Electrochemical reduction of maleic acid and maleic anhydride in [BMIM]BF4 room temperature ionic liquid and in situ FTIR spectroscopic studies

室温离子液体是指在室温或接近室温温度下由阴阳离子组成的液态物质,具有不挥发、不易燃、电化学窗口宽、电导率高、可循环使用等优点。近几年来，室温离子液体因其独特的物理化学性质，作为绿色溶剂或电解液在基础研究和工业应用等方面都引起了极大的关注。迄今为止将离子液体应用于有机电合成方面的研究尚处于起步阶段。本论文自行合成1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)室温离子液体,以此为电解液，研究了马来酸及马来酸酐的电还原过程。主要内容和结果如下：1.采用两步合成法成功制备了离子液体[BMIM]BF4，并用微波辐射的新方法制备了[BMIM]Cl，同时运用FTIR、NMR和循环伏安法对[BMIM]...Room-Temperature Ionic Liquids (RTILs) are those materials that are composed anions and cations and are liquids at or near room temperature. The RTILs exhibit wide electrochemical windows, negligible vapor pressures and high ionic conductivities, and have attracted extensive attentions in fundamental research and industrial applications. As a green solvent or electrolyte the RTILs present interest...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：20042514

Electrochemical and In situ FTIR Studies of Maleic Acid Reduction in BF_4

作者自行合成了离子液体[BMIM]BF4,用循环伏安法(CV)、计时电量法(CA)和电化学原位红外反射光谱(in situFTIR),从分子水平考察了离子液体中马来酸在玻碳(GC)电极上的电化学还原过程。结果表明,[BMIM]BF4中马来酸在GC电极上的还原为不可逆过程,测得扩散系数D=9.62×10-8cm2/s;in situFTIRS研究发现,马来酸在离子液体[BMIM]BF4和水溶液中的电还原生成丁二酸的机理不同。在[BMIM]BF4中马来酸还原发生在其中的一个羧基上,即马来酸首先获得一个电子生成阴离子自由基,随后可能获得一个电子生成二价阴离子,或者获得一个电子并在2个H+的作用下生成醛类物质和水。The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborates(BF4) was synthesized and used as both solvent and electrolyte.Electrochemical reduction of maleic acid in the ionic liquid was studied by cyclic voltammetry(CV),chronoamperometry(CA) and in situ FTIR spectroscopy.The results demonstrated that the reduction of maleic acid on GC electrode is an irreversible process controlled by diffusion.The diffusion coefficient D of maleic acid is determined to be 9.62×10-8 cm2/s.in situ FTIR results illustrated that the reduction of maleic acid in ionic liquids occurs on the carboxyl.The first step is to geaerte radical anions,which are reduced then to aldehyde species and water with two hydrogen ions.国家自然科学基金(批准号:20673091,20833005)~

Electrochemical and in situ FTIRS of maleic acid reduction in[BMIM]BF_4 on Pt electrode

采用循环伏安法(CV)、计时电量法(CA)和电化学原位红外反射光谱(in situ FTIRS),从分子水平上研究了离子液体[BMIM]BF_4中马来酸在Pt电极上的电化学还原过程。结果表明,[BMIM]BF_4中马来酸在Pt电极上的还原是受扩散控制的准可逆过程,测得扩散系数为1.0×10~(-7)cm~2·s~(-1);in situ FTIRS研究发现, [BMIM]BF_4中马来酸在Pt电极上的还原发生在其中的一个羧基位上,即马来酸首先获得一个电子生成阴离子自由基,随后再获得一个电子生成二价阴离子。Electrochemical reduction of maleic acid in the ionic liquid was studied by cyclic voltammetry (CV),chronoamperometry(CA)and in situ FTIR spectroscopy.The results demonstrated that the reduction of maleic acid on Pt electrode is a quasireversible process controlled by diffusion.The diffusion coefficient of maleic acid is determined to be 1.0×10~(-7)cm~2·s~(-1).In situ FTIRS results illustrated that the reduction of maleic acid in ionic liquids occurs on the carboxyl.The first step is to generate radical anions, which are reduced to aldehyde species.国家自然科学基金项目(20833005,20873113)。~