论文标题
pH-sumps in Protic离子液体通过车辆质子运输进行
pH-jumps in a Protic Ionic Liquid Proceed by Vehicular Proton Transport
论文作者
论文摘要
使用可见的泵中型中红外探针光谱法研究了普通液体甲酸甲酸甲酯(EAF)中过量质子的动力学。可见光酸(8-羟基苯乙烯-1,3,6-三硫酸三硫酸盐,HPTS)的光激发后的pH突变导致质子转移到EAF的甲酸盐。质子转移主要发生在picseconds上,这是通过HPT和EAF之间的预氢键复合物。我们通过从拥挤的瞬态瞬时光谱中获得地面偶联物(RO-)动力学来研究离子液体中较长范围和更长的时间尺度质子的传输过程。光谱动力学表明,质子在与ro-重组之前仅从父摄影中扩散了几个溶剂壳。接近统一的动力学同位素效应(kh/kd〜1)表明在这种离子液体中过量质子的车辆转移和运输。我们的发现提供了对普罗尼代面液体中过量质子的完整光周期循环的全面见解。
The dynamics of excess protons in the protic ionic liquid ethylammonium formate (EAF) have been investigated from femtosecond to microseconds using visible pump mid-infrared probe spectroscopy. The pH-jump following visible photoexcitation of a photoacid (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS) results in proton transfer to the formate of the EAF. The proton transfer predominantly occurs over picoseconds through a pre-formed hydrogen-bonded complex between HPTS and EAF. We investigate the longer range and longer timescale proton transport processes in the ionic liquid by obtaining the ground-state conjugate base (RO-) dynamics from the congested transient-infrared spectra. The spectral kinetics indicate that the protons diffuse only a few solvent shells from the parent photoacid before recombining with RO-. A kinetic isotope effect of near unity (kH/kD~1) suggests vehicular transfer and transport of excess protons in this ionic liquid. Our findings provide a comprehensive insight into the complete photoprotolytic cycle of excess protons in a protic ionic liquid.