Metal organic-inorganic hybrid crystal based on 2-F-5 methylpyridine ligand and preparation method and application thereof
阅读说明：本技术 一种基于2-f-5甲基吡啶配体的金属有机无机杂化晶体及其制备方法和应用 (Metal organic-inorganic hybrid crystal based on 2-F-5 methylpyridine ligand and preparation method and application thereof ) 是由 王守宇 贾云东 刘卫芳 马晓婷 陈畅 于 2020-07-22 设计创作，主要内容包括：本发明提供了一种基于2-F-5甲基吡啶配体的金属有机无机杂化晶体,属于光电材料技术领域,其分子式为(C<Sub>7</Sub>H<Sub>9</Sub>NF)<Sub>2</Sub>[BiBr<Sub>4</Sub>],空间群为P21/n,晶胞参数<Image he="38" wi="700" file="DDA0002596117970000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>α＝90°；β＝109.462(2)°；γ＝90°。在本发明中,2-F-5甲基吡啶配体具有良好的缺电子特性,是一种理想的供电子接受体,与[BiBr<Sub>4</Sub>]<Sup>2-</Sup>杂化后,所得(C<Sub>7</Sub>H<Sub>9</Sub>NF)<Sub>2</Sub>[BiBr<Sub>4</Sub>]金属有机无机杂化晶体具有良好的光电效应,且在电流测试下具有特殊的光响应的性质,即加光之后光电导电阻反而增大,能用作激光报警器的光响应材料。(The invention provides a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, belongs to the technical field of photoelectric materials, and has a molecular formula of (C) 7 H 9 NF) 2 [BiBr 4 ]Space group is P21/n, cell parameter α is 90 °; β 109.462(2) °; γ is 90 °. In the present invention, the 2-F-5 methylpyridine ligand has good electron deficiency characteristics, is an ideal electron donor acceptor, and [ BiBr ] 4 ] 2‑ After hybridization, (C) is obtained 7 H 9 NF) 2 [BiBr 4 ]The metal organic inorganic hybrid crystal has good photoelectric effect and can generate currentThe test shows that the material has special light response property, namely, the photoconductive resistance is increased after light is added, and the material can be used as a light response material of a laser alarm.)
1. A metal organic-inorganic hybrid crystal based on 2-F-5 methylpyridine ligand has a molecular formula of (C)7H9NF)2[BiBr4]Wherein (C)7H9NF)2Is a 2-F-5 methylpyridine ligand, C7H9The structural formula of NF is shown as formula 1:
said (C)7H9NF)2[BiBr4]Has a space group of P21/n, the unit cell parameter
2. The method for preparing a 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal according to claim 1, comprising the following steps:
hydrobromic acid, 2-F-5 methylpyridine, bismuth bromide and methanol are mixed, subjected to solvothermal reaction, and cooled to obtain the 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal.
3. The method of claim 2, wherein the molar ratio of 2-F-5 methylpyridine to bismuth bromide is 41: 10;
the volume ratio of the 2-F-5 methylpyridine to the methanol is 0.1-0.2: 9-11.
4. The preparation method according to claim 2, wherein the hydrobromic acid has a mass concentration of 47-50%, and the volume ratio of the 2-F-5 methylpyridine to the hydrobromic acid is 0.1-0.2: 0.9-1.2.
5. The preparation method according to claim 2, wherein the temperature of the solvothermal reaction is 145-180 ℃ and the time is 10-18 h.
6. The preparation method according to claim 2, wherein the rate of temperature reduction is 0.1-0.2 ℃/min.
7. The method according to claim 2, further comprising, after the solvothermal reaction, subjecting the obtained solvothermal reaction solution to a post-treatment, wherein the post-treatment comprises the steps of:
and carrying out solid-liquid separation on the solvothermal reaction liquid, and drying the obtained solid to obtain the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand.
8. The preparation method according to claim 7, wherein the drying temperature is 60 ℃ and the drying time is 20-40 min.
9. Use of the 2-F-5 methylpyridine ligand based metal organic-inorganic hybrid crystal according to claim 1 in the field of optoelectronics.
10. Use according to claim 9, characterized in that the optoelectronic field is the field of photodetectors and laser alarms.
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, and a preparation method and application thereof.
Background
Photodetectors based on semiconductor materials can convert optical signals into electrical signals, and have wide applications in optical imaging sensors, security monitoring, and chemical/biological sensing. Most photodetectors are made of inorganic materials, such as InSe, ZnO, MoS2、WS2However, the application of such materials is still limited due to the disadvantages of slow light response speed, high material preparation cost and complex preparation process.
The lead halide-based organic-inorganic hybrid perovskite has the advantages of extremely high light absorption coefficient, balanced electron and hole mobility, ultra-long photogenerated carrier diffusion length and service life, low trap density, small exciton binding energy and the like, and has great application potential in the photoelectric field, such as MAPbI3The power conversion efficiency of the base solar cell can reach 23.3%. However, lead halide-based hybrid perovskites are less stable and are easily decomposed under conditions of heat, ultraviolet light irradiation and humidity; and the lead halide-based hybrid perovskite contains lead element, so that the lead halide-based hybrid perovskite has a destructive effect on the environment. These disadvantages limit the commercial application of lead halide based hybrid perovskites.
Disclosure of Invention
In view of the above, the invention aims to provide a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, and a preparation method and an application thereof, and the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand provided by the invention has a good photoelectric effect, good stability and no environmental pollution.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, and the molecular formula is (C)7H9NF)2[BiBr4]Wherein (C)7H9NF)2Is a 2-F-5 methylpyridine ligand, C7H9The structural formula of NF is shown as formula 1:
said (C)7H9NF)2[BiBr4]Has a space group of P21/n, the unit cell parameter α＝90°；β＝109.462(2)°；γ＝90°。
The invention provides a preparation method of the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand, which comprises the following steps:
hydrobromic acid, 2-F-5 methylpyridine, bismuth bromide and methanol are mixed, subjected to solvothermal reaction, and cooled to obtain the 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal.
Preferably, the molar ratio of the 2-F-5 methylpyridine to the bismuth bromide is 41: 10;
the volume ratio of the 2-F-5 methylpyridine to the methanol is 0.1-0.2: 9-11.
Preferably, the mass concentration of the hydrobromic acid is 47-50%, and the volume ratio of the 2-F-5 methylpyridine to the hydrobromic acid is 0.1-0.2: 0.9-1.2.
Preferably, the temperature of the solvothermal reaction is 145-180 ℃ and the time is 10-18 h.
Preferably, the cooling rate is 0.1-0.2 ℃/min.
Preferably, after the solvothermal reaction, the method further comprises performing post-treatment on the obtained solvothermal reaction solution, wherein the post-treatment comprises the following steps:
and carrying out solid-liquid separation on the solvothermal reaction liquid, and drying the obtained solid to obtain the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand.
Preferably, the drying temperature is 60 ℃ and the drying time is 20-40 min.
The invention provides application of the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand in the photoelectric field.
Preferably, the photoelectric field is the fields of photoelectric detectors and laser alarms.
The invention provides a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, and the molecular formula is (C)7H9NF)2[BiBr4]Wherein (C)7H9NF)2Is a 2-F-5 methylpyridine ligand; said (C)7H9NF)2[BiBr4]Has a space group of P21/n, the unit cell parameter α＝90°；β＝109.462(2)°；γ＝90°。
In the present invention, the 2-fluoro-5-methylpyridine ligand has good electron deficiency characteristics, is an ideal organic electron donor acceptor, and [ BiBr ]4]2-After hybridization, (C) is obtained7H9NF)2[BiBr4]The metal organic inorganic hybrid crystal has good photoelectric effect and special photoresponse property under the current test, namely the photoconductive resistance is increased after light is added, and the metal organic inorganic hybrid crystal can be used as a photoresponse material of a laser alarm. Meanwhile, the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand has good stability under the conditions of heat, ultraviolet irradiation and humidity, does not contain elements harmful to the environment, and is environment-friendly.
The invention provides a preparation method of a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, which only needs one-step solvothermal reaction, is simple to operate and is easy to realize industrial production.
Drawings
FIG. 1 is (C)7H9NF)2[BiBr4]A schematic of the structure of the crystal;
FIG. 2 is (C)7H9NF)2[BiBr4]An inorganic framework of a crystal;
FIG. 3 is (C)7H9NF)2[BiBr4]I-V curve under crystal current test;
fig. 4 is a schematic connection diagram of components of the laser alarm in application example 2.
Detailed Description
The invention provides a metal organic-inorganic hybrid crystal based on a 2-F-5 methylpyridine ligand, and the molecular formula is (C)7H9NF)2[BiBr4]Wherein (C)7H9NF)2Is a 2-F-5 methylpyridine ligand, C7H9The structural formula of NF is shown as formula 1:
said (C)7H9NF)2[BiBr4]Has a space group of P21/n, the unit cell parameter α＝90°；β＝109.462(2)°；γ＝90°。
In the present invention, (C) provided by the present invention7H9NF)2[BiBr4]The structure of the crystal is schematically shown in FIG. 1, (C)7H9NF)2[BiBr4]The inorganic framework of the crystal is shown in FIG. 2, and can be seen from FIGS. 1 and 2, wherein (C)7H9NF)2[BiBr4]Middle, four [ BiBr ]6]The inorganic structure composed of angle-sharing octahedron is independently distributed, and the organic part C7H9NF is interspersed between them, illustrating a typical zero-dimensional structure.
The invention provides a preparation method of the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand, which comprises the following steps:
hydrobromic acid, 2-F-5 methylpyridine, bismuth bromide and methanol are mixed, subjected to solvothermal reaction, and cooled to obtain the 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal.
In the present invention, the molar ratio of the 2-F-5 methylpyridine to the bismuth bromide is preferably 41: 10; the volume ratio of the 2-F-5 methylpyridine to the methanol is preferably 0.1-0.2: 9-11. In the invention, the mass concentration of the hydrobromic acid is preferably 48%, and the volume ratio of the 2-F-5 methylpyridine to the hydrobromic acid is preferably 0.1-0.2: 9-11.
The present invention preferably performs the solvothermal reaction in a reaction kettle.
In the present invention, the methanol functions as a solvent. In the present invention, the methanol is preferably added in two times, and as a specific embodiment of the present invention, the mixing manner is preferably: adding hydrobromic acid and 2-F-5 methylpyridine for first mixing, standing for 30min, adding a first part of methanol and bismuth bromide, transferring the obtained mixed solution to the inner liner of a reaction kettle, and adding a second part of methanol for second mixing. In the present invention, the volume ratio of the first part of methanol to the second part of methanol is preferably 1: 3. The present invention is prepared by adding methanol in two portions, wherein the first portion of methanol is intended to dissolve solids and the second portion is intended to flush all of the remaining reactants into the inner liner of the reactor.
In the invention, the temperature of the solvothermal reaction is preferably 145-180 ℃, and more preferably 150-170 ℃; the time is preferably 10 to 18 hours, and more preferably 12 to 16 hours. In the invention, the heating rate of the solvent thermal reaction is preferably 40-60 ℃/h; the reaction time is calculated from the temperature rise to the solvothermal reaction temperature.
In the present invention, after the solvothermal reaction, the obtained solvothermal reaction solution is preferably cooled in the present invention. In the present invention, the rate of the temperature reduction is preferably 0.1 ℃/min; the invention can control the growth rate of the crystal by a slow cooling mode, and obtain the crystal with good crystallization quality.
In the invention, the reaction formula of the solvothermal reaction is shown as
HBr+2CH3OH+C6H6FN+BiBr3→(C7H9NF)2[BiBr4]And (3)
After the solvothermal reaction, the method also preferably comprises post-treatment of the obtained solvothermal reaction solution, wherein the post-treatment preferably comprises the following steps:
and carrying out solid-liquid separation on the solvothermal reaction liquid, and drying the obtained solid to obtain the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand.
The invention has no special requirements on the solid-liquid separation mode, and the solid-liquid separation mode which is well known by the technical personnel in the field can be used; as a specific example of the present invention, the solid-liquid separation is performed by taking out the crystals using tweezers. After taking out the crystals, the present invention preferably uses paper to dip the liquid remaining on the crystals. In the invention, the drying temperature is preferably 60 ℃, and the drying time is preferably 20-40 min, and more preferably 30 min. The present invention preferably uses a drying oven for the drying.
And after the drying is finished, obtaining orange crystals in the obtained solid, namely the metal organic-inorganic hybrid crystals based on the 2-F-5 methylpyridine ligand. The orange crystals are picked out and sealed for storage.
The invention provides application of the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand in the photoelectric field. In the present invention, the photoelectric field is preferably the fields of photodetectors and laser alarms.
In the present invention, when the 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal is used for a photodetector, the method for preparing the photodetector preferably comprises the steps of:
and silver plating electrodes at two end points of the metal organic-inorganic hybrid crystal based on the 2-F-5 methylpyridine ligand to obtain the photoelectric detector.
In the present invention, when the 2-F-5 methylpyridine ligand-based metal organic-inorganic hybrid crystal is used for a laser alarm, the preparation method of the laser alarm preferably comprises the following steps:
(1) will (C)7H9NF)2[BiBr4]Preparation of crystals of (C)7H9NF)2[BiBr4]A crystalline thin film;
(2) in the (C)7H9NF)2[BiBr4]Depositing electrodes on the upper and lower surfaces of the crystal film to obtain (C)7H9NF)2[BiBr4]A crystal device;
(3) will be (C)7H9NF)2[BiBr4]And the crystal device is connected with the power supply and the buzzer in series to obtain the laser alarm.
In the present invention, said (C)7H9NF)2[BiBr4]The method for preparing the crystalline thin film preferably includes the steps of:
will (C)7H9NF)2[BiBr4]Placing the material at one end of the crucible, placing the conductive substrate at the other end of the crucible, heating the crucible under nitrogen atmosphere to obtain (C) on the conductive substrate7H9NF)2[BiBr4]And (5) a crystal thin film. In the present invention, said (C)7H9NF)2[BiBr4]The thickness of the crystal thin film is preferably 90 to 110 nm.
The invention has no special requirements on the mode of depositing the electrode, and the mode of depositing the electrode, which is well known to the technical personnel in the field, can be used; in the present invention, the electrode is preferably a silver electrode. In the present invention, the thickness of the electrode is preferably 0.8 to 1 mm.
In the invention, the power supply is preferably a 3-6V constant voltage power supply; the invention has no special requirements on the type of the buzzer, and the buzzer known by the technicians in the field can be used.
The metal organic-inorganic hybrid crystal based on 2-F-5 methylpyridine ligand and the preparation method and application thereof provided by the present invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.