Direct imaging of charge transport in progressively reduced graphene oxide using electrostatic force microscopy.

Graphene oxide (GO) has emerged as a multifunctional material that can be synthesized in bulk quantities and can be solution processed to form large-area atomic layered photoactive, flexible thin films for optoelectronic devices. This is largely due to the potential ability to tune electrical and optical properties of GO using functional groups. For the successful application of GO, it is key to understand the evolution of its optoelectronic properties as the GO undergoes a phase transition from its insulating and optically active state to the electrically conducting state with progressive reduction. In this paper, we use a combination of electrostatic force microscopy (EFM) and optical spectroscopy to monitor the emergence of the optoelectronic properties of GO with progressive reduction. EFM measurements enable, for the first time, direct visualization of charge propagation along the conducting pathways that emerge on progressively reduced graphene oxide (rGO) and demonstrate that with the increasing degree of reduction, injected charges can rapidly migrate over a distance of several micrometers, irrespective of their polarities. Direct imaging reveals the presence of an insurmountable potential barrier between reduced GO (rGO) and GO, which plays the decisive role in the charge transport. We complement charge imaging with theoretical modeling using quantum chemistry calculations that further demonstrate that the role of barrier in regulating the charge transport. Furthermore, by correlating the EFM measurements with photoluminescence imaging and electrical conductivity studies, we identify a bifunctional state in GO, where the optical properties are preserved along with good electrical conductivity, providing design principles for the development of GO-based, low-cost, thin-film optoelectronic applications.

Ozonated graphene oxide film as a proton-exchange membrane.

Graphene oxide (GO) contains several chemical functional groups that are attached to the graphite basal plane and can be manipulated to tailor GO for specific applications. It is now revealed that the reaction of GO with ozone results in a high level of oxidation, which leads to significantly improved ionic (protonic) conductivity of the GO. Freestanding ozonated GO films were synthesized and used as efficient polymer electrolyte fuel cell membranes. The increase in protonic conductivity of the ozonated GO originates from enhanced proton hopping, which is due to the higher content of oxygenated functional groups in the basal planes and edges of ozonated GO as well as the morphology changes in GO that are caused by ozonation. The results of this study demonstrate that the modification of dispersed GO presents a powerful opportunity for optimizing a nanoscale material for proton-exchange membranes.

Carbon nanotube-nanocup hybrid structures for high power supercapacitor applications.

Here, we design and develop high-power electric double-layer capacitors (EDLCs) using carbon-based three dimensional (3-D) hybrid nanostructured electrodes. 3-D hybrid nanostructured electrodes consisting of vertically aligned carbon nanotubes (CNTs) on highly porous carbon nanocups (CNCs) were synthesized by a combination of anodization and chemical vapor deposition techniques. A 3-D electrode-based supercapacitor showed enhanced areal capacitance by accommodating more charges in a given footprint area than that of a conventional CNC-based device.

Paintable battery.

If the components of a battery, including electrodes, separator, electrolyte and the current collectors can be designed as paints and applied sequentially to build a complete battery, on any arbitrary surface, it would have significant impact on the design, implementation and integration of energy storage devices. Here, we establish a paradigm change in battery assembly by fabricating rechargeable Li-ion batteries solely by multi-step spray painting of its components on a variety of materials such as metals, glass, glazed ceramics and flexible polymer substrates. We also demonstrate the possibility of interconnected modular spray painted battery units to be coupled to energy conversion devices such as solar cells, with possibilities of building standalone energy capture-storage hybrid devices in different configurations.

Controlled, Stepwise Reduction and Band Gap Manipulation of Graphene Oxide.

Graphene oxide (GO) has drawn tremendous interest as a tunable precursor in numerous areas, due to its readily manipulable surface. However, its inhomogeneous and nonstoichiometric structure makes achieving chemical control a major challenge. Here, we present a room-temperature based, controlled method for the stepwise reduction of GO, with evidence of sequential removal of each organic moiety. By analyzing signature infrared absorption frequencies, we identify the carbonyl group as the first to be reduced, while the tertiary alcohol takes the longest to be completely removed from the GO surface. Controlled reduction allows for progressive tuning of the optical gap from 3.5 eV down to 1 eV, while XPS spectra show a concurrent increase in the C/O ratio. This study is the first step toward selectively enhancing the chemical homogeneity of GO, thus providing greater control over its structure, and elucidating the order of removal of functional groups and hydrazine-vapor reduction.

Quasi-molecular fluorescence from graphene oxide.

Aqueous dispersions of graphene oxide (GO) have been found to emit a structured, strongly pH-dependent visible fluorescence. Based on experimental results and model computations, this is proposed to arise from quasi-molecular fluorophores, similar to polycyclic aromatic compounds, formed by the electronic coupling of carboxylic acid groups with nearby carbon atoms of graphene. Sharp and structured emission and excitation features resembling the spectra of molecular fluorophores are present near 500 nm in basic conditions. The GO emission reversibly broadens and red-shifts to ca. 680 nm in acidic conditions, while the excitation spectra remain very similar in shape and position, consistent with excited state protonation of the emitting species in acidic media. The sharp and structured emission and excitation features suggest that the effective fluorophore size in the GO samples is remarkably well defined.

Competing effects of surface phonon softening and quantum size effects on the superconducting properties of nanostructured Pb.

The superconducting transition temperature (T(C)) in nanostructured Pb decreases from 7.24 to 6.4 K as the particle size is reduced from 65 to 7 nm, below which superconductivity is lost rather abruptly. In contrast, there is a large enhancement in the upper critical field (H(C2)) in the same size regime. We explore the origin of the unusual robustness of T(C) over such a large particle size range in nanostructured Pb by measuring the temperature dependence of the superconducting energy gap in planar tunnel junctions of Al/Al(2)O(3)/nano-Pb. We show that below 22 nm, the electron-phonon coupling strength increases monotonically with decreasing particle size, and almost exactly compensates for the quantum size effect, which is expected to suppress T(C).