Burke D J, Wolff A J, Edridge J L, Brown W A
Department of Chemistry, University College London, London, UK.
J Chem Phys. 2008 Mar 14;128(10):104702. doi: 10.1063/1.2888556.
Reflection absorption infrared spectroscopy (RAIRS) and temperature programed desorption (TPD) have been used to probe the adsorption and desorption of ethanol on highly ordered pyrolytic graphite (HOPG) at 98 K. RAIR spectra for ethanol show that it forms physisorbed multilayers on the surface at 98 K. Annealing multilayer ethanol ices (exposures >50 L) beyond 120 K gives rise to a change in morphology before crystallization within the ice occurs. TPD shows that ethanol adsorbs and desorbs molecularly on the HOPG surface and shows four different species in desorption. At low coverage, desorption of monolayer ethanol is observed and is described by first-order kinetics. With increasing coverage, a second TPD peak is observed at a lower temperature, which is assigned to an ethanol bilayer. When the coverage is further increased, a second multilayer, less strongly bound to the underlying ethanol ice film, is observed. This peak dominates the TPD spectra with increasing coverage and is characterized by fractional-order kinetics and a desorption energy of 56.3+/-1.7 kJ mol(-1). At exposures exceeding 50 L, formation of crystalline ethanol is also observed as a high temperature shoulder on the TPD spectrum at 160 K.
反射吸收红外光谱(RAIRS)和程序升温脱附(TPD)已被用于探测98K下乙醇在高度有序热解石墨(HOPG)上的吸附和解吸。乙醇的RAIR光谱表明,在98K时它在表面形成物理吸附的多层结构。将多层乙醇冰(暴露量>50L)在120K以上退火,会在冰内结晶之前导致形态变化。TPD表明乙醇在HOPG表面以分子形式吸附和解吸,并且在脱附过程中显示出四种不同的物种。在低覆盖度下,观察到单层乙醇的脱附,并由一级动力学描述。随着覆盖度增加,在较低温度下观察到第二个TPD峰,它被归因于乙醇双层。当覆盖度进一步增加时,观察到第二个多层结构,它与下面的乙醇冰膜结合较弱。随着覆盖度增加,这个峰在TPD光谱中占主导地位,其特征是分数级动力学和56.3±1.7kJ mol⁻¹的脱附能量。在暴露量超过50L时,在160K的TPD光谱上也观察到结晶乙醇的形成,表现为一个高温肩峰。