杂多酸盐催化剂中反荷离子对V^（4＋）离子影响的ESR研究

ESR Studies of the Effects of Counter Ions on V￣(4+) Ion in Heteropolyacid Salts Catlysts

用ＥＳＲ方法研究了异丁醛一步氧化制甲基丙烯酸杂多酸盐催化剂中过渡金属离子Ｃｕ^（２＋）、Ｖ^（４＋）的状态。将卷积差方法应用于ＥＳＲ谱增强了过渡金属离子的分辨率。从复杂和重叠谱中检测配位到杂多阴离子上的Ｖ^（４＋）波谱参数，计算了α^（２＋）和Ｋ值。讨论了反荷离子Ｃｕ^（２＋）及各种碱金属对Ｖ^（４＋）上电子云密度、未成对电子离域性及Ｖ－Ｏ键性质的影响。

The transition metal ions Cu2+ and V4+ in heteropolyacid salts used in one-stepoxidition of isobutyraldehyde(IBL)to produce methacrylic acid(MAA) were studied by ESRmethod. The convolution difference method was applied to the resolution enhancement ofESR spectra of transition metal ions. Spectral parameters of V4+ coordinated to heteropolyanion was detected from complicated and superposed spectra. Furthermore,α2 and K werecomputed.We have also discussed the effects of the counter ions Cu2+ and various kinds ofalkali metals on the electron cloud density and delocalization of unpaired electrons and property of V-O bond.