Quantum chemical aided molecular design of ionic liquids as green electrolytes for electrodeposition of active metals  

作　　者：田国才 周雪娇 李坚 华一新 

机构地区：[1]Faculty of Materials and Metallurgical Engineering,Kunming University of Science and Technology

出　　处：《中国有色金属学会会刊：英文版》2009年第6期1639-1644,共6页Transactions of Nonferrous Metals Society of China

基　　金：Projects(50564006,50904031)supported by the National Natural Science Foundation of China;Projects(2005E0004Z,2008E0049M)supported by the Natural Science Foundation of Yunnan Province,China;Project(07Z40082)supported by the Science Foundation of the Education Department of Yunnan Province,China;Project(2007-16)supported by the Science Foundation of Kunming University of Science and Technology,China

摘　　要：Quantum chemical calculation was used to estimate the reduction potentials of 25 organic cations and the oxidation potentials of 11 anions.This information was used to select promising cations and anions for the preparation of ionic liquids as green electrolytes for electrodeposition of active metals.The reasonable linear correlations between the lowest unoccupied molecular orbital(LUMO)energies and the reduction potentials of cations,and the linear relationships between the oxidation potentials and the highest occupied molecular orbital(HOMO)energies of anions were obtained.The orders of electrochemical stability for cations and anions being obtained agree well with the experimental measurements.The suitable ionic liquids with sufficiently wide electrochemical windows for electrodeposition of active metals are suggested to be[Emim]NTf2,[Bmim]NTf2,[Bmim]BF4, [Bmim]PF6,[Bmim]CTf3,[Emim]BF4,[Emim]PF6,[Emim]CTf3..Quantum chemical calculation was used to estimate the reduction potentials of 25 organic cations and the oxidation potentials of 11 anions. This information was used to select promising cations and anions for the preparation of ionic liquids as green electrolytes for electrodeposition of active metals. The reasonable linear correlations between the lowest unoccupied molecular orbital （LUMO） energies and the reduction potentials of cations, and the linear relationships between the oxidation potentials and the highest occupied molecular orbital （HOMO） energies of anions were obtained. The orders of electrochemical stability for cations and anions being obtained agree well with the experimental measurements. The suitable ionic liquids with sufficiently wide electrochemical windows for electrodeposition of active metals are suggested to be [Emim]NTf2, [Bmim]NTf2, [Bmim]BF4, [Bmim]PF6, [Bmim]CTf3, [Emim]BF4, [Emim]PF6, [Emim]CTf3.

关 键 词：量子化学计算 液体电解质 金属离子 计算机辅助 分子设计 电活性 氧化还原电位 有机阳离子 

分 类 号：O611.3[理学—无机化学]