Berger Claudia A, Arkhipova Maria, Farkas Attila, Maas Gerhard, Jacob Timo
Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081 Ulm, Germany.
Institute of Organic Chemistry I, Ulm University, Ulm, Germany.
Phys Chem Chem Phys. 2016 Feb 14;18(6):4961-5. doi: 10.1039/c5cp07152f.
In this study titanium isopropoxide was dissolved in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) and further in a custom-made guanidinium-based ionic liquid (N11N11NpipGuaTFSI). Electrochemical investigations were carried out by means of cyclic voltammetry (CV) and the initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). For BMITFSI we found one large cathodic reduction peak at a potential of -1.2 V vs. Pt, corresponding to the growth of monoatomic high islands. The obtained deposit was identified as elemental titanium by Auger Electron Spectroscopy (AES). Furthermore, we found a corresponding anodic peak at -0.3 V vs. Pt, which is associated with the dissolution of the islands. This observation leads to the assumption that titanium deposition from the imidazolium-based room-temperature ionic liquid (RTIL) proceeds in a one-step electron transfer. In contrast, for the guanidinium-based RTIL we found several peaks during titanium reduction and oxidation, which indicates a multi-step electron transfer in this alternative electrolyte.
在本研究中,异丙醇钛溶解于1-丁基-3-甲基咪唑双(三氟甲基磺酰)亚胺(BMITFSI)中,进而溶解于一种定制的胍基离子液体(N11N11NpipGuaTFSI)中。通过循环伏安法(CV)进行电化学研究,并利用原位扫描隧道显微镜(STM)跟踪金属沉积的初始阶段。对于BMITFSI,我们在相对于铂为-1.2 V的电位处发现一个大的阴极还原峰,对应于单原子高岛的生长。通过俄歇电子能谱(AES)将所得沉积物鉴定为元素钛。此外,我们在相对于铂为-0.3 V处发现一个相应的阳极峰,这与岛状物的溶解有关。这一观察结果导致这样一种假设,即从咪唑基室温离子液体(RTIL)中沉积钛是通过一步电子转移进行的。相比之下,对于胍基RTIL,我们在钛的还原和氧化过程中发现了几个峰,这表明在这种替代电解质中存在多步电子转移。