期刊
NANO LETTERS
卷 10, 期 2, 页码 398-405出版社
AMER CHEMICAL SOC
DOI: 10.1021/nl902741x
关键词
Graphene; electron-transfer chemistry; diazonium salt; Raman spectroscopy; Marcus theory
类别
资金
- U.S. Office of Naval Research Multi University Research Initiative (MURI)
- NSF [NSF-CHE 0111370]
- NIH [NIH-RR02594]
- Korean Government [KRF-2007-357-D00053]
- National Research Foundation of Korea [2007-357-D00053] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The reactivity of graphene and its various multilayers toward electron transfer chemistries with 4-nitrobenzene diazonium tetrafluoroborate is probed by Raman spectroscopy after reaction on-chip. Single graphene sheets are found to be almost 10 times more reactive than bi- or multilayers of graphene according to the relative disorder (D) peak in the Raman spectrum examined before and after chemical reaction in water. A model whereby electron puddles that shift the Dirac point locally to values below the Fermi level is consistent with the reactivity difference. Because the chemistry at the graphene edge is important for controlling its electronic properties, particularly in ribbon form, we have developed a spectroscopic test to examine the relative reactivity of graphene edges versus the bulk. We show, for the first time, that the reactivity of edges is at least two times higher than the reactivity of the bulk single graphene sheet, as supported by electron transfer theory. These differences in electron transfer rates may be important for selecting and manipulating graphitic materials on-chip.
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