Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland.
J Phys Chem A. 2013 Jan 17;117(2):401-9. doi: 10.1021/jp3102332. Epub 2013 Jan 9.
Ice plays a key role in the environment, and the ice-air interface influences heterogeneous chemical reactions between snowpack or cirrus clouds and the surrounding air. Soluble gases have been suspected to affect the topmost, disordered layer on ice (often referred to as a quasiliquid layer, QLL). Changes are especially expected in the hydrogen-bonding structure of water in the presence of solutes at the ice surface. Here, we used ambient-pressure X-ray photoelectron spectroscopy (XPS) to detect acetic acid at the ice surface at 230-240 K under atmospheric conditions for the first time. Electron-kinetic-energy-dependent C 1s spectra indicate that acetic acid remains confined to the topmost ice surface layers. Spectral analysis provides information about the protonation state of acetate at the ice surface. Surface-sensitive Auger-electron-yield C-edge near-edge X-ray absorption fine structure (NEXAFS) spectra were recorded to probe the molecular state of the adsorbed species. The O-edge NEXAFS spectra show only minor differences between clean ice and ice with adsorbed acetic acid and thus indicate that acetic acid does not lead to an extended disordered layer on the ice surface between 230 and 240 K.
冰在环境中起着关键作用,冰-气界面影响着雪或卷云中的异相化学反应与周围空气之间的反应。人们怀疑可溶性气体影响冰的最上面无序层(通常称为准液态层,QLL)。在冰表面存在溶质的情况下,水的氢键结构预计会发生变化。在这里,我们首次在大气条件下于 230-240 K 首次使用常压 X 射线光电子能谱(XPS)在冰表面检测到乙酸。电子动力学能相关的 C 1s 谱表明,乙酸仍局限于最上面的冰表面层。光谱分析提供了关于冰表面上乙酸盐的质子化状态的信息。记录了表面敏感的俄歇电子产额 C 边近边 X 射线吸收精细结构(NEXAFS)谱,以探测吸附物种的分子状态。O 边 NEXAFS 谱在清洁冰和吸附乙酸的冰之间仅显示出微小的差异,因此表明在 230 至 240 K 之间,乙酸不会导致冰表面上无序层的扩展。