过渡金属掺杂YInO3/Ba2In2O5新型无机颜料的合成及显色机理研究

The narrow color range is the obstacle of the development of inorganic pigments. Mixed Metal Oxide Pigments (MMO pigments), of which the colors can be tuned by the modification of the structures, are the trend for the research of inorganic pigments. However, the research of MMO pigments lies in the starting stage right now. Therefore, the category of oxides developed is limited and the colors are not comprehensive. Our group discovered that oxides based on transition metal doped hexagonal YInO3 and brownmillerite Ba2In2O5 exhibited intense orange and turquoise color which were absent from synthetic MMO pigments. But research on the pigments based on these two structures is not sufficient and the theoretical explanations are not well built, which slow down the discovery of new pigments. Therefore in this project, we propose to prepare new MMO color pigments by doping transition metal ions into Ba2In2O5 and YInO3. Based on First Principle Theory, calculations of the oxides stability before and after doping are applied to select the proper transition metal ions and the oxides doped with certain transition metal ions are prepared. XRD, TEM, UV-Vis spectrum are employed to comprehensively characterize the MMO pigments and GSAS software are used to manipulate the crystal structure of the oxides. Through relationships between structure and optical properties, we will master in understanding the effect of transition metal ions and developing new MMO pigments.

颜色范围窄大大限制了无机颜料的发展和应用。金属混相氧化物（MMO）可通过结构的微调而改变颜色，成为无机颜料研究发展的趋势。但目前该领域尚处于起步阶段，可利用的氧化物结构类型有限，色系不完备。本课题组前期以六方结构的YInO3和钙铁矿结构的Ba2In2O5为基体，制备出橙色、绿松石色的新型MMO颜料，补足了该色彩缺失的问题。鉴于目前对这两类氧化物颜料的研究较少，理论体系不完善，阻碍了该类结构新颜料的开发,本课题在前期实验基础上，通过第一性原理进行掺杂氧化物结构的稳定性计算，优化合适的过渡金属掺杂离子种类，制备过渡金属离子掺杂YInO3和Ba2In2O5新型MMO颜料；通过XRD、TEM、UV-Vis光谱等手段表征性质；利用GSAS软件计算晶体结构；分析结构与光学性质的关系，掌握过渡金属离子对氧化物颜色的作用规律，拓展MMO颜料的颜色范围。

金属氧化物混相无机颜料（MMO颜料）可通过改变氧化物结构调整颜色，成为无机颜料研究发展趋势。但目前研究尚处于起步阶段，色系不够完备，探索氧化物结构十分有限。本课题组通过研究过渡金属离子掺杂YInO3和Ba2In2O5，拓展MMO颜料的颜色范围。通过课题研究，采用溶胶-凝胶法、共沉淀法、高温固相烧结法、微波辅助烧结法等方法成功制备出Fe/Mn/Al/Cr/Co等离子掺杂的YInO3/Ba2In2O5新型无机颜料体系，补充目前未成功合成的颜色，拓展了无机颜料的颜色范围。同时，探索不同过渡金属离子的掺杂极限，对制备氧化物体系的表面特征、光学性质、电磁性质进行表征。对合成的氧化物体系，通过模拟计算，得到具体晶体结构。通过对结构的深入分析，推导YInO3和Ba2In2O5的结构以及过渡金属掺杂对其光学性质的影响，分析不同过渡金属离子掺杂的作用规律，掌握这两种结构的氧化物显色的机理。同时，通过该项目的执行，发现了新型Ba4In2O7/BaAl2O4/Ba3Al2O6等新型颜料基体，在未来新型环保无机颜料研究中具有巨大应用前景。