Are Graphitic Surfaces Hydrophobic?

Graphitic carbons are important solid materials with myriad applications including electrodes, adsorbents, catalyst support, and solid lubricants. Understanding the interaction between water and graphitic carbons is critically important for both fundamental material characterization and practical device fabrication because the water-graphitic interface is essential to many applications. Research interests in graphene and carbon nanotubes over the past decades have brought renewed interest to elucidate wettability of graphitic carbons and understand their interaction with the surrounding environment. Research on this topic can be traced back to the 1940s, and the prevailing notion has been that graphitic carbons are hydrophobic. Though there have been different voices, this conclusion is supported by many previous water contact angle tests and well accepted by the community since sp² carbon is nonpolar in nature. However, recent results from our groups showed that graphitic surfaces are intrinsically mildly hydrophilic and adsorbed hydrocarbon contaminants from the ambient air render the surface hydrophobic. This unexpected finding challenges the long-lasting conception and could completely change the way graphitic materials are made, modeled, and modified. With several other research groups reporting similar findings, it is important for the community to realize the importance of airborne contamination on the surface-related properties of graphitic materials and revisit the intrinsic water-graphite interaction. This Account aims to summarize our recent work on water wettability of graphitic surfaces and discuss future research directions toward understanding the intrinsic water-graphite interaction. Historical perspective will first be provided highlighting the long accepted notion that graphite is hydrophobic along with a few reports suggesting otherwise. Next, our recent experimental data will be presented showing that pristine graphene and graphite are mildly hydrophilic; chemical analysis showed that hydrocarbons adsorb onto the clean surfaces thus rendering them hydrophobic. These results are further rationalized by analyzing the change in surface energy of the graphitic surfaces before and after hydrocarbon contamination. Facile methods to remove hydrocarbons from a contaminated surface will be discussed along with a convenient water treatment method that we developed to inhibit hydrocarbon adsorption onto a pristine graphitic surface. Implications of contamination will be illustrated through comparing the electrochemical activity of pristine and contaminated graphite. Lastly, consequences of these findings and future research directions to address a few important unanswered questions will be discussed.