KMgF_3:Eu~(2+)中电荷补偿的途径

KMgF_3,立方钙钛矿结构,空间群O_h~1。原胞内F~-位于面心,Mg~(2+)位于体心,K~+占据顶角。Mg-F间距约为2A,Mg~(2+)为六配位,K-F间距的为2.8A,K~+为十二配位。KMgF_3晶体光学透明区域宽(200～1000nm),掺入稀土离子Eu~(2+)会观察到Eu~(2+)的f→f跃迁尖峰发射,峰值位于360nm附近,KMgF_3:Eu~(2+)是短波可见固体激光晶体的候备材料。Eu~(2+)占据KMgF_3中十二配位的K~+格位,产生杂质缺陷Eu_k。形成的K~+空位通常以晶格间隙中的F~-完成电荷补偿。

黄土高原半干旱区苜蓿草地土壤干燥化特征与粮草轮作土壤水分恢复效应

实地测定了黄土高原半干旱区固原不同生长年限苜蓿草地和连作8a苜蓿草地翻耕轮作不同年限粮食作物后深层土壤水分特征,分析了苜蓿草地土壤干燥化特征和粮草轮作对土壤水分的恢复效应。结果表明:(1)苜蓿连作1a、5a、8a和12a等4类苜蓿草地0~1000cm土层平均土壤湿度值为6.6%,平均土壤水分过耗量702.8mm,平均土壤干燥化速率147.1 mm/a,达到强烈干燥化程度,苜蓿连作5a土壤干层深度超过1000cm,苜蓿连作8a土壤干层深度超过1360cm,苜蓿草地合理利用年限为7a。(2)连作8a苜蓿草地翻耕并轮作4~7a和25a粮食作物等5类粮田0~1000cm土层土壤湿度介于6.74%~11.95%,土壤贮水量恢复值介于210.6~887.3mm,平均土壤水分恢复速率为80.8mm/a。轮作6a后粮田土壤干层轻度恢复程度以上深度达到1000cm。通过粮草轮作使苜蓿草地土壤湿度恢复到当地土壤稳定湿度需要13a以上。黄土高原半干旱区适宜的粮草轮作模式为:7a苜蓿→13a粮食作物。

Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization

A series of binuclear neutral nickel and palladium complexes [(XC6H2CH=NC6H3-iPr(2))MRL](2) 4b-f (X=NO2, M=Ni, R=Ph, L=PPh3, 4b; X=H, M=Pd, R=Me, L=PPh3,4c; X=H,M=Pd, R=Me, L=Py, 4d; X=NO2,M=Pd, R=Me, L=PPh3, 4e; X=NO2, M=Pd, R=Me, L=Py, 4f) and [(C10H7CH=NC6H3-iPr(2))MRL](2) 8a-c (M=Ni, R=Ph, L=PPh3, 8a; M=Pd, R=Me, L=PPh3, 8b; M=Pd, R=Me, L=Py, 8c) have been synthesized and characterized. The structures of complexes 4e and 8b have also been confirmed by X-ray crystallographic analysis. With modified methylalummoxane (MMAO) as cocatalysts, these complexes and complex [(C6H3CH=NC6H3-iPr(2))NiPh(PPh3)](2) 4a are capable of catalyzing the addition polymerization of norbomene (NBE) with the high activity up to 2.3 x 10(8) g PNBE/(mol(M) h). The structure of complexes affects considerably catalytic activity towards norbomene polymerization. The polymers obtained with nickel complexes are soluble, while those obtained with palladium complexes are insoluble. Palladium complexes 4c, 4e and 8b bearing PPh3 ligands exhibit much higher activities than the corresponding complexes 4d, M and 8c bearing pyridine ligands under the same conditions.