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Quantum　Chemistry　Studies　on　the　Heteropoly　Blues　of　Molybdosilic　Series　with　α-keggin　structure

Chemical Research in Chinese Universities 1997年第3期13卷 262-267页

作者： FU Qiang, YANG Ming , CHEN Bin , WANC En-Bo, XIE De-Min , JIANG Zhong-Ming,PENG Jun (Department of Chemistry,Northeast Normal University,Changchun,130024) NE NORMAL UNIV DEPT CHEMCHANGCHUN 130024PEOPLES R CHINA

SCC-DV-X method was used for the theoretical calculation of heteropoly an- ion , [SiMoO40]4- . and heteropoly blue anions,[SiMo2 Mo10O40]6 and [SiMo4 Mo!; O' 1,-. Th. ***.. .ol...l.. orbital. , orbital ***.. , *** 1...l. , the o.- cupied numbers of basis functions , free valences , Mulliken populations and the fig- ure of the total density of states have been obtained. The theoretical analysis indi- cates that all the atoms in the anions participate in chemical reactions , but Oc and Od have higher chemical activities than other atonts , which is supported by the ex- perimental results. The heteropoly hue anions with the α-keggin structure distort a little and the levels of valence orbitals demonstrate that [SiMo4 Mo8O40]8 can form a six-electron heteropoly blue anoint by accepting two electrons.

关键词： SCC-DV-X method α-keggin structure Fermi level Mulliken popu- lations

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Synthesis, Characterization and Conductivity of α-keggin-type Nanoparticles, Co(en)_3PMo_(12)O_(40)·8H_2O with Optical Activity

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Chemical Research in Chinese Universities 2005年第1期21卷 1-3页

作者： HUANGRu-dan LIJuan ZHANGJing DepartmentofChemistry SchoolofScienceBeijingInstituteofTechnologyBeijing100081P.R.China KeyLaboratoryofRareEarthChemistryandPhysics ChangchunInstituteofAppliedChemistryChineseAcademyofSciencesChangchun130022P.R.China／／DepartmentofChemistryNormalCollegeBeihuaUniversityJilin132013P.R.China

Polyoxometallates Co(en) 3PMo 12O 40·8H 2O(+,-)[abbreviated as PMo 12-Co(+,-)], nanoparticles were synthesized by the chemical precipitation reaction at room temperature for the first time. They were characterized by means of elemental analyses, IR spectrometry and X-ray diffraction. The images of scanning electron microscopy(SEM) and the results of calculation by using the Scherrer equation for the line widths of the XRD patterns were used to estimate the average particle size of the powder products, which was 40 nm. The results show that the nanoparticle size was affected by starting materials′ concentrations. The particles had a small size and a narrow distribution, when the concentrations of H 3PMo 12O 40·24H 2O and Co(en) 3I 3·H 2O were around 1.7×10 -4 and 1.0×10 -3 mol/L, respectively. When the concentration was increased, there was no significant increase in the particle size, but more polydisperse Co(en) 3(PMo 12O 40) (+, -) were obtained. In poly(ethylene glycol)(PEG) with an average molecular weight(M W) of 600 g/mol and containing LiClO 4[n(O)/n(Li)=100∶1] as the supporting electrolyte, the conductivity of the composite system increases upon the addition of PMo 12-Co(+ or -) nanoparticles, which was measured by the a.c. impedance technique. The interactions among PEG, LiClO 4, PMo 12, and Co can be used to explain that the PMo 12-Co(+ or -) nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

关键词： Polyoxometallates Nanoparticles α-keggin structure Optical activity

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