硅酸盐学报

Cl^-/F^-取代及增加Na⁺位调控Eu²⁺在α-堇青石中占位发光

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邓文娇 ¹^,² , 朱伟华 ² , 张志峰 ¹^,² , 刘建 ¹ , 曹发斌 ¹^,² , 申星梅 ¹

硅酸盐学报 | 研究论文 2025,53(2): 267-279

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硅酸盐学报 |研究论文 2025 , 53 (2) : 267 -279

Cl^-/F^-取代及增加Na⁺位调控Eu²⁺在α-堇青石中占位发光

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邓文娇¹^,², 朱伟华², 张志峰¹^,², 刘建¹, 曹发斌¹^,², 申星梅¹

作者信息

^1．安徽工业大学，冶金减排与资源综合利用教育部重点实验室，安徽马鞍山 243002

^2．安徽工业大学，冶金工程与资源综合利用安徽省重点实验室，安徽马鞍山 243002

通讯作者:

曹发斌（1973—），男，博士，副教授。

申星梅（1982—），女，博士，副教授。

作者简介:

邓文娇（2001—），女，硕士研究生。

Regulation of Eu²⁺ Occupancy Luminescence in α-cordierite by Cl^-/F^- Substitution and Na⁺ Site Addition

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

Corresponding Author:

CAO Fabin (1973-), male, Ph.D., Associate Professor; E-mail: fbcao7309@126.com;

SHEN Xingmei (1982-), female, Ph.D., Assosiate Professor. xxxxmx@126.com

DENG Wenjiao (2001-), female, Master candidate. E-mail: 13786572428@139.com

出版时间: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240119

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摘要

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在α-Mg₂Al₄Si₅O₁₈结构中，引入了Na⁺位、Cl^-/F^-取代O^2-调控Eu²⁺选择性占位，以其作为发光结构探针，将成为区分亚晶结构演变的补充手段。本工作采用玻璃弛豫结晶法制备了一系列的Mg_2-_xNa_xAl₄Si₅O_18-_xQ_x：1%Eu²⁺（摩尔分数，Q=Cl，F）荧光粉，系统地研究了Eu²⁺占位诱导发光结构演变规律。通过Cl^-和F^-取代O^2-使六元环开环调控Eu²⁺在α-堇青石结构中Mg²⁺位、通道位及Na⁺位中占位，诱导出光色可调的温度高敏性光发射。引入Na⁺-F^-进入基体晶格内可明显改进荧光粉热猝灭性能，其在150 ℃时热稳定性好，可广泛用于可调发光、防伪和检测领域。

关键词

选择性占位 / 取代 / 发光结构 / 六元环通道位 / 可调发光

Abstract

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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 Mg_2-_xNa_xAl₄Si₅O_18-_xQ_x:1%Eu²⁺ (Q=Cl, F) by glass relaxation crystallization method, which introduces Na⁺ sites and replaces 1O^2- 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 Mg_2-_xNa_xAlSiO_18-_xQ_x: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 O^2- 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 O^2- than Cl^-, replacing O^2- with Cl^- can introduce more covalences in the lattice, that means Eu²⁺- Cl^- has stronger contradiction and polarization than Eu²⁺-O^2-. Moreover, the ionic radius of Cl^- differs significantly from that of O^2-, 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⁺-O^2-, 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 O^2-) 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 O^2- 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 O^2- to regulate the selective occupancy of Eu²⁺, temperature sensitive emission from blue white to yellow light is achieved. Cl^-/F^- substituted O^2- 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.

Key words

selective occupancy / substitution / luminescent structure / six element ring channel position / tunable luminescence

引用本文

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

基金

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安徽省自然科学基金项目(1808085ME136)

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2025年第53卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240119

接收时间：2024-02-07
首发时间：2026-10-22
出版时间：2025-02-20

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收稿日期：2024-02-07
修回日期：2024-03-02

基金

安徽省自然科学基金项目(1808085ME136)

作者信息

^1．安徽工业大学，冶金减排与资源综合利用教育部重点实验室，安徽马鞍山 243002

^2．安徽工业大学，冶金工程与资源综合利用安徽省重点实验室，安徽马鞍山 243002

通讯作者:

曹发斌（1973—），男，博士，副教授。

申星梅（1982—），女，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240119

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2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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