有机-无机杂化磷酸锆及胺插层化合物的MAS NMR研究  

MAS NMR Study on Zirconium Phosphonate-phosphates and Their Amine-intercalated Compounds

作　　者：马学兵[1] 傅相锴[1] 牛丽明[1] 王宁[1] 

机构地区：[1]西南大学化学化工学院应用化学研究所,重庆400715

出　　处：《无机化学学报》2006年第1期111-114,共4页Chinese Journal of Inorganic Chemistry

基　　金：重庆市自然科学基金资助项目(No.2003-8117)。

摘　　要：The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH2CO2H)2]x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N(CH2CO2H)2 in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO42- and [O3PCH2N(CH2CO2H)2]2- group in the 31P MAS NMR spectra. After intercala- tion of n-butyl amine, the 31P chemical shift of HPO42- group at - 8.0￣- 10.0 ppm moved to 6.0 ppm with a change of 14.0￣16.0 ppm and that of [O3PCH2N(CH2CO2H)2]2- group at - 29.1 ppm changed only 0.5 ppm. Due to the pil- lared effect of [O3PCH2N(CH2CO2H)2]2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO42- group in ZPPMIDA (x=0.66) rather than that in α- ZrP, and carboxylic group (-CO2H) in ZPPMIDA (x=0.66).The layered zirconium [N-（phosphonomethyl）iminodiacetic acid-phosphate] Zr（HPO4）1.34[O3PCH2N（CH2CO2H）2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr（HPO4）2-x[O3PCH2N（CH2CO2H）2]x·H2O （ZPPMIDA） by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N（CH2CO2H）2 in the designed x range of 0 〈 x 〈 2, which had been monitored by using the phosphorus integration value ratio of HPO4^2- and [O3PCH2N（CH2CO2H）2]^2- group in the ^31P MAS NMR spectra. After intercalation of n-butyl amine, the ^31P chemical shift of HPO4^2- group at -8.0--10.0 ppm moved to 6.0 ppm with a change of 14.0-16.0 ppm and that of [O3PCH2N（CH2CO2H）2]^2- group at -29.1 ppm changed only 0.5 ppm. Due to the pillared effect of [O3PCH2N（CH2CO2H）2]^2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO4^2- group in ZPPMIDA （x=0.66） rather than that in α- ZrP, and carboxylic group （-CO2H） in ZPPMIDA （x=0.66）.

关 键 词：有机-无机杂化磷酸锆 胺插层化合物 MAS NMR 

分 类 号：P614.412[天文地球—矿床学] O611.4[天文地球—地质学]