The stable dispersion of graphene flakes in an aqueous medium is highly desirable for the development of materials based on this two-dimensional carbon structure, but current production protocols that make use of a number of surfactants typically suffer from limitations regarding graphene concentration or the amount of surfactant required to colloidally stabilize the sheets. Here, we demonstrate that an innocuous and readily available derivative of vitamin B2, namely the sodium salt of flavin mononucleotide (FMNS), is a highly efficient dispersant in the preparation of aqueous dispersions of defect-free, few-layer graphene flakes. Most notably, graphene concentrations in water as high as ∼50 mg mL(-1) using low amounts of FMNS (FMNS/graphene mass ratios of about 0.04) could be attained, which facilitated the formation of free-standing graphene films displaying high electrical conductivity (∼52000 S m(-1)) without the need of carrying out thermal annealing or other types of post-treatment. The excellent performance of FMNS as a graphene dispersant could be attributed to the combined effect of strong adsorption on the sheets through the isoalloxazine moiety of the molecule and efficient colloidal stabilization provided by its negatively charged phosphate group. The FMNS-stabilized graphene sheets could be decorated with nanoparticles of several noble metals (Ag, Pd, and Pt), and the resulting hybrids exhibited a high catalytic activity in the reduction of nitroarenes and electroreduction of oxygen. Overall, the present results should expedite the processing and implementation of graphene in, e.g., conductive inks, composites, and hybrid materials with practical utility in a wide range of applications.
Chemically exfoliated MoS2 (ce-MoS2) nanosheets that incorporate a large fraction of metallic 1T phase have been recently shown to possess a high electrocatalytic activity in the hydrogen evolution reaction, but the potential of this two-dimensional material as a catalyst has otherwise remained mostly uncharted. Here, we demonstrate that ce-MoS2 nanosheets are efficient catalysts for a number of model reduction reactions (namely, those of 4-nitrophenol, 4-nitroaniline, methyl orange, and [Fe(CN)6](3-)) carried out in aqueous medium using NaBH4 as a reductant. The performance of the nanosheets in these reactions is found to be comparable to that of many noble metal-based catalysts. The possible reaction pathways involving ce-MoS2 as a catalyst are also discussed and investigated. Overall, the present results expand the scope of this two-dimensional material as a competitive, inexpensive, and earth-abundant catalyst.
a b s t r a c tAnodic exfoliation of graphite has emerged as an attractive method to access graphene nanosheets in large quantities, but oxidation reactions associated to this process compromise the structural quality of the resulting materials. Here, we demonstrate that the type of starting graphite material impacts the oxygen and defect content of anodically exfoliated graphenes obtained thereof. We investigated highly oriented pyrolytic graphite (HOPG) as well as graphite foil, flakes and powder as electrode in the anodic process. Importantly, materials with low levels of oxidation and disorder (similar to those typically achieved with cathodic exfoliation approaches) could be attained through proper choice of the graphite electrode. Specifically, using graphite foil afforded nanosheets of higher quality than that of HOPG-derived nanosheets. This discrepancy was interpreted to arise from the structural peculiarities of the former, where the presence of folds, voids and wrinkles would make its exfoliation process to be less reliant on oxidation reactions. Furthermore, cell viability tests carried out with murine fibroblasts on thin graphene films suggested that the anodically exfoliated graphenes investigated here (possessing low or high oxidation levels) are highly biocompatible. Overall, control upon the extent of oxidation and disorder should expand the scope of anodically exfoliated graphenes in prospective applications.
Chemically exfoliated MoS (ce-MoS) has emerged in recent years as an attractive two-dimensional material for use in relevant technological applications, but fully exploiting its potential and versatility will most probably require the deployment of appropriate chemical modification strategies. Here, we demonstrate that extensive covalent functionalization of ce-MoS nanosheets with acetic acid groups (∼0.4 groups grafted per MoS unit) based on the organoiodide chemistry brings a number of benefits in terms of their processability and functionality. Specifically, the acetic acid-functionalized nanosheets were furnished with long-term (>6 months) colloidal stability in aqueous medium at relatively high concentrations, exhibited a markedly improved temporal retention of catalytic activity toward the reduction of nitroarenes, and could be more effectively coupled with silver nanoparticles to form hybrid nanostructures. Furthermore, in vitro cell proliferation tests carried out with murine fibroblasts suggested that the chemical derivatization had a positive effect on the biocompatibility of ce-MoS. A hydrothermal annealing procedure was also implemented to promote the structural conversion of the functionalized nanosheets from the 1T phase that was induced during the chemical exfoliation step to the original 2H phase of the starting bulk material, while retaining at the same time the aqueous colloidal stability afforded by the presence of the acetic acid groups. Overall, by highlighting the benefits of this type of chemical derivatization, the present work should contribute to strengthen the position of ce-MoS as a two-dimensional material of significant practical utility.
Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg and 3220 W kg, respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.
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