工程科学学报.第42卷，第7期：869-874.2020年7月 Chinese Journal of Engineering,Vol.42,No.7:869-874,July 2020 https://doi.org/10.13374/j.issn2095-9389.2020.02.19.001;http://cje.ustb.edu.cn 纳米锰方硼石的合成与结构性能表征 曹诗瑶，武秋池，闫小琴，纪箴⑧，曹林 北京科技大学材料科学与工程学院，北京100083 ☒通信作者，E-mail:jizhen@mater.ustb.edu.cn 摘要通过溶胶-凝胶(Sol-Gl)法成功合成了纳米锰方硼石并对其进行了稀土Eu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50m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0.8565nm.在490nm激发光激发下，天然锰方硼石、合成锰方硼石和稀土Eu掺杂锰方硼石晶体中的Mn2+发光. 其中发绿光的M在晶体中占据四面体格位中心，发红光的M+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E掺杂的纳米锰方硼石光谱的发光强度得到了提升. 关键词天然锰方硼石；合成锰方硼石；稀土Eu掺杂：纳米结构：发光性能 分类号TB303 Synthesis and characterization of nano-chambersite CAO Shi-yao,WU Qiu-chi,YAN Xiao-qin,JI Zhen,CAO Lin School of Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:jizhen @mater.ustb.edu.cn ABSTRACT Chambersite (Mn3BOCl)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 Eu"-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 Eu"-doped chambersite crystal all showed a Mnemitting center.The Mnthat filled the center of the tetrahedral lattice site of the crystal exhibited a green emission,whereas the Mn"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.Eu doping in the artificially synthesized chamversite further increased the intensity of the luminescence. 收稿日期：2020-02-19 基金项目：天津蓟县锰方硼石利用研究之锰方硼石材料科学研究(08300140)纳米锰方硼石的合成与结构性能表征 曹诗瑶，武秋池，闫小琴，纪    箴苣，曹    林 北京科技大学材料科学与工程学院，北京 100083 苣通信作者，E-mail：jizhen@mater.ustb.edu.cn 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. 关键词    天然锰方硼石；合成锰方硼石；稀土 Eu3+掺杂；纳米结构；发光性能 分类号    TB303 Synthesis and characterization of nano-chambersite CAO Shi-yao，WU Qiu-chi，YAN Xiao-qin，JI Zhen苣 ，CAO Lin School of Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China 苣 Corresponding author, E-mail: jizhen@mater.ustb.edu.cn 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. 收稿日期: 2020−02−19 基金项目: 天津蓟县锰方硼石利用研究之锰方硼石材料科学研究（08300140） 工程科学学报，第 42 卷，第 7 期：869−874，2020 年 7 月 Chinese Journal of Engineering, Vol. 42, No. 7: 869−874, July 2020 https://doi.org/10.13374/j.issn2095-9389.2020.02.19.001; http://cje.ustb.edu.cn