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

• 作 者: 田国才 周雪娇 李坚 华一新
• 机 构: Faculty of Materials and Metallurgical Engineering,Kunming University of Science and Technology,
• 出 处: Transactions of Nonferrous Metals Society of China
• 发表日期: 2009年06期
• 关键词: liquids ionic orbital imidazolium occupied aided anion quaternary electrolysis d

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 committed 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 enhanced 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.