Graphene layers were selectively edge-functionalized maintaining their bulk structure unaltered.

Polyurethane nanocomposites were prepared with a nanosized high surface area graphite (HSAG) functionalized on its edges with hydroxyl groups as a building block. Edge functionalization of HSAG was obtained through reaction with KOH. The addition of OH groups was demonstrated by means of infrared (FTIR) and thermogravimetric analysis (TGA), and the Boehm titration allowed estimation of a level of about 5.0 mmolOH/gHSAG. Results from wide-angle X-ray diffraction (WAXD) and Raman spectroscopy suggested that functionalization of the graphene layers occurred on the edges. The evaluation of the Hansen solubility parameters of G-OH revealed a substantial increase of δPand δH parameters with respect to HSAG. In line with these findings, homogeneous and stable dispersions of G-OH in a polyol were obtained. PU were prepared by mixing a dispersion of G-OH in cis-1,4-butenediol with hexamethylene diisocyanate. A model reaction between catechol, 1,4-butanediol, and hexamethylene diisocyanate demonstrated the reactivity of hydroxylated aromatic rings with isocyanate groups. PU-based G-OH, characterized with WAXD and differential scanning calorimetry (DSC), revealed lower Tg, higher Tc, Tm, and crystallinity than PU without G-OH. These results could be due to the higher flexibility of the polymer chains, likely a consequence of the dilution of the urethane bonds by the carbon substrate. Hence, G-OH allowed the preparation of PU with a larger temperature range between Tg and Tm, with potential positive impact on material applications. The model reaction between butylisocyanate and 1-butanol revealed that HSAG and G-OH promote efficient formation of the urethane bond, even in the absence of a catalyst. The effect of high surface area carbon on the nucleophilic oxygen attack to the isocyanate group can be hypothesized. The results here reported lead us to comment that a reactive nanosized sp2 carbon allotrope, such as G-OH, can be used as a multifunctional building block of PU. Indeed, G-OH is a comonomer of PU, a promoter of the polymerization reaction, and can definitely act as reinforcing filler by tuning its amount in the final nanocomposite leading to highly versatile materials. The larger temperature range between Tg and Tm, together with the presence of G-OH acting as a reinforcing agent, could allow the production of piezoresistive sensing, shape-memory PU with good mechanical features.

In this study, carbon papers and aerogels were prepared from chitosan and graphene layers with aldehydic edge functional groups (G-CHO) able to form chemical bonds with chitosan and thus to form a crosslinked network. A high surface area graphite was edge functionalized with hydroxyl groups (G-OH) through the reaction with KOH. G-CHO, with 4.5 mmol/g of functional group, was prepared from G-OH by means of the Reimer-Tieman reaction. Characterization of the graphitic materials was performed with elemental analysis, titration, X-ray analysis, Raman spectroscopy and by estimating their Hansen solubility parameters. CS and G-CHO were mixed with mortar and pestle and carbon papers and aerogels were obtained from a stable acidic water suspension through casting and liophilization, respectively. Free standing and foldable carbon papers and monolithic aerogels based on a continuous covalent network between G-CHO and CS were prepared. G-CHO, which had about 22 stacked layers, was extensively exfoliated in the carbon paper, as confirmed by the absence of the 002 reflection of the graphitic crystallites in the XRD pattern. Carbon paper was found to be resistant to solvents and to be stable for pH ⩾ 7. Composites revealed electrical conductivity. The covalent network between the graphene layers and CS, suggested by the IR findings, accounts for these results. This work demonstrates the effectiveness of a continuous covalent network between chitosan and graphene layers edge functionalized with tailor made functional groups for the preparation of carbon papers and aerogels and paves the way for the scale up of such a type of composites.