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Preparetion of Rare-earth Metal Films by Electrochemical Deposition from Non-aqueous Madia with High-purity

高纯非水介质电化学沉积制备稀土金属薄膜

基本信息

批准号：
09650808
负责人：
HIRATO Tetsuji
金额：
$ 1.86万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

Triflate-type rare earth salts, Ln(TfO)_3 or Ln(Tf_2N)_3 (Ln = Nd, Eu), were dissolved in imidazolium-type room temperature molten salts with corresponding anion, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITfO) and 1-ethyl-3-methylimidazoium bis((trifluoromethyl)sulfonyl)amide (EMILTf_2N), in order to investigate redox behavior of rare earth ions in the nonaqueous ionic liquids. EMITfO was prepared by the reaction of 1-ethylimidazol with Methyl trifluoromethanesulfonate in dried 1,1,1-trichloroethane. EMITf_2N was prepared by the reaction of 1-ethyl-3-methylimidazolium bromide (EMIBr) with lithium bis((trifluoromethyl)sulfonyl)amide (LiTf_2N) in deionized water followed by extraction with dichloromethane ; the EMIBr was obtained by the reaction of 1-methylimidazol with bromoethane in 1,1,1-trichioroethane. The resulting molten salts were dried in vacuo at 120-150 。C for more than 3 days.Solubility of the rare earth salts into the corresponding molten salts exceeds 0.1 mol dm^<-3>. Ln(TfO)_3 is not soluble in EMITf_2N, whereas Ln(Tf_2N)_3 soluble in both EMIITfO and EMITf_2N.Cyclic voltammograms show that the redox potentials of Eu^<2+>/Eu^<3+> were ca. -0.9 V in EMITfO, +0.3 V in EMITf_2N, and ca.. -0.9 V vs. I_3^-/I^- in 1/1 mixture (in volume) of EMJTfO and EMITf_2N.These phenomena are explained by a lower Lewis basicity of Tf_2N^- anion compared to TfO, suggesting Tf_2N^--type room temperature molten salts are promising solvents for cathode electrolysis of rare earth ions.A new ammonium-type room temperature molten salt, trimethylhexylammonium bis((trifluoromethyl)sulfonyl)amide (TMHATf_2N), was also prepared by the reaction of trimethylhexylammonium bromide (TMHABr) with LiTf_2N.Solubility of Nd(Tf_2N)_3 into the TMHATf_2N was more than 0.1 mol dm^<-3>. Since the electrochemical window of TMHATf_2N exceeds 5.5 V, the molten salt is also a promising solvent for electrodeposition of rare earths at ambient temperature.

将三氟甲磺酸型稀土盐Ln（TfO）_3或Ln（Tf 2N）_3（Ln = Nd，Eu）分别溶解于咪唑型室温熔盐中，并分别加入相应的阴离子1-乙基-3-甲基咪唑三氟甲磺酸盐（EMITfO）和1-乙基-3-甲基咪唑双（（三氟甲基）磺酰基）酰胺（EMILTf 2N），研究稀土离子在非水离子液体中的氧化还原行为。EMITfO是由1-乙基咪唑和三氟甲磺酸甲酯在干燥的1，1，1-三氯乙烷中反应制得的。EMITf_2N是由1-乙基-3-甲基溴化咪唑（EMIBr）与双（（三氟甲基）磺酰基）氨基锂（LiTf_2N）在去离子水中反应，然后用二氯甲烷萃取制得; EMIBr是由1-甲基咪唑与溴乙烷在1，1，1-三氯乙烷中反应制得。将所得熔盐在120-150 ℃下真空干燥。稀土盐在相应的熔融盐中的溶解度超过0.1摩尔dm 2<-3>。Ln（TfO）_3不溶于EMITf_2N，而Ln（Tf_2N）_3既溶于EMITfO又溶于EMITf_2N。-0.9 V（EMITfO），+0.3 V（EMITf_2N），约-0.9 V vs. I_3^-/I^-（1/1混合物）Tf_2N^-型室温熔盐是稀土离子阴极电解的理想溶剂。用三甲基己基溴化铵（TMHABr）与LiTf_2N反应制备了三甲基己基双（三氟甲基磺酰基）酰胺铵（TMHATf_2N），Nd（Tf_2N）_3在TMHATf_2N中的溶解度大于0.1moldm ~（3+）<-3>。由于TMHATf_2N的电化学窗口超过5.5V，该熔盐也是一种很有前途的室温电沉积稀土的溶剂。