曹诗瑶, 武秋池, 闫小琴, 纪箴, 曹林. 纳米锰方硼石的合成与结构性能表征[J]. 工程科学学报, 2020, 42(7): 869-874. DOI: 10.13374/j.issn2095-9389.2020.02.19.001
引用本文: 曹诗瑶, 武秋池, 闫小琴, 纪箴, 曹林. 纳米锰方硼石的合成与结构性能表征[J]. 工程科学学报, 2020, 42(7): 869-874. DOI: 10.13374/j.issn2095-9389.2020.02.19.001
CAO Shi-yao, WU Qiu-chi, YAN Xiao-qin, JI Zhen, CAO Lin. Synthesis and characterization of nano-chambersite[J]. Chinese Journal of Engineering, 2020, 42(7): 869-874. DOI: 10.13374/j.issn2095-9389.2020.02.19.001
Citation: CAO Shi-yao, WU Qiu-chi, YAN Xiao-qin, JI Zhen, CAO Lin. Synthesis and characterization of nano-chambersite[J]. Chinese Journal of Engineering, 2020, 42(7): 869-874. DOI: 10.13374/j.issn2095-9389.2020.02.19.001

纳米锰方硼石的合成与结构性能表征

Synthesis and characterization of nano-chambersite

  • 摘要: 通过溶胶−凝胶(Sol−Gel)法成功合成了纳米锰方硼石并对其进行了稀土Eu3+掺杂。使用X射线衍射、透射电子显微镜和高分辨透射电子显微镜等表征了锰方硼石晶体结构,并通过荧光光谱测试对其发光性能进行了研究。结果表明:合成纳米锰方硼石为粒径小于50 nm的球状颗粒,与天然锰方硼石的物相结构相同,属于斜方晶系,与尖晶石类似,(010)晶面的晶面间距为0.8565 nm。在490 nm激发光激发下,天然锰方硼石、合成锰方硼石和稀土Eu3+掺杂锰方硼石晶体中的Mn2+发光,其中发绿光的Mn2+在晶体中占据四面体格位中心,发红光的Mn2+在晶体占据八面体格位中心。合成的锰方硼石随激发波长变长,产生发射光谱的红移现象,有利于实现冷暖发光转换;在稀土Eu3+掺杂的纳米锰方硼石光谱的发光强度得到了提升。

     

    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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