CN-116574272-B - Cerium-based metal-organic framework material capable of emitting white light as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of luminescent materials, relates to a cerium-based metal-organic frame for white light emission, and a preparation method and application thereof, and aims to solve the problems that a traditional white light LED can only prepare multi-color fluorescent powder by utilizing multi-metal compounding or multi-matrix compounding and high-temperature sintering, and can emit white light only by matching with a corresponding LED chip, and the corresponding preparation condition is complex and high in cost. Adding 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid into N, N-dimethylformamide, adding cerium salt into water, mixing the two solutions, adding nitric acid, and carrying out hydrothermal reaction to obtain the cerium-based metal-organic framework material with white light emission. The preparation method disclosed by the invention is simple, and the yield is higher (more than or equal to 82%). The prepared cerium-based metal-organic framework material can realize full-spectrum white light emission of single matrix and single metal ion, and the luminous color coordinate value of the cerium-based metal-organic framework material is close to a white light emission area (0.33 ).

Inventors

• Yue dan
• WANG ZHENLING
• CHEN DONG
• LI WEIDONG
• ZHANG BING
• QIN BOWEN
• MA QIANG
• LIU YAN
• ZHANG XIANGDAN
• DUAN QUNPENG

Assignees

• 河南工程学院

Dates

Publication Date

20260505

Application Date

20230612

Claims (6)

1. 1. A method for preparing a cerium-based metal-organic framework material for white light emission, which is characterized by comprising the following steps: (1) Adding 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid into N, N-dimethylformamide to form a 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution, wherein the concentration of the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution is 13.3-40 mg/mL; (2) Adding cerium salt into water to form cerium salt solution, wherein the concentration of the cerium salt solution is 1.5-2.7 mg/mL; (3) Mixing the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution obtained in the step (1) and the cerium salt solution obtained in the step (2), adding nitric acid, and performing hydrothermal reaction to obtain the cerium-based metal-organic framework material with white light emission, wherein the temperature of the hydrothermal reaction is 150-180 ℃, and the time of the hydrothermal reaction is 72-96 hours.
2. 2. The method of claim 1, wherein the cerium salt in the step (2) is any one of cerium chloride, cerium acetate or cerium nitrate.
3. 3. The method for preparing a white light-emitting cerium-based metal-organic framework material according to claim 1, wherein the mass ratio of 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid to cerium salt in the step (3) is 1 (0.95-1.3).
4. 4. The method for preparing a white light-emitting cerium-based metal-organic framework material according to claim 3, wherein the volume ratio of the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution, cerium salt solution and nitric acid in the step (3) is (0.5-1.5): (10-12): (0.1-0.15), and the mass fraction of nitric acid is 68%.
5. 5. The white light-emitting cerium-based metal-organic framework material prepared by the method according to any one of claims 1 to 4, wherein the white light-emitting cerium-based metal-organic framework material has an ordered crystal structure, is monoclinic, has a space group of P21/c, and has unit cell parameters of a= 17.4278 (5)/a, b= 12.1359 (3)/a, c= 7.4214 (2)/a, α=90 °, β= 92.644 °, γ=90°, v= 1567.97 (7)/a 3 , and z=4.
6. 6. Use of the white light emitting cerium based metal-organic framework material of claim 5 in a white light emitting diode.

Description

Cerium-based metal-organic framework material capable of emitting white light as well as preparation method and application thereof Technical Field The invention belongs to the technical field of luminescent materials, and relates to a preparation method and application of a cerium-based metal-organic framework for white light emission. Background White-light-emitting-diode (WLED) has the advantages of long service life, high efficiency, small volume and the like, and is one of the most ideal light-emitting elements at present. The white light LED is prepared by combining LED chips with different luminous colors to obtain white light, the method needs fluorescent powder and chips with various colors, the power of the different chips is different, the circuit design is complex, the cost is high, the blue light or ultraviolet LED chip is matched with corresponding fluorescent powder, for example, the blue light, green light and red light emitted fluorescent powder is matched with the ultraviolet LED chip to obtain the white light LED, or the blue light LED chip is matched with yellow fluorescent powder to obtain the white light LED, and the efficiency of the white light LED prepared by the method is high. YAG: ce 3+ yellow fluorescent material is synthesized by adopting a high-temperature solid phase method, such as von, and the influence of calcination time, calcination temperature and Ce 3+ concentration on the luminous intensity of the fluorescent powder is studied by utilizing an orthogonal analysis method. The obtained fluorescent powder has the best luminous performance under the conditions of the calcination temperature of 1600 ℃ and the Ce 3+ concentration of 0.12 mol and the calcination time of 4 h. Boric acid is used as a fluxing agent, and when the concentration content of the boric acid is 1.2 wt%, the luminous intensity of the fluorescent powder is increased by about 40%. The excitation peak of the YAG-Ce 3+ fluorescent powder shows a bimodal characteristic, wherein the maximum excitation peak is 467-nm, and the maximum emission peak is 529-nm. Therefore, YAG:Ce 3+ yellow fluorescent powder can be matched with a blue light GaN chip to prepare the double-primary-color LED. However, the same needs different color fluorescent powder, and the traditional fluorescent powder preparation method needs high temperature sintering, and the preparation condition is complex (Feng Ying, tong Yiping, jie Fang, etc. the synthesis of YAG for white light LED: ce 3+ fluorescent powder and the luminescence property research [ J ]. Guangzhou chemical industry, 2019,47 (10): 69-71+84). Therefore, the preparation of the fluorescent powder with full spectrum white light emission by adopting a simple method has important research significance. Disclosure of Invention Aiming at the technical problems that a traditional white light LED in the prior art can be prepared into multi-color fluorescent powder by multi-metal compounding or multi-matrix compounding and high-temperature sintering, white light can be emitted by matching with a corresponding LED, and the corresponding preparation condition is complex and the cost is high, the invention provides a preparation method and application of a cerium-based metal-organic framework for white light emission. The cerium-based metal-organic framework material is synthesized by a hydrothermal method in one step, the method is simple, the yield is high, and the full spectrum white light emission of single matrix and single metal ion can be realized. In order to achieve the above purpose, the technical scheme of the invention is realized as follows: A preparation method of a cerium-based metal-organic framework material capable of emitting white light comprises the following steps: (1) Adding 4,4'- (1H-pyrazole-1, 3-diyl) dibenzoic acid to N, N-dimethylformamide to form a solution of 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid; (2) Adding cerium salt into water to form cerium salt solution; (3) Mixing the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution obtained in the step (1) and the cerium salt solution obtained in the step (2), adding nitric acid, and performing hydrothermal reaction to obtain the cerium-based metal-organic framework material with white light emission. The concentration of the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution in the step (1) is 13.3-40 mg/mL. And (3) cerium salt in the step (2) is any one of cerium chloride, cerium acetate or cerium nitrate. The cerium chloride is cerium chloride hexahydrate, and the cerium nitrate is cerium nitrate hexahydrate. And (3) the concentration of the cerium salt solution in the step (2) is 1.5-2.7 mg/mL. In the step (3), the mass ratio of the 4,4' - (1H-pyrazol-1, 3-diyl) dibenzoic acid to the cerium salt is 1 (0.95-1.3). In the step (3), the volume ratio of the 4,4' - (1H-pyrazole-1, 3-diyl) dibenzoic acid solution to the cerium salt solution to the nitric acid is (0.5-1.5): 10-12): 0.1-0.15, wherein the