The structure of graphene oxide membranes in liquid water, ethanol and water -ethanol mixtures. ABSTRACT. Structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate absence of "negative thermal expansion" and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed by the same graphene oxide flakes.

Luminescent solar concentrators (LSCs) are large-area sunlight collectors coupled to small area solar cells, for efficient solar-to-electricity conversion. The three key points for successful market penetration of LSCs are: (i)...

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A structural study of swelling of Hummers graphite oxide (H-GO) in excess of liquid alcohols was performed as a function of temperature using synchrotron X-ray diffraction and revealed a strong "negative thermal expansion" effect. The increase of the distance between graphene oxide layers is explained by insertion of additional solvent upon cooling of the H-GO/solvent system. The interlayer distance of H-GO is found to increase gradually upon temperature decrease, reaching 19.4 and 20.6 Å at 140 K for methanol and ethanol, respectively. The gradual expansion of the H-GO lattice upon cooling corresponds to insertion of at least two additional solvent monolayers and can be described as osmotic swelling. This phenomenon is distinctly different from the solvation of Brodie graphite oxide (B-GO), which was found earlier to exhibit crystalline swelling: single-step insertion of an additional solvent monolayer at low temperatures. The enormous structural expansion of H-GO at low temperatures is suggested to be useful for solution-based intercalation of graphite oxide with relatively large molecules and the synthesis of various composite materials.

It is demonstrated that solvent-saturated graphite oxide can be considered to be solid solvate, and two phases with distinctly different solvent composition are found near room temperature. Phase transitions between these two solvated phases were observed using synchrotron powder X-ray diffraction and DSC for methanol, ethanol, acetone, and dimethylformamide (DMF) solvents. Solvate A, formed at room temperature, undergoes a reversible phase transition into expanded Solvate L at temperatures slightly below ambient due to insertion of one monolayer of solvent molecules between the GO planes. The phase transition is reversible upon heating, whereas the low-temperature expanded phase L can be quenched to room temperature for ethanol and DMF solvates.

Graphite oxide is selectively intercalated by methanol when exposed to liquid water/methanol mixtures with methanol fraction in the range 20–100%. Insertion of water into the GO structure occurs only when the content of water in the mixture with methanol is increased up to 90%. This conclusion is confirmed by both ambient temperature XRD data and specific temperature variations of the GO structure due to insertion/deinsertion of an additional methanol monolayer observed upon cooling/heating. The composition of GO–methanol solvate phases was determined for both low temperature and ambient temperature phases. Understanding of graphite oxide structural properties in binary water/methanol mixtures is important for understanding the unusual permeation properties of graphene oxide membranes for water and alcohols. It is suggested that graphite oxide prepared by Brodie’s method can be used for purification of water using selective extraction of methanol from water/alcohol mixtures.

In this work, we present all-oxide p-n junction core-shell nanowires (NWs) as fast and stable self-powered photodetectors. Hydrothermally grown n-type ZnO NWs were conformal covered by different thicknesses (up to 420 nm) of p-type copper oxide layers through metalorganic chemical vapor deposition (MOCVD).The ZnO NWs exhibit a single crystalline Wurtzite structure, preferentially grown along the [002] direction, and energy gap Eg=3.24 eV. Depending on the deposition temperature, the copper oxide shell exhibits either a crystalline cubic structure of pure Cu2O phase (MOCVD at 250 C) or a cubic structure of Cu2O with the presence of CuO phase impurities (MOCVD at 300 C), with energy gap of 2.48 eV.The electrical measurements indicate the formation of a p-n junction after the deposition of the copper oxide layer. The core-shell photodetectors present a photoresponsivity at 0V bias voltage up to 7.7 µA/W and time response ≤0.09 s, the fastest ever reported for oxide photodetectors in the visible range, and among the fastest including photodetectors with response limited to the UV region. The bare ZnO NWs have slow photoresponsivity, without recovery after the end of photo-stimulation. The fast time response for the core-shell structures is due to the presence of the p-n junctions, which enables fast exciton separation and charge extraction. Additionally, the suitable electronic structure of the ZnO-Cu2O heterojunction enables self-powering of the device at 0V bias voltage. These results represent a significant advancement in the development of low-cost, high efficiency and self-powered photodetectors, highlighting the need of fine tuning the morphology, composition and electronic properties of p-n junctions to maximize device performances.

Self-powered photodetectors operating in the UV–visible–NIR window made of environmentally friendly, earth abundant, and cheap materials are appealing systems to exploit natural solar radiation without external power sources. In this study, we propose a new p–n junction nanostructure, based on a ZnO–Co3O4 core–shell nanowire (NW) system, with a suitable electronic band structure and improved light absorption, charge transport, and charge collection, to build an efficient UV–visible–NIR p–n heterojunction photodetector. Ultrathin Co3O4 films (in the range 1–15 nm) were sputter-deposited on hydrothermally grown ZnO NW arrays. The effect of a thin layer of the Al2O3 buffer layer between ZnO and Co3O4 was investigated, which may inhibit charge recombination, boosting device performance. The photoresponse of the ZnO–Al2O3–Co3O4 system at zero bias is 6 times higher compared to that of ZnO–Co3O4. The responsivity (R) and specific detectivity (D*) of the best device were 21.80 mA W–1 and 4.12 × 1012 Jones, respectively. These results suggest a novel p–n junction structure to develop all-oxide UV–vis photodetectors based on stable, nontoxic, low-cost materials.