CN111205860A - Grinding preparation method of copper (I) -bromine hybrid fluorescent material - Google Patents
Grinding preparation method of copper (I) -bromine hybrid fluorescent material Download PDFInfo
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Abstract
The invention provides a grinding preparation method of a copper (I) -bromine hybrid fluorescent material. The copper (I) -bromine hybrid fluorescent material with different fluorescent colors can be prepared by adopting tetraalkylammonium bromide with different alkyl chain lengths. The preparation method is simple and convenient, mild in condition, low in cost, short in time consumption, high in yield, suitable for batch production, and the prepared copper (I) -bromine hybrid material is good in fluorescence stability and has great application potential in the fields of chemical sensing analysis, optics, electrical devices and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic-organic hybrid materials, and particularly relates to a grinding preparation method of a copper (I) -bromine hybrid fluorescent material.
Background
Inorganic-organic hybrid materials are a class of functional materials based on the mixing of inorganic components with organic components at the nanoscale. The material not only has the excellent performance of two independent components, but also can develop the excellent performance which is not possessed by the two independent components, so that the material can be widely applied to the fields of optics, electrics and magnetism. Wherein the copper (I) -halogen hybrid [ CunXm (L) z; x ═ Cl, Br, I; l ═ organic ligands containing N, P, S ] have attracted considerable attention due to their excellent optical properties, structural diversity and abundance of copper in the natural world. At present, more than two thousand copper (I) -halogen hybrids are successfully prepared, and in recent years, researchers have successfully applied some copper (I) -halogen hybrids with excellent fluorescence property to the fields of photoelectric devices, fluorescent probes, biosensing and the like. Most of these reports are based on the study of copper (I) -iodide hybrids, and few reports have been made on copper (I) -bromide hybrids.
On the other hand, the conventional methods for preparing the copper (I) -halogen hybrid mainly include a solvothermal method, a redox method, a precursor reaction method and a vapor deposition method. The solvent method and the precursor reaction method mainly adopt cuprous as a raw material, but cuprous is poor in solubility in various organic solvents and unstable in water, so that a suitable solvent is difficult to find. In addition, the precursor synthesis method needs to firstly synthesize the precursor by using the monovalent halogen copper salt as the raw material, and then further react with the organic ligand, so the reaction steps are complex. According to the redox method, cupric salt is used as a raw material, and is subjected to reduction reaction with a reducing agent to obtain cuprous, so that the cuprous reacts with an organic ligand, and the reduction step increases the preparation cost and also makes the reaction step complicated. The vapor deposition method requires high temperature and high pressure, consumes high energy, and is prone to divalent copper-related by-products. Therefore, the development of a convenient and energy-saving preparation method of the copper (I) -bromine hybrid fluorescent material which is not limited by the solubility of the monovalent copper is of great significance.
Disclosure of Invention
Aiming at the problems, the grinding preparation method of the copper (I) -bromine hybrid fluorescent material is provided, and the copper (I) -bromine hybrid fluorescent material is prepared by mixing and grinding cuprous bromide and tetraalkylammonium bromide salt, dissolving the mixture after grinding reaction in a boiling organic solvent, and recrystallizing. The preparation method is simple and convenient, mild in condition, low in cost, short in time consumption, high in yield, suitable for batch production, and the prepared copper (I) -bromine hybrid material is good in fluorescence stability and has great application potential in the fields of chemical sensing analysis, optics, electrical devices and the like.
The invention relates to a grinding preparation method of a copper (I) -bromine hybrid fluorescent material, which is realized by the following technical scheme:
mixing and grinding cuprous bromide and tetraalkylammonium bromide, dissolving the mixture after grinding reaction in a boiling organic solvent, filtering while hot, standing and cooling the filtrate to separate out a solid, and drying the obtained solid in vacuum to obtain a product, thereby preparing the copper (I) -bromine hybrid fluorescent material.
The tetraalkylammonium bromide is one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, methyltriethylammonium bromide or methyltributylammonium bromide.
The cuprous bromide and the tetraalkylammonium bromide are mixed and ground, the feeding molar ratio of the cuprous bromide to the tetraalkylammonium bromide is 0.1-20: 1, and the grinding time is 0.1-6 hours.
The organic solvent comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, tert-pentanol, n-hexanol, cyclohexanol, n-octanol, ethylene glycol and glycerol;
the dosage of the organic solvent is 1-500 ml/g, and the cooling time is 0.1-72 hours; the vacuum drying temperature is 0-70 ℃, and the time is 0.5-72 hours.
The invention has the following advantages:
1. the preparation method is simple and convenient, has mild conditions, low cost, short time consumption and high yield, and is suitable for batch production.
2. The prepared copper (I) -bromine hybrid material has good fluorescence stability and has great application potential in the fields of chemical sensing analysis, optics, electrical devices and the like.
Drawings
FIG. 1 is a graph of fluorescence spectra of various copper (I) halogen cluster compounds;
FIG. 2 is a graph of X-ray powder diffraction peaks versus theoretical simulated peaks for different copper (I) halogen cluster compounds experimentally prepared;
detailed description of the invention
The present invention is described in further detail below with reference to examples, but it should not be construed that the present invention is limited to the examples, and any technologies implemented based on the present invention should be considered as the scope of the present invention.
A grinding preparation method of a copper (I) -bromine hybrid fluorescent material is characterized in that cuprous bromide and tetraalkylammonium bromide are mixed and ground, and then recrystallization is carried out to prepare the copper (I) -bromine hybrid material with different fluorescent colors.
Example 1
0.308 g of tetramethylammonium bromide and 0.572 g of cuprous bromide were weighed into a mortar, exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after the grinding reaction in 20ml of boiling isopropanol, filtering while the mixture is hot, standing and cooling the filtrate to separate out a solid, and drying the obtained solid in vacuum to obtain a product [ N (CH)3)4]3[Cu2Br5]. Obtained [ N (CH)3)4]3[Cu2Br5]The cluster compound emits yellow-green fluorescence under 254nm ultraviolet excitation, the maximum emission wavelength is about 510nm, and fluorescence spectrum data are shown in figure 1. The X-ray powder diffraction pattern of the prepared copper (I) halogen cluster compound is shown in figure 2, and the diffraction peak position of the copper (I) halogen cluster compound is consistent with a theoretical simulation pattern.
Example 2
0.82 g tetraethylammonium bromide and 0.28 g cuprous bromide were weighed into a mortar and exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after the grinding reaction in 20ml of boiling ethanol, filtering while the mixture is hot, standing and cooling the filtrate to separate out a solid, and drying the solid in vacuum to obtain a product [ N (C)2H5)4]2[Cu2Br4]. Obtained [ N (C)2H5)4]2[Cu2Br4]The cluster compound emits blue fluorescence under 254nm ultraviolet excitation, the maximum emission wavelength is about 460nm, and fluorescence spectrum data are shown in figure 1. The X-ray powder diffraction pattern of the prepared copper (I) halogen cluster compound is shown in figure 2, and the diffraction peak position of the copper (I) halogen cluster compound is consistent with a theoretical simulation pattern.
Example 3
0.80 g of tetrapropylammonium bromide and 0.28 g of cuprous bromide were weighed into a mortar, exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after grinding reaction in 20ml boiling ethanol, filtering while it is hot, and standing the filtrateCooling to separate out solid, vacuum drying to obtain product [ N (C)3H7)4]2[Cu4Br6]. Obtained [ N (C)3H7)4]2[Cu4Br6]The cluster compound emits orange-red fluorescence under 254nm ultraviolet excitation, the maximum emission wavelength is about 660nm, and fluorescence spectrum data are shown in figure 1. The X-ray powder diffraction pattern of the prepared copper (I) halogen cluster compound is shown in figure 2, and the diffraction peak position of the copper (I) halogen cluster compound is consistent with a theoretical simulation pattern.
Example 4
0.27 g of tetrapropylammonium bromide and 0.56 g of cuprous bromide were weighed into a mortar, exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after the grinding reaction in 20ml of boiling isopropanol, filtering while the mixture is hot, standing and cooling the filtrate to separate out a solid, and drying the obtained solid in vacuum to obtain a product [ N (C)3H7)4]2[CuBr2]. Obtained [ N (C)3H7)4]2[CuBr2]The cluster compound emits green fluorescence under 254nm ultraviolet excitation, the maximum emission wavelength is about 480nm, and fluorescence spectrum data are shown in figure 1. The X-ray powder diffraction pattern of the prepared copper (I) halogen cluster compound is shown in figure 2, and the diffraction peak position of the copper (I) halogen cluster compound is consistent with a theoretical simulation pattern.
Example 5
0.64 g of tetrabutylammonium bromide and 0.28 g of cuprous bromide were weighed into a mortar, exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after the grinding reaction in 20ml of boiling ethanol, filtering while the mixture is hot, standing and cooling the filtrate to separate out a solid, and drying the solid in vacuum to obtain a product [ N (C)4H9)4][CuBr2]. Obtained [ N (C)4H9)4][CuBr2]The cluster compound emits green fluorescence under 254nm ultraviolet excitation, the maximum emission wavelength is about 480nm, and fluorescence spectrum data are shown in figure 1. The X-ray powder diffraction pattern of the prepared copper (I) halogen cluster compound is shown in figure 2, and the diffraction peak position of the copper (I) halogen cluster compound is consistent with a theoretical simulation pattern.
Example 6
0.56 g of tributylmethylammonium bromide and 0.28 g of cuprous bromide were weighed into a mortar, exposed to air at room temperature of 25 ℃ and ground for 30 min. Dissolving the mixture after the grinding reaction in 20ml of boiling methanol, filtering while the mixture is hot, standing and cooling the filtrate to separate out solid, and drying the solid in vacuum to obtain the product [ N (C)4H9)3CH3]2[Cu4Br6]. Obtained [ N (C)4H9)3CH3]2[Cu4Br6]The cluster compound emits orange yellow fluorescence under the excitation of 254nm ultraviolet, and the maximum emission wavelength is about 620 nm.
Claims (5)
1. A grinding preparation method of a copper (I) -bromine hybrid fluorescent material is characterized by comprising the following steps: mixing and grinding cuprous bromide and tetraalkylammonium bromide, dissolving the mixture after grinding reaction in a boiling organic solvent, filtering while hot, standing and cooling the filtrate to separate out a solid, and drying the obtained solid in vacuum to obtain a product, thereby preparing the copper (I) -bromine hybrid fluorescent material.
2. The grinding preparation method of copper (I) -bromine hybrid fluorescent material according to claim 1, characterized in that: the tetraalkylammonium bromide is one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, methyltriethylammonium bromide or methyltributylammonium bromide.
3. The grinding preparation method of copper (I) -bromine hybrid fluorescent material according to claim 1, characterized in that: the cuprous bromide and the tetraalkylammonium bromide are mixed and ground, the feeding molar ratio of the cuprous bromide to the tetraalkylammonium bromide is 0.1-20: 1, and the grinding time is 0.1-6 hours.
4. The grinding preparation method of copper (I) -bromine hybrid fluorescent material according to claim 1, characterized in that: the organic solvent comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, tert-pentanol, n-hexanol, cyclohexanol, n-octanol, ethylene glycol or glycerol.
5. The grinding preparation method of copper (I) -bromine hybrid fluorescent material according to claim 1, characterized in that: the dosage of the organic solvent is 10-500ml/g, and the cooling time is 0.1-72 hours; the vacuum drying temperature is 0-70 ℃, and the time is 0.5-72 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521938A (en) * | 2020-10-20 | 2021-03-19 | 西安交通大学 | Organic-inorganic hybrid halide luminescent material and preparation method and application thereof |
| CN112898961A (en) * | 2021-01-25 | 2021-06-04 | 深圳大学 | Organic-inorganic hybrid scintillator and preparation method and application thereof |
| CN114621100A (en) * | 2022-03-10 | 2022-06-14 | 深圳大学 | Organic-inorganic hybrid copper-based halide material and preparation method thereof |
| CN115385804A (en) * | 2022-08-10 | 2022-11-25 | 重庆大学 | White-light amine copper halide single crystal and low-temperature preparation method and application thereof |
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| CN108127124A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of preparation method of the regulatable copper nano-cluster of fluorescence color |
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| CN108127124A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of preparation method of the regulatable copper nano-cluster of fluorescence color |
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| MILJA ASPLUND ET AL.,: ""Crystal Structure of Bis(tetraethylammonium) Di-μ-bromo-dibromodicuprate(I), [N(C2H5)4]2[Cu2Br4]"", 《ACTA CHEMICA SCANDINAVICA A》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521938A (en) * | 2020-10-20 | 2021-03-19 | 西安交通大学 | Organic-inorganic hybrid halide luminescent material and preparation method and application thereof |
| CN112521938B (en) * | 2020-10-20 | 2022-02-22 | 西安交通大学 | Organic-inorganic hybrid halide luminescent material and preparation method and application thereof |
| CN112898961A (en) * | 2021-01-25 | 2021-06-04 | 深圳大学 | Organic-inorganic hybrid scintillator and preparation method and application thereof |
| CN114621100A (en) * | 2022-03-10 | 2022-06-14 | 深圳大学 | Organic-inorganic hybrid copper-based halide material and preparation method thereof |
| CN114621100B (en) * | 2022-03-10 | 2023-09-15 | 深圳大学 | Organic-inorganic hybrid copper-based halide material and preparation method thereof |
| CN115385804A (en) * | 2022-08-10 | 2022-11-25 | 重庆大学 | White-light amine copper halide single crystal and low-temperature preparation method and application thereof |
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