Syntheses of Lanthanide-containing Polyoxotungstates Substituted by Transitionmetal-Nonmetal pairs : Its Developments for Photo-electron Molecular Catalysts

2000年：人们尝试了合成双钒离子取代的镧系十聚钨酸盐[LnV 2 W8]。此外，尝试用硅烷试剂将由此获得的LnV 2 W8固定在氧化钛氢氧化物[TiO（OH）2]上。在LnW 10上考察了碳氢化合物的光催化氧化，并比较了不同过渡金属离子对LnW 10光催化活性的影响。2001年：以有机基团[org-LnV_2 W_8]修饰LnV_2W_10，并将LnV_2W_8和org-LnV_2 W_8固定在硅烷修饰的TiO（OH）_2上，制备了LnV_2W_8/sil-TiO_2和org-LnV_2 W_8/sil-TiO_2催化剂。结果表明：1）V2取代的LnV 2 W8催化剂对H2 O2氧化烃类反应的催化活性显著提高，对甲硫醚、2-己烯醇和薄荷醇的催化活性分别提高了约4倍、3倍和2倍。特别是有机钒钨/硅纳米TiO 2催化剂在无有机溶剂体系中表现出优异的H2 O2-烃氧化活性，从绿色催化剂化学的角度来看是非常合适的。2）在紫外光照射下对org-GdV_2 W_8/sil-TiO_2进行ESR测量，比较了Gd（III）、V（IV）和Ti（III）在TiO_2上的ESR信号强度随电子转移的变化，并在引入有机气体的情况下考察了这些变化。3)紫外-可见光谱和荧光光谱的变化，伴随着强度的变化，现在正在进行测量。4)同时用钒和硅醇基团取代的新的LnW_（10）样品的合成及其在sil-TiO_2上的固定已被尝试。5）LnW 10与Cu（II）和Cu（II）+Pd（II）离子复合后，其光催化活性显著提高，如对醇类的光催化氧化。

In 2000 : Synthesis of lanthanide decatungstates substituted by two-vanadium ions[LnV2W8] have been variously attempted. Further, LnV2W8 thus obtained was tried to fix on titanium-oxide-hydroxides[TiO(OH)2] with silane agents. Photocatalytic oxidation of hydrocarbons were examined prelininarly on LnW10, and effects of various transition metal ions added to LnW10 on the photocatalytic activities were compared, as previously reported. In 2001 : Modification of LnV2W10 with organic group[org-LnV2W8] and further fixzation of LnV2W8 and org-LnV2W8 on TiO(OH)2 modified previously with silane agents[sil-TiO2] were attempted variously to obtain LnV2W8/sil-TiO2 and org-LnV2W8/sil-TiO2 catalysts. Those samples were successfully analyzed by FT-IR,UV-vis,ICP,ESR, so on. 1)The catalytic activities of LnV2W8 for H2O2-oxidation of hydrocarbons were greatly enhanced with the V2-substitution, LnV2W8 ; the activities for methyl-sulfide, 2-hexene-1-ol, and menthol increased ca.4-times,3-times, and 2-times, respectively. Especially, org-LnV2W8/sil-TiO2 catalyst showed an excellent activity for H2O2-oxidation of hydrocarbons in an organic solvent free system, being very suitable from a viewpoint of green catalyst chemistry. 2)ESR-measurements of org-GdV2W8/sil-TiO2 were taken place under UV-light irradiation ; changes in the intensities of ESR-signals among Gd(III),V(IV), and Ti(III) on TiO2,accompanied with an electron-transfer, were compared and also those changes were examined under introducing organic gasses. 3)Measurements of variations in UV-vis and fluorescence spectra, accompanied with the changes in the intensities, are now in progress. 4)Syntheses of new LnW10 samples as substituted simultaneously by vanadium and silanol-groups, and their fixzation on sil-TiO2 have been attempted. 5)Photo-catalytic activities of LnW10 were enhanced greatly in the combination with Cu(II) and Cu(II)+Pd(II) ions, for instance, for photo-catalytic oxidation of alcohols.