稀土配合物功能材料: 从分子设计和性能调控到前沿应用★

doi:10.6023/A26060211

化学学报 ›› 2026, Vol. 84 ›› Issue (8): 1326-1342.DOI: 10.6023/A26060211 上一篇下一篇

综述

稀土配合物功能材料: 从分子设计和性能调控到前沿应用^★

宋福嘉^a, 苏平如^a, 唐瑜^a^,^b^,^*()

^a 兰州大学化学化工学院稀土功能材料教育部工程研究中心稀土功能材料教育部工程研究中心兰州 730000
^b 白云鄂博稀土资源研究与综合利用全国重点实验室包头稀土研究院包头 014030

投稿日期:2026-06-20 发布日期:2026-07-30

作者简介:

宋福嘉, 兰州大学化学化工学院2025级博士研究生, 师从唐瑜教授. 主要研究兴趣为手性超分子组装体的构建及手性传递.

苏平如, 兰州大学青年研究员, 硕士生导师. 2020 年 12 月毕业于兰州大学无机化学专业, 获理学博士学位, 导师唐瑜教授; 2021 至 2023 年, 在深圳大学李霄鹏教授课题组从事博士后工作; 2023 年 8 月加入兰州大学化学化工学院, 从事无机化学教学科研工作. 研究方向为稀土配合物自组装及其应用.

唐瑜, 兰州大学二级萃英学者, 博士生导师. 教育部长江学者特聘教授, 国家高层次人才特支计划教学名师, 基金委稀土功能材料创新研究群体负责人, 中国化学会会士, 英国皇家化学会会士, 国务院政府特殊津贴专家. 兼任国务院学位委员会第八届化学学科评议组成员, 中国化学会副秘书长, 中国化学会无机化学学科委员会、科普工作委员会、女化学工作者委员会委员; Aggregate期刊顾问编委, Inorg. Chem. 副主编, Inorg. Chem. Front.、《中国稀土学报》(中、英文版) 、《高等学校化学学报》(中英文版)、《无机化学学报》和《结构化学》等期刊编委. 近期的研究工作主要集中在稀土配位化学和功能材料研究, 主持国家自然科学基金创新研究群体项目、重点项目和面上项目, 111 引智基地项目, 甘肃省重大专项、重点研发计划和企业合作项目等研究课题. 以通讯作者或第一作者在 Chem. Soc. Rev.、Acc. Chem. Res.、Natl. Sci. Rev.、CCS Chem.、Angew. Chem. Int. Ed.、J. Am. Chem. Soc.、Energy Environ. Sci.、Adv. Mater.、ACS Nano 和 Sci. China Chem. 等刊物发表论文 200 余篇.

^★“纪念兰州大学化学学科创建80周年”专辑

基金资助:
国家自然科学基金(22221001); 国家自然科学基金(22131007); 国家自然科学基金(22401119); 111引智计划项目(B20027); 甘肃省科技计划项目(24ZD13GA015); 甘肃省科技计划项目(23ZDGA012); 甘肃省科技计划项目(26JDRA008); 中央高校基本科研业务费专项资金项目(lzujbky-2025-jdzx13)

Rare-Earth Complex Functional Materials: From Molecular Design and Property Modulation to Cutting-Edge Applications^★

Fu-jia Song^a, Pingru Su^a, Yu Tang^a^,^b^,^*()

^a College of Chemistry and Chemical Engineering, Lanzhou University, Engineering Research Center of Rare Earth Functional Materials, Ministry of Education, Lanzhou 730000, China
^b State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou Research Institute of Rare Earths, Baotou 014030, China

Received:2026-06-20 Published:2026-07-30
Contact: *E-mail: tangyu@lzu.edu.cn
About author:
^★For the VSI “Celebration of 80th Anniversary of Chemistry in Lanzhou University”
Supported by:
National Natural Science Foundation of China(22221001); National Natural Science Foundation of China(22131007); National Natural Science Foundation of China(22401119); 111 project(B20027); Science and Technology Program of Gansu Province(24ZD13GA015); Science and Technology Program of Gansu Province(23ZDGA012); Science and Technology Program of Gansu Province(26JDRA008); Fundamental Research Funds for the Central Universities(lzujbky-2025-jdzx13)

文章分享

1. Supporting Information-A26050148.pdf(1922KB)

摘要/Abstract

稀土元素因其特殊的4f电子构型而展现出优异的光、电、磁性能, 已在信息、能源和医疗等领域获得广泛应用. 将稀土离子与有机配体相结合所形成的稀土配合物, 兼具稀土离子和有机配体的结构性质特点, 同时具有分子设计的灵活性, 另外, 其独特的组装特性可以实现从配合物分子到功能材料的跨尺度构筑和性能调控, 已成为实现稀土资源高效利用的重要途径. 理性设计配体不仅能够精确构筑配合物结构, 还可实现对性能的定向调控, 这对揭示构效关系以及发展光电、传感、催化及能源等新型材料具有重要意义. 尽管已取得显著进展, 该领域在合成方法优化、新材料创制以及稳定性提升等方面仍面临挑战. 本文综述了本课题组近年的研究工作, 涵盖分子设计、性能调控与应用探索, 重点介绍了利用配位自组装、原位配位和微结构演化等策略实现的精准合成与功能调控, 并展示了这些材料在智能发光及光功能材料和器件中的应用. 最后, 分析了该领域面临的机遇与挑战, 以期为稀土配合物功能材料的精准合成方法学提供参考.

关键词: 稀土配合物, 功能材料, 精准合成, 分子设计, 性能调控

Rare earth elements exhibit outstanding optical, electrical, and magnetic properties owing to their unique 4f electronic configuration, and have found widespread applications in fields such as information technology, energy, and healthcare. Rare earth complexes formed by combining rare earth ions with organic ligands integrate the structural characteristics of both components, while offering considerable flexibility in molecular design. Furthermore, their distinctive assembly features enable the cross-scale construction and performance modulation of materials ranging from discrete complex molecules to functional materials, thus representing a crucial pathway toward the efficient utilization of rare earth resources. The rational design of ligands not only facilitates the precise construction of complex structures, but also enables the targeted regulation of their properties, which is of great significance for elucidating structure-property relationships and for developing novel materials for optoelectronics, sensing, catalysis, and energy-related applications. Despite remarkable progress, challenges remain in this field concerning the optimization of synthetic methodologies, the creation of new materials, and the enhancement of stability. This review summarizes the recent research advances made by our group, covering aspects from molecular design and property modulation to application exploration. Emphasis is placed on the precise synthesis and functional regulation achieved through strategies such as coordination-driven self-assembly, in situ coordination, and microstructure evolution, along with the demonstration of these materials in intelligent luminescent and photo-functional materials and devices. Finally, we analyze the opportunities and challenges confronting this field, with the aim of providing a reference for the development of precise synthetic methodologies for rare earth complex-based functional materials.

Key words: rare earth complexes, functional materials, precise synthesis, molecular design, property regulation

引用此文

宋福嘉, 苏平如, 唐瑜. 稀土配合物功能材料: 从分子设计和性能调控到前沿应用^★[J]. 化学学报, 2026, 84(8): 1326-1342.

Fu-jia Song, Pingru Su, Yu Tang. Rare-Earth Complex Functional Materials: From Molecular Design and Property Modulation to Cutting-Edge Applications^★[J]. Acta Chimica Sinica, 2026, 84(8): 1326-1342.

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图/表 17

图1. 稀土配合物功能材料的精准合成与分子/原子级性能调控及其在智能发光材料和光转换材料及器件领域应用的示意图

Figure 1. Schematic representation of precision synthesis and molecular/atomic-scale property modulation of rare-earth complex functional materials, and their applications in smart luminescent materials and light-conversion materials and devices

图2. EuL1的合成途径及EuL1的三个检测通道

Figure 2. Synthetic route of EuL1 and its three detection channels

图3. 构筑策略及自组装过程示意图: (a) Zn2Er4L24 超分子笼的构筑策略及自组装过程示意图; (b) Zn4Er6L36 和 Zn2Er8L48 超分子笼的构筑策略及自组装过程示意图

Figure 3. Schematic illustration of the construction strategies and self-assembly processes for (a) the Zn2Er4L24 supramolecular cage; and (b) the Zn4Er6L36 and Zn2Er8L48 supramolecular cages

图4. (a) Eu配合物自组装的示意图; (b) Eu-NPs的SEM图像; (c, d) Eu-NPs的TEM图像; (e) Eu-NPs的元素分布图; (f, g) Eu配合物在丙酮/水中的发光光谱; (h) Eu配合物在丙酮/D2O或丙酮/H2O中的发光寿命; (i) Eu配合物在不同比例丙酮/水中的总发光量子产率(Φoverall)和从配体到Eu3+的能量转移效率(Φsen)

Figure 4. (a) Schematic illustration of the self-assembly of Eu complexes; (b) SEM image of Eu-NPs; (c, d) TEM images of Eu-NPs; (e) Elemental mapping of Eu-NPs; (f, g) Luminescence spectra of Eu complexes in acetone/water; (h) Luminescence lifetimes of Eu complexes in acetone/D2O or acetone/H2O; (i) Total luminescence quantum yields (Φoverall) and energy transfer efficiencies from the ligand to Eu3+ (Φsen) of Eu complexes in acetone/water with different ratios

图5. 配合物(Eu-L)与碳点(CD)的杂化组装及其pH响应荧光调制机理

Figure 5. Schematic illustration of the hybrid assembly of the Eu-L complex with carbon dots (CDs) and the mechanism of pH-responsive fluorescence modulation

图6. (a) [YbL3]3+介导的CsPbBr3纳米晶自组装形成有序三维立方结构示意图; (b) 带负电的银纳米颗粒(Ag-NPs)通过静电作用组装于带正电的[EuL3]3+周围, 形成Eu/Ag-NPs, 从而增强荧光强度和拉曼信号并调控发光寿命, 随后将其涂覆于基底, 干燥后形成随机二维图案, 采用共聚焦荧光-拉曼联用系统对PUF标签进行读取

Figure 6. (a) Schematic illustration of [YbL3]3+-mediated self-assembly of CsPbBr3 nanocrystals into ordered three-dimensional cubic superstructures; (b) Negatively charged Ag nanoparticles (Ag-NPs) assemble around positively charged [EuL3]3+ via electrostatic interactions to form Eu/Ag-NPs, which simultaneously enhance fluorescence intensity and Raman signals while modulating luminescence lifetimes. The resulting assemblies are then coated onto a substrate and dried to form random two-dimensional patterns. A confocal fluorescence-Raman combined system is employed to read the PUF tags

图7. (a) 基于稀土配合物构筑系列功能材料的方法示意图; (b) Fe3O4@mSiO2@MOF复合材料的合成过程及K+离子分离机理示意图; (c) 将Eu离子与HPBA封装于介孔二氧化硅中, 得到SiO2-(Eu2+, Eu3+)-HPBA

Figure 7. (a) Schematic illustration of the methodology for constructing a series of functional materials based on rare-earth complexes; (b) Schematic illustration of the synthesis process of Fe3O4@mSiO2@MOF composites and the mechanism of K+ ion separation; (c) Encapsulation of Eu ions and HPBA into mesoporous silica to obtain SiO2-(Eu2+, Eu3+)-HPBA

图8. (a) CHOL-A和CHOL-B分别组装形成纳米颗粒(NPs)和螺旋纳米带(HNRs)的示意图; (b) CHOL-A与CHOL-B组装体形貌; (c) HNRs-Eu和 HNRs-Eu(L1)3 CPL信号对于温度和湿度响应的示意图; (d~g) N HNRs-Eu和HNRs-Eu(L1)3的荧光强度在不同温度及水含量下的变化及循环性

Figure 8. (a) Schematic illustration of the assembly of CHOL-A/B into nanoparticles (NPs) and helical nanoribbons (HNRs), respectively; (b) Morphology of the assemblies formed from CHOL-A/B; (c) Schematic illustration of the CPL signal responses of HNRs-Eu and HNRs-Eu(L1)3 to temperature and humidity; (d~g) Fluorescence intensity variations and reversibility of HNRs-Eu and HNRs-Eu(L1)3 under different temperatures and water contents

图9. (a) 在纳米材料表面上原位配位生长MOF示意图; (b) 沿CeO2 [111]方向观察的CeO2@NiFe-MOFs的原子级HAADF-STEM图像(c) 对应的(b)的傅里叶变换图案; (d) CeO2@NiFe-MOFs中CeO2的投影结构模型; (e) 经FFT滤波的原子分辨率模拟图像; (f) CeO2@NiFe-MOFs的高分辨TEM图像; (g) CeO2@NiFe-MOF异质结构的元素分布图; (h) 在反应过程中CeO2@NiFe-MOF异质结构中可能发生的电子转移路径; (i) CeO2/CoS杂化纳米结构合成过程示意图; CoS前驱体(j, m)和14.6% CeO2/CoS (k, n)的SEM和TEM图像; (l, o) 14.6% CeO2/CoS的高分辨TEM图像; (p) 14.6% CeO2/CoS的元素分布图

Figure 9. (a) Schematic illustration of in situ coordination growth of MOF on the surface of nanomaterials; (b) Atomic-scale HAADF-STEM image of CeO2@NiFe-MOFs viewed along the [111] direction of CeO2; (c) Corresponding Fourier transform (FFT) pattern of (b); (d) Projected structural model of CeO2 within CeO2@NiFe-MOFs; (e) Atomic-resolution simulated image after FFT filtering; (f) High-resolution TEM image of CeO2@NiFe-MOFs; (g) Elemental mapping of the CeO₂@NiFe-MOF heterostructure; (h) Possible electron transfer pathways in the CeO2@NiFe-MOF heterostructure during the reaction process; (i) Schematic representation of the synthesis procedure for CeO2/CoS hybrid nanostructures. SEM and TEM images of the CoS precursor (j, m) and of 14.6 % CeO2/CoS (k, n); (l, o) High-resolution TEM images of 14.6 % CeO2/CoS; (p) Elemental mapping of 14.6 % CeO2/CoS

图10. (a) Ce掺杂MIL-88A辅助制备中空Ni-Fe-Ce LDH微胶囊示意图; (b, c) 30% Ce-NiFe-LDH微胶囊的SEM和(d) TEM图像; (e) 30% Ce-NiFe-LDH的HAADF-STEM图像; (f, g) HR-TEM图像和相应的SAED图案(插图); (h, i) 30% Ce-NiFe-LDH的单个微胶囊和局部放大微胶囊的HAADF-STEM图像及元素分布图

Figure 10. (a) Schematic illustration of the preparation of hollow Ni-Fe-Ce LDH microcapsules assisted by Ce-doped MIL-88A; (b, c) SEM images and (d) TEM image of 30 % Ce-NiFe-LDH microcapsules; (e) HAADF-STEM image of 30 % Ce-NiFe-LDH, and (f, g) HR-TEM images with the corresponding SAED patterns (insets); (h, i) HAADF-STEM images and elemental mapping of a single microcapsule and a magnified region of the microcapsule for 30 % Ce-NiFe-LDH

图11. (a) Ce1-xTixO2/CeO2制备的示意图; (b, c) MOF(Ti)和MOF(Ce)/a-TiO2-0.8的SEM图像; (d) MOF(Ce)/a-TiO2-0.8的TEM图像; (e) MOF(Ce)/a-TiO2-0.8的HAADF-STEM图像和元素分布图; (f) CTO/CeO2-0.8的SEM图像; (g) CTO/CeO2-0.8的TEM图像; (h) CTO/CeO2-0.8的HR-TEM图像及相应的SAED图案; (i) CTO/CeO2-0.8的HAADF-STEM图像和元素分布图; (j) CTO/CeO2-0.8中CTO部分的原子级HAADF-STEM图像; (k) (j)对应的FFT图案. (l) CTO/CeO2-0.8的FFT滤波原子分辨率模拟图像; (m) CTO/CeO2-0.8中CTO部分对应的能谱元素分布图

Figure 11. (a) Schematic illustration of the preparation of Ce1-xTixO2/CeO2; (b, c) SEM images of MOF(Ti) and MOF(Ce)/a-TiO2-0.8, respectively; (d) TEM image of MOF(Ce)/a-TiO2-0.8; (e) HAADF-STEM image and elemental mapping of MOF(Ce)/a-TiO2-0.8; (f) SEM image of CTO/CeO2-0.8; (g) TEM image of CTO/CeO2-0.8; (h) HR-TEM image and the corresponding SAED pattern of CTO/CeO2-0.8; (i) HAADF-STEM image and elemental mapping of CTO/CeO2-0.8; (j) Atomic-scale HAADF-STEM image of the CTO region in CTO/CeO2-0.8; (k) Corresponding FFT pattern of (j); (l) FFT-filtered atomic-resolution simulated image of CTO/CeO2-0.8; (m) Corresponding EDS elemental mapping of the CTO region in CTO/CeO2-0.8

图12. (a) QDs-Eu(PBA)3AA的形成过程示意图; (b) 荧光图像展示双响应光学记录与加密, 包含图案设计流程及加密−解密机制; (c) 比色荧光时间−温度指示器及其多功能应用示意图; (d) 在不同温度和时间下加密信息的荧光图像; (e) 利用荧光颜色进行文本编码的图示

Figure 12. (a) Schematic illustration of the formation of QDs-Eu(PBA)₃AA; (b) Fluorescence images showing dual-responsive optical recording and encryption, including the pattern design process and encryption-decryption mechanism; (c) Schematic illustration of the colorimetric fluorescent time-temperature indicator and its multifunctional applications; (d) Fluorescence images of encrypted information at different temperatures and times; (e) Illustration of text encoding using fluorescent colors

图13. (a) 铕配合物自组装成纳米粒子(Eu-NPs)及其与二噻吩乙烯共组装成杂化纳米粒子(Eu/O-DAE-NPs)的过程示意图; (b) Eu-NPs及Eu/O-DAE-NPs的多重刺激响应性质示意图; (c) 基于多重刺激响应型Eu/DTE-NPs体系的光学防伪平台; (d) 物理不可克隆函数(PUF)标签的示意图

Figure 13. (a) Schematic illustration of the self-assembly of europium complexes into nanoparticles (Eu-NPs) and their co-assembly with dithienylethene into hybrid nanoparticles (Eu/O-DAE-NPs); (b) Schematic representation of the multi-stimuli-responsive properties of Eu-NPs and Eu/O-DAE-NPs; (c) Optical anti-counterfeiting platform based on the multi-stimuli-responsive Eu/DTE-NP system; (d) Schematic diagram of a (PUF) tag

图14. TPA-OS⊂CP5@CeOx材料制备及声动力治疗可控过程的示意图 (a) TPA-OS⊂CP5@CeOx材料制备示意图; (b) 基于双细胞器靶向及界面工程增强声动力效应的体内肿瘤治疗示意图; (c) CP5与TPA-OS的化学结构

Figure 14. Schematic illustration of the preparation of TPA-OS⊂CP5@CeOx materials and the controlled process of sonodynamic therapy (a) Schematic diagram of the preparation of TPA-OS⊂CP5@CeOx materials; (b) Schematic diagram of in vivo tumor therapy based on dual-organelle targeting and interface engineering-enhanced sonodynamic effects; (c) Chemical structures of CP5 and TPA-OS

图15. (a) HEAs/CeO2/C的合成路线; (b) HEAs(10L)/CeO2/C, Pt/CeO2/C, Pd/CeO2/C, Ni/CeO2/C, Cu/CeO2/C, Ag/CeO2/C的光催化产氢速率; (c) HEAs(xL)/CeO2/C (x=5、7.5、10、12.5、15、20、25、30) 的光催化分解水产氢速率; (d) HEAs(10L)/CeO2/C的光催化产氢稳定性

Figure 15. (a) Synthesis route of HEAs/CeO2/C; (b) Photocatalytic hydrogen production rates of HEAs(10L)/CeO2/C, Pt/CeO2/C, Pd/CeO2/C, Ni/CeO2/C, Cu/CeO2/C, and Ag/CeO2/C; (c) Photocatalytic water-splitting hydrogen production rates of HEAs(xL)/CeO2/C (x=5, 7.5, 10, 12.5, 15, 20, 25, 30); (d) Photocatalytic hydrogen production stability of HEAs(10L)/CeO2/C

图16. (a) 稀土配合物用于增强钙钛矿太阳能电池抗紫外线和热稳定性的示意图; (b) 2D-3D杂化钙钛矿结构及用于构建2D-3D梯度的Eu-pyP滴涂策略示意图; (c) 由(ZnPc)0.5MAn−1PbnI3n+1缝合的MAPbI3薄膜及(ZnPc)0.5MAn−1PbnI3n+1的结构

Figure 16. (a) Schematic illustration of rare-earth complexes for enhancing the UV and thermal stability of perovskite solar cells; (b) Schematic diagram of the 2D-3D hybrid perovskite structure and the drop-casting strategy using Eu-pyP to construct a 2D-3D gradient; (c) MAPbI3 thin film stitched with (ZnPc)0.5MAn−1PbnI3n+1 and the chemical structure of (ZnPc)0.5MAn−1PbnI3n+1

图17. (a) λ-MnO2带隙调控示意图; (b) Mn PE同时实现选择性锂离子捕获与淡水提取; (c) 大规模制备的Mn PE实物照片; (d) 定制的扩展蒸发单元

Figure 17. (a) Schematic illustration of bandgap engineering of λ-MnO2; (b) Mn PE enabling simultaneous selective lithium-ion capture and freshwater extraction; (c) Photograph of the large-scale prepared Mn PE; (d) Customized expanded evaporation unit

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稀土配合物功能材料: 从分子设计和性能调控到前沿应用^★

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稀土配合物功能材料: 从分子设计和性能调控到前沿应用★

Rare-Earth Complex Functional Materials: From Molecular Design and Property Modulation to Cutting-Edge Applications★

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稀土配合物功能材料: 从分子设计和性能调控到前沿应用^★

Rare-Earth Complex Functional Materials: From Molecular Design and Property Modulation to Cutting-Edge Applications^★