Journal
FARADAY DISCUSSIONS
Volume 172, Issue -, Pages 273-291Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4fd00038b
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Funding
- Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences on Understanding Charge Separation and Transfer at Interfaces in Energy Materials (EFRC:CST) [DE-SC0001091]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Science and Engineering
- Sandia National Laboratories Laboratory Directed Research and Development
- U.S. Department of Energy's National Nuclear Security Administration [DE-AC04-94AL85000]
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Controlled covalent modification of graphene via electrochemically assisted grafting of molecules is expected to be a robust method for tuning the doping levels and work function and therefore enabling the deployment of graphene in photovoltaic and battery applications. By using aryliodonium salts, in particular, bis(4-nitrophenyl) iodonium tetrafluoroborate, the grafting density can be adjusted from 4 x 10(13) to 3 x 10(14) molecules per cm(2). New insights on the grafting mechanism and the reactivity of the graphene are reported here. Clean basal planes were found to have increased reactivity compared to atomic-level point defects (single vacancies). High resolution scanning tunnelling microscopy (STM) shows that some of the grafts present three-fold symmetry, which may indicate that the grafts are pairs of molecules. The point of attachment of the second molecule is under investigation using computational work which includes simulations of the STM images. Elongated as well as extended grafts (larger than 4 nm) are also observed.
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