Electrochemical Study on Redox Behavior of the multivalent Metal Ions in the glass Melts

玻璃熔体中多价金属离子氧化还原行为的电化学研究

• 批准号: 09450327
• 负责人: MAEKAWA Takashi
• 金额: $ 8.64万
• 依托单位: Ehime University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450327/
• 关键词: Redox equilibria; Differential pulse voltammetry; Half-wave potential; Glass melt; Multivalent metal ion; Basicity; MAS-NMR; 微分パルスポルタンメトリー; 状態別分析

The Sn^<4+>-Sn^<2+> and Fe^<3+>-Fe^<2+> equilibrium in alkali borate and silicate melts was studied by means of differential pulse voltammetry. The half-wave potentials in Fe-containing glasses become negative with decrease of temperature and increase of alkali oxide when they exceed 20 mol%. When alkali oxide is less than about 20 mol%, the data can be fitted by two reduction peaks, i.e. the Fe^<3+>-containing complex and free Fe^<3+> to Fe^<2+>. The half-wave potentials of Sn^<4+>-Sn^<2+> equilibrium in borate melts shift to the negative with an increase in Na_2O content and a decrease in temperature. On the other hand, the half-wave potentials in the silicate melts shift to the positive with an increase in Na_2O content. There results can be interpreted in terms of complex formations of Sn^<4+> and Sn^<2+>, in which the coordination numbers of the oxide ion for both ions do not differ significantly and their equilibrium constants for complex formation depend largely on the alkali species.The ^<29>Si and ^<31>P nuclear magnetic resonance (NMR) chemical shifts and the Q_n distribution in ternary sodium phosphosilicate glasses were examined. When the P_2O_5 content increases at fixed mole fractions of SiO_2 equal to 0.1 and 0.05, the 6-coordinated silicon atoms appear. The presence of 6-coordinated silicon atoms is expected in glasses where the [P_2O_5]/[Na_2O] composition ratio is greater than unity. From the NMR spectra of 30Na_2O ・ 5SiO_2 ・ 65[(1-x)P_2O_5 ・ xB_2O_3] glasses, the distribution curves derived from the deconvolution of the spectra by component signal of each phosphate and borate species agree with those calculated using species with different [Na_2O] / [P_2O_5] ratios when P_2O_5 reacts with Na_2O and B_2O_3 preferably.

本文用微分脉冲伏安法研究了碱金属硼酸盐和硅酸盐熔体中Sn^<4+>-Sn^<2+>和Fe^<3+>-Fe^<2+>平衡。当含铁玻璃中碱金属氧化物含量超过20mol%时，玻璃的半波电位随温度的降低和碱金属氧化物含量的增加而变负。当碱金属氧化物含量小于20 mol%时，数据可用两个还原峰拟合，即含Fe^<3+>络合物和游离Fe^<3+>还原为Fe^<2+>。硼酸盐熔体中Sn^<4+>-Sn^<2+>平衡的半波电位随Na_2O含量的增加和温度的降低而负移。硅酸盐熔体的半波电位随Na_2O含量的增加而正移。结果表明，Sn^&lt;4+&gt;和Sn^&lt;2+&gt;的配位数相差不大，配位平衡常数主要取决于碱金属的种类.<29><31>本文研究了三元磷硅酸钠玻璃中~（13）Si和~（13）P核磁共振化学位移和Q_n分布.当SiO_2的摩尔分数为0.1和0.05时，随着P_2O_5含量的增加，6配位的硅原子出现。在[P_2O_5]/[Na_2O]组成比大于1的玻璃中，预期存在六配位的硅原子。从30Na_2O · 5SiO_2 · 65[（1-x）P_2O_5 · xB_2O_3]玻璃的核磁共振谱中，当P_2O_5与Na_2O和B_2O_3优先反应时，用磷酸盐和硼酸盐各组分的成分信号对谱图进行解卷积得到的分布曲线与用不同[Na_2O] / [P_2O_5]比的组分计算得到的分布曲线一致。

项目成果

Isamu YAMAGUCHI: "^<29>Si MAS NMR Study of Porous Silica Glass Prepared from Sodium Boroshilicate Glasses" J.Ceram.Soc.Jpn.105・8. 700-702 (1997)

Isamu YAMAGUCHI：“^<29>由硼硅酸钠玻璃制备的多孔二氧化硅玻璃的Si MAS NMR研究”J.Ceram.Soc.Jpn.105・8(1997)。

H.Yamashita, K.Nozaki, K.Toshinari, T.Mima, T.Maekawa: "Synthesis of Spherical Porous Zirconia and Titania Particles in W/O Emulsion" J.Ceram.Soc.Jpn.106-12. 1184-1189 (1998)

H.Yamashita、K.Nozaki、K.Toshinari、T.Mima、T.Maekawa：“W/O 乳液中球形多孔氧化锆和二氧化钛颗粒的合成”J.Ceram.Soc.Jpn.106-12。

Makoto NAKASHIMA: "Electrochemical Study of Fe Ions in Alakali Borate Melts" J.Non-Cryst.Solids. 223. 133-140 (1998)

Makoto NAKASHIMA：“碱硼酸盐熔体中铁离子的电化学研究”J.Non-Cryst.Solids。

H.Yamashita, T.Taniguchi, K.Tanaka, T.Maekawa: "Structure of Spherical Porous Silica Particles Derived from Tetramethoxysilane and Methyltrimethoxysilane" J.Ceram.Soc.Jpn.105-4. 335-340 (1997)

H.Yamashita、T.Taniguchi、K.Tanaka、T.Maekawa：“由四甲氧基硅烷和甲基三甲氧基硅烷衍生的球形多孔二氧化硅颗粒的结构”J.Ceram.Soc.Jpn.105-4。

Hiroshi YAMASHITA: "Redox Equilibria of Tin lons in Alkali Borate Melts" J.Ceram.Soc.Jpn.105巻. (1998)

Hiroshi YAMASHITA：“碱硼酸盐熔体中锡的氧化还原平衡”J.Ceram.Soc.Jpn.105 卷（1998 年）。