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Title: Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

Abstract

For 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 fi ndings 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. Moreover, 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. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.

Authors:
 [1];  [1];  [2];  [3];  [2];  [3];  [4];  [4];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States)
  4. Drexel Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1265705
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Volume: 2; Journal Issue: 17; Journal ID: ISSN 2196-7350
Publisher:
Wiley-VCH
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhou, Hua, Uysal, Ahmet, Anjos, Daniela M., Cai, Yu, Overbury, Steven H., Neurock, Matthew, McDonough, John K., Gogotsi, Yury, and Fenter, Paul. Understanding Defect-Stabilized Noncovalent Functionalization of Graphene. United States: N. p., 2015. Web. doi:10.1002/admi.201500277.
Zhou, Hua, Uysal, Ahmet, Anjos, Daniela M., Cai, Yu, Overbury, Steven H., Neurock, Matthew, McDonough, John K., Gogotsi, Yury, & Fenter, Paul. Understanding Defect-Stabilized Noncovalent Functionalization of Graphene. United States. doi:10.1002/admi.201500277.
Zhou, Hua, Uysal, Ahmet, Anjos, Daniela M., Cai, Yu, Overbury, Steven H., Neurock, Matthew, McDonough, John K., Gogotsi, Yury, and Fenter, Paul. Tue . "Understanding Defect-Stabilized Noncovalent Functionalization of Graphene". United States. doi:10.1002/admi.201500277. https://www.osti.gov/servlets/purl/1265705.
@article{osti_1265705,
title = {Understanding Defect-Stabilized Noncovalent Functionalization of Graphene},
author = {Zhou, Hua and Uysal, Ahmet and Anjos, Daniela M. and Cai, Yu and Overbury, Steven H. and Neurock, Matthew and McDonough, John K. and Gogotsi, Yury and Fenter, Paul},
abstractNote = {For 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 fi ndings 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. Moreover, 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. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.},
doi = {10.1002/admi.201500277},
journal = {Advanced Materials Interfaces},
number = 17,
volume = 2,
place = {United States},
year = {2015},
month = {9}
}

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