Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.; Cai, Yu; Overbury, Steven H.; Neurock, Matthew; McDonough, John K.; Gogotsi, Yury; Fenter, Paul

doi:10.1002/admi.201500277

Title: Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

Journal Article · Tue Sep 01 00:00:00 EDT 2015 · Advanced Materials Interfaces

DOI:https://doi.org/10.1002/admi.201500277· OSTI ID:1392421

Zhou, Hua ^[1]; Uysal, Ahmet ^[1]; Anjos, Daniela M. ^[2]; Cai, Yu ^[3]; Overbury, Steven H. ^[2]; Neurock, Matthew ^[3]; McDonough, John K. ^[4]; Gogotsi, Yury ^[4]; Fenter, Paul ^[1]

Chemical Science and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA
Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA
Department of Chemical Engineering and Department of Chemistry, University of Virginia, Charlottesville VA 22904 USA
Department of Materials Science and Engineering and A. J. Drexel Nanomaterials Institute, Drexel University, Philadelphia PA 19104 USA

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science - Energy Frontier Research Center - Fluid Interface Reactions, Structures and Transport (FIRST)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1392421

Journal Information:: Advanced Materials Interfaces, Vol. 2, Issue 17; ISSN 2196-7350

Publisher:: Wiley-VCH

Country of Publication:: United States

Language:: English

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