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Regulation of Eu2+ Occupancy Luminescence in α-cordierite by Cl-/F- Substitution and Na+ Site Addition
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Wenjiao DENG1, 2, Weihua ZHU2, Zhifeng ZHANG1, 2, Jian LIU1, Fabin CAO1, 2, Xingmei SHEN1
Journal of the Chinese Ceramic Society | 2025, 53(2) : 267 - 279
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Journal of the Chinese Ceramic Society | 2025, 53(2): 267-279
• Research Article •
Regulation of Eu2+ Occupancy Luminescence in α-cordierite by Cl-/F- Substitution and Na+ Site Addition
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Wenjiao DENG1, 2, Weihua ZHU2, Zhifeng ZHANG1, 2, Jian LIU1, Fabin CAO1, 2, Xingmei SHEN1
Affiliations
  • 1.Key Laboratory of Metallurgical Emission Reduction&Resources Recycling, Anhui University of Technology, Minstry of Education, Maanshan 243002, Anhui, China
  • 2.Key Laboratory of Metallurgical Engineering and Comprehensive Utilization of Resources, Anhui Industrial University, Maanshan 243002, Anhui, China
  • DENG Wenjiao (2001-), female, Master candidate. E-mail:

About Author:

DENG Wenjiao (2001-), female, Master candidate. E-mail:

Published: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240119
Outline
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With the development of technology and the increasing emphasis on patent protection, anti-counterfeiting technologies are emerging one after another. Among numerous anti-counterfeiting technologies, photoluminescence anti-counterfeiting technology is widely used in the field of anti-counterfeiting due to its excellent optical properties. However, traditional fluorescent powder anti-counterfeiting only changes its color when the UV excitation light source is changed, lacking dynamic changes in the time dimension. Therefore, it is necessary to develop an efficient anti-counterfeiting new luminescent material. Currently, the use of cation substitution and multiple occupied sites has become a popular strategy for tunable emission. Due to the interaction between activators and anions, the energy difference between the energy levels of the luminescent center ion can be altered. Therefore, anion substitution can also be an effective strategy to adjust the photoluminescence performance. This article describes the preparation of Mg2-xNaxAl4Si5O18-xQx:1%Eu2+ (Q=Cl, F) by glass relaxation crystallization method, which introduces Na+ sites and replaces 1O2- with 2F-/2Cl- to achieve the opening of the [Al/Si]6O18 hexagonal ring structure, providing a rich field environment for the central ion Eu2+ to enter the α-Mg2Al4Si5O18 structure: Na+ sites, Mg2+ sites, and hexagonal ring channel sites. By regulating the Eu2+ occupation, , and structures are formed, achieving blue to yellow light emission.

Methods

Based on the composition of 2MgO-2Al2O3-5SiO2, a series of Mg2-xNaxAlSiO18-xQx:1%Eu2+ (Q=Cl, F) fluorescent powders (abbreviated as 1Eu2+, 1Eu2+-xNaCl and 1Eu2+-xNaF) were prepared by introducing NaCl (A.R.), NaF (A.R.), and Eu2O3 (A.R.), and glass crystallization after quenching the reactants in ice water. Doping concentration: NaCl are 0, 1%, 2%, 3%, and 5% molar fraction and NaF are 1%, 2.0%, 2.5%, and 3.0%. Weigh according to the set reactant stoichiometry, and grind the mixture thoroughly in an agate mortar for 30 minutes to ensure even mixing. Transfer it to a graphite crucible, place it in a well furnace, heat it up to 1550 ℃ at a heating rate of 5°/min, and keep it in an argon atmosphere for 30 minutes. Then, pour the molten reactants into ice water for rapid cooling, dry and grind to obtain the precursor glass sample PG. Finally, the precursor glass sample PG will be kept in a reducing atmosphere at 1100 ℃ for 1 hour, and then ground into a crystalline sample after cooling in the furnace.

Results and discussion

When single doped with Eu2+, Eu2+ occupies the Mg2+ and channel sites in the α- cordierite structure, forming and luminescent structural units. When NaF is introduced, Eu2+ occupies the Na+ site to form a new luminescent structural unit . Introducing NaCl/NaF can enhance the occupation of channel sites by Eu2+. When F-/Cl- replaces O2- and partially opens the hexagonal ring of the channel, the channel sites can accommodate more Eu2+, which makes it easier to explain the increased structure formed when NaCl/NaF is introduced. When NaCl is introduced, Eu2+ hardly occupies the Na+ sites, while when NaF is introduced, as the amount of NaF introduced increases, Eu2+ occupies more Na+ sites. That is because the stronger electronegativity of O2- than Cl-, replacing O2- with Cl- can introduce more covalences in the lattice, that means Eu2+- Cl- has stronger contradiction and polarization than Eu2+-O2-. Moreover, the ionic radius of Cl- differs significantly from that of O2-, making the formation of Eu2+-Cl- more difficult. Therefore, when Cl- is introduced, Eu2+ does not occupy the Na+ sites. Similarly, when F- is introduced, Eu2+ is more likely to occupy Na+ sites. In addition, the amount of Eu2+ introduced is constant, and when Na+-Cl- is introduced, Eu2+ does not occupy the Na+ sites. As the structure increases, the corresponding generated structure will decrease. As a ligand, compared to Mg2+-O2-, the introduction of Na+-F- has a smaller steric hindrance and greater bonding ability due to the smaller radius and greater electronegativity of F- (compared to O2-) ions. Eu2+ will preferentially occupy Na+ sites with similar radii and then occupy sites. As the amount of NaF introduced increases, more structures are formed while the corresponding structures decrease.

Conclusions

The main conclusions of this paper are summarized as following. This article mainly studies the effect of introducing Na+ sites and Cl-/F- substituted O2- on the occupancy of Eu2+ in the α- cordierite structure. Exploring the mechanism of distinguishing subgrain structure evolution for luminescent structural probes. By introducing Na+ sites and anionic Cl-/F- substituted O2- to regulate the selective occupancy of Eu2+, temperature sensitive emission from blue white to yellow light is achieved. Cl-/F- substituted O2- opens the hexagonal ring structure of the channel, which facilitates the occupation of channel sites by Eu2+. The proportion of the formed structure increases from 33.32% to 64.89%. When introducing Na+ sites, the presence of F- increases the proportion of Eu2+ occupying Na+ sites to form structures to 18.63%. This series of fluorescent powders can significantly improve their thermal quenching performance when NaF is introduced, and have superior thermal stability at 150 ℃. This series of fluorescent powders can be widely used in the fields of adjustable luminescence, detection, and anti-counterfeiting.

selective occupancy  /  substitution  /  luminescent structure  /  six element ring channel position  /  tunable luminescence
邓文娇, 朱伟华, 张志峰, 刘建, 曹发斌, 申星梅. Cl-/F-取代及增加Na+位调控Eu2+在α-堇青石中占位发光. 硅酸盐学报, 2025 , 53 (2) : 267 -279 . DOI: 10.14062/j.issn.0454-5648.20240119
Wenjiao DENG, Weihua ZHU, Zhifeng ZHANG, Jian LIU, Fabin CAO, Xingmei SHEN. Regulation of Eu2+ Occupancy Luminescence in α-cordierite by Cl-/F- Substitution and Na+ Site Addition[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (2) : 267 -279 . DOI: 10.14062/j.issn.0454-5648.20240119
Year 2025 volume 53 Issue 2
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2
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Article Info
doi: 10.14062/j.issn.0454-5648.20240119
  • Receive Date:2024-02-07
  • Online Date:2026-10-22
  • Published:2025-02-20
Article Data
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History
  • Received:2024-02-07
  • Revised:2024-03-02
Funding
Affiliations
    1.Key Laboratory of Metallurgical Emission Reduction&Resources Recycling, Anhui University of Technology, Minstry of Education, Maanshan 243002, Anhui, China
    2.Key Laboratory of Metallurgical Engineering and Comprehensive Utilization of Resources, Anhui Industrial University, Maanshan 243002, Anhui, China

Corresponding:

CAO Fabin (1973-), male, Ph.D., Associate Professor; E-mail: ;
SHEN Xingmei (1982-), female, Ph.D., Assosiate Professor.
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表12种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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