Direct liquid-phase exfoliation of layered materials by means of ultrasound, shear forces or electrochemical intercalation holds enormous promise as a convenient, cost-effective approach to the mass ...production of two-dimensional (2D) materials, particularly in the form of colloidal suspensions of high quality and micrometer- and submicrometer-sized flakes. Of special relevance due to environmental and practical reasons is the production of 2D materials in aqueous medium, which generally requires the use of certain additives (surfactants and other types of dispersants) to assist in the exfoliation and colloidal stabilization processes. In this context, biomolecules have received, in recent years, increasing attention as dispersants for 2D materials, as they provide a number of advantages over more conventional, synthetic surfactants. Here, we review research progress in the use of biomolecules as exfoliating and dispersing agents for the production of 2D materials. Although most efforts in this area have focused on graphene, significant advances have also been reported with transition metal dichalcogenides (MoS
2
, WS
2
,
etc.
) or hexagonal boron nitride. Particular emphasis is placed on the specific merits of different types of biomolecules, including proteins and peptides, nucleotides and nucleic acids (RNA, DNA), polysaccharides, plant extracts and bile salts, on their role as efficient colloidal dispersants of 2D materials, as well as on the potential applications that have been explored for such biomolecule-exfoliated materials. These applications are wide-ranging and encompass the fields of biomedicine (photothermal and photodynamic therapy, bioimaging, biosensing,
etc.
), energy storage (Li- and Na-ion batteries), catalysis (
e.g.
, catalyst supports for the oxygen reduction reaction or electrocatalysts for the hydrogen evolution reaction), or composite materials. As an incipient area of research, a number of knowledge gaps, unresolved issues and novel future directions remain to be addressed for biomolecule-exfoliated 2D materials, which will be discussed in the last part of this review.
A review of the use of biomolecules for the direct exfoliation and dispersion of graphene and other two-dimensional materials, as well as of the applications of such materials, is presented.
The preparation of solution-processable graphene from graphite oxide typically involves a hydrazine reduction step, but the use of such a reagent in the large-scale implementation of this approach is ...not desirable due to its high toxicity. Here, we compare the deoxygenation efficiency of graphene oxide suspensions by different reductants (sodium borohydride, pyrogallol, and vitamin C, in addition to hydrazine), as well as by heating the suspensions under alkaline conditions. In almost all cases, the degree of reduction attainable and the subsequent restoration of relevant properties (e.g., electrical conductivity) lag significantly behind those achieved with hydrazine. Only vitamin C is found to yield highly reduced suspensions in a way comparable to those provided by hydrazine. Stable suspensions of vitamin C-reduced graphene oxide can be prepared not only in water but also in common organic solvents, such as N,N-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP). These results open the perspective of replacing hydrazine in the reduction of graphene oxide suspensions by an innocuous and safe reductant of similar efficacy, thus facilitating the use of graphene-based materials for large-scale applications.
The preparation of aqueous graphene dispersions by exfoliation of pristine graphite in the presence of a wide range of surfactants is reported. High graphene concentrations, up to about 1
mg
mL
−1, ...were obtained with the use of some non-ionic surfactants. The dispersions consisted of single- and few-layer graphene platelets with their basal planes virtually free of even atomic-sized (point) defects. The potential utility of such highly concentrated dispersions toward the low-cost, large-scale manipulation and processing of graphene was demonstrated by processing them into electrically conductive, free-standing paper-like films.
Graphene nanosheets produced in the form of stable aqueous dispersions by chemical reduction of graphene oxide and deposited onto graphite substrates have been investigated by atomic force and ...scanning tunneling microscopy (AFM/STM). The chemically reduced graphene oxide nanosheets were hardly distinguishable from their unreduced counterparts in the topographic AFM images. However, they could be readily discriminated through phase imaging in the attractive regime of tapping-mode AFM, probably because of differences in hydrophilicity arising from their distinct oxygen contents. The chemically reduced nanosheets displayed a smoothly undulated, globular morphology on the nanometer scale, with typical vertical variations in the subnanometer range and lateral feature sizes of ∼5−10 nm. Such morphology was attributed to be the result of significant structural disorder in the carbon skeleton, which originates during the strong oxidation that leads to graphene oxide and remains after chemical reduction. Direct evidence of structural disorder was provided by atomic-scale STM imaging, which revealed an absence of long-range periodicity in the graphene nanosheets. Only structured domains a few nanometers large were observed instead. Likewise, the nanosheet edges appeared atomically rough and ill-defined, though smooth on the nanometer scale. The unreduced graphene oxide nanosheets could only be imaged by STM at very low tunneling currents (∼1 pA), being visualized in some cases with inverted contrast relative to the graphite substrate, a result that was attributed to their extremely low conductivity. Complementary characterization of the unreduced and chemically reduced nanosheets was carried out by thermogravimetric analysis as well as UV−visible absorption and X-ray photoelectron and Raman spectroscopies. In particular, the somewhat puzzling Raman results were interpreted to be the result of an amorphous character of the graphene oxide material.
The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N,N-dimethylformamide, N-methyl-2-pyrrolidone, ...tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.
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–1 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–1 and 3220 W kg–1, respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.
Strategies that improve the yield of graphene nanosheets in anodic exfoliation processes are desirable for the mass production of this material. Here, a simple pre-treatment of graphite foil with ...concentrated H2SO4 is demonstrated to be such an effective strategy, affording overall exfoliation yields up to ∼50 wt% under certain experimental conditions, compared with a baseline value of ∼10 wt% for untreated graphite. Filling of inner voids and interstices of the graphite foil with H2SO4 molecules was concluded to be responsible for the enhanced exfoliation performance. Additional approaches to further increase the anodic exfoliation yield are also proposed and discussed.
Anodic 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.
The ability to use RNA/DNA nucleotides as colloidal stabilizers for graphene would be an important asset, as a close graphene-nucleotide association would facilitate access to hybrid systems where ...the rich covalent and supramolecular chemistry of these biomolecules could be exploited alongside graphene in a number of applications. Unfortunately, single RNA/DNA nucleotides are inefficient graphene dispersants. Here we propose and demonstrate a supramolecular strategy which overcomes this limitation, affording aqueous dispersions of high quality graphene flakes with much improved colloidal stability. A nucleotide is combined with its complementary nucleobase yielding stable hydrogen-bonded supramolecular entities that adsorb more strongly on the graphene surface than their individual components. Based on this approach, graphene-nucleotide hybrid hydrogels could be readily obtained, where the graphene flakes were intimately and uniformly intermixed with the nucleotide-based gel phase. Such hydrogels exhibited higher uptakes and/or slower release profiles of dyes and drugs (rhodamine B, methylene blue and tetracycline) than their graphene-free counterparts. Cell proliferation tests suggested the graphene materials obtained with nucleotide-nucleobase stabilizers to be biocompatible. The present results constitute a novel strategy in the processing and molecular integration of graphene that could be extended to other (bio)molecules of interest towards the realization of functional materials for different applications.
Display omitted
The use of UV light to trigger different processes involving graphene oxide sheets suspended in aqueous medium at room temperature has been investigated. These processes include (1) deoxygenation of ...the sheets in the absence of photocatalysts, reducing agents and stabilizers, (2) selective nucleation and growth of metal nanoparticles on the sheets to yield graphene-based hybrids and (3) decomposition of the dye molecule rhodamine B in the presence of only graphene oxide. Photoinduced heating of the suspended graphene oxide sheets by intense UV irradiation (∼1
W
cm
−2 delivered at the surface of the dispersion) was interpreted to generate at high temperature and reactive environment strictly localized at the sheets and their immediate aqueous medium, which in turn brings about the mentioned processes. In addition to providing a simple route toward reduction of graphene oxide dispersions, the present results suggest that intense UV light can be used to promote reactions at ambient conditions with this material that would otherwise require high temperatures, chemical reactants and/or catalysts.
PDF
