Insight on Structure of Water and Ice Next to Graphene Using Surface-Sensitive Spectroscopy

The water/graphene interface has received considerable attention in the past decade due to its relevance in various potential applications including energy storage, sensing, desalination, and catalysis. Most of our knowledge about the interfacial water structure next to graphene stems from simulations, which use experimentally measured water contact angles (WCAs) on graphene (or graphite) to estimate the water-graphene interaction strength. However, the existence of a wide spectrum of reported WCAs on supported graphene and graphitic surfaces makes it difficult to interpret the water-graphene interactions. Here, we have used surface-sensitive infrared-visible sum frequency generation (SFG) spectroscopy to probe the interfacial water structure next to graphene supported on a sapphire substrate. In addition, the ice nucleation properties of graphene have been explored by performing in situ freezing experiments as graphitic surfaces are considered good ice nucleators. For graphene supported on sapphire, we observed a strong SFG peak associated with highly coordinated, ordered water next to graphene. Similar ordering was not detected next to bare sapphire, implying that the observed ordering of water molecules in the former case is a consequence of the presence of graphene. Our analysis indicates that graphene behaves like a hydrophobic (or negatively charged) surface, leading to enhanced ordering of water molecules. Although liquid water orders next to graphene, the ice formed is proton disordered. This research sheds light on water-graphene interactions relevant in optimizing the performance of graphene in various applications.