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

关键词：钨掺杂二氧化钒水解法相变温度

分类号：TB303

出版年,卷(期):页码：2014,42(9):00-00

DOI：

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（XRD）、Fourier变换红外谱（FTIR）、差示扫描量热仪（DSC）、X射线光电子谱仪（XPS）和X–射线精细结构谱（XAFS）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⁺_2xW_xO₂。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-dopedVO2(M) powders were prepared by a hydrolysis method.The compositions and structures of W doped VO2(M) powders were analyzed X-ray diffractometry (XRD),Fouriertransform infrared spectroscopy(FTIR),differential scanning calorimetry (DSC), X-ray photoelectronspectroscopy (XPS) and X-ray absorption fine structure(XAFS), respectively. The results indicate that W6+ion can substitute for V4+ion in VO2and forms asolid solution ofV⁴⁺_1-3xV³⁺_2xW_xO₂.The phase transition temperature (Tc)reduces almost linearly with increasing W-doped concentration at a rateofapproximately18℃/1 % W (in mole fraction). The replacement of V4+ion by greater W6+ion causes the lattice distortion of VO2lattice, and the W-O coordination has a local rutile structure and a shorterW-O bond length, compared to V-O in VO2(M), which causes acompressivestress on the neighborV-Ocoordination and an increase of thesymmetryofVO6octahedronwith increasing W-doped concentration.The bonding lengths of V-O1and V-V1ain VO2(M) decrease, and the bonding lengths ofV-O2and V-V1bin VO2(M) increase withincreasing W-doped concentration. V-O1peakand V-O2peak combine into V-O peak, and V-V1apeak andV-V1bpeak merge into V-V1peak, i.e., VO2(M)becomes VO2(R) whenW-doped concentration is2.5 %.

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参考文献：

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