| 1. |
- Klechikov, Alexey, et al.
(författare)
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Multilayered intercalation of 1-octanol into Brodie graphite oxide
- 2017
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 9:20, s. 6929-6936
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Tidskriftsartikel (refereegranskat)abstract
- Multilayered intercalation of 1-octanol into the structure of Brodie graphite oxide (B-GO) was studied as a function of temperature and pressure. Reversible phase transition with the addition/removal of one layer of 1-octanol was found at 265 K by means of X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). The same transition was observed at ambient temperature upon a pressure increase above 0.6 GPa. This transition was interpreted as an incongruent melting of the low temperature/high pressure B-GO intercalated structure with five layers of 1-octanol parallel to GO sheets (L-solvate), resulting in the formation of a four-layered structure that is stable under ambient conditions (A-solvate). Vacuum heating allows the removal of 1-octanol from the A-solvate layer by layer, while distinct sets of (00 l) reflections are observed for three-, two-, and one-layered solvate phases. Step by step removal of the 1-octanol layers results in changes of distance between graphene oxide planes by similar to 4.5 angstrom. This experiment proved that both L- and A-solvates are structures with layers of 1-octanol parallel to GO planes. Unusual intercalation with up to five distinct layers of 1-octanol is remarkably different from the behaviour of small alcohol molecules (methanol and ethanol), which intercalate B-GO structure with only one layer under ambient conditions and a maximum of two layers at lower temperatures or higher pressures. The data presented in this study make it possible to rule out a change in the orientation of alcohol molecules from parallel to perpendicular to the GO planes, as suggested in the 1960s to explain larger expansion of the GO lattice due to swelling with larger alcohols.
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| 2. |
- Korobov, Mikhail V., et al.
(författare)
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Sorption of polar organic solvents and water by graphite oxide : thermodynamic approach
- 2016
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Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 102, s. 297-303
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Tidskriftsartikel (refereegranskat)abstract
- Sorption of polar organic solvents CH3OH, C4H8O (THF), CH3CN, C3H7NO (DMF), C2H6OS (DMSO), C5H9NO (NMP) and water was quantitatively evaluated for Hummers (H-GO) and Brodie (B-GO) graphite oxides at T = 298K and at melting temperature (Tm) of the solvents. H-GO showed stronger sorption compared to B-GO for all studied solvents and the increase of sorption upon lowering temperature was observed for both H-GO and B-GO. Thermodynamic equations allowed to explain earlier reported "maximums" of swelling/sorption in the binary systems H-GO – solvent at Tm. The specific relation between the values of enthalpies of sorption and melting leads to the change of sign in enthalpies of sorption at Tm and causes maximal swelling/sorption. The same thermodynamic explanation was given for the "maximum" on the swelling vs. pressure dependence in B-GO and H-GO – H2O systems earlier reported at pressure of phase transition "liquid water-ice VI". Notably higher sorption of H2O was observed for H-GO compared to H-GO membrane (H-GOm) at high relative humidity (RH), RH > 0.75. Experimental sorption isotherm of H-GOm was used to simulate permeation rates of water through H-GOm and to estimate effective diffusion coefficient of water through the membrane.
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| 3. |
- You, Shujie, et al.
(författare)
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Selective Intercalation of Graphite Oxide by Methanol in Water/Methanol Mixtures
- 2013
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 117:4, s. 1963-1968
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Tidskriftsartikel (refereegranskat)abstract
- 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 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.
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| 4. |
- Chumakova, Natalia A., et al.
(författare)
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Properties of Graphite Oxide Powders and Membranes as Revealed by Electron Paramagnetic Resonance Spectroscopy
- 2018
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:39, s. 22750-22759
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Tidskriftsartikel (refereegranskat)abstract
- The spin probe technique was used to study graphite oxide (GO) powders swelled in polar liquids (CH3CN, CH3OH, and H2O) and liquid-free GO membranes (GOM). The nitroxide radicals TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) and TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl) readily penetrated into the interplane space of GO from the solution. Electron paramagnetic resonance (EPR) spectra of these radical probes were sensitive to molecular mobility and orientation ordering within the internal space of GO. The radicals embedded in swelled GO were in two states with different rotational mobilities. The small fraction of radicals located in the interplane space of GO and detected in the broad range of temperatures was in the state of fast rotation, similar to the same radicals dissolved in bulk liquids, thus providing experimental evidence of formation of a liquid-like media within the interplane space of GO. Such mobile media may be responsible for the unusual permeation properties of GOM, which is reported in the literature. Second, less-mobile fraction of radicals was found to be immobilized at the internal surface of GO and was sensitive to phase transformations in the swelled GO structures. The transformations were detected as anomalies at temperature dependences of rotational mobility of radicals. The detected dependence of EPR spectra of probe radicals on orientation of GOM, relative to the direction of magnetic field in the EPR spectrometer, was used for quantitative characterization of orientation alignment of GO planes within the membranes. Such an approach may serve as an elegant method to estimate the relative quality of membranes and other GO-layered structures.
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| 5. |
- Iakunkov, Artem, et al.
(författare)
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Activated graphene as a material for supercapacitor electrodes : effects of surface area, pore size distribution and hydrophilicity
- 2019
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : RSC Publishing. - 1463-9076 .- 1463-9084. ; 21:32, s. 17901-17912
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Tidskriftsartikel (refereegranskat)abstract
- Activated reduced graphene oxide (a-rGO) is a material with a rigid 3D porous structure and high specific surface area (SSA). Using variation of activation parameters and post-synthesis mechanical treatment we prepared two sets of materials with a broad range of BET (N2) SSA ∼1000–3000 m2 g−1, and significant differences in pore size distribution and oxygen content. The performance of activated graphene as an electrode in a supercapacitor with KOH electrolyte was correlated with the structural parameters of the materials and water sorption properties. a-rGO is a hydrophobic material as evidenced by the negligibly small BET (H2O) SSA determined using analysis of water vapor sorption isotherms. However, the total pore volume determined using water vapor sorption and sorption of liquid water is almost the same as the one found by analysis of nitrogen sorption isotherms. Ball milling is found to provide an improved bulk density of activated graphene and collapse of all pores except the smallest ones (<2 nm). A decrease in the activation temperature from 850 °C to 550 °C is found to result in materials with a narrow micropore size distribution and increased oxygen content. Elimination of mesopores using ball milling or a lower activation temperature provided materials with better specific capacitance despite a significant decrease (by ∼30%) of the BET (N2) SSA. The best gravimetric and volumetric capacitances in KOH electrolyte were achieved not for samples with the highest value of the BET (N2) SSA but for materials with 80–90% of the total pore volume in micropores and an increased BET (H2O) SSA. Comparing the performance of electrodes prepared using rGO and a-rGO shows that a more hydrophilic surface is favorable for charge storage in supercapacitors with KOH electrolyte.
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| 6. |
- Iakunkov, Artem, et al.
(författare)
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Swelling of graphene oxide membranes in alcohols : effects of molecule size and air ageing
- 2019
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 7, s. 11331-11337
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Tidskriftsartikel (refereegranskat)abstract
- Swelling of Hummers graphene oxide (HGO) membranes in a set of progressively longer liquid alcohols (methanol to 1-nonanol) was studied using synchrotron radiation XRD after air ageing over prolonged periods of time. Both precursor graphite oxides and freshly prepared HGO membranes were found to swell in the whole set of nine liquid alcohols with an increase of interlayer spacing from ∼7 Å (solvent free) up to ∼26 Å (in 1-nonanol). A pronounced effect of ageing on swelling in alcohols was found for HGO membranes stored in air. The HGO membranes aged for 0.5–1.5 years show progressively slower swelling kinetics, a non-monotonic decrease of saturated swelling in some alcohols and complete disappearance of swelling for alcohol molecules larger than hexanol. Moreover, the HGO membranes stored under ambient conditions for 5 years showed a nearly complete absence of swelling in all alcohols but preserved swelling in water. In contrast, precursor graphite oxide powder showed unmodified swelling in alcohols even after 4 years of ageing. Since the swelling defines the size of permeation channels, the ageing effect is one of the important parameters which could explain the strong variation in reported filtration/separation properties of GO membranes. The time and conditions of air storage require standardization for better reproducibility of results related to performance of GO membranes in various applications. The ageing of GO membranes can be considered not only as a hindrance/degradation for certain applications, but also as a method to tune the swelling properties of HGO membranes for better selectivity in sorption of solvents and for achieving better selective permeability.
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| 7. |
- Iakunkov, Artem, et al.
(författare)
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Swelling of graphene oxide membranes in alcohols : effects of molecule size and air ageing
- 2019
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Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 7:18, s. 11331-11337
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Tidskriftsartikel (refereegranskat)abstract
- Swelling of Hummers graphene oxide (HGO) membranes in a set of progressively longer liquid alcohols (methanol to 1-nonanol) was studied using synchrotron radiation XRD after air ageing over prolonged periods of time. Both precursor graphite oxides and freshly prepared HGO membranes were found to swell in the whole set of nine liquid alcohols with an increase of interlayer spacing from approximate to 7 angstrom (solvent free) up to approximate to 26 angstrom (in 1-nonanol). A pronounced effect of ageing on swelling in alcohols was found for HGO membranes stored in air. The HGO membranes aged for 0.5-1.5 years show progressively slower swelling kinetics, a non-monotonic decrease of saturated swelling in some alcohols and complete disappearance of swelling for alcohol molecules larger than hexanol. Moreover, the HGO membranes stored under ambient conditions for 5 years showed a nearly complete absence of swelling in all alcohols but preserved swelling in water. In contrast, precursor graphite oxide powder showed unmodified swelling in alcohols even after 4 years of ageing. Since the swelling defines the size of permeation channels, the ageing effect is one of the important parameters which could explain the strong variation in reported filtration/separation properties of GO membranes. The time and conditions of air storage require standardization for better reproducibility of results related to performance of GO membranes in various applications. The ageing of GO membranes can be considered not only as a hindrance/degradation for certain applications, but also as a method to tune the swelling properties of HGO membranes for better selectivity in sorption of solvents and for achieving better selective permeability.
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| 8. |
- Klechikov, Alexey, et al.
(författare)
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Graphite oxide swelling in molten sugar alcohols and their aqueous solutions
- 2018
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Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 140, s. 157-163
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Tidskriftsartikel (refereegranskat)abstract
- Graphite oxides (GO) are intercalated rapidly by one to several layers of solvent when immersed in liquid but the GO solvates are typically unstable on air due to solvent evaporation. Here we study swelling of GO in solvents (sugar alcohols) with melting temperature point above ambient. Using in situ synchrotron radiation XRD experiments we demonstrated GO swelling in molten xylitol and sorbitol. The expanded GO structure intercalated with one layer of xylitol or sorbitol is preserved upon solidification of melt and cooling back to ambient conditions. The structure of solid solvates of GO with xylitol and sorbitol is based on non-covalent interaction and pristine GO can be recovered by washing in water. Intercalation of xylitol and sorbitol into GO structure in aqueous solutions yields similar but less ordered structure of GO/sugar alcohol solid solvates. Very similar inter-layer distance was observed for GO intercalated by sugar alcohols in melt and for GO immersed in sugar solutions. This result shows that sugar alcohols penetrate into GO inter-layer space without hydration shell forming 2D layers with orientation parallel to graphene oxide sheets. Therefore, hydration diameter of molecules should not be considered as decisive factor for permeation through graphene oxide inter-layers in multilayered membranes.
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| 9. |
- Rebrikova, Anastasiya T., et al.
(författare)
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Swollen Structures of Brodie Graphite Oxide as Solid Solvates
- 2020
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:42, s. 23410-23418
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Tidskriftsartikel (refereegranskat)abstract
- Swelling of Brodie graphite oxide (B-GO) was studied for a series of normal alcohols from methanol to 1-nonanol. Isopiestic, X-ray diffraction (XRD), thermogravimetric, and differential scanning calorimetry data demonstrated that sorption of polar liquids into GO lamellas formed the set of regular swollen structures, simple binary "solid solvates", characterized by the distance between the GO planes and the value of sorption. Temperature-composition behavior of the swollen structures was adequately described by conventional binary phase diagrams. Phase transformation of the low-temperature swollen structure of B-GO with 1-nonanol gave a clear example of incongruent melting transition typical for the binary solvates. A discreet set of the interplane distances observed by XRD and the stepwise equilibrium desorption pointed to the layered arrangement of solvent molecules in the swollen structures. The swollen structures with one to five parallel layers were observed for a series of normal alcohols with B-GO. The average volume of one layer, 0.36 +/- 0.06 cm(3) g(-1) B-GO, was almost the same for rather different organic liquids and was possibly restricted by the internal geometry of B-GO. This internal volume available for the sorption of the first layer was reasonably estimated from geometrical parameters of B-GO.
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| 10. |
- Talyzin, Alexandr, et al.
(författare)
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Delamination of graphite oxide in a liquid upon cooling
- 2015
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 7:29, s. 12625-12630
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Tidskriftsartikel (refereegranskat)abstract
- Graphite oxide (GO) in liquid acetonitrile undergoes a transition from an ordered phase around ambient temperature to a gel-like disordered phase at temperatures below 260 K, as demonstrated by in situ X-ray diffraction. The stacking order of GO layers is restored below the freezing point of acetonitrile (199 K). The reversible swelling transition between a stacked crystalline phase and an amorphous delaminated state observed upon cooling provides an unusual example of increased structural disorder at lower temperatures. The formation of the gel-like phase is attributed to the thermo-responsive conformational change of individual GO flakes induced by stronger solvation. Scanning force microscopy demonstrates that GO flakes deposited onto a solid substrate from acetonitrile dispersions at a temperature below 260 K exhibit corrugations and wrinkling which are not observed for the flakes deposited at ambient temperature. The thermo-responsive transition between the delaminated and stacked phases reported here can be used for sonication-free dispersion of graphene oxide, micro-container applications, or the preparation of new composite materials.
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