Unifying Principles of the Reductive Covalent Graphene Functionalization

• DOI: 10.1021/jacs.7b00704
• Publication Date: 2017-03-22T08:52:37Z
• Authors: Gonzalo Abellán; Milan Schirowski; Konstantin F. Ede...; Michael Fickert; Katharina Werbach; Herwig Peterlik; Frank Hauke; Andreas Hirsch
• Keywords: Surface Modification; Thermogravimetric analysis

Covalently functionalized graphene derivatives were synthesized via benchmark reductive routes using graphite intercalation compounds (GICs), in particular KC8. We have compared the arylation and alkylation of GIC 4-tert-butylphenyldiazonium bis(4-(tert-butyl)phenyl)iodonium salts, as well phenyl iodide, n-hexyl n-dodecyl electrophiles model reactions. put a focus on evaluation degree addition bulk functionalization homogeneity (Hbulk). For this purpose, we employed statistical Raman spectroscopy (SRS), forefront characterization tool thermogravimetric analysis coupled with FT-IR, gas chromatography, mass spectrometry (TGA/FT-IR/GC/MS). The present study unambiguously shows that alkyl iodides leads to best results, terms both Hbulk. Moreover, identified reversible character covalent chemistry, even at temperatures below 200 °C. thermally induced addend cleavage proceeds homolytically, which allows for detection dimeric products by TGA/FT-IR/GC/MS. This dimerization points certain regioselectivity, leading low sheet (Hsheet). Finally, developed concept performing reaction monolayer CVD films. work provides important insights into understanding basic principles will serve guide design new concepts.