Mario Maggio

Graphene oxide as a catalyst for ring opening reactions in amine crosslinking of epoxy resins

The influence of different graphite-based nanofillers on epoxide ring opening reactions, as induced by amines for diglycidyl ether of bisphenol A (DGEBA), is studied. Direct kinetic studies, with full chemical characterization and quantitative evaluation of the low molecular mass products, for reactions of DGEBA with primary and secondary monoamines as well with alcohols, are conducted. Moreover, the kinetic behavior of a commercial epoxy resin based on DGEBA and a diamine, leading to crosslinked insoluble networks, is studied by indirect methods, such as differential scanning calorimetry (DSC) and rheometry. The reported results show a relevant catalytic activity of graphene oxide on epoxy resin crosslinking by amines. For instance, for a graphene oxide content of 3 wt%, the exothermic crosslinking DSC peak is shifted (upon heating at 10 °C min−1) from 113 °C down to 96 °C, while the gel time at 50 °C is reduced by a factor of 2.5. This behavior is due to the ability of graphene oxide to catalyze primary amine–epoxy, secondary amine–epoxy and mainly hydroxyl–epoxy additions.

Green Regio‐ and Enantioselective Aminolysis Catalyzed by Graphite and Graphene Oxide under Solvent‐Free Conditions

The ring‐opening reactions of epoxides with amines were efficiently and regioselectively catalyzed by high‐surface‐area graphite and graphene oxide under metal‐free and solvent‐free conditions. For epoxides without aryl groups, catalytic activity was observed only for graphene oxide, and hence, the activity must have been due to its acidic groups. For styrene oxide, instead, graphite and graphene oxide exhibited rather similar catalytic activities, and hence, the activity was mainly due to activation of the electrophilic epoxide by π‐stacking interactions with the graphitic π system. The described aminolysis procedure is green and cheap because the catalyst can be recovered and recycled without loss of efficiency. Moreover, these heterogeneous catalysts exert high stereoselective control in the presence of nonracemic epoxides and provide chiral β‐amino alcohols with enantiomeric excess values up to 99 %.

Thermally stable, solvent resistant and flexible graphene oxide paper

The ability of graphene oxide (GO) aqueous suspensions to form robust GO paper is largely improved by basification of the suspension before processing. In particular, casting procedures, which are generally unsuitable for production of robust GO paper, become suitable for basified GO (b-GO) suspensions, leading to dense and free-standing papers, which are also highly flexible. Thermal or microwave treatments of paper from b-GO suspensions (b-GO paper) easily produce loss in stacking order of graphene oxide layers, with maintenance of a high degree of parallelism (0.6 < f ≡ orientation function < 0.7) with respect to the paper surface. Differently from usual GO papers, b-GO papers maintain their dimensional integrity when thermally treated or when dispersed in organic solvents or in aqueous solutions. Many relevant b-GO features (improved film ability by casting, maintenance of film integrity and reduced deoxygenation by heating and improved solvent resistance) can be rationalized by formation of covalent bridges between GO layers. Infrared spectra and simple chemical arguments suggest that these covalent bridges between GO layers could be mainly constituted by ether bonds.

Intercalation compounds of oxidized carbon black

Oxidation studies on carbon black (CB) show that the degree of oxidation largely increases with initial BET surface areas. WAXD patterns suggest that oCB samples are mainly constituted by a disordered spatial arrangement of highly defective graphene oxide structural layers, with short in-plane correlation length (2–3 nm). This is confirmed by the ability of oCB to form ordered intercalation compounds, as for the first time reported here. In fact, tetraalkylammonium cations in which two of the alkyl groups possess long hydrocarbon tails (2HT) are able to induce formation of intercalate crystalline structures not only by ion exchange in ordered GO crystals but also by self-assembling with small and disordered oCB layers. WAXD patterns of oCB/2HT adducts show few 00l reflections, indicating formation of an intercalate structure with a spacing between graphitic layers of 4.8 nm, as well as a diffraction peak at d = 0.42 nm, indicating the occurrence of a hexagonal rotator order of the intercalated hydrocarbon chains. The spacing between graphitic layers for oCB/2HT adducts (4.8 nm) is definitely higher than for the analogous GO/2HT adducts (3.4 nm) and corresponds to an orientation of the hydrocarbon tails nearly perpendicular to graphene planes.

Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins

This article compares the catalytic activities of oxidized carbon black (oCB) and graphene oxide (eGO) samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA) with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC). Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m2/g), as oxidized by the Hummers’ method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.

Carbon Papers and Aerogels Based on Graphene Layers and Chitosan: Direct Preparation from High Surface Area Graphite

In this work, carbon papers and aerogels based on graphene layers and chitosan were prepared. They were obtained by mixing chitosan (CS) and a high surface area nanosized graphite (HSAG) in water in the presence of acetic acid. HSAG/CS water dispersions were stable for months. High resolution transmission electron microscopy revealed the presence of few graphene layers in water suspensions. Casting or lyophilization of such suspensions led to the preparation of carbon paper and aerogel, respectively. In X-ray spectra of both aerogels and carbon paper, peaks due to regular stacks of graphene layers were not detected: graphene with unaltered sp2 structure was obtained directly from graphite without the use of any chemical reaction. The composites were demonstrated to be electrically conductive thanks to the graphene. Chitosan thus makes it possible to obtain monolithic carbon aerogels and flexible and free-standing graphene papers directly from a nanosized graphite by avoiding oxidation to graphite oxide and successive reduction. Strong interaction between polycationic chitosan and the aromatic substrate appears to be at the origin of the stability of HSAG/CS adducts. Cation-π interaction is hypothesized, also on the basis of X-ray photoelectron spectroscopy findings. This work paves the way for the easy large-scale preparation of carbon papers through a method that has a low environmental impact and is based on a biosourced polymer, graphene, and water.

Oxidized Carbon Black as an Activator of Transesterification Reactions under Solvent-Free Conditions

A metal-free procedure for oxidation of carbon black (CB), under mild and ecofriendly conditions, is described. The procedure, based on 5/1 w/w H2O2/H2SO4, when applied to high-surface-area CB, leads to oxidation contents (O/C = 0.66) comparable to those obtained for graphite with the more aggressive and metal-based Hummers method (O/C 0.63). Oxidized nanocarbons are able to activate transesterification reactions under solvent-free conditions. Activation of transesterification reactions is much more effective by oxidized CB than by graphene oxide.

Green and Facile Esterification Procedure Leading to Crystalline-Functionalized Graphite Oxide

A simple and eco-friendly procedure of esterification of graphite oxide (GO), which uses acetic anhydride as a model reagent and ethyl acetate as a green solvent, is reported. The procedure leads to high functionalization degrees (at least up to 4.5 mol % of acetyl groups, referred to as graphitic C atoms) and it is much more effective than the literature method based on pure acetic anhydride. Surprisingly, our acetylation procedure does not destroy or reduce GO crystallinity but, irrespective of a substantial increase of distance between GO layers (from 0.84 nm up to 0.95 nm), leads to an increased order in the direction perpendicular to the graphitic planes. This phenomenon indicates that acetyl groups of acetylated GO (AcGO) are easily accommodated between graphitic layers, even improving interlayer order. The esterification procedure is generally applicable with various anhydrides providing differently functionalized graphite oxide. Dispersion of crystalline functionalized GO in volatile organic solvents followed by solvent fast removal, can easily lead to complete exfoliation.