Abstract
The mechanism for the functionalization of graphene layers with pyrrole compounds was investigated. Liquid 1,2,5-trimethylpyrrole (TMP) was heated in air in the presence of a high surface area nanosized graphite (HSAG), at temperatures between 80 °C and 180 °C. After the thermal treatments solid and liquid samples, separated by centrifugation, were analysed by means of Raman, Fourier Transform Infrared (FT-IR) spectroscopy, X-Rays Photoelectron Spectroscopy (XPS) and 1H-Nuclear Magnetic Resonance (1H NMR) spectroscopy and High Resolution Transmission Electron Microscopy (HRTEM). FT-IR spectra were interpreted with the support of Density Functional Theory (DFT) quantum chemical modelling. Raman findings suggested that the bulk structure of HSAG remained substantially unaltered, without intercalation products. FT-IR and XPS spectra showed the presence of oxidized TMP derivatives on the solid adducts, in a much larger amount than in the liquid. For thermal treatments at T ≥ 150 °C, IR spectral features revealed not only the presence of oxidized products but also the reaction of intra-annular double bond of TMP with HSAG. XPS spectroscopy showed the increase of the ratio between C(sp2)N bonds involved in the aromatic system and C(sp3)N bonds, resulting from reaction of the pyrrole moiety, observed while increasing the temperature from 130 °C to 180 °C. All these findings, supported by modeling, led to hypothesize a cascade reaction involving a carbocatalyzed oxidation of the pyrrole compound followed by Diels-Alder cycloaddition. Graphene layers play a twofold role: at the early stages of the reaction, they behave as a catalyst for the oxidation of TMP and then they become the substrate for the cycloaddition reaction. Such sustainable functionalization, which does not produce by-products, allows us to use the pyrrole compounds for decorating sp2 carbon allotropes without altering their bulk structure and smooths the path for their wider application.
Highlights
A large number of applications can be envisaged for graphene [1,2,3,4,5], because of its fascinating properties: high charge-carrier mobility [6,7,8], in-plane thermal conductivity [9,10,11], and elastic modulus of the order of 1 TPa [12,13,14]
In a first series of experiments, a TMP sample, whose 1 H NMR spectrum did not reveal any impurity (Supplementary Information), was split in different portions, which were heated in air at 25 ◦ C, 80 ◦ C, 100 ◦ C, 130 ◦ C, 150 ◦ C and 180 ◦ C, both in the absence and in the presence of a catalytic amount of high surface area nanosized graphite (HSAG)
Theoretical IR spectra were generated by means of Density Functional Theory (DFT) calculations (B3LYP/6-311++G(d,p)) in vacuo, both for TMP and for model molecules derivatives of TMP which were hypothesized to arise from the thermal treatments
Summary
A large number of applications can be envisaged for graphene [1,2,3,4,5], because of its fascinating properties: high charge-carrier mobility [6,7,8], in-plane thermal conductivity [9,10,11], and elastic modulus of the order of 1 TPa [12,13,14]. Nanomaterials 2018, 8, x FOR PEER REVIEW for cancer treatment [19,20], and drug transportation in transportation biological systems [21,22,23,24]. Graphene, preserving its bulk structure and controlling size, shape, and edge structure of the layers. Functionalization of graphene, preserving its bulk structure and controlling size, shape, and edgeis a of challenging [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42]. Functionalization occurred in the absence of solvents and catalysts, providing thermal or thermal mechanical energy; functionalization yield was almost quantitative, by either providing either or mechanical energy; functionalization yield was almost it was larger than
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