the synthesis of the single crystal sample is that the hot transparent solution A is transferred into a preheated 25ml polytetrafluoroethylene reaction kettle, then the reaction kettle is transferred into a drying oven with the temperature of 90 ℃ for heat preservation for 60 minutes, then the temperature is reduced to the room temperature at the speed of 30 ℃/day, finally colorless and transparent flaky crystals are obtained, the crystals are washed by ethanol, and the crystals are dried in the drying oven with the temperature of 60 ℃ for 6 hours to obtain the Sb-based metal halide single crystal with near infrared emission.
As shown in fig. 1a, the synthesized phase was confirmed by XRD comparison. As shown in FIG. 1b as (C)13H22N)SbCl4The excitation and emission spectra of (A) can be seen in the figure, where the excitation peak is at 350nm and the emission peak is at 880 nm.
According to the synthetic method of the invention, the pollution-free and low-cost near-infrared emission (C) can be prepared13H22N)SbCl4A metal halide material.
Example 2
The chemical composition formula of the near-infrared emitting metal halide of this example is (C)13H22N)SbCl4In the synthesis process of this example, the ratio of benzyltriethylammonium chloride to antimony trichloride was 2: 1. The mass concentration of the aqueous hydrogen chloride solution in which benzyltriethylammonium chloride and antimony trichloride were dissolved was 30% and the volume was 15 ml.
Step 1: washing 1 beaker and polytetrafluoroethylene reaction kettle with deionized water and ethanol, and drying in a drying oven for later use;
step 2: weighing high-purity powdery raw materials of benzyltriethylammonium chloride (2mmol) and antimony trichloride (1mmol) according to a specified proportion, adding the weighed raw materials into 15ml of 30% aqueous hydrogen chloride solution, and heating and dissolving at 100 ℃ to form a transparent solution A;
and step 3: the powder sample was obtained by directly cooling the hot clear solution a to room temperature. Washing the obtained powder sample with ethanol, and drying in an oven at 70 ℃ for 12 hours for later use;
and 4, step 4: the synthesis of the single crystal sample is that the hot transparent solution A is transferred into a preheated 25ml polytetrafluoroethylene reaction kettle, then the reaction kettle is transferred into a 100 ℃ oven to be kept warm for 60 minutes, then the temperature is reduced to room temperature at the speed of 25 ℃/day, finally colorless and transparent flaky crystals are obtained, the crystals are washed by ethanol, and the crystals are dried in a 70 ℃ oven for 12 hours to obtain the Sb-based metal halide single crystal with near infrared emission.
As shown in fig. 2a, the synthesized phase was confirmed by XRD comparison. As shown in FIG. 2b as (C)13H22N)SbCl4The excitation and emission spectra of (A) can be seen in the figure, where the excitation peak is at 350nm and the emission peak is at 880 nm.
According to the synthetic method of the invention, the pollution-free and low-cost near-infrared emission (C) can be prepared13H22N)SbCl4A metal halide material.
Example 3
The chemical composition formula of the near-infrared emitting metal halide of this example is (C)13H22N)SbCl4In the synthesis process of this example, the ratio of benzyltriethylammonium chloride to antimony trichloride was 3: 1. The aqueous hydrogen chloride solution in which benzyltriethylammonium chloride and antimony trichloride were dissolved had a mass concentration of 38% and a volume of 20 ml.
Step 1: washing 1 beaker and polytetrafluoroethylene reaction kettle with deionized water and ethanol, and drying in a drying oven for later use;
step 2: weighing high-purity powdery raw materials of benzyltriethylammonium chloride (3mmol) and antimony trichloride (1mmol) according to a specified proportion, adding the weighed raw materials into 20ml of 38% aqueous hydrogen chloride solution, and heating and dissolving at 110 ℃ to form a transparent solution A;
and step 3: the powder sample was obtained by directly cooling the hot clear solution a to room temperature. Washing the obtained powder sample with ethanol, and drying in an oven at 80 ℃ for 18 hours for later use;
and 4, step 4: the single crystal sample is synthesized by transferring the hot transparent solution A into a preheated 25ml polytetrafluoroethylene reaction kettle, transferring the reaction kettle into a 110 ℃ oven, keeping the temperature for 60 minutes, then reducing the temperature to room temperature at the speed of 22 ℃/day to finally obtain colorless and transparent flaky crystals, washing the flaky crystals with ethanol, and drying the flaky crystals in the 80 ℃ oven for 18 hours to obtain the Sb-based metal halide single crystal with near infrared emission.
As shown in fig. 3a, the synthesized phase was confirmed by XRD comparison. As shown in FIG. 3b as (C)13H22N)SbCl4The excitation and emission spectra of (A) can be seen in the figure, where the excitation peak is at 350nm and the emission peak is at 880 nm.
According to the synthetic method of the invention, the pollution-free and low-cost near-infrared emission (C) can be prepared13H22N)SbCl4A metal halide material.
Example 4
The chemical composition formula of the near-infrared emitting metal halide of this example is (C)13H22N)SbCl4In this example, the ratio of benzyltriethylammonium chloride to antimony trichloride was 4:1 during the synthesis. Of aqueous solutions of hydrogen chloride in which benzyltriethylammonium chloride and antimony trichloride are dissolvedThe mass concentration is 38%, and the volume is 25 ml.
Step 1: washing 1 beaker and polytetrafluoroethylene reaction kettle with deionized water and ethanol, and drying in a drying oven for later use;
step 2: weighing high-purity powdery raw materials of benzyltriethylammonium chloride (1mmol) and antimony trichloride (1mmol) according to a specified proportion, adding the weighed raw materials into 25ml of 38% aqueous hydrogen chloride solution, and heating and dissolving at 120 ℃ to form a transparent solution A;
and step 3: the powder sample was obtained by directly cooling the hot clear solution a to room temperature. Washing the obtained powder sample with ethanol, and drying in an oven at 90 ℃ for 24 hours for later use;
and 4, step 4: the synthesis of the single crystal sample is that the hot transparent solution A is transferred into a preheated 25ml polytetrafluoroethylene reaction kettle, then the reaction kettle is transferred into a 120 ℃ oven to be kept warm for 60 minutes, then the temperature is reduced to room temperature at the speed of 20 ℃/day, finally colorless and transparent flaky crystals are obtained, the crystals are washed by ethanol, and the crystals are dried in the 90 ℃ oven for 24 hours to obtain the Sb-based metal halide single crystal with near infrared emission.
As shown in fig. 4a, the synthesized phase was confirmed by XRD comparison. As shown in FIG. 4b as (C)13H22N)SbCl4The excitation and emission spectra of (A) can be seen in the figure, where the excitation peak is at 350nm and the emission peak is at 880 nm.
According to the synthetic method of the invention, the pollution-free and low-cost near-infrared emission (C) can be prepared13H22N)SbCl4A metal halide material.
Although the present invention has been described above with reference to the accompanying drawings, the present invention is not limited to the above-described specific embodiments. The foregoing detailed description is to be construed as illustrative only and not restrictive, and many changes and modifications may be made by those skilled in the art in light of the above teachings, and it is intended to cover all modifications, equivalents, improvements, and equivalents that fall within the spirit and scope of the present invention.