Tang Yongan, Zeng Xiangqun
Department of Chemistry, Oakland University, Rochester, Michigan 48309, United States.
J Phys Chem C Nanomater Interfaces. 2016 Oct 20;120(41):23542-23551. doi: 10.1021/acs.jpcc.6b07067. Epub 2016 Sep 12.
The electrochemical behavior of hydrogen oxidation on a platinum electrode in two aprotic room temperature ionic liquids (RTILs)-1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf] and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Bmpy][NTf]-was investigated in both anaerobic and aerobic conditions. At platinum electrode in the ILs, the first step of hydrogen oxidation is the formation of Pt-H(ad) (the Tafel step), which is similar to those observed in the aqueous electrolytes. However, there are differences in the oxidation steps (the Heyrovsky and Volmer steps). In ILs, the oxidation of Pt-H(ad) forms a hydrogen radical and a proton rather than a proton or a water in aqueous acid or alkaline electrolytes, respectively. This difference is significant as it results in a completely different following reaction pathway in the anaerobic vs aerobic conditions. A coupled chemical reaction between oxygen and hydrogen oxidation intermediates was observed in aerobic conditions which has a correlation with hydrogen concentrations. Furthermore, the overall rate of hydrogen oxidation is shown to be much higher in [Bmpy][NTf] than that of [Bmim][NTf], which is rationalized as the result of both higher solubility of hydrogen and the unique IL-electrode interface structure which promotes the hydrogen adsorption in [Bmpy][NTf] than that of [Bmim][NTf]. This study is the first example showing that hydrogen oxidation mechanism in aprotic ILs follows two different oxidation mechanisms in anaerobic and aerobic conditions.
研究了在两种非质子室温离子液体(RTILs)——1-丁基-3-甲基咪唑双(三氟甲基磺酰)亚胺[Bmim][NTf]和1-丁基-1-甲基吡咯烷双(三氟甲基磺酰)亚胺[Bmpy][NTf]中,铂电极上氢氧化的电化学行为,研究在厌氧和好氧条件下均进行。在离子液体中的铂电极上,氢氧化的第一步是形成Pt-H(ad)(塔菲尔步骤),这与在水性电解质中观察到的情况相似。然而,氧化步骤(海洛夫斯基步骤和沃尔默步骤)存在差异。在离子液体中,Pt-H(ad)的氧化形成一个氢自由基和一个质子,而不是像在酸性或碱性水性电解质中分别形成一个质子或一个水分子。这种差异很显著,因为它导致在厌氧与好氧条件下后续反应途径完全不同。在好氧条件下观察到氧气与氢氧化中间体之间的耦合化学反应,该反应与氢气浓度相关。此外,[Bmpy][NTf]中氢氧化的总速率显示比[Bmim][NTf]中的高得多,这被解释为氢气在[Bmpy][NTf]中的溶解度更高以及独特的离子液体-电极界面结构促进氢气吸附的结果,与[Bmim][NTf]相比,[Bmpy][NTf]中氢气吸附效果更好。本研究是首个表明非质子离子液体中氢氧化机制在厌氧和好氧条件下遵循两种不同氧化机制的例子。