A “Nanopore Lithography” Strategy for Synthesizing Hierarchically Micro/Mesoporous Carbons from ZIF-8/Graphene Oxide Hybrids for Electrochemical Energy Storage

Porous carbons derived from metal-organic frameworks (MOFs) are promising materials for a number of energy- and environment-related applications, but their almost exclusively microporous texture can be an obstacle to their performance in practical uses. Here, we introduce a novel strategy for the generation of very uniform mesoporosity in a prototypical MOF, namely, zeolitic imidazolate framework-8 (ZIF-8). The process, referred to as “nanopore lithography”, makes use of graphene oxide (GO) nanosheets enclosing ZIF-8 particles as masks or templates for the transfer of mesoporous texture to the latter. Upon controlled carbonization and activation, nanopores created in the GO envelope serve as selective entry points for localized etching of carbonized ZIF-8, so that such nanopores are replicated in the MOF-derived carbonaceous structure. The resulting porous carbons are dominated by uniform mesopores ∼3–4 nm in width and possess specific surface areas of ∼1300–1400 m² g^–1. Furthermore, we investigate and discuss the specific experimental conditions that afford the mesopore-templating action of the GO nanosheets. Electrochemical characterization revealed an improved capacitance as well as a faster, more reversible charge/discharge kinetics for the ZIF-8-derived porous carbons obtained through nanopore lithography, relative to those for their counterparts with standard activation (no GO templating), thus indicating the potential practical advantage of the present approach in capacitive energy storage applications

Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental 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