Exclusively Proton Conductive Membranes Based on Reduced Graphene Oxide Polymer Composites.

Proton exchange membranes are at the heart of various technologies utilizing electrochemical storage of intermittent energy sources and powering electrical devices. Current state of the art membranes are based on perfluorosulfonic acid, introduced more than a half century ago. Low specificity to protons accompanied by permeance by other species is one of the main impediments for various promising applications in green technologies in an energy sustainable economy. Here we present composite membranes that are exclusively proton selective and do not allow crossover of any ionic or molecular species other than protons. Membranes have high proton conductivity and exceptional mechanical and chemical stability and thus may significantly improve performance of hydrogen-based technologies such as electrolyzers, various kinds of fuel cells, and flow batteries in the future.

Shear Assisted Electrochemical Exfoliation of Graphite to Graphene.

The exfoliation characteristics of graphite as a function of applied anodic potential (1-10 V) in combination with shear field (400-74 400 s(-1)) have been studied in a custom-designed microfluidic reactor. Systematic investigation by atomic force microscopy (AFM) indicates that at higher potentials thicker and more fragmented graphene sheets are obtained, while at potentials as low as 1 V, pronounced exfoliation is triggered by the influence of shear. The shear-assisted electrochemical exfoliation process yields large (∼10 µm) graphene flakes with a high proportion of single, bilayer, and trilayer graphene and small ID/IG ratio (0.21-0.32) with only a small contribution from carbon-oxygen species as demonstrated by X-ray photoelectron spectroscopy measurements. This method comprises intercalation of sulfate ions followed by exfoliation using shear induced by a flowing electrolyte. Our findings on the crucial role of hydrodynamics in accentuating the exfoliation efficiency suggest a safer, greener, and more automated method for production of high quality graphene from graphite.

Large-area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide.

Graphene-based membranes demonstrating ultrafast water transport, precise molecular sieving of gas and solvated molecules shows great promise as novel separation platforms; however, scale-up of these membranes to large-areas remains an unresolved problem. Here we demonstrate that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially adaptable method to produce large-area membranes (13 × 14 cm(2)) in <5 s. Pressure driven transport data demonstrate high retention (>90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30-40%) retention of monovalent and divalent salts. The highly ordered graphene sheets in the plane of the membrane make organized channels and enhance the permeability (71 ± 5 l m(-2) hr(-1) bar(-1) for 150 ± 15 nm thick membranes).

Counter-ion dependent, longitudinal unzipping of multi-walled carbon nanotubes to highly conductive and transparent graphene nanoribbons.

Here we report for the first time, a simple hydrothermal approach for the bulk production of highly conductive and transparent graphene nanoribbons (GNRs) using several counter ions from K2SO4, KNO3, KOH and H2SO4 in aqueous media, where, selective intercalation followed by exfoliation gives highly conducting GNRs with over 80% yield. In these experiments, sulfate and nitrate ions act as a co-intercalant along with potassium ions resulting into exfoliation of multi-walled carbon nanotubes (MWCNTs) in an effective manner. The striking similarity of experimental results in KOH and H2SO4 that demonstrates partially damaged MWCNTs, implies that no individual K(+), SO4(2-) ion plays a key role in unwrapping of MWCNTs, rather this process is largely effective in the presence of both cations and anions working in a cooperative manner. The GNRs can be used for preparing conductive 16 kΩsq(-1), transparent (82%) and flexible thin films using low cost fabrication method.

Sequential electrochemical unzipping of single-walled carbon nanotubes to graphene ribbons revealed by in situ Raman spectroscopy and imaging.

We report an in situ Raman spectroscopic and microscopic investigation of the electrochemical unzipping of single-walled carbon nanotubes (SWNTs). Observations of the radial breathing modes (RBMs) using Raman spectral mapping reveal that metallic SWNTs are opened up rapidly followed by gradual unzipping of semiconducting SWNTs. Consideration of the resonant Raman scattering theory suggests that two metallic SWNTs with chiralities (10, 4) and (12, 0) get unzipped first at a lower electrode potential (0.36 V) followed by the gradual unzipping of another two metallic tubes, (9, 3) and (10, 1), at a relatively higher potential (1.16 V). The semiconducting SWNTs with chiralities (11, 7) and (12, 5), however, get open up gradually at ±1.66 V. A rapid decrease followed by a subsequent gradual decrease in the metallicity of the SWNT ensemble as revealed from a remarkable variation of the peak width of the G band complies well with the variations of RBM. Cyclic voltammetry also gives direct evidence for unzipping in terms of improved capacitance after oxidation followed by more important removal of oxygen functionalities during the reduction step, as reflected in subtle changes of the morphology confirming the formation of graphene nanoribbons. The density functional-based tight binding calculations show additional dependence of chirality and diameter of nanotubes on the epoxide binding energies, which is in agreement with the Raman spectroscopic results and suggests a possible mechanism of unzipping determined by combined effects of the structural characteristics of SWNTs and applied field.

Mitigating the Cytotoxicity of Graphene Quantum Dots and Enhancing Their Applications in Bioimaging and Drug Delivery.

Despite the promising photophysical properties of fluorescent graphene quantum dots (GQDs), their cellular toxicity needs to be addressed before their full potential could be completely realized in biomedicine. A simple method for mitigating the toxicity of GQDs by embedding them in PEG matrix is reported here. The enhanced biocompatibility of polymer modified, P-GQDs, is attributed to reduced reactive oxygen species generation, as measured by an intracellular ROS assay. We also demonstrate the enhanced loading and efficient intracellular delivery of therapeutics by P-GQDs.

Stabilization of graphene quantum dots (GQDs) by encapsulation inside zeolitic imidazolate framework nanocrystals for photoluminescence tuning.

Luminescent graphene quantum dots (GQDs) are encapsulated and stabilized in Zeolitic Imidazolate Framework (ZIF-8) nanocrystals. The GQDs are well confined due to the adsorption on the growing face of the ZIF-8 nanocrystals and have a profound effect on the shape of the nanocrystals from rhombic dodecahedron to spherical. Stabilizing GQDs inside the ZIF-8 nanocrystals results in tailoring of the photoluminescence emission (ca. 32 nm, bathochromic shift) of the GQD@ZIF-8 nanocrystal composite even after 3 months of aging under normal laboratory conditions. Also the water adsorption (at STP) capacity increased for the GQD@ZIF-8 composite as compared to the pristine ZIF-8.

Electrochemical resolution of multiple redox events for graphene quantum dots.

Quantum dots: A sequential, single-electron charging process of monodisperse graphene quantum dots (GQDs) encapsulated in a dodecylamine envelope, facilitating a capacitance of a few attofarads is reported. The average GQDs dimensions, as ascertained from high-resolution transmission electron microscopy and atomic force microscopy, of about 3±0.3, 2.6±0.2, and 2.2±0.3 nm control this unprecedented behavior.

Electrochemical preparation of luminescent graphene quantum dots from multiwalled carbon nanotubes.

Green luminescent, graphene quantum dots (GQDs) with a uniform size of 3, 5, and 8.2(±0.3) nm in diameter were prepared electrochemically from MWCNTs in propylene carbonate by using LiClO(4) at 90 °C, whereas similar particles of 23(±2) nm were obtained at 30 °C under identical conditions. Both these sets of GQDs displayed a remarkable quantum efficiency of 6.3 and 5.1%, respectively. This method offers a novel strategy to synthesise size-tunable GQDs as evidenced by multiple characterisation techniques like transmission and scanning electron microscopy, atomic force microscopy, Raman spectroscopy and X-ray diffraction (XRD). Photoluminescence of these GQDs can be tailored by size variation through a systematic change in key process parameters, like diameter of carbon nanotube, electric field, concentration of supporting electrolyte and temperature. GQDs are promising candidates for a variety of applications, such as biomarkers, nanoelectronic devices and chemosensors due to their unique features, like high photostability, biocompatibility, nontoxicity and tunable solubility in water.

In situ electrochemical organization of CdSe nanoclusters on graphene during unzipping of carbon nanotubes.

In situ decoration of very small CdSe quantum dots on graphene nanoribbons (GNRs) has been achieved during the electrochemical unzipping of single walled carbon nanotubes. Critical parameters like the width of the GNRs, size distribution of quantum dots and their organization on GNRs have been shown to be strongly dependent on the electric field and time.

Electrochemical unzipping of multi-walled carbon nanotubes for facile synthesis of high-quality graphene nanoribbons.

Here we report a remarkable transformation of carbon nanotubes (CNTs) to nanoribbons composed of a few layers of graphene by a two-step electrochemical approach. This consists of the oxidation of CNTs at controlled potential, followed by reduction to form graphene nanoribbons (GNRs) having smooth edges and fewer defects, as evidenced by multiple characterization techniques, including Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. This type of "unzipping" of CNTs (single-walled, multi-walled) in the presence of an interfacial electric field provides unique advantages with respect to the orientation of CNTs, which might make possible the production of GNRs with controlled widths and fewer defects.