Graphite oxide

Graphite oxide (GO), formerly called graphitic oxide or graphitic acid, is a compound of carbon, oxygen, and hydrogen in variable ratios, obtained by treating graphite with strong oxidizers and acids for resolving of extra metals. The maximally oxidized bulk product is a yellow solid with C:O ratio between 2.1 and 2.9, that retains the layer structure of graphite but with a much larger and irregular spacing. The bulk material spontaneously disperses in basic solutions or can be dispersed by sonication in polar solvents to yield monomolecular sheets, known as graphene oxide by analogy to graphene, the single-layer form of graphite. Graphene oxide sheets have been used to prepare strong paper-like materials, membranes, thin films, and composite materials. Initially, graphene oxide attracted substantial interest as a possible intermediate for the manufacture of graphene. The graphene obtained by reduction of graphene oxide still has many chemical and structural defects which is a problem for some applications but an advantage for some others.

History and preparation Graphite oxide was first prepared by Oxford chemist Benjamin C. Brodie in 1859 by treating graphite with a mixture of potassium chlorate (KClO3) and fuming nitric acid (HNO3). He reported synthesis of "paper-like foils" with 0.05 mm thickness. In 1957, Hummers and Offeman developed a safer, quicker, and more efficient process called Hummers' method, using a mixture of sulfuric acid (H2SO4), sodium nitrate (NaNO3), and potassium permanganate (KMnO4), which is still widely used, often with some modifications. Largest monolayer GO with highly intact carbon framework and minimal residual impurity concentrations can be synthesized in inert containers using highly pure reactants and solvents. Graphite oxides exhibit considerable variation in properties with oxidation degree and synthesis method. For example, the temperature point of explosive exfoliation is generally higher for graphite oxide prepared by the Brodie method compared to Hummers graphite oxide, the difference is up to 100 degrees with the same heating rates. The hydration and solvation properties of Brodie and Hummers graphite oxides are also remarkably different. Recently a mixture of H2SO4 and KMnO4 has been used to cut open carbon nanotubes lengthwise, resulting in microscopic flat ribbons of graphene, a few atoms wide, with the edges "capped" by oxygen atoms (=O) or hydroxyl groups (–OH). Graphite (graphene) oxide has also been prepared by using a "bottom-up" synthesis method (Tang-Lau method) in which the sole reagent source is glucose; the process is safer, simpler, and more environmentally friendly compared to the traditional "top-down" method, in which strong oxidizers are involved. Another important advantage of the Tang-Lau method is the control of thickness, ranging from monolayer to multilayers, by adjusting growth parameters.

Structure The structure and properties of graphite oxide depend on the particular synthesis method and degree of oxidation. It typically preserves the layer structure of the parent graphite, but the layers are buckled and the interlayer spacing is about two times larger (~0.7 nm) than that of graphite. Strictly speaking "oxide" is an incorrect but historically established name. Besides epoxide groups (bridging oxygen atoms), other functional groups found experimentally are: carbonyl (C=O), hydroxyl (-OH), phenol and for graphite oxides prepared using sulphuric acid (e.g. Hummers method) some impurity of sulphur is often found, for example in a form of organosulfate groups. The detailed structure is still not understood due to the strong disorder and irregular packing of the layers. Graphene oxide layers are about 1.1 ± 0.2 nm thick. Scanning tunneling microscopy shows the presence of local regions where oxygen atoms are arranged in a rectangular pattern with lattice constant 0.27 nm × 0.41 nm. The edges of each layer are terminated with carboxyl and carbonyl groups. X-ray photoelectron spectroscopy shows the presence of several C1s peaks, their number and relative intensity depending on the particular oxidation method used. Assignment of these peaks to certain carbon functionalization types is somewhat uncertain and still under debate. For example, one interpretation goes as follows: non-oxygenated ring contexts (284.8 eV), C-O (286.2 eV), C=O (287.8 eV) and O-C=O (289.0 eV). Another interpretation, using density functional theory calculation, goes as follows: C=C with defects such as functional groups and pentagons (283.6 eV), C=C (non-oxygenated ring contexts) (284.3 eV), sp3C-H in the basal plane and C=C with functional groups (285.0 eV), C=O and C=C with functional groups, C-O (286.5 eV), and O-C=O (288.3 eV). Graphite oxide is hydrophilic and easily hydrated when exposed to water vapor or immersed in liquid water, resulting in a distinct increase of the inter-planar distance (up to 1.2 nm in saturated state). Additional water is also incorporated into the interlayer space due to high pressure induced effects. The maximal hydration state of graphite oxide in liquid water corresponds to insertion of 2-3 water monolayers. Cooling the graphite oxide/H2O samples results in "pseudo-negative thermal expansion" and cooling below the freezing point of water results in de-insertion of one water monolayer and lattice contraction. Complete removal of water from the structure seems difficult since heating at 60–80 °C results in partial decomposition and degradation of the material.

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