1. |
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2. |
- Abou-Hamad, Edy, et al.
(author)
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Hydrogenation of C-60 in Peapods: Physical Chemistry in Nano Vessels
- 2009
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In: The Journal of Physical Chemistry C. - WASHINGTON, DC 20036 : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 113:20, s. 8583-8587
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Journal article (peer-reviewed)abstract
- Hydrogenation of C-60 molecules inside SWNT was achieved by direct reaction with hydrogen gas at elevated pressure and temperature. Evidence for the C-60 hydrogenation in peapods is provided by isotopic engineering with specific enrichment of encapsulated species and high resolution C-13 and H-1 NMR spectroscopy with the observation of characteristic diamagnetic and paramagnetic shifts of the NMR lines and the appearance of sp(3) carbon resonances. We estimate that approximately 78% of the C-60 molecules inside SWNTs are hydrogenated to an average degree of 14 hydrogen atoms per C-60 molecule. As a consequence, the rotational dynamics of the encapsulated C60Hx molecules is clearly hindered. Our successful hydrogenation experiments open completely new roads to understand and control confined chemical reactions at the nano scale
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3. |
- Ajuria, Jon, et al.
(author)
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Graphene-based lithium ion capacitor with high gravimetric energy and power densities
- 2017
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In: Journal of Power Sources. - : Elsevier. - 0378-7753 .- 1873-2755. ; 363, s. 422-427
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Journal article (peer-reviewed)abstract
- Hybrid capacitor configurations are now of increasing interest to overcome the current energy limitations of supercapacitors. In this work, we report a lithium ion capacitor (LIC) entirely based on graphene. On the one hand, the negative-battery-type- electrode consists of a self-standing, binder-free 3D macroporous foam formed by reduced graphene oxide and decorated with tin oxide nanoparticles (SnO2-rGO). On the other hand, the positive-capacitor-type- electrode is based on a thermally expanded and physically activated reduced graphene oxide (a-TEGO). For comparison purposes, a symmetric electrical double layer capacitor (EDLC) using the same activated graphene in 1.5 M Et4NBE4/ACN electrolyte is also assembled. Built in 1 M LiPF6 EC:DMC, the graphene-based LIC shows an outstanding, 10-fold increase in energy density with respect to its EDLC counterpart at low discharge rates (up to 200 Wh kg(-1)). Furthermore, it is still capable to deliver double the energy in the high power region, within a discharge time of few seconds.
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4. |
- Andersson, Ove, et al.
(author)
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Phase coexistence and hysteresis effects in the pressure-temperature phase diagram of NH3BH3
- 2011
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In: Physical Review B. Condensed Matter and Materials Physics. - : American Physical Society. - 1098-0121 .- 1550-235X. ; 84:2, s. 024115-
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Journal article (peer-reviewed)abstract
- The potential hydrogen storage compound NH3BH3 has three known structural phases in the temperature and pressure ranges 110–300 K and 0–1.5 GPa, respectively. We report here the boundaries between, and the ranges of stability of, these phases. The phase boundaries were located by in situ measurements of the thermal conductivity, while the actual structures in selected areas were identified by in situ Raman spectroscopy and x-ray diffraction. Below 0.6 GPa, reversible transitions involving only small hysteresis effects occur between the room-temperature tetragonal plastic crystal I4mm phase and the low-temperature orthorhombic Pmn21 phase. Transformations of the I4mm phase into the high-pressure orthorhombic Cmc21 phase, occurring above 0.8 GPa, are associated with very large hysteresis effects, such that the reverse transition may occur at up to 0.5 GPa lower pressures. Below 230 K, a fraction of the Cmc21 phase is metastable to atmospheric pressure, suggesting the possibility that dense structural phases of NH3BH3, stable at room temperature, could possibly be created and stabilized by alloying or by other methods. Mixed orthorhombic Pmn21/Cmc21 phases were observed in an intermediate pressure-temperature range, but a fourth structural phase predicted by Filinchuk et al. [ Phys. Rev. B 79 214111 (2009)] was not observed in the pressure-temperature ranges of this experiment. The thermal conductivity of the plastic crystal I4mm phase is about 0.6 W m−1 K−1 and only weakly dependent on temperature, while the ordered orthorhombic phases have higher thermal conductivities limited by phonon-phonon scattering.
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5. |
- Anoshkin, Ilya, et al.
(author)
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Coronene Encapsulation in Single-Walled Carbon Nanotubes : Stacked Columns, Peapods, and Nanoribbons
- 2014
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In: ChemPhysChem. - : Wiley. - 1439-4235 .- 1439-7641. ; 15:8, s. 1660-1665
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Journal article (peer-reviewed)abstract
- Encapsulation of coronene inside single-walled carbon nanotubes (SWNTs) was studied under various conditions. Under high vacuum, two main types of molecular encapsulation were observed by using transmission electron microscopy: coronene dimers and molecular stacking columns perpendicular or tilted (45-608) with regard to the axis of the SWNTs. A relatively small number of short nanoribbons or polymerized coronene molecular chains were observed. However, experiments performed under an argon atmosphere (0.17 MPa) revealed reactions between the coronene molecules and the formation of hydrogen-terminated graphene nanoribbons. It was also observed that the morphology of the encapsulated products depend on the diameter of the SWNTs. The experimental results are explained by using density functional theory calculations through the energies of the coronene molecules inside the SWNTs, which depend on the orientation of the molecules and the diameter of the tubes.
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6. |
- Araujo, Carlos Moyses, et al.
(author)
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Pressure-induced structural phase transition in NaBH4
- 2005
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In: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 72:5, s. 054125-
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Journal article (peer-reviewed)abstract
- We present a combined experimental and theoretical study of the technologically important NaBH4 compound under high pressure. Using Raman spectroscopy at room temperature, we have found that NaBH4 undergoes a structural phase transformation starting at 10.0 GPa with the pure high-pressure phase being established above 15.0 GPa. In order to compare the Raman data recorded under high pressure with the low-temperature tetragonal phase of NaBH4, we have also performed a cooling experiment. The known order-disorder transition from the fcc to the tetragonal structure was then observed. However, the new high pressure phase does not correspond to this low-temperature structure. Using first-principle calculations based on the density functional theory, we show that the high-pressure phase corresponds to the alpha-LiAlH4–type structure. We have found a good agreement between the measured and calculated transition pressures. Additionally, we present the electronic structure of both the fcc and the high-pressure phases.
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7. |
- Baburin, Igor A, et al.
(author)
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Hydrogen adsorption by perforated graphene
- 2015
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In: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 40:20, s. 6594-6599
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Journal article (peer-reviewed)abstract
- We performed a combined theoretical and experimental study of hydrogen adsorption in graphene systems with defect-induced additional porosity. It is demonstrated that perforation of graphene sheets results in increase of theoretically possible surface areas beyond the limits of ideal defect-free graphene (∼2700 m2/g) with the values approaching ∼5000 m2/g. This in turn implies promising hydrogen storage capacities up to 6.5 wt% at 77 K, estimated from classical Grand canonical Monte Carlo simulations. Hydrogen sorption was studied for the samples of defected graphene with surface area of ∼2900 m2/g prepared using exfoliation of graphite oxide followed by KOH activation. The BET surface area of studied samples thus exceeded the value of single-layered graphene. Hydrogen uptake measured at 77 K and 296 K amounts to 5.5 wt% (30 bar) and to 0.89 wt% (120 bar), respectively.
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8. |
- Barzegar, Hamid Reza, et al.
(author)
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Synthesis of graphene nanoribbons inside boron nitride nanotubes
- 2016
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In: Physica status solidi. B, Basic research. - : Wiley. - 0370-1972 .- 1521-3951. ; 253:12, s. 2377-2379
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Journal article (peer-reviewed)abstract
- We report on bottom-up synthesis of graphene nanoribbons inside boron nitride nanotubes, using coronene molecules as building blocks. The synthesized ribbons are one or two coronene molecules wide, depending on the diameter of the host nanotube. The encapsulated carbon nanostructures can be eliminated from the inner cavity of the filled boron nitride nanotube via oxidation without any damage to the nanotube structure.
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9. |
- Boulanger, Nicolas, et al.
(author)
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Spray deposition of supercapacitor electrodes using environmentally friendly aqueous activated graphene and activated carbon dispersions for industrial implementation
- 2021
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In: ChemElectroChem. - : John Wiley & Sons. - 2196-0216. ; 8:7, s. 1349-1361
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Journal article (peer-reviewed)abstract
- A spray gun machine was used to deposit high‐surface‐area supercapacitor electrodes using green non‐toxic aqueous dispersions based on different kinds of high specific surface area nanostructured carbon materials: activated graphene (a‐rGO) and activated carbon (AC). Tuning the spray conditions and dispersion formulation allowed us to achieve good adhesion to stainless‐steel current collectors in combination with high surface area and a satisfactory mechanical stability of the electrodes. The specific surface area of approximately 2000 m2/g was measured directly on a‐rGO and AC electrodes showing only around a 20 % decrease compared to the precursor powder materials. The performance of the electrodes deposited on stainless‐steel and aluminum current collectors was tested in supercapacitor devices using three electrolytes. The electrodes were tested in an “as‐deposited” state and after post‐deposition annealing at 200 °C. The spray deposition method and post‐deposition annealing are completely compatible with roll‐to‐roll industrial production methods. The a‐rGO demonstrated superior performance compared to AC in supercapacitor electrodes with gravimetric capacitance, energy, and power density parameters, which exceed commercially available analogues. The formulation of the dispersions used in this study is environmentally friendly, as it is based on only on water as a solvent and commercially available non‐toxic additives (graphene oxide, fumed silica, and carbon nanotubes).
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10. |
- Chernov, Alexander I, et al.
(author)
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Optical properties of graphene nanoribbons encapsulated in single-walled carbon nanotubes
- 2013
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In: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 7:7, s. 6346-6353
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Journal article (peer-reviewed)abstract
- We report the photoluminescence (PL) from graphene nanoribbons (GNRs) encapsulated in single-walled carbon nanotubes (SWCNTs). New PL spectral features originating from GNRs have been detected in the visible spectral range. PL peaks from GNRs have resonant character, and their positions depend on the ribbon geometrical structure in accordance with the theoretical predictions. GNRs were synthesized using confined polymerization and fusion of coronene molecules. GNR@SWCNTs material demonstrates a bright photoluminescence both in infrared (IR) and visible regions. The photoluminescence excitation mapping in the near-IR spectral range has revealed the geometry-dependent shifts of the SWCNT peaks (up to 11 meV in excitation and emission) after the process of polymerization of coronene molecules inside the nanotubes. This behavior has been attributed to the strain of SWCNTs induced by insertion of the coronene molecules.
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11. |
- Dmitriev, Vladimir, et al.
(author)
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Pressure-temperature phase diagram of LiBH4: Synchrotron x-ray diffraction experiments and theoretical analysis
- 2008
-
In: Physical Review B. Condensed Matter and Materials Physics. - : American Physical Society. - 1098-0121 .- 1550-235X. ; 77:17
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Journal article (peer-reviewed)abstract
- An in situ combined high-temperature high-pressure synchrotron radiation diffraction study has been carried out on LiBH4. The phase diagram of LiBH4 is mapped to 10 GPa and 500 K, and four phases are identified. The corresponding structural distortions are analyzed in terms of symmetry-breaking atomic position shifts and anion ordering. Group-theoretical and crystal-chemical considerations reveal a nontrivial layered structure of LiBH4. The layers and their deformations define the structural stability of the observed phases.
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12. |
- Dzwilewski, Andrzej, et al.
(author)
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Characterization of phases synthesized close to the boundary of C60 collapse at high temperature high pressure conditions
- 2007
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In: Diamond and related materials. - : Elsevier BV. - 0925-9635 .- 1879-0062. ; 16:8, s. 1550-1556
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Journal article (pop. science, debate, etc.)abstract
- Two sets of samples were synthesized at high pressure high temperature conditions in the P-T region where C-60 molecules collapse into a nearly amorphous graphite-like hard carbon phase. For the first set, heating temperature was varied at fixed pressure and preparation time. For the second set, synthesis time was varied at fixed pressure and fixed temperature. Detailed structural characterization of samples was performed using Raman spectroscopy and powder XRD. Mechanical properties of the samples have been studied by nanoindentation method. It has been found that duration of heat treatment under high pressure is an important parameter which influences the temperature of fullerene cage collapse. Both tetragonal and rhombohedral polymeric phases transform into hard carbon phase over a rather narrow temperature interval, but the tetragonal phase shows somewhat increased stability against C-60 collapse. Viscoelastic mechanical behavior during nanoindentation was observed for fullerene polymers but not for graphite-like hard carbon phase. Possible mechanism for nucleation of the hard carbon phase in polymeric C-60 networks is discussed.
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13. |
- Feicht, Patrick, et al.
(author)
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Systematic evaluation of different types of graphene oxide in respect to variations in their in-plane modulus
- 2017
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In: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 114, s. 700-705
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Journal article (peer-reviewed)abstract
- Graphene oxide samples prepared in various laboratories following a diversity of synthesis protocols based on Brodie's (BGO) and Hummers/Offeman's (HGO) methods were compared in respect of their in plane moduli. A simple wrinkling method allowed for a spatial resolution <1.5 pm by converting the wrinkling frequency. Quite surprisingly, a drastic variation of the in-plane moduli was found spanning the range from 600 GPa for the best BGO types, which is in the region of chemically derived graphene, all the way down to less than 200 GPa for HGO types. This would suggest that there are no two equal GO samples and GO should not be regarded a compound but rather a class of materials with very variable physical properties. While large differences between Brodie's and Hummers/Offeman's types might have been expected, even within the group of Hummers/Offeman's types pronounced differences are observed that, based on C-13 solid-state NMR, were related to over-functionalization versus over-oxidation.
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14. |
- Filinchuk, Yaroslav, et al.
(author)
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Cation Size and Anion Anisotropy in Structural Chemistry of Metal Borohydrides. The Peculiar Pressure Evolution of RbBH4
- 2010
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 49:11, s. 5285-5292
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Journal article (peer-reviewed)abstract
- The pressure evolution of RbBH4 has been characterized by synchrotron powder X-ray diffraction and Raman spectroscopy up to 23 GPa. Diffraction experiments at ambient temperature reveal three phase transitions, at 3.0, 10.4, and 18 GPa (at 2.6, 7.8, and 20 GPa from Raman data), at which the space group symmetry changes in the order Fm-3m(Z=4) → P4/nmm(2) → C222(2) → I-42m(4). Crystal structures and equations of state are reported for all four phases. The three high-pressure structure types are new in the crystal chemistry of borohydrides. RbBH4 polymorphs reveal high coordination numbers (CNs) for cation and anion sites, increasing with pressure from 6 to 8, via an intermediate 4 + 4 coordination. Different arrangements of the tetrahedral BH4 group in the Rb environment define the crystal symmetries of the RbBH4 polymorphs. The structural evolution in the MBH4 series is determined by the cation’s size, as it differs drastically for M = Li (CNs = 4, 6), Na (CN = 6), and Rb. The only structure common to the whole MBH4 family is the cubic one. Its bulk modulus linearly decreases as the ionic radius of M increases, indicating that the compressibility of the material is mainly determined by the repulsive BH4···BH4 interactions.
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15. |
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16. |
- Gorkina, Alexandra L, et al.
(author)
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Transparent and conductive hybrid graphene/carbon nanotube films
- 2016
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In: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 100, s. 501-507
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Journal article (peer-reviewed)abstract
- Carbon nanomaterials (carbon nanotubes (CNTs) and graphene) are promising materials for optoelectronic applications, including flexible transparent and conductive films (TCFs) due to their extraordinary electrical, optical and mechanical properties. However, the performance of CNT- or graphene-only TCFs still needs to be improved. One way to enhance the optoelectrical properties of TCFs is to hybridize CNTs and graphene. This approach leads to creation of a novel material that exhibits better properties than its individual constituents. In this work, the novel hybrid CNT-graphene nanomaterial was fabricated by graphene oxide deposition on top of CNT films. The graphene oxide was then reduced by thermal annealing at ambient atmosphere or in H2 atmosphere. At the final step the CNT-graphene hybrids were chemically doped using gold(III) chloride. As a result, we show that the hybrids demonstrate excellent optoelectrical performance with the sheet resistance as low as 73 Ω/□ at 90% transmittance.
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17. |
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18. |
- Iakunkov, Artem, et al.
(author)
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Swelling of graphene oxide membranes in alcohols : effects of molecule size and air ageing
- 2019
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In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 7:18, s. 11331-11337
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Journal article (peer-reviewed)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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19. |
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20. |
- Klechikov, Alexey G., et al.
(author)
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Hydrogen storage in bulk graphene-related materials
- 2015
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In: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 210, s. 46-51
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Journal article (peer-reviewed)abstract
- Hydrogen sorption properties of graphene-related materials were studied by gravimetric and volumetric methods at 2931< and 77K. Rapid thermal exfoliation of different types of graphite oxide (GO) precursors yielded samples with maximal surface areas up to 850 m(2)/g, whereas surface areas up to 2300 m(2)/g were achieved by post-exfoliation activation treatments. Therefore, hydrogen storage parameters of graphene materials could be evaluated in a broad range of surface areas. The H-2 uptake vs surface area trend revealed in this study shows that hydrogen storage by graphene materials do not exceed 1 Wt% at 120 Bar H-2 at ambient temperatures. Linear increase of hydrogen adsorption vs surface area was observed at 77 K with maximal observed value of similar to 5 Wt% for 2300 m(2)/g sample. It can be concluded that bulk graphene samples obtained using graphite oxide exfoliation and activation follow standard for other nanostructured carbons hydrogen uptake trends and do not demonstrate superior hydrogen storage parameters reported in several earlier studies. Nevertheless, graphene remains to be one of the best materials for physisorption of hydrogen, especially at low temperatures.
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21. |
- Klechikov, Alexey, et al.
(author)
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Graphene decorated with metal nanoparticles : Hydrogen sorption and related artefacts
- 2017
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In: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 250, s. 27-34
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Journal article (peer-reviewed)abstract
- Hydrogen sorption by reduced graphene oxides (r-GO) is not found to increase after decoration with Pd and Pt nanoparticles. Treatments of metal decorated samples using annealing under hydrogen or air were tested as a method to create additional pores by effects of r-GO etching around nanoparticles. Increase of Specific Surface Area (SSA) was observed for some air annealed r-GO samples. However, the same treatments applied to activated r-GO samples with microporous nature and higher surface area result in breakup of structure and dramatic decrease of SSA. Our experiments have not revealed effects which could be attributed to spillover in hydrogen sorption on Pd or Pt decorated graphene. However, we report irreversible chemisorption of hydrogen for some samples which can be mistakenly assigned to spillover if the experiments are incomplete.
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22. |
- Klechikov, Alexey, 1989-
(author)
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Graphite oxides for preparation of graphene related materials : structure, chemical modification and hydrogen storage properties
- 2018
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Doctoral thesis (other academic/artistic)abstract
- Carbon materials have been studied for hydrogen storage for decades, but they showed too low capacity at ambient temperature compared to target values for practical applications. This thesis includes two parts. First one is fundamental study of graphite oxides (GO) structure and properties. Second part is focused on hydrogen storage properties of graphene related materials prepared using GO as a precursor.We studied the effects of synthesis methods and oxidation degree on solvation/intercalation properties of GOs. New effect of temperature induced reversible delamination was observed for Hummers GO (HGO) immersed in liquid acetonitrile. Experiments with swelling of Brodie GO (BGO) in 1-octanol revealed parallel orientation of the intercalated solvent molecules relative to graphene oxide (GnO) layers. Chemical functionalization of GO in swelled state allowed us to synthesize the materials with subnanometer slit pores supported by molecular pillars. Structure and properties of pillared GO were characterized by variety of methods. Swelling properties of multilayered GnO membranes were compared to properties of precursor GO. GnO membranes were found to swell similarly to GO powders in some solvents and rather differently in other. Our experiments revealed important limitations in application of GO membranes for nanofiltration. Several parameters were found to affect the size of permeation “channels” provided by interlayers of GnO membrane structure: e.g. nature of solvent, pH of solutions and concentration of solutes.Hydrogen storage parameters were studied for a set of graphene related materials with broad range of surface areas (SSA) (200 - 3300 m2/g). Hydrogen sorption weight percent (wt%) is found to correlate with SSA for all studied graphene materials following the trend standard for other nanostructured carbon materials. The highest hydrogen uptakes of ~1.2 wt% at 296 K and ~7.5 wt% at 77 K were measured for graphene material with SSA of over 3000 m2/g. Addition of Pd and Pt nanoparticles to graphene materials did not resulted in improvement of hydrogen storage compared to nanoparticles-free samples. No deviation from the standard wt% vs. SSA trends was also observed for pillared GO materials. Therefore, hydrogen storage properties of graphene related materials at room temperatures are not confirmed to be exceptional. However, high surface area graphene materials are found to be among the best materials for physisorption of hydrogen at liquid nitrogen temperature. Moreover, hydrogen storage capacity of 4 wt%, comparable to target values, was observed at temperature of solid CO2 (193 K) which can be maintained using common refrigeration methods.
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23. |
- Klechikov, Alexey, et al.
(author)
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Hydrogen storage in high surface area graphene scaffolds
- 2015
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In: Chemical Communications. - : Royal Society of Chemistry. - 1359-7345 .- 1364-548X. ; 51:83, s. 15280-15283
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Journal article (peer-reviewed)abstract
- Using an optimized KOH activation procedure we prepared highly porous graphene scaffold materials with SSA values up to 3400 m2 g−1 and a pore volume up to 2.2 cm3 g−1, which are among the highest for carbon materials. Hydrogen uptake of activated graphene samples was evaluated in a broad temperature interval (77–296 K). After additional activation by hydrogen annealing the maximal excess H2 uptake of 7.5 wt% was obtained at 77 K. A hydrogen storage value as high as 4 wt% was observed already at 193 K (120 bar H2), a temperature of solid CO2, which can be easily maintained using common industrial refrigeration methods.
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24. |
- Klechikov, Alexey, et al.
(author)
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Multilayered intercalation of 1-octanol into Brodie graphite oxide
- 2017
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In: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 9:20, s. 6929-6936
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Journal article (peer-reviewed)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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25. |
- Klechikov, Alexey, et al.
(author)
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Structure of graphene oxide membranes in solvents and solutions
- 2015
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In: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3372 .- 2040-3364. ; 7:37, s. 15374-15384
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Journal article (peer-reviewed)abstract
- The change of distance between individual graphene oxide sheets due to swelling is the key parameter to explain and predict permeation of multilayered graphene oxide (GO) membranes by various solvents and solutions. In situ synchrotron X-ray diffraction study shows that swelling properties of GO membranes are distinctly different compared to precursor graphite oxide powder samples. Intercalation of liquid dioxolane, acetonitrile, acetone, and chloroform into the GO membrane structure occurs with maximum one monolayer insertion (Type I), in contrast with insertion of 2-3 layers of these solvents into the graphite oxide structure. However, the structure of GO membranes expands in liquid DMSO and DMF solvents similarly to precursor graphite oxide (Type II). It can be expected that Type II solvents will permeate GO membranes significantly faster compared to Type I solvents. The membranes are found to be stable in aqueous solutions of acidic and neutral salts, but dissolve slowly in some basic solutions of certain concentrations, e.g. in NaOH, NaHCO3 and LiF. Some larger organic molecules, alkylamines and alkylammonium cations are found to intercalate and expand the lattice of GO membranes significantly, e.g. up to similar to 35 angstrom in octadecylamine/methanol solution. Intercalation of solutes into the GO structure is one of the limiting factors for nano-filtration of certain molecules but it also allows modification of the inter-layer distance of GO membranes and tuning of their permeation properties. For example, GO membranes functionalized with alkylammonium cations are hydrophobized and they swell in non-polar solvents.
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