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納米錳方硼石的合成與結構性能表征

Synthesis and characterization of nano-chambersite

  • 摘要: 通過溶膠?凝膠(Sol?Gel)法成功合成了納米錳方硼石并對其進行了稀土Eu3+摻雜。使用X射線衍射、透射電子顯微鏡和高分辨透射電子顯微鏡等表征了錳方硼石晶體結構,并通過熒光光譜測試對其發光性能進行了研究。結果表明:合成納米錳方硼石為粒徑小于50 nm的球狀顆粒,與天然錳方硼石的物相結構相同,屬于斜方晶系,與尖晶石類似,(010)晶面的晶面間距為0.8565 nm。在490 nm激發光激發下,天然錳方硼石、合成錳方硼石和稀土Eu3+摻雜錳方硼石晶體中的Mn2+發光,其中發綠光的Mn2+在晶體中占據四面體格位中心,發紅光的Mn2+在晶體占據八面體格位中心。合成的錳方硼石隨激發波長變長,產生發射光譜的紅移現象,有利于實現冷暖發光轉換;在稀土Eu3+摻雜的納米錳方硼石光譜的發光強度得到了提升。

     

    Abstract: Chambersite (Mn3B7O13Cl) is both a rare inorganic macromolecular manganese chloroborate and a rare mineral. The chambersite deposit was firstly discovered in Jixian, Tianjin, China, which is the only mineable chambersite deposit in the world. Due to its unique multi-element composition and structure type, it has great application potential as a light-emitting material in biological anti-virus, anti-tumor, and anti-microbial applications, as well as a nuclear-protection and LED applications. However, as yet there are few reports on the material science of chambersite. Rare-earth and transition-group ion-activated borate are important constituent systems in luminescent materials. In this paper, nano-chambersite and rare-earth-element Eu3+-doped nano-chambersite were successfully synthesized by Sol-Gel method. The crystal structure of the nano-chambersite was characterized by X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. The performance comparison between natural chambersite and synthetic chambersite was provided to provide a basis for the rational development and utilization of chambersite. The results show that the artificially synthesized chambersite has a spherical shape with a particle size of less than 50 nm, and has the same phase structure as natural chambersite. It belongs to the orthorhombic system and has a structure similar to that of spinel. The inter planar spacing of (010) is 0.8565 nm. Under 490 nm excitation light, the natural chambersite, artificially synthesized chambersite, and rare-earth-element Eu3+-doped chambersite crystal all showed a Mn2+ emitting center. The Mn2+ that filled the center of the tetrahedral lattice site of the crystal exhibited a green emission, whereas the Mn2+ that filled the center of the octahedral lattice site of the crystal exhibited a red emission. The artificially synthesized chambersite showed a unique red shift of the emission spectrum with increases in the emitting-light wavelength. This unique phenomenon is beneficial to the conversion of cold and warm luminescence. Eu3+ doping in the artificially synthesized chamversite further increased the intensity of the luminescence.

     

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