Controlled functionalization of carbon-based materials such as diamond is challenging. Here, we describe the use of radical-based grafting to selectively functionalize carbon surfaces with self-terminating monolayers. Starting with H-terminated surfaces of nanodiamond, glassy carbon, and polymeric carbon dots, we demonstrate that the surfaces can be selectively functionalized by introducing a small amount of radical initiator into a reactant organic alkene. We find that this approach leads to formation of self-terminating monolayers with the molecules bound exclusively by the terminal carbon atom, as shown by detailed proton and carbon NMR studies. Density functional calculations show that the enthalpy change in abstracting an H atom from a H-terminated diamond surface is much lower than that required to remove an H atom from an organic alkene; as a result, the radical initiators selectively remove H atoms from the surface, which can then react with the terminal organic alkene. DFT calculations further show that the preference for bonding to the terminal side large arises from steric considerations, as forming a surface bond to the second carbon atom would result in a sterically constrained configuration of higher energy. Overall, these results demonstrate a new, scalable method for functionalization of carbon surfaces that can be applied to powders and non-planar surfaces.

Versatile, scalable monolayer functionalization of carbon-based materials by radical-initiated grafting

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.