Department of Chemistry, University of Leicester, Leicester, UK LE1 7RH.
Phys Chem Chem Phys. 2010 Feb 28;12(8):1862-72. doi: 10.1039/b917351j. Epub 2009 Nov 18.
The deposition of aluminium from a chloroaluminate based ionic liquid was studied to elucidate the effect of a diluent (toluene) and electrolyte (LiCl) on the deposit morphology. A wide variety of analytical techniques was applied to this system to determine the speciation and mechanism of material growth. These included: (27)Al NMR, FAB-MS, cyclic voltammetry, chronocoulometry, chronopotentiometry, scanning electron microscopy and atomic force microscopy. It was found that under-potential deposition (upd) causes a change in the way in which metal grows on the electrode surface. Metal grows in two regimes which are believed to be nano-material and bulk material. The addition of toluene causes a change in speciation and a decrease in upd which in turn changes the morphology of the deposit obtained and can lead to mirror finish aluminium. The addition of LiCl has the opposite effect encouraging upd and leading to larger crystallites and a dark grey deposit. It is also shown for the first time that under many conditions the rate of the anodic dissolution process is overall rate controlling and one effect of the addition of toluene is to increase the rate of anodic dissolution.
研究了从基于氯铝酸盐的离子液体中沉积铝,以阐明稀释剂(甲苯)和电解质(LiCl)对沉积物形态的影响。该系统应用了多种分析技术来确定物质生长的形态和机制。这些技术包括:(27)Al NMR、FAB-MS、循环伏安法、计时库仑法、计时电位法、扫描电子显微镜和原子力显微镜。研究发现,欠电位沉积(upd)导致金属在电极表面生长的方式发生变化。金属在两种区域生长,据信这两种区域是纳米材料和块状材料。甲苯的加入会引起形态和 upd 的变化,从而改变获得的沉积物的形态,并导致镜面光洁度的铝。添加 LiCl 则具有相反的效果,它会鼓励 upd,导致更大的晶粒和深灰色沉积物。这也是首次表明,在许多条件下,阳极溶解过程的速率是整体速率控制的,甲苯的加入会增加阳极溶解的速率。