Bi_(2)O_(3)-AlPO_(4)-SiO_(2)溶胶-凝胶玻璃的制备及固体核磁共振结构解析

Structural Investigations of Sol-Gel Prepared Bi_(2)O_(3)-AlPO_(4)-SiO_(2) Glasses by Solid State Nuclei Magnetic Resonance Spectroscopy

针对铋掺杂玻璃发光机理不明确的问题,以Bi_(2)O_(3)-Al PO_(4)-SiO_(2)玻璃为研究对象,对其开展结构研究。采用硝酸铋、乳酸铝、磷酸三乙酯和正硅酸四乙酯作为前驱体,通过溶胶-凝胶法制备了x Bi_(2)O_(3)-AlPO_(4)-SiO_(2)(0≤x≤0.15)的三元体系玻璃,并使用固态核磁共振(NMR)技术及X射线光电子能谱系统解析了x Bi_(2)O_(3)-AlPO_(4)-SiO_(2)玻璃的原子级结构。NMR结果证明:制备的玻璃由AlPO_(4)和SiO_(2)纳米团簇组成。XPS结果表明该系列的玻璃中没有形成Bi—O—Bi键。通过^(27)Al{^(31)P}REDOR、^(31)P{^(27)Al}REAPDOR,^(31)P CT-DRENAR-BABA-xy16,及^(29)Si MAS单共振实验证明:Bi_(2)O_(3)的加入促进了AlPO_(4)团簇逐步增大,直到最后形成明显的分相,Bi_(2)O_(3)同时存在于SiO_(2)和AlPO_(4)两相中。

A series of x Bi_(2)O_(3)-Al PO_(4)-SiO_(2) glasses(0≤x≤0.15)were prepared by a sol-gel process.The local structures of glasses were investigated by magic angle spinning nuclei magnetic resonance(MAS NMR)and X-ray photoelectron spectroscopy(XPS).Based on the ^(27)Al MAS NMR spectra.The results show that trere is Bi-O-Bi connectivity in all these glasses.In addition,the prepared glass is composed of AlPO_(4)-and SiO_(2)-nanodomains according to the results of ^(27)Al{^(31)P}REDOR,^(31)P{^(27)Al}REAPDOR,^(31)P CT-DRENAR-BABA-xy16,and ^(29)Si MAS NMR.The addition of Bi_(2)O_(3) promotes the increase of AlPO_(4) clusters,forming the final phase,and Bi_(2)O_(3) exists both in SiO_(2) and AlPO_(4) nanodomains.