Divalent Fe Atom Coordination in Two-Dimensional Microporous Graphitic Carbon Nitride.

Graphitic carbon nitride (g-C3N4) is a rising two-dimensional material possessing intrinsic semiconducting property with unique geometric configuration featuring superimposed heterocyclic sp(2) carbon and nitrogen network, nonplanar layer chain structure, and alternating buckling. The inherent porous structure of heptazine-based g-C3N4 features electron-rich sp(2) nitrogen, which can be exploited as a stable transition metal coordination site. Multiple metal-functionalized g-C3N4 systems have been reported for versatile applications, but local coordination as well as its electronic structure variation upon incoming metal species is not well understood. Here we present detailed bond coordination of divalent iron (Fe(2+)) through micropore sites of graphitic carbon nitride and provide both experimental and computational evidence supporting the aforementioned proposition. In addition, the utilization of electronic structure variation is demonstrated through comparative photocatalytic activities of pristine and Fe-g-C3N4.

Selective and Regenerative Carbon Dioxide Capture by Highly Polarizing Porous Carbon Nitride.

Energy-efficient CO2 capture is a stringent demand for green and sustainable energy supply. Strong adsorption is desirable for high capacity and selective capture at ambient conditions but unfavorable for regeneration of adsorbents by a simple pressure control process. Here we present highly regenerative and selective CO2 capture by carbon nitride functionalized porous reduced graphene oxide aerogel surface. The resultant structure demonstrates large CO2 adsorption capacity at ambient conditions (0.43 mmol·g(-1)) and high CO2 selectivity against N2 yet retains regenerability to desorb 98% CO2 by simple pressure swing. First-principles thermodynamics calculations revealed that microporous edges of graphitic carbon nitride offer the optimal CO2 adsorption by induced dipole interaction and allows excellent CO2 selectivity as well as facile regenerability. This work identifies a customized route to reversible gas capture using metal-free, two-dimensional carbonaceous materials, which can be extended to other useful applications.

Liquid crystal size selection of large-size graphene oxide for size-dependent N-doping and oxygen reduction catalysis.

Graphene oxide (GO) is aqueous-dispersible oxygenated graphene, which shows colloidal discotic liquid crystallinity. Many properties of GO-based materials, including electrical conductivity and mechanical properties, are limited by the small flake size of GO. Unfortunately, typical sonochemical exfoliation of GO from graphite generally leads to a broad size and shape distribution. Here, we introduce a facile size selection of large-size GO exploiting liquid crystallinity and investigate the size-dependent N-doping and oxygen reduction catalysis. In the biphasic GO dispersion where both isotropic and liquid crystalline phases are equilibrated, large-size GO flakes (>20 µm) are spontaneously concentrated within the liquid crystalline phase. N-Doping and reduction of the size-selected GO exhibit that N-dopant type is highly dependent on GO flake size. Large-size GO demonstrates quaternary dominant N-doping and the lowest onset potential (-0.08 V) for oxygen reduction catalysis, signifying that quaternary N-dopants serve as principal catalytic sites in N-doped graphene.

Chemical structures of hydrazine-treated graphene oxide and generation of aromatic nitrogen doping.

Chemically modified graphene platelets, produced via graphene oxide, show great promise in a variety of applications due to their electrical, thermal, barrier and mechanical properties. Understanding the chemical structures of chemically modified graphene platelets will aid in the understanding of their physical properties and facilitate development of chemically modified graphene platelet chemistry. Here we use (13)C and (15)N solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy to study the chemical structure of (15)N-labelled hydrazine-treated (13)C-labelled graphite oxide and unlabelled hydrazine-treated graphene oxide, respectively. These experiments suggest that hydrazine treatment of graphene oxide causes insertion of an aromatic N(2) moiety in a five-membered ring at the platelet edges and also restores graphitic networks on the basal planes. Furthermore, density-functional theory calculations support the formation of such N(2) structures at the edges and help to elucidate the influence of the aromatic N(2) moieties on the electronic structure of chemically modified graphene platelets.

Workfunction-tunable, N-doped reduced graphene transparent electrodes for high-performance polymer light-emitting diodes.

Graphene is a promising candidate to complement brittle and expensive transparent conducting oxides. Nevertheless, previous research efforts have paid little attention to reduced graphene, which can be of great benefit due to low-cost solution processing without substrate transfer. Here we demonstrate workfunction-tunable, highly conductive, N-doped reduced graphene film, which is obtainable from the spin-casting of graphene oxide dispersion and can be successfully employed as a transparent cathode for high-performance polymer light-emitting diodes (PLEDs) as an alternative to fluorine-doped tin oxide (FTO). The sheet resistance of N-doped reduced graphene attained 300 Ω/□ at 80% transmittance, one of the lowest values ever reported from the reduction of graphene oxide films. The optimal doping of quaternary nitrogen and the effective removal of oxygen functionalities via sequential hydrazine treatment and thermal reduction accomplished the low resistance. The PLEDs employing N-doped reduced graphene cathodes exhibited a maximum electroluminescence efficiency higher than those of FTO-based devices (4.0 cd/A for FTO and 7.0 cd/A for N-doped graphene at 17,000 cd/m(2)). The reduced barrier for electron injection from a workfunction-tunable, N-doped reduced graphene cathode offered this remarkable device performance.

Graphene oxide thin films for flexible nonvolatile memory applications.

There has been strong demand for novel nonvolatile memory technology for low-cost, large-area, and low-power flexible electronics applications. Resistive memories based on metal oxide thin films have been extensively studied for application as next-generation nonvolatile memory devices. However, although the metal oxide based resistive memories have several advantages, such as good scalability, low-power consumption, and fast switching speed, their application to large-area flexible substrates has been limited due to their material characteristics and necessity of a high-temperature fabrication process. As a promising nonvolatile memory technology for large-area flexible applications, we present a graphene oxide based memory that can be easily fabricated using a room temperature spin-casting method on flexible substrates and has reliable memory performance in terms of retention and endurance. The microscopic origin of the bipolar resistive switching behavior was elucidated and is attributed to rupture and formation of conducting filaments at the top amorphous interface layer formed between the graphene oxide film and the top Al metal electrode, via high-resolution transmission electron microscopy and in situ X-ray photoemission spectroscopy. This work provides an important step for developing understanding of the fundamental physics of bipolar resistive switching in graphene oxide films, for the application to future flexible electronics.

Surface energy modification by spin-cast, large-area graphene film for block copolymer lithography.

We demonstrate a surface energy modification method exploiting graphene film. Spin-cast, atomic layer thick, large-area reduced graphene film successfully played the role of surface energy modifier for arbitrary surfaces. The degree of reduction enabled the tuning of the surface energy. Sufficiently reduced graphene served as a neutral surface modifier to induce surface perpendicular lamellae or cylinders in a block copolymer nanotemplate. Our approach integrating large-area graphene film preparation with block copolymer lithography is potentially advantageous in creating semiconducting graphene nanoribbons and nanoporous graphene.

Peptide-templating dye-sensitized solar cells.

A hollow TiO(2) nanoribbon network electrode for dye-sensitized solar cells (DSSC) was fabricated by a biotemplating process combining peptide self-assembly and atomic layer deposition (ALD). An aromatic peptide of diphenylalanine was assembled into a three-dimensional network consisting of highly entangled nanoribbons. A thin TiO(2) layer was deposited at the surface of the peptide template via the ALD process. After the pyrolysis of the peptide template, a highly entangled nanotubular TiO(2) framework was successfully prepared. Evolution of the crystal phase and crystallite size of the TiO(2) nanostructure was exploited by controlling the calcination temperature. Finally, the hollow TiO(2) nanoribbon network electrode was integrated into DSSC devices and their photochemical performances were investigated. Hollow TiO(2) nanoribbon-based DSSCs exhibited a power conversion efficiency of 3.8%, which is comparable to the conventional TiO(2) nanoparticle-based DSSCs (3.5%). Our approach offers a novel pathway for DSSCs consisting of TiO(2) electrodes via biotemplating.