室温离子液体的合成及应用
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摘要
本文合成了N-烷基吡啶类和N-甲基咪唑类室温离子液体。测定了他们的电化学窗口和电导率,为下一步离子液体在电解活泼金属和电镀领域的应用奠定了基础。
首先利用1-氯丁烷与吡啶或1-甲基咪唑反应合成了作为室温离子液体中间体的氯化N-正丁基吡啶(BPC)、氯化1-甲基-3-丁基咪唑([bmim]Cl)。AlCl_3和BPC按摩尔比为2:1、1:1和0.8:1可以分别合成酸性、中性和碱性室温离子液体;利用BPC与NH_4BF_4,[bmim]Cl与NH_4BF_4或KHSO_4在乙腈中的复分解反应,合成了四氟硼酸N-正丁基吡啶(BPBF_4)、四氟硼酸1-甲基-3-丁基咪唑([bmim]BF_4)和硫酸氢盐1-甲基-3-丁基咪唑([bmim][HSO_4])三种室温离子液体。通过核磁共振氢谱(~1H NMR)、拉曼光谱(Raman)和红外光谱(IR)手段对合成产物的化学结构进行了表征,证明了合成物分别是BPC、[bmim]Cl、AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]。
利用循环伏安法测定了室温离子液体的电化学窗口。酸性、中性和碱性AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]离子液体的电化学窗口分别为3.4V、4.0V、2.25V、3.1V、2.2V和2.2V,它们的电化学窗口都比较宽,且大于水的电化学窗口(1.229V),因而许多不能通过水溶液电解得到的活泼金属如铝一等,可以通过含有相应金属元素的离子液体电解得到。
测定了酸性、中性和碱性AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]离子液体的电导率,结果表明每种离子液体的电导率均随着温度的升高而增大,电导率大小顺序依次为K_a>K_b>K_c>K_d>K_e>K>_f,其中K_a,K_b,k_c,K_d,K_e和K_f分别为[bmim]BF_4、BPBF_4、酸性、碱性、中性AlCl_3-BPC和[bmim][HSO_4]室温离子液体的电导率。并且每种离子液体的电导率对数与温度倒数的关系呈线性关系,满足Arrhenius方程。
测定了BPBF_4、[bmim]BF_4和[bmim][HSO_4]三种室温离子液体在22℃时
In this paper, four kinds of room temperature ionic liquids (RTIL) are prepared. Their electric conductivity and electrochemical window, which play an important role in the applications of ionic liquids to electrodeposition and electroplating of active metals, are determined.The intermediates N-butylpyridium chloride(BPC) and l-butyl-3-methylimidazolium chloride([bmim]Cl) for the synthesis of ionic liquids are prepared by the reactions between N-butyl halide and pyridium or N-methylimidazolium. Acidic, basic and neutral BPC-AlCl3 ionic liquids are prepared by directly mixing BPC and AlCl3 with different ratios of BPC to AlCl3 under inert atmosphere. For other ionic liquids such as N-butylpyridium tetrafluoride (BPBF4), l-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BFi|) and l-butyl-3-methylimidazolium hydrogen sulphate ([bmim][HSO4]), they are synthesized through anion exchange reactions in acetonitrile medium. Their chemical structures are determined
by H NMR, IR and Raman spectra, respectively.The electrochemical window of the ionic liquids synthesized is measured by Cyclic Voltammogram. The chemical potential windows of the RTILs prepared are 3.4V, 4.0V, 2.25V, 3.1V, 2.2V and 2.2V for acidic, neutral and basic A1C13-BPC, BPBF4, [bmim]BF4 and [bmim][HSO4] RTILs respectively. The electrochemical windows of these ionic liquids are broader than of water (1.229V), so some active metals such as aluminium can be electrolysed in these ionic liquids.The electric conductivity of the RTILs is measured at different temperatures. The electric conductivity is increased with increasing temperature. It is shown that the sequence of electric conductivity can be expressed as Ka>Kb>Kc>Kd>Ke>Kf, where Ka kb kc, Kd Ke and Kf are electric conductivity for [bmim]BF4, BPBF4, acidic, basic and neutral AlCl3-BPC and [bmim][HSO4] RTILs, respectively. Moreover, the relations of electric conductivity and temperature can be described with Arrhenius equation.The viscosity of BPBF4, [bmim]BF4 and [bmim][HSO4] RTILs is determined at 22℃. It is demonstrated that [bmim]BF4 ionic liquid has better fluidity than BPBF4, and [bmim][HSO4 ] is the worst in fluidity among them.
首先利用1-氯丁烷与吡啶或1-甲基咪唑反应合成了作为室温离子液体中间体的氯化N-正丁基吡啶(BPC)、氯化1-甲基-3-丁基咪唑([bmim]Cl)。AlCl_3和BPC按摩尔比为2:1、1:1和0.8:1可以分别合成酸性、中性和碱性室温离子液体;利用BPC与NH_4BF_4,[bmim]Cl与NH_4BF_4或KHSO_4在乙腈中的复分解反应,合成了四氟硼酸N-正丁基吡啶(BPBF_4)、四氟硼酸1-甲基-3-丁基咪唑([bmim]BF_4)和硫酸氢盐1-甲基-3-丁基咪唑([bmim][HSO_4])三种室温离子液体。通过核磁共振氢谱(~1H NMR)、拉曼光谱(Raman)和红外光谱(IR)手段对合成产物的化学结构进行了表征,证明了合成物分别是BPC、[bmim]Cl、AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]。
利用循环伏安法测定了室温离子液体的电化学窗口。酸性、中性和碱性AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]离子液体的电化学窗口分别为3.4V、4.0V、2.25V、3.1V、2.2V和2.2V,它们的电化学窗口都比较宽,且大于水的电化学窗口(1.229V),因而许多不能通过水溶液电解得到的活泼金属如铝一等,可以通过含有相应金属元素的离子液体电解得到。
测定了酸性、中性和碱性AlCl_3-BPC、BPBF_4、[bmim]BF_4和[bmim][HSO_4]离子液体的电导率,结果表明每种离子液体的电导率均随着温度的升高而增大,电导率大小顺序依次为K_a>K_b>K_c>K_d>K_e>K>_f,其中K_a,K_b,k_c,K_d,K_e和K_f分别为[bmim]BF_4、BPBF_4、酸性、碱性、中性AlCl_3-BPC和[bmim][HSO_4]室温离子液体的电导率。并且每种离子液体的电导率对数与温度倒数的关系呈线性关系,满足Arrhenius方程。
测定了BPBF_4、[bmim]BF_4和[bmim][HSO_4]三种室温离子液体在22℃时
In this paper, four kinds of room temperature ionic liquids (RTIL) are prepared. Their electric conductivity and electrochemical window, which play an important role in the applications of ionic liquids to electrodeposition and electroplating of active metals, are determined.The intermediates N-butylpyridium chloride(BPC) and l-butyl-3-methylimidazolium chloride([bmim]Cl) for the synthesis of ionic liquids are prepared by the reactions between N-butyl halide and pyridium or N-methylimidazolium. Acidic, basic and neutral BPC-AlCl3 ionic liquids are prepared by directly mixing BPC and AlCl3 with different ratios of BPC to AlCl3 under inert atmosphere. For other ionic liquids such as N-butylpyridium tetrafluoride (BPBF4), l-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BFi|) and l-butyl-3-methylimidazolium hydrogen sulphate ([bmim][HSO4]), they are synthesized through anion exchange reactions in acetonitrile medium. Their chemical structures are determined
by H NMR, IR and Raman spectra, respectively.The electrochemical window of the ionic liquids synthesized is measured by Cyclic Voltammogram. The chemical potential windows of the RTILs prepared are 3.4V, 4.0V, 2.25V, 3.1V, 2.2V and 2.2V for acidic, neutral and basic A1C13-BPC, BPBF4, [bmim]BF4 and [bmim][HSO4] RTILs respectively. The electrochemical windows of these ionic liquids are broader than of water (1.229V), so some active metals such as aluminium can be electrolysed in these ionic liquids.The electric conductivity of the RTILs is measured at different temperatures. The electric conductivity is increased with increasing temperature. It is shown that the sequence of electric conductivity can be expressed as Ka>Kb>Kc>Kd>Ke>Kf, where Ka kb kc, Kd Ke and Kf are electric conductivity for [bmim]BF4, BPBF4, acidic, basic and neutral AlCl3-BPC and [bmim][HSO4] RTILs, respectively. Moreover, the relations of electric conductivity and temperature can be described with Arrhenius equation.The viscosity of BPBF4, [bmim]BF4 and [bmim][HSO4] RTILs is determined at 22℃. It is demonstrated that [bmim]BF4 ionic liquid has better fluidity than BPBF4, and [bmim][HSO4 ] is the worst in fluidity among them.
引文
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