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Progress in the Design and Mechanism of Long-persistent Luminescence Materials
WANG Yuhua, FENG Peng, DING Songsong, MA Xilin, CAO Junlong, ZHANG Hongzhe, LI Gen, GUO Haijie
Materials Reports
2023,37(3 ):22110279 -13. DOI:10.11896/cldb.22110279
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This paper focuses on the research achievements of our laboratory in the last 20 years in the field of long-persistent luminescence materials. Starting from the key issues of long persistent luminescence materials, this paper makes a detailed analysis and summary of the matrix selection of materials, the exploration methods of doping and solid solution, the discussion on the mechanism of material lasting glow, and the extended research on special lasting glow phenomena. The future research direction of long-persistent luminescence materials has also been prospected. The future research direction of long-persistent luminescence materials has also been prospected, which is purpose on providing a reference for researchers in this field.
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Recent Research on Luminescent Materials Derived from Layered Rare-earth Hydroxides
CHEN Lu, ZHU Qi, SUN Xudong
Materials Reports
2023,37(3 ):22090241 -10. DOI:10.11896/cldb.22090241
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Layered rare-earth hydroxides (LRHs), having a unique combination of a layered structure and the functional properties of rare-earth elements, are a new family of functional materials. The compounds have potential applications in electro-optic, catalytic, biomedical fields and so forth. This review summarizes the recent research on LRHs, including controlled synthesis, structural features, anion exchange, nanosheet exfoliation, and application in the field of luminescence for both the Ln
2
(OH)
5
(A
x
-)
1/
x
·nH
2
O (251-LRHs) and Ln
2
(OH)
4
SO
4
·
n
H
2
O (241-LRHs). Particular attention is paid to the size and morphology control and nano sheets exfoliation in 251-LRHs. The luminescent behaviors of LRHs themselves and calcined derivatives of the oxide, oxysulfate, and oxysulfide for phosphors, highly oriented transparent films, and optical temperature sensors are the main content. Finally, the prospects of LRHs on novel functional materials are proposed, which provides a new way for future functional design.
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Electronegativity Evaluation of Charge Transfer Transition Theory of Rare Earth Ions and Its Application in Quantum Regulation Luminescence
SHI Guoqiang, XUE Dongfeng
Materials Reports
2023,37(3 ):22110122 -5. DOI:10.11896/cldb.22110122
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The interaction between microscopic particles in the luminescence process can be attributed to quantum behavior. As the carrier of luminescence, rare earth crystalline materials contain many degrees of freedom including lattice, charge, spin and orbit. Rare earth ions can be regarded as an inorganic lattice active dopant in crystals. Due to the large radius of rare earth ions, their doping into the crystal is easy to cause lattice distortion, forms vacancy defects, and further leads to changes in the electronic structure and lattice environment of the crystal, forming defects, lattice, electronic structure and other multiscale structures. The defects caused by the doping of rare earth ions can be attributed to the local symmetry broken, which affects the lattice degree of freedom. In addition, the complexity of rare earth ion f electrons leads to the instability of charge, spin, orbit and other degrees of freedom in the system. Therefore, the essence of luminescence sources in rare earth crystalline materials can be determined by the multiple degrees of freedom coupling method. By evaluating the charge transfer transition theory of rare earth ions through electronegativity, we can integrate the lattice degree of freedom of ionic scale and the charge, spin and orbital degrees of freedom of electronic scale in rare earth crystalline materials, and realize the quantum control of luminescence of rare earth crystalline materials. This paper mainly discusses the electronegativity evaluation of charge transfer transition theory of rare earth ions and its application in quantum controlled luminescence.
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Single Fiber Crystal Growth Techniques by Laser Heating Pedestal Growth Method
WU Anhua, ZHOU Shengyao, DAI Yun, ZHANG Zhonghan, ZHANG Zhen, KOU Huamin, WANG Xibin, SU Liangbi
Materials Reports
2023,37(3 ):22110264 -9. DOI:10.11896/cldb.22110264
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Single-crystal fiber (SCF) is a fiber-shaped monocrystalline material, which maintains the morphological advantage of glass fiber and the excellent physical and chemical properties of bulk single crystal, therefore providing a way to replace traditional glass fiber in high-power laser applications. With the continuous expansion of SCF in material types and application directions, SCF also has potential application prospects in radiation detection, high temperature sensing and other fields. In this paper, based on the introduction of the application background of SCF, the growth technology of SCF by laser heating pedestal growth (LHPG) method at home and abroad is summarized, and the problems in the growth process of SCF and the improvement scheme are discussed in detail, and finally the future development direction of SCF is prospected.
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Progress in Size-controlled Synthesis of Rare Earth Fluoride Upconversion Nanocrystals
WU Suli, XUN Wenfei, ZHANG Shufen
Materials Reports
2023,37(3 ):22110116 -8. DOI:10.11896/cldb.22110116
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Rare earth ions doped upconversion nanocrystals is a kind of material which can absorb low frequency photons and emit high frequency photons. Rare earth fluoride (NaREF
4
) is considered to be a kind of most efficient matrix for rare earth doped upconversion material. Due to their long luminescence lifetime, low background interference, deep penetration and high stability, upconversion nanocrystals are widely used in the field of display and anticounterfeiting, biomarker, bioimaging and sensors. During recent years, researchers found that the performance of NaREF
4
based upconversion nanocrystals can be effectively improved by controlling their size. In this paper, the influence of the size of NaREF
4
crystals on its luminescent properties is summarized, and the size controllable synthesis methods of NaREF
4
are introduced in detail.
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Rare Earth Luminous Complexes and Their Applications in Organic Light-emitting Diodes
ZHUO Mingpeng, YU Yanjun, DING Lingyi, CHEN Weifan, LIAO Liangsheng
Materials Reports
2023,37(3 ):21060045 -10. DOI:10.11896/cldb.21060045
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Rare earth materials have been regarded as ‘industrial vitamin’ or ‘industrial monosodium glutamate’, which were widely applied in information, energy, transportation, environment, aerospace and the other fields. Due to the unique 4f shell electronic structure, the rare earth materials demonstrate the excellent physical property of the optical, electrical, magnetic and nuclear aspects, acting as the strategic resources in China. Notably, the rare earth materials with the outstanding fluorescence emission from ultraviolet light to infrared light region play an important role among all kinds of luminescent materials. Significantly, the rare earth luminous complexes expected to become high-performance electroluminescence materials with the characteristics of narrow luminescence peak, high luminescence stability, and adjustable light color, and so on, which are attributed to the novel photoluminescence mechanism of both parity inhibited 4f-4f transition and parity allowed 5d-4f transition. Furthermore, a summary of recent advances in organic light-emitting diodes (OLEDs) of organic rare earth complexes supplies an insight for rationally designing and optimizing the high-performant OLEDs.
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Research Progress on Rare Earth Oxide Composites in Electrocatalysis
JIANG Yong, DU Yaping
Materials Reports
2023,37(3 ):22110067 -9. DOI:10.11896/cldb.22110067
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Rare earth is an important strategic resource, and the rare earth elements (REEs) are a class of 17 elements in the periodic table that include 15 lanthanides (atomic numbers from 57 to 71), scandium (atomic number 21), and yttrium (atomic number 39). Rare earth elements show excellent catalytic performance in many reactions in the field of catalysis due to their special 4f electron configuration, abundant electron structure and flexible coordination numbers. Among all kinds of rare earth catalytic materials, the rare earth oxide based composite catalysts show superior performance in electrocatalytic reactions due to its simple preparation process, versatile structural tunability. However, at present, the relationship between the electrocatalytic activity of rare earth oxides based composite catalyst and their electronic structures is still not clear, which hinders the understanding of REEs in electrocatalytic reactions. Therefore, in this review paper, we tried to summarize and highlight the applications of rare earth oxides based composites in electrocatalytic reactions based on the characteristics of their electronic structures.
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Recent Progress on Phase Transformations of 2∶17-type Sm-Co Permanent Magnets
SONG Xin, JIA Wentao, LI Jian, ZHOU Xianglong, MA Tianyu
Materials Reports
2023,37(3 ):22120078 -9. DOI:10.11896/cldb.22120078
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The second-generation rare-earth (RE) permanent magnets (PMs), 2∶17-type Sm-Co-Fe-Cu-Zr magnets, are the strongest high-temperature PMs, which have wide applications in advanced industries. However, the fundamental interest in REPMs was moved from 2∶17-type magnets to the third-generation Nd-Fe-B magnets in 1980s, leaving some fundamental questions unsettled. One of the fundamental issues is the long-standing dispute on phase decomposition mechanism, which cannot provide clear guidance to develop high-performance 2∶17-type magnets. With the advanced techniques, such as in-situ high-energy synchrotron X-ray diffraction (HES-XRD) and Cs-HRTEM, the detailed decomposition process of supersaturated solid solutions into multi-phase coexisting cellular nanostructure has clearly been revealed, clarifying this dispute. In this short review, the latest advances in solid-state phase transformation mechanism, defects formation and dissociation processes, correlation between defects and magnetic properties, and defects-control oriented fabrication methods of 2∶17-type Sm-Co-Fe-Cu-Zr magnets were briefly reviewed. We hope that this review article can be helpful for the community, from the understanding of fundamental contributions to the future development of high-performance magnets.
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Recent Advances and Perspective on Rare Earth Element Modified Lithium-based Oxide Solid Electrolytes
ZHANG Jiaqing, ZHANG Da, CHEN Kunfeng, XUE Dongfeng, LIANG Feng
Materials Reports
2023,37(3 ):22110300 -9. DOI:10.11896/cldb.22110300
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All-solid-state lithium batteries have been a hot topic of research in the field of new energy because of their high energy density and high safety.The solid electrolyte, which is the key component of all-solid-state lithium battery, has significant influence on the energy density, cycle stability and safety of the battery. Among solid electrolytes, oxide solid electrolytes possess many merits of the high ionic conductivity, wide electrochemical window, and excellent mechanical property, including garnet-type, NASICON-type and perovskite-type solid electrolytes. However, the high sintering temperature, low ionic conductivity at room temperature, and unstable structure of oxide solid electrolytes cannot meet demands of the practical application. In this review, the research status and existing problems of garnet-type, NASICON-type and perovskite-type solid electrolytes in recent years are summarized. The functions of rare earth elements with large ionic radius, high valence, low electronegativity, variable coordination number and special electronic structure of 4f5d modified oxide solid electrolytes are concluded, including increasing the relative density, improving the ionic conductivity, and stabilizing the high ionic conductive crystal phase. The main scientific problems and technical bottlenecks of rare earth modified oxide solid electrolytes are analyzed. Finally, the future development direction of rare earth modified oxide solid electrolyte is prospected.
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Research Progress of Cerium Dioxide Supported Catalyst
SUN Fuli, ZHANG Wei, YU Yifan, SHENG Yinxiao, ZHUANG Guilin
Materials Reports
2023,37(3 ):22120058 -12. DOI:10.11896/cldb.22120058
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At present, the transformation of the global energy structure is accelerating the construction of green, safe and sustainable development. The energy conversion is one of the most important. The exploration of efficient catalyst is an important branch to solve this problem. Cerium dioxide(CeO
2
), as a rare earth oxide catalyst or an excellent carrier of heterogeneous catalysts, has unique geometric and electronic structural properties (such as rich oxygen site, Ce valence tautomization(Ce
3+
↔Ce
4+
), etc.), which can effectively affect the performance of catalysts through geometric and electronic effects. In recent years, CeO
2
-based supported catalysts have been widely explored and applied in chemical, energy, environment, materials and other fields, effectively helping to solve urgent problems such as energy conversion, environmental pollution. Although there have been reviews on CeO
2
-based supported catalysts, they mainly focus on single catalytic directions(such as electrocatalysis or thermal catalysis)and lack a systematic overview. In this paper, the research progress of CeO
2
-based supported catalysts is summarized from two aspects: (Ⅰ) preparation and synthesis of CeO
2
and CeO
2
-based supported catalysts; (Ⅱ) study on the structure-activity of various CeO
2
catalysts in electrocatalysis, photocatalysis, thermal catalysis and photothermal catalysis. A comprehensive review of CeO
2
-based supported catalysts will be helpful for its practical application in various fields.
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Research Progress of the Rare Earth Sesquioxide Crystal Materials
LIU Feng, CHEN Kunfeng, XUE Dongfeng
Materials Reports
2023,37(3 ):22110093 -7. DOI:10.11896/cldb.22110093
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Rare earth sesquioxide crystals are very suitable for ultrafast laser gain and magneto-optical medium. Its research began in the 1920s. Because of high thermal conductivity, wide fluorescence spectrum, low phonon energy and other advantages, they're still a research highlight in the field of advanced materials. Ranking first in the top 10 cutting-edge scientific issues issued by the China Association for Science and Technology in 2021, is ‘how to break through the preparation theory and technology of large size crystal materials’. It is clear that improving the preparation technology of large size crystal materials is the key to the commercial application of crystals. The crystalline intrinsic properties and crystal quality of materials are the result of the coupling of multiple degrees of freedom at the multi-scale level. Therefore, it is needed to study the multi-level and multi factor problems of rare earth such as ion bonding, melt structure evolution, crystal growth, etc., in the system at the multi-scale level, for the development of high-quality rare earth sesquioxide materials. In this paper, we focus on the influence of the electronegativity of rare earth ions on the coordination number of cations in the melt at the micro scale, the melt structure researched by the experiment and computational simulation, and the latest progress in crystal growth. The high melting point of rare earth sesquioxide (≥2 400 ℃) are the limits to the use of iridium crucibles and most growth technologies, and it is accordingly slow to develop the rare earth sesquioxide crystals at the inch grade. It is the key point for the preparation of large size and high-quality rare-earth sesquioxide crystals to adopt cosolvent method, heat exchange method and design low melting point components. In order to promote the commercial application of rare earth sesquioxide, revealing the coordination structure of rare earth ions, the evolution of melt structure, the formation mechanism of defects in the growth process, and developing the large-scale crystal growth technology are the key scientific challenges and technical bottlenecks that need to be solved urgently.
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Development and Application of the Rare Earth Yttrium
ZHANG Chi, DANG Qian, LIU Guohuai, WANG Zhaodong
Materials Reports
2023,37(3 ):22120049 -8. DOI:10.11896/cldb.22120049
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In recent years, rare earth yttrium has been widely used in various applications, especially in crystalline luminescent materials, due to its excellent physical and chemical properties. And it gradually becomes an important additive in industrial production all over the world. However, China is the world's largest exporter of rare earth yttrium resources, yet the use of rare-earth yttrium processing in industrial production is still at a low level. How to develop and utilize rare earth yttrium resources has gradually become a huge problem on China's industrialization path. In this paper, we have focused on the current research status of Y/Y
2
O
3
in related industries, such as luminescent crystals, metallurgy, superconductivity, biomedicine and other important fields, expecting to provide assistance in the design and development of yttrium resources in China.
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Preparation and Polishing Properties of CuO-modified CeO
2
Nanocomposite Abrasives
SUN Jiaying, FANG Yangfei, ZHANG Yibo, LIU Qiuwen, LIU Kaijie, YANG Xiangguang
Materials Reports
2023,37(3 ):22120092 -5. DOI:10.11896/cldb.22120092
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The cerium oxide polishing powder with good dispersion and uniform particle size was prepared by ethylene glycol solvothermal method, and copper oxide (CuO) was introduced on the surface of cerium oxide by impregnation method. The effects of different contents of CuO on the phase structure, specific surface area, size, surface morphology and redox capacity of cerium oxide were studied, and it was found that there was no significant effect on the phase structure, morphology and macroscopic particle size distribution of cerium oxide within the loading range, but the specific surface area and redox capacity changed significantly. The polishing test showed that the introduction of CuO would significantly change the polishing ability of cerium-based polishing powder. When Cu accounts for 5% of the total molar amount of Cu and Ce atoms, the polishing performance was the best, the polishing rate was as high as 213.4 nm/min, and the roughness of the surface of the silicon wafer after polishing was only 0.239 nm (
R
q
) and 0.188 nm (
R
a
). The morphology and size of cerium oxide polishing powder synthesized by solvothermal method were fine, and the preparation method was simple and cost-effective. What’s more, the morphology and size of cerium oxide modified by CuO were not changed, and the polishing performance has been greatly improved. This work has certain universality in improving the polishing ability of cerium-based polishing powder.
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