Accurate chemical analysis of oxygenated graphene-based materials using X-ray photoelectron spectroscopy
CARBON
Authors: Kovtun, Alessandro; Jones, Derek; Dell'Elce, Simone; Treossi, Emanuele; Liscio, Andrea; Palermo, Vincenzo
Abstract
A simple, fast and general protocol for quantitative analysis of X-ray photoelectron spectroscopy (XPS) data provides accurate estimations of chemical species in graphene and related materials (GRMs). XPS data are commonly used to estimate the quality of and defects in graphene and graphene oxide (GO), by comparing carbon and oxygen 1s XPS peaks, obtaining an O/C ratio. This approach, however, cannot be used in the presence of extraneous oxygen contamination. The protocol, based on quantitative line-shape analysis of C 1s signals, uses asymmetric pseudo-Voigt line-shapes (APV), in contrast to Gaussian-based approaches conventionally used in fitting XPS spectra, thus allowing better accuracy in quantifying C 1s contributions from graphitic carbon (sp2), defects (sp3 carbon), carbons bonded to hydroxyl and epoxy groups, and from carbonyl and carboxyl groups. The APV protocol was evaluated on GRMs with O/C ratios ranging from 0.02 to 0.30 with film thicknesses from monolayers to bulk-like (>30 nm) layers and also applied to previously published data, showing better results compared to those from conventional XPS fitting protocols. Based uniquely on C 1s data, the APV protocol can quantify O/C ratio and the presence of specific functional groups in GRMs even on SiOx, substrates, or in samples containing water. (C) 2018 Elsevier Ltd. All rights reserved.
Graphene oxide-catalyzed C-Sp3-H activation of methylarenes in aqueous medium: A unified metal-free access to amides and benzimidazoles
APPLIED ORGANOMETALLIC CHEMISTRY
Authors: Dandia, Anshu; Mahawar, Dinesh Kumar; Sharma, Ruchi; Badgoti, Ranveer Singh; Rathore, Kuldeep S.; Parewa, Vijay
Abstract
Graphene oxide (GO)-catalyzed selective synthesis of amides via C-Sp3-H activation of methylarenes and consequent C-N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co-oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal-free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform-infrared, UV-Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over-oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.