广西桂林磷氯铅矿的振动光谱表征  

Study on the Vibrational Spectra of Pyromorphite From Guilin of Guangxi Province

作　　者：钱雪雯 刘衔宇 李净净 袁野[4] QIAN Xue-wen;LIU Xian-yu;LI Jing-jing;YUAN Ye(College of Jewelry,Shanghai Jian Qiao University,Shanghai 201306,China;Key Laboratory of Non-Ferrous Metal Oxide Electronic Functional Materials and Devices(Guilin University of Technology),Education Department of Guangxi Zhuang Autonomous Region,Guilin University of Technology,Guilin 541004,China;School of Jewelry,City Polytechnic of Shenzhen,Shenzhen 518116,China;School of Gemmology,China University of Geosciences(Beijing),Beijing 100083,China)

机构地区：[1]上海建桥学院珠宝学院,上海201306 [2]广西高校有色金属氧化物电子功能材料与器件重点实验室,桂林理工大学,广西桂林541004 [3]深圳城市职业学院珠宝学院,广东深圳528116 [4]中国地质大学(北京)珠宝学院,北京100083

出　　处：《光谱学与光谱分析》2025年第3期735-741,共7页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金面上项目(41772045);上海建桥学院校级科研项目(BBYQ2104)资助。

摘　　要：广西桂林产出的磷氯铅矿,颜色鲜艳,晶体完整,深受矿物及宝石收藏爱好者们的青睐。选取6颗广西桂林产不同颜色的磷氯铅矿样品。采用能量色散X射线荧光光谱仪、红外光谱仪、拉曼光谱仪及X射线粉晶衍射仪对样品的化学成分及振动光谱进行测试,以探讨其振动光谱与化学组成(类质同象)和晶体结构之间的关系。结果表明,其主要化学组成元素为Pb,其次是P和Cl;中红外及拉曼光谱主要表征了PO_(4)^(3-)的弯曲和伸缩振动,其中300 cm^(-1)以下的谱带与晶格振动有关,882/822 cm^(-1)处可见AsO_(4)^(3-)的反对称伸缩振动,1461 cm^(-1)处则与CO_(3)^(2-)振动有关,表明在广西桂林磷氯铅矿结构中,CO_(3)^(2-)和AsO_(4)^(3-)少量取代了其中的PO_(4)^(3-);近红外光谱测试表明,样品中存在与过渡金属离子Fe^(2+)和Cu^(2+)相关的谱带,说明Fe^(2+)和Cu^(2+)可能同时取代了Pb 2+,存在于晶体结构中;4000~8000 cm^(-1)区域主要显示了磷酸根离子、砷酸根离子以及两者的合频和倍频,水分子、羟基、羟基与金属离子的合频和倍频,并证实了样品中存在结晶水、结构水和吸附水,其中通道离子Cl部分被OH取代;综合中红外、近红外以及拉曼光谱分析结果表明,广西桂林磷氯铅矿样品中广泛存在着类质同象,该现象导致磷酸根离子对称性降低,结构产生畸变,谱带发生分裂及位移。同时X射线粉晶衍射表明类质同象对晶胞参数a_(0)和b_(0)基本没有影响,c_(0)在较小范围内波动。The pyromorphite in Guilin,Guangxi,has bright colors and complete crystals,favored by mineral and gem collectors.In this paper,six pyromorphite samples from Guilin and Guangxi with different colors were selected.The samples chemical composition and vibration spectrum were tested by energy-dispersive X-ray fluorescence spectrometer,infrared spectrometer,Raman spectrometer,and X-ray powder diffractometer to explore the relationship between the vibration spectrum and the chemical composition(isomorphism)and crystal structure.The results show that the main chemical element of the samples is Pb,followed by P and Cl.The mid-infrared and Raman spectra mainly characterize the bending and stretching vibrations of PO_(4)^(3-),in which the bands below 300 cm^(-1)are related to the lattice vibration.The antisymmetric stretching vibration of AsO_(4)^(3-)is visible at 882/822 cm^(-1),and the CO_(3)^(2-)vibration is related at 1461 cm^(-1),indicating that CO_(3)^(2-)and AsO 3-4 replace a small amount of PO_(4)^(3-)in the structure of Guangxi Guilin pyromorphite.Near-infrared spectroscopy tests show spectral bands related to transition metal ions Fe^(2+)and Cu^(2+)in the sample,indicating that Fe^(2+)and Cu^(2+)may simultaneously replace Pb^(2+)and exist in the crystal structure.The 4000~8000 cm^(-1)region mainly displays phosphate ions,arsenate ions,and their overtone and combination tones,as well as the overtone and combination tones of water molecules,hydroxyl groups,hydroxyl,and metal ions.It is confirmed that crystal,structural,and adsorption water are in the sample,with the channel ion Cl partially replaced by OH.The results of the comprehensive analysis of mid-infrared,near-infrared,and Raman spectra show a wide range of isomorphism in the samples of pyromorphite in Guilin,Guangxi.This phenomenon leads to a decrease in the symmetry of phosphate ions,a distortion of the structure,and a splitting and displacement of the spectral band.Meanwhile,X-ray powder diffraction shows that isomorphism has little effect on the cell par

关 键 词：磷氯铅矿 近红外吸收光谱 中红外吸收光谱 激光拉曼光谱 

分 类 号：P575[天文地球—矿物学]