硅酸盐学报

钨掺杂M型二氧化钒粉体的水解法制备与结构分析

作者：杨修春1 2 陈超1 周石山1 王胤博1

单位：1.同济大学材料科学与工程学院上海201804 2.先进土木工程材料教育部重点实验室上海201804

分类号：TB303

出版年,卷(期):页码：2014,42(9):1140-1145

DOI：10.7521/j.issn.0454－5648.2014.09.10

摘要：

采用水解法制备不同W掺杂量的VO2(M)粉体。借助于X射线衍射仪、Fourier变换红外谱、差示扫描量热仪、X射线光电子谱仪和X射线精细结构谱对粉体的成分和结构进行表征。结果表明，W6＋进入VO2晶格，形成固溶体V4＋1－3xV3＋2xWxO2。W掺杂降低了VO2(M)的相变温度，相变温度与W掺杂量在一定范围内成线性关系，掺杂效率约为18℃/1%(摩尔分数)。掺杂的大半径W原子部分替换了VO2(M)晶格中的V原子，晶格膨胀畸变产生的压应力通过共享顶点O，沿着W—O—V链传递到邻近的次晶格，造成V—O键键长变化，促使V周围的氧分布对称性随W掺杂量的增加而增大。当W掺杂量增大至2.5%时，单斜结构中的V—O1键和V—V1a键伸长，V—O2键和V—V1b键缩短，V—O1和V—O2峰合并成金红石结构的V—O峰，V—V1a峰和V—V1b峰合并成金红石结构的V—V1峰，即样品已转变为金红石结构。

W－doped VO2 (M) powders were prepared by a hydrolysis method. The compositions and structures of W doped VO2 (M) powders were analyzed by X－ray diffractometry, Fourier transform infrared spectroscopy, differential scanning calorimetry, X－ray photoelectron spectroscopy and X－ray absorption fine structure, respectively. The results indicate that W6+ ion can substitute for V4+ ion in VO2 and forms a solid solution of V4+1-3xV3+2xWxO2. The phase transition temperature (TC) reduces almost linearly with increasing W－doped content at a rate of approximately 18℃/1% W(mole fraction). The replacement of V4+ ion by greater W6+ ion causes the lattice distortion of VO2 lattice, and the W－O coordination has a local rutile structure and a shorter W－O bond length, compared to V－O in VO2 (M), which causes a compressive stress on the neighbor V－O coordination and an increase of the symmetry of VO6 octahedron with increasing W－doped concentration. The bonding lengths of V－O1 and V－V1a in VO2(M) decrease, and the bonding lengths of V－O2 and V－V1b in VO2(M) increase with increasing W－doped concentration. V－O1 peak and V－O2 peak combine into V－O peak, and V－V1a peak and V－V1b peak merge into V－V1 peak, i.e., VO2(M) becomes VO2(R) when W－doped content is 2.5%.

基金项目：

基金项目：上海纳米专项(11nm0500700)资助。

作者简介：

第一作者：杨修春(1965—)，男，博士，教授。

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