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水溶液体系铝硅酸钠微结构的拉曼光谱和量子化学从头计算研究

Raman Spectra and Quantum Chemistry ab initio Calculation Study on Microstructure of Sodium Aluminosilicate Aqueous Solutions

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摘要

选取了代表性水溶液体系铝硅酸钠的典型试样: 铝酸钠溶液、硅酸钠溶液、铝硅酸钠溶液, 分别测定了它们的拉曼光谱。构建了系列铝硅酸钠溶液微结构模型, 应用量子化学从头计算方法优化了空间几何构型, 并计算了其拉曼光谱, 计算结果分别与相应试样的实验拉曼光谱进行对比。结果表明: 在高浓度条件下, 铝酸钠溶液中铝物种的主要存在形式是AlOH-4(Q0)和Al2OOH2-6(2Q1), 低浓度时只存在Q0结构的铝酸根离子, 以4Q0聚集态的四水合分子形式存在;在2.0M Na2SiO3溶液中, 硅酸钠团簇结构可能的存在形式是四水合Na2H2SiO4;在铝硅酸钠溶液中, 铝硅酸根离子的形态是由Si-O-Si和Al-O-Si键以不同铝硅原子配比相互连接形成的环状或链状结构。

Abstract

Three kinds of typical samples of sodium aluminosilicate aqueous solutions including sodium aluminate, sodium silicate and sodium aluminosilicate solutions were investigated by Raman scattering spectroscopy respectively. Quantum chemistry ab initio calculation was applied to optimize geometric structure and calculate Raman spectra of a series of solution model cluster structural units. Calculated and experimental Raman spectra were compared with each other. The results show the dominant aluminate ions exist in the form of AlOH-4(Q0) and Al2OOH2-6(2Q1) in high concentration sodium aluminate solution while the fundamental structural unit which may be present under dilute condition is 4Q0with four H2O molecules of hydration. In 2.0M Na2SiO3 solution, it appears that Na2H2SiO4monomer with at most four H2O molecules of hydration is the most probable form of sodium silicate clusters. The structure of aluminosilicate species in sodium aluminosilicate solutions would appear to be ring or chain structure combined by Si-O-Si and Al-O-Si bond with different Al/Si atomic ratio.

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中图分类号:O657.37

DOI:10.13883/j.issn1004-5929.201403010

所属栏目:化学和生物研究中的应用

基金项目:国家自然科学基金重点项目(50932005)、国家自然科学基金(20973107, 40973046)和上海市科委国际合作基金(12520709200)资助

收稿日期:2013-07-01

修改稿日期:2013-12-14

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伏清:上海大学材料科学与工程学院, 上海200072
尤静林:上海大学材料科学与工程学院, 上海200072
王媛媛:上海大学材料科学与工程学院, 上海200072
柳晓飞:上海大学材料科学与工程学院, 上海200072
余立旺:上海大学材料科学与工程学院, 上海200072

联系人作者:伏清(fuqing881111@sina.com)

备注:伏清(1988年), 女, 上海, 上海大学材料科学与工程学院硕士研究生, 铝硅酸钠溶液微结构及其拉曼光谱的研究.

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引用该论文

FU Qing,YOU Jing-lin,WANG Yuan-yuan,LIU Xiao-fei,YU Li-wang. Raman Spectra and Quantum Chemistry ab initio Calculation Study on Microstructure of Sodium Aluminosilicate Aqueous Solutions[J]. The Journal of Light Scattering, 2014, 26(3): 265-271

伏清,尤静林,王媛媛,柳晓飞,余立旺. 水溶液体系铝硅酸钠微结构的拉曼光谱和量子化学从头计算研究[J]. 光散射学报, 2014, 26(3): 265-271

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