We measured the proton conductivity of bulk graphite oxide (GO'), a graphene oxide/proton hybrid (GO-H), and a graphene oxide (GO) nanosheet for the first time. GO is a well-known electronic insulator, but for proton conduction we observed the reverse trend, as it exhibited superionic conductivity. The hydrophilic sites present in GO as -O-, -OH, and -COOH functional groups attract the protons, which propagate through hydrogen-bonding networks along the adsorbed water film. The proton conductivities of GO' and GO-H at 100% humidity were ∼10(-4) and ∼10(-5) S cm(-1), respectively, whereas that for GO was amazingly high, nearly 10(-2) S cm(-1). This finding indicates the possibility of GO-based perfect two-dimensional proton-conductive materials for applications in fuel cells, sensors, and so on.
Supporting Information. Raman spectra, UVÀvis spectra, reaction equations, photoelectrochemical data, XPS spectra, and UPS spectra. This material is available free of charge via the Internet at http://pubs.acs.org.
One-nanometer-thick nickel hydroxide nanosheets were prepared by exfoliation of layered nickel hydroxides intercalated with dodecyl sulfate (DS) ions. The shape of the nanosheets was hexagonal, as was that of the layered nickel hydroxides intercalated with DS ions. The nickel hydroxide nanosheets exhibited charge-discharge properties in strong alkaline electrolyte. The morphology of the nanosheet changed during the electrochemical reaction.
Graphene oxide (GO) nanosheets were reduced by UV irradiation in H2 or N2 under mild conditions (at room temperature) without a photocatalyst. Photoreduction proceeded even in an aqueous suspension of nanosheets. The GO nanosheets reduced by this method were analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. It was found that epoxy groups attached to the interiors of aromatic domains of the GO nanosheet were destroyed during UV irradiation to form relatively large sp2 islands resulting in a high conductivity. I-V curves were measured by conductive atomic force microscopy (AFM; perpendicular to a single nanosheet) and a two-electrode system (parallel to the nanosheet). They revealed that photoreduced GO nanosheets have high conductivities, whereas nonreduced GO nanosheets are nearly insulating. Ag+ adsorbed on GO nanosheets promoted the photoreduction. This photoreduction method was very useful for photopatterning a conducting section of micrometer size on insulating GO. The developed photoreduction process based on a photoreaction will extend the applications of GO to many fields because it can be performed in mild conditions without a photocatalyst.
X-ray photoelectron spectroscopy (XPS) is among the most powerful techniques to analyze defective structures of carbon materials such as graphene and activated carbon. However, reported assignments of defects, especially sp(3)C and sp(2)C, are questionable. Most reports assign sp(3)C peaks to be higher than sp(2)C peaks, whereas a few reports assign sp(3)C peaks to be lower than sp(2)C peaks. Our group previously reported that calculated binding energies of sp(3)C were basically lower than those of sp(2)C. This work clarified that one of the reasons for the prevailing ambiguous assignments of sp(3)C peaks is charging effects of diamond.
Proton conductivities of layered solid electrolytes can be improved by minimizing strain along the conduction path. It is shown that the conductivities (σ) of multilayer graphene oxide (GO) films (assembled by the drop-cast method) are larger than those of single-layer GO (prepared by either the drop-cast or the Langmuir-Blodgett (LB) method). At 60% relative humidity (RH), the σ value increases from 1×10(-6) S cm(-1) in single-layer GO to 1×10(-4) and 4×10(-4) S cm(-1) for 60 and 200 nm thick multilayer films, respectively. A sudden decrease in conductivity was observed for with ethylenediamine (EDA) modified GO (enGO), which is due to the blocking of epoxy groups. This experiment confirmed that the epoxide groups are the major contributor to the efficient proton transport. Because of a gradual improvement of the conduction path and an increase in the water content, σ values increase with the thickness of the multilayer films. The reported methods might be applicable to the optimization of the proton conductivity in other layered solid electrolytes.
Graphene oxide (GO) walled channels filled by sulfate ions exhibit an optimized proton conductivity, which is higher than the proton conductivity of all other forms of GO. The sulphate ion increases the water absorbing capacity and hydrogen bond reformation process in GO.
Many unique properties of graphene oxide (GO) strongly
depend on the oxygenated functional groups and morphologies. Here,
the photoreaction process is demonstrated to be very useful to control
these factors. We report the fast, simple production of nanopores
in porous GO via photoreaction in O2 under UV irradiation
at room temperature. Quantitative analysis using X-ray photoelectron
spectroscopy showed that nanopores were produced in areas of oxygenated
groups (sp3 carbon bonds), creating porous reduced graphene
oxide (rGO). The photoreaction mechanism was proposed on the basis
of changes in the number of oxygenated groups. Proton conduction occurred
at the basal plane of epoxide groups in virgin GO, even at low humidity,
and at carboxyl groups for porous rGO at high humidity. Thus, GO and
rGO samples with various morphologies, oxygenated functional groups,
and conduction types can be easily fabricated by controlling the photoreaction
conditions.
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