ZnSe及其Mn掺杂复合材料光吸收催化性能和高压结构性能研究  

Study on Photocatalysis & Light Absorption and High-Pressure Structural Properties of ZnSe and Its Mn Doping Composites

作　　者：王世霞 王晓雨 胡天意 WANG Shi-xia;WANG Xiao-yu;HU Tian-yi(School of Materials and Chemistry,University of Shanghai for Science and Technology,Shanghai 200093,China)

机构地区：[1]上海理工大学材料与化学学院,上海200093

出　　处：《光谱学与光谱分析》2024年第2期380-385,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(42273052);上海理工大学计划外项目(H2020341001)资助。

摘　　要：ZnSe半导体材料是制备光电器件和光催化反应催化剂的重要原材料。其单体材料具有强光下易变质、电子-空穴复合等现象。通过元素掺杂制备ZnSe复合材料,并与单体材料对比研究了元素掺杂所提升的ZnSe的光学及结构性能。首先采用水热法实验室制备纯ZnSe和Mn∶Zn加入比分别为5%、10%、15%和20%的ZnSe复合材料,对比材料形貌、结构,光吸收和催化性能,结果显示掺杂比为10%的样品结晶度最高,杂质成型量最少,催化性能最佳。采用Mao-Bell型金刚石压腔结合原位拉曼光谱探究纯ZnSe和掺杂比为10%的样品的高压结构相变行为,以探究元素掺杂对样品结构性能的影响。研究结果:(1)扫描电子显微镜(SEM)图显示,加入Mn元素后制得的ZnSe样品形貌为球状,与纯样大致相同,球状颗粒表面有小颗粒负载,且随着Mn加入量的增加,表面负载的物质增多;(2)X射线衍射(XRD)图谱表明,ZnSe样品结构为立方闪锌矿结构,随着Mn加入量的增加,样品MnSe特征峰增强,杂质MnO_(2)成型越完全。掺杂比为10%的样品ZnSe结晶度高,杂质成型量少;(3)固体紫外漫反射(UV-Vis)结果表明,掺杂比为10%的样品对光的吸收边最大,禁带宽度最小,为1.65 eV;(4)光催化实验结果显示,掺杂比为10%的样品催化降解甲基橙的效率最大,6 h降解85.4%。研究表明掺杂Mn元素比为10%的ZnSe复合材料,光吸收和催化性能相对最好。金刚石压腔结合原位拉曼光谱探究ZnSe样品和掺杂比为10%的样品的高压相变结果表明,(1)纯ZnSe的LO声子模在压力上升到12.3 GPa时基本消失,TO声子模在压力上升到20.8 GPa时消失,整个加压过程中没有新峰生成,纯ZnSe发生闪锌矿相向岩盐矿相转变的高压行为;(2)复合材料的TO声子模在6.9 GPa时发生劈裂,在8.0 GPa时208 cm^(-1)处有新峰出现,表明在此压力下部分样品由闪锌矿相转变为辰砂矿相。在10.8 GPa时辰砂矿相的峰消失,体系发生由辰�ZnSe semiconductor material is an important raw material for preparing optoelectronic devices and photocatalytic reaction catalysts.The monomer material exhibits deterioration under strong light and electron-hole recombination.In this study,ZnSematerials were prepared by element doping,and the optical and structural properties of ZnSe enhanced by element doping were studied and compared with those of monomer materials.Pure ZnSe and Mn/Zn with doping ratios of 5%,10%,15%,and 20%were prepared by the hydrothermal method in the laboratory to compare the morphology,structure,light absorption,and catalytic performance of the composite materials.The results showed that the sample with a doping ratio of 10%had the highest crystallinity,the least impurities,and the best catalytic performance.Subsequently,the high-pressure structural phase transformation behavior of pure ZnSe and samples doped with 10%Mn/Zn was investigated by in-situ Raman spectroscopy using Diamond Anvil Cell to explore the effect of element doping on the structural properties of the samples.The results are as follows:(1)Scanning electron microscope(SEM)images show that the morphology of the ZnSe sample prepared with Mn element is spherical and similar to the pure sample.Small particles are on the surface of the spherical particles,and with the increase of Mn addition,more substances are loaded on the surface.(2)X-ray diffraction(XRD)patterns show that the structure of the ZnSe sample is a cubic zinc blende structure.With the increase of Mn addition,the characteristic peak of MnSe in the sample is enhanced and the formation of impurity MnO_(2) is more completed.The sample with a doping ratio of 10%has a high ZnSe crystallinity and a low impurities formation.(3)Solid-state ultraviolet diffuse reflectance(UV-Vis)results show that the sample with a doping ratio of 10%has the maximum light absorption edge and the smallest bandgap width of 1.65 eV.(4)The results of the photocatalytic experiment show that the sample with a doping ratio of 10%has the highest ef

关 键 词：ZNSE MN掺杂 光吸收性能 光催化性能 高压相变 

分 类 号：O521.2[理学—高压高温物理]