Muge Acik

Structural evolution during the reduction of chemically derived graphene oxide

The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

Unusual infrared-absorption mechanism in thermally reduced graphene oxide

Infrared absorption of atomic and molecular vibrations in solids can be affected by electronic contributions through non-adiabatic interactions, such as the Fano effect. Typically, the infrared-absorption lineshapes are modified, or infrared-forbidden modes are detectable as a modulation of the electronic absorption. In contrast to such known phenomena, we report here the observation of a giant-infrared-absorption band in reduced graphene oxide, arising from the coupling of electronic states to the asymmetric stretch mode of a yet-unreported structure, consisting of oxygen atoms aggregated at the edges of defects. Free electrons are induced by the displacement of the oxygen atoms, leading to a strong infrared absorption that is in phase with the phonon mode. This new phenomenon is only possible when all other oxygen-containing chemical species, including hydroxyl, carboxyl, epoxide and ketonic functional groups, are removed from the region adjacent to the edges, that is, clean graphene patches are present.

Room-temperature metastability of multilayer graphene oxide films.

Graphene oxide potentially has multiple applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is crucial to enable future applications of this material. Here, a combined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene through the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly stable reduced O/C ratio, and exhibits a structure deprived of epoxide groups and enriched in hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favours the reduction of epoxide groups and the formation of water molecules.

Probing the catalytic activity of porous graphene oxide and the origin of this behaviour

Graphene oxide, a two-dimensional aromatic scaffold decorated by oxygen-containing functional groups, possesses rich chemical properties and may present a green alternative to precious metal catalysts. Graphene oxide-based carbocatalysis has recently been demonstrated for aerobic oxidative reactions. However, its widespread application is hindered by the need for high catalyst loadings. Here we report a simple chemical treatment that can create and enlarge the defects in graphene oxide and impart on it enhanced catalytic activities for the oxidative coupling of amines to imines (up to 98% yield at 5 wt% catalyst loading, under solvent-free, open-air conditions). This study examines the origin of the enhanced catalytic activity, which can be linked to the synergistic effect of carboxylic acid groups and unpaired electrons at the edge defects. The discovery of a simple chemical processing step to synthesize highly active graphene oxide allows the premise of industrial-scale carbocatalysis to be explored.

The Role of Intercalated Water in Multilayered Graphene Oxide

A detailed in situ infrared spectroscopy analysis of single layer and multilayered graphene oxide (GO) thin films reveals that the normalized infrared absorption in the carbonyl region is substantially higher in multilayered GO upon mild annealing. These results highlight the fact that the reduction chemistry of multilayered GO is dramatically different from the single layer GO due to the presence of water molecules confined in the ∼1 nm spacing between sheets. IR spectroscopy, XPS analysis, and DFT calculations all confirm that the water molecules play a significant role interacting with basal plane etch holes through passivation, via evolution of CO(2) leading to the formation of ketone and ester carbonyl groups. Displacement of water from intersheet spacing with alcohol significantly changes the chemistry of carbonyl formation with temperature.

Nature of Graphene Edges: A Review

Graphene edges determine the optical, magnetic, electrical, and electronic properties of graphene. In particular, termination, chemical functionalization and reconstruction of graphene edges leads to crucial changes in the properties of graphene, so control of the edges is critical to the development of applications in electronics, spintronics and optoelectronics. Up to date, significant advances in studying graphene edges have directed various smart ways of controlling the edge morphology. Though, it still remains as a major challenge since even minor deviations from the ideal shape of the edges significantly deteriorate the material properties. In this review, we discuss the fundamental edge configurations together with the role of various types of edge defects and their effects on graphene properties. Indeed, we highlight major demanding challenges to find the most suitable technique to characterize graphene edges for numerous device applications such as transistors, sensors, actuators, solar cells, light-emitting displays, and batteries in graphene technology.

Field emission from atomically thin edges of reduced graphene oxide.

Point sources exhibit low threshold electron emission due to local field enhancement at the tip. The development and implementation of tip emitters have been hampered by the need to position them sufficiently apart to achieve field enhancement, limiting the number of emission sites and therefore the overall current. Here we report low threshold field (< 0.1 V/μm) emission of multiple electron beams from atomically thin edges of reduced graphene oxide (rGO). Field emission microscopy measurements show evidence for interference from emission sites that are separated by a few nanometers, suggesting that the emitted electron beams are coherent. On the basis of our high-resolution transmission electron microscopy, infrared spectroscopy, and simulation results, field emission from the rGO edge is attributed to a stable and unique aggregation of oxygen groups in the form of cyclic edge ethers. Such closely spaced electron beams from rGO offer prospects for novel applications and understanding the physics of linear electron sources.

Oriented Graphene Nanoribbon Yarn and Sheet from Aligned Multi‐Walled Carbon Nanotube Sheets

Highly oriented graphene nanoribbons sheets and yarns are produced by chemical unzipping of self-standing multiwalled carbon nanotube (MWNT) sheets. The as-produced yarns - after being chemically and thermally reduced - exhibit a good mechanical, electrical, and electrochemical performance.

Partially oxidized graphene as a precursor to graphene

Solution exfoliation of graphite holds promise for large-scale bulk synthesis of graphene. Non-covalent exfoliation is attractive because the electronic structure of graphene is preserved but the yield is low and the lateral dimensions of the sheets are small. Chemical exfoliation via formation of graphite oxide is a highly versatile and scalable route but the covalent functionalization of graphene with oxygen significantly alters the properties. Here, we report a new method for large-scale facile synthesis of micron-sized partially oxidized graphene (POG) sheets with dramatically improved electronic properties compared to other solution-phase exfoliated graphene. Due to low initial oxygen content (∼12%), POG requires only mild annealing (<300 °C) to achieve a sheet resistance of 28 kΩ sq−1 at the neutrality point, only a factor of ∼4 larger than the intrinsic sheet resistance of pristine graphene (∼6 kΩ sq−1) and substantially lower than graphene exfoliated by other methods. Such a partial oxidation approach opens up new promising routes to solution based high-performance, low temperature, transparent and conducting graphene-based flexible electronics.

Materials Science of Graphene for Novel Device Applications

Realization of graphene based devices will require a controlled integration of graphene into a device structure with multiple material components of metals and insulators. To investigate the fundamental materials problems of graphene devices, a complimentary team of researchers at UTD is applying experimental and theoretical methods to the graphene/metal and graphene/dielectric interface problems. To assess the large area graphene synthesis and the corresponding material properties, graphene oxides and grain boundaries in graphene are also examined by experiments in close connection with modeling study. Through a strong collaborative research in synthesis, characterization, and modeling, we have developed a fundamental understanding of graphene material properties which can facilitate diverse graphene based devices applications.