摘要
合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm^3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10^(-2)S·cm^(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。
The synthesis of K8H3[Y(PW11O39) (2)] . 25H(2)O is reported for the first time. The composition is confirmed by chemical analysis, TG-DTA and ICP. IR, XRD, UV, W-183-NMR and CV are used to characterize the title complex and the results show that the complex is beta(2) type Keggin structure. Rare earth co-permeation is used to treat this complex and the results of ICP and XPS indicate that rare earth elements (La and Ce) have permeated and diffused into the body of this sample and exist in the forms of binding with other components. Its chemical formula is (K8H6YLa0.11Ce0.18P2W4W18O78)-W-V-O-VI . 1.5H(2)O and the crystal structure parameters were obtained by the analysis of XRD, those are crystal system: Monoclinic, lattice parameter: a = 6.3775nm, b = 3.6771nm, c = 3.7727nm, beta = 90.192degrees, V = 88.47326nm(3); The conductivity of permeated sample, at room temperature, is about 10(3) times of that of K8H3[Y(PW11O39)(2)] . 25H(2)O and reach to 1.33 x 10(-2)S . cm(-1) at 523K. The results of H-1 MAS NMR spectrum indicate three kinds of proton exit, which implies a proton conduct mechanism. So, this compound shows a promising application as conductive material.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2003年第10期1053-1058,共6页
Chinese Journal of Inorganic Chemistry
基金
黑龙江省重点攻关资助项目(No.GB02A301)
哈尔滨工业大学校基金(HIT.2002.54)
