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Chemically modified germanium(Ⅳ) alkoxides: molecular precursors for nano-sized germania

机译:化学改性的锗(Ⅳ)醇盐:纳米锗的分子前体

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Modification of germanium(Ⅳ) alkoxides with haloacetic acids in different molar ratios yielded,germanium(IV) alkoxo-halocarboxylates of the type [Ge(OR)_(4-n)(OOCCX_3)_n] [1-4] [where R = Pr~I;X = Cl; n = 1 (1)/ 2 (2) or R = ~tBu; n = 1; X = Cl (3)/ F (4)]. Based on the molecular weightdeterminations, IR, NMR [~1H, ~(13)C{1H} and ~(19)F{~1H,~(13)C}] and FAB mass spectral studies, a distortedtetrahedral geometry around germanium atom is proposed for all compounds.Thermogravimetric (TG) analyses of (1) and (2) reveal low temperature decomposition togermania. Hydrolysis of (1), (3) and (4) by sol-gel technique yielded nano-sized germania (ⅰ),(ⅱ) and (ⅲ), respectively. The powder XRD patterns suggest formation of hexagonal phase ofnano-sized germania and the SEM images of the materials depict regularity of the particles.Smaller particle size of pure germania can be easily obtained from the chlorinated carboxylatesas compared to the corresponding fluorinated carboxylate.
机译:用卤代乙酸以不同的摩尔比对烷氧基锗(Ⅳ)进行改性,得到[Ge(OR)_(4-n)(OOCCX_3)_n]类型的锗(IV)烷氧基卤代羧酸盐[1-4] [其中R = Pr〜I; X = Cl; n = 1(1)/ 2(2)或R =〜tBu; n = 1; X = Cl(3)/ F(4)]。根据分子量测定,IR,NMR [〜1H,〜(13)C {1H}和〜(19)F {〜1H,〜(13)C}]和FAB质谱研究,锗原子周围的四面体几何形状失真(1)和(2)的热重(TG)分析显示低温分解托格曼病。通过溶胶-凝胶技术水解(1),(3)和(4)分别产生纳米级的氧化锗(ⅰ),(ⅱ)和(ⅲ)。粉末XRD图谱表明形成了六方相的纳米二氧化锗,材料的SEM图像显示了颗粒的规则性。与相应的氟化羧酸盐相比,氯化二羧酸盐可以轻松获得更细的纯二氧化锗粒径。

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