Tarábková Hana, Janda Pavel
Department of Electrochemical Materials, J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 2155/3, CZ-182 23 Prague 8, Czech Republic.
Langmuir. 2023 Oct 3;39(39):14154-14161. doi: 10.1021/acs.langmuir.3c02151. Epub 2023 Sep 21.
Early works considered basal planes of highly ordered pyrolytic graphite (HOPG) as hydrophobic, relatively inert materials with low electrocatalytic activity due to nonpolar sp carbon. On the contrary, a freshly prepared HOPG surface exhibits intrinsically mildly hydrophilic properties, with a low contact angle of water, which increases after exposure to an ambient atmosphere. This process, called aging, ascribed to adsorption of airborne hydrocarbons, is reportedly accompanied by strong decay of electron transfer kinetics, the mechanism of which is not yet fully understood. Examining both freshly prepared and aged basal plane HOPG immersed in water by PeakForce quantitative nanomechanical imaging, we have found that aged HOPG is occupied by ambient gaseous nanodomains, the existence of which is explained by incomplete wetting. They cover up to 60% of the immersed surface and their incidence is in direct relation with graphite aging time. In contrast with aged graphite, gaseous nanodomains were absent on the freshly stripped HOPG surface. It can be concluded that ambient gaseous nanodomains can prevent aged basal plane HOPG from contact with aqueous media and may thus affect processes at the solid-liquid interface.
早期的研究认为,高度有序热解石墨(HOPG)的基面是疏水的、相对惰性的材料,由于其非极性的sp碳,电催化活性较低。相反,新制备的HOPG表面具有固有的轻度亲水性,水的接触角较低,在暴露于环境大气后接触角会增大。这个过程称为老化,据报道是由于空气中碳氢化合物的吸附所致,同时伴随着电子转移动力学的强烈衰减,其机制尚未完全理解。通过PeakForce定量纳米力学成像研究了新制备的和老化的浸入水中的基面HOPG,我们发现老化的HOPG被环境气态纳米域占据,其存在可以用不完全润湿来解释。它们覆盖了高达60%的浸入表面,并且它们的发生率与石墨老化时间直接相关。与老化石墨相反,新剥离的HOPG表面没有气态纳米域。可以得出结论,环境气态纳米域可以阻止老化的基面HOPG与水性介质接触,因此可能会影响固液界面处的过程。