| 1. |
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| 2. |
- Abou-Hamad, Edy, et al.
(författare)
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Hydrogenation of C-60 in Peapods: Physical Chemistry in Nano Vessels
- 2009
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Ingår i: 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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Tidskriftsartikel (refereegranskat)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.
(författare)
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Graphene-based lithium ion capacitor with high gravimetric energy and power densities
- 2017
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Ingår i: Journal of Power Sources. - : Elsevier. - 0378-7753 .- 1873-2755. ; 363, s. 422-427
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Phase coexistence and hysteresis effects in the pressure-temperature phase diagram of NH3BH3
- 2011
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - : American Physical Society. - 1098-0121 .- 1550-235X. ; 84:2, s. 024115-
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Coronene Encapsulation in Single-Walled Carbon Nanotubes : Stacked Columns, Peapods, and Nanoribbons
- 2014
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Ingår i: ChemPhysChem. - : Wiley. - 1439-4235 .- 1439-7641. ; 15:8, s. 1660-1665
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Pressure-induced structural phase transition in NaBH4
- 2005
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 72:5, s. 054125-
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Hydrogen adsorption by perforated graphene
- 2015
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Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 40:20, s. 6594-6599
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Synthesis of graphene nanoribbons inside boron nitride nanotubes
- 2016
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Ingår i: Physica status solidi. B, Basic research. - : Wiley. - 0370-1972 .- 1521-3951. ; 253:12, s. 2377-2379
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Tidskriftsartikel (refereegranskat)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.
(författare)
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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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Ingår i: ChemElectroChem. - : John Wiley & Sons. - 2196-0216. ; 8:7, s. 1349-1361
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Optical properties of graphene nanoribbons encapsulated in single-walled carbon nanotubes
- 2013
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 7:7, s. 6346-6353
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Pressure-temperature phase diagram of LiBH4: Synchrotron x-ray diffraction experiments and theoretical analysis
- 2008
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - : American Physical Society. - 1098-0121 .- 1550-235X. ; 77:17
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Tidskriftsartikel (refereegranskat)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.
(författare)
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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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Ingår i: Diamond and related materials. - : Elsevier BV. - 0925-9635 .- 1879-0062. ; 16:8, s. 1550-1556
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Tidskriftsartikel (populärvet., debatt m.m.)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.
(författare)
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Systematic evaluation of different types of graphene oxide in respect to variations in their in-plane modulus
- 2017
-
Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 114, s. 700-705
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Cation Size and Anion Anisotropy in Structural Chemistry of Metal Borohydrides. The Peculiar Pressure Evolution of RbBH4
- 2010
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 49:11, s. 5285-5292
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Transparent and conductive hybrid graphene/carbon nanotube films
- 2016
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Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 100, s. 501-507
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Tidskriftsartikel (refereegranskat)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.
(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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| 19. |
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| 20. |
- Klechikov, Alexey G., et al.
(författare)
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Hydrogen storage in bulk graphene-related materials
- 2015
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 210, s. 46-51
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Tidskriftsartikel (refereegranskat)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.
(författare)
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Graphene decorated with metal nanoparticles : Hydrogen sorption and related artefacts
- 2017
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 250, s. 27-34
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Tidskriftsartikel (refereegranskat)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-
(författare)
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Graphite oxides for preparation of graphene related materials : structure, chemical modification and hydrogen storage properties
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)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.
(författare)
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Hydrogen storage in high surface area graphene scaffolds
- 2015
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Ingår i: Chemical Communications. - : Royal Society of Chemistry. - 1359-7345 .- 1364-548X. ; 51:83, s. 15280-15283
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Tidskriftsartikel (refereegranskat)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.
(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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| 25. |
- Klechikov, Alexey, et al.
(författare)
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Structure of graphene oxide membranes in solvents and solutions
- 2015
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3372 .- 2040-3364. ; 7:37, s. 15374-15384
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Tidskriftsartikel (refereegranskat)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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| 26. |
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| 27. |
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| 28. |
- Luzan, Serhiy, et al.
(författare)
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Hydration of graphite oxide in electrolyte and non-electrolyte solutions
- 2011
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Ingår i: The Journal of Physical Chemistry C. - Washington DC : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 115:50, s. 24611-24614
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Tidskriftsartikel (refereegranskat)abstract
- Pressure induced insertion of liquid media was studied for graphite oxide (GO) immersed in excess amounts of aqueous copper acetate and sucrose solutions and compared to previous experiments with GO immersed in solute-free water media. Compression of GO in copper acetate solution resulted in significant enhancement of high pressure anomaly compared to pure water: interlayer distance reached 17.4 Å at 2.3 GPa while for pure water the maximal observed layer separation was 13.08 Å. Compression of GO in sucrose solution was found to be very similar to compression in solute-free water. These results confirm that copper ions can be pressure-inserted into GO structure while the expansion of structure is attributed to osmotic swelling. Sucrose dissolves in water in molecular form (nonelectrolyte) which results in weaker absorption into the GO structure and the absence of osmotic swelling. Pressure induced insertion of various solutions into the GO structure could possibly be promising for synthesis of new graphite intercalation materials or graphene-related composites.
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| 29. |
- Luzan, Serhiy, 1985-, et al.
(författare)
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Hydrogen adsorption in Pt catalyst/MOF-5 materials
- 2010
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier. - 1387-1811 .- 1873-3093. ; 135:1-3, s. 201-205
-
Tidskriftsartikel (refereegranskat)abstract
- Hydrogen adsorption properties of well-known MOF-5 were studied at near ambient temperature and hydrogen pressures up to 120 bar. Pristine material was doped with Pt catalysts supported on activated carbon (AC) using two previously described procedures: physical mixture of a catalyst with MOF-5 and “bridging” procedure (MOF-5 and catalyst particles connected via carbon bridges) MOF-5. The maximum hydrogen adsorption measured on doped MOF-5 was 0.43 wt.%. These values are on the same level or even less than for catalyst free MOF-5 material. Therefore, doping of MOF-5 material with Pt catalyst has not resulted in increase of hydrogen storage value. Hydrogen adsorption for the samples with added catalyst showed correlation with BET surface area, exhibited isotherms typical for physisorption and no features which could be assigned to spillover effect.
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| 30. |
- Luzan, Serhiy, 1985-, et al.
(författare)
-
Hydrogen storage in Co-and Zn-based metal-organic frameworks at ambient temperature
- 2009
-
Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 34:24, s. 9754-9759
-
Tidskriftsartikel (refereegranskat)abstract
- Hydrogen adsorption properties of some Co-and Zn-based Metal-Organic Framework (MOF) materials were studied at near ambient temperatures. Maximal hydrogen storage capacity of 0.75 wt% was found for a Zn-based material at 175 Bar hydrogen pressure and T = -4 degrees C. Hydrogen adsorption correlated linearly with BET surface area and strongly depends on temperature. Relatively low structural stability of some MOF's results in framework collapse during degassing and hydrogen adsorption measurements.
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| 31. |
- Luzan, Serhiy M, 1985-, et al.
(författare)
-
Effect of catalysts on the reaction of C60 with hydrogen
- 2012
-
Ingår i: Fullerenes, nanotubes, and carbon nanostructures. - : Taylor & Francis Group. - 1536-383X .- 1536-4046. ; 20:4-7, s. 319-323
-
Tidskriftsartikel (refereegranskat)abstract
- The reaction of C-60/catalyst with hydrogen gas was studied at 400 degrees C and 50 bar of H-2 pressure. The addition of Pt- or Ni-catalysts significantly accelerated kinetics of the hydrogenation reaction and resulted in a dramatic change of the C60Hx crystal structure. Samples reacted without catalyst preserved the fcc structure typical for pristine C-60 but with expanded unit cells. Fulleranes C60Hx obtained using catalytic hydrogenation exhibited not only the fcc structure (at relatively low hydrogenation degree) but also the bcc structure of C60Hx (with x > 18). The bcc structure corresponds to highly hydrogenated material with an average volume per C-60 molecule of 817-849 angstrom(3).
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| 32. |
- Luzan, Serhiy, 1985-
(författare)
-
Materials for Hydrogen storage and synthesis of new materials by hydrogenation
- 2012
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The search for new materials for hydrogen storage is important for the development of future hydrogen energy applications. In this Thesis, it is shown that new materials with interesting properties can be synthesized by the reaction of hydrogen with various nanocarbon precursors. The thesis consists of two parts. The first part is devoted to studies of hydrogen storage in some metal-organic frameworks (MOFs) and nanostructured carbon materials, while the second part describes synthesis of new materials by the reaction of hydrogen gas with various carbon materials (i.e. fullerene C60, single-walled carbon nanotubes (SWCNTs), and fullerene C60 encapsulated inside SWCNTs (C60@SWCNTs)).Hydrogen adsorption was measured for a set of Zn- and Co-based MOFs at near ambient temperatures. MOFs synthesized using different metal clusters and organic connecting ligands allowed to study effects of different surface area, pore volume, and pore shapes on hydrogen storage parameters. Hydrogen adsorption values in the studied MOFs correlated well with surface area and pore volume but did not exceed 0,75wt.%. Therefore, new methods to improve the hydrogen storage capacity in MOFs were investigated. The addition of metal catalysts was previously reported to improve significantly hydrogen storage in MOFs. In this thesis the effect of Pt catalyst addition on hydrogen adsorption in MOF-5 was not confirmed. Contrary to previous reports, hydrogen adsorption in MOF-5 mixed/modified with Pt catalysts had fast kinetics, correlated well with surface area, and was on the same level as for unmodified MOF-5. New nanostructured carbon materials were synthesized by the reaction between fullerene C60 and coronene/anthracene. Despite negligible surface area these materials adsorbed up to 0,45wt.% of hydrogen at ambient temperatures.The reaction of fullerene C60 with hydrogen gas was studied at elevated temperatures and hydrogen pressures. In situ gravimetric monitoring of the reaction was performed in a broad temperature interval with/without addition of metal catalysts (i.e. Pt and Ni). The reaction resulted in synthesis of hydrogenated fullerenes C60Hx (with x≤56) followed by fullerene cage fragmentation and collapse upon prolonged duration of hydrogen treatment. Possible mechanisms of C60 hydrogenation and fragmentation were discussed. It is demonstrated that reaction of SWCNTs with hydrogen gas at elevated temperatures and hydrogen pressures can be used for nanotube opening, purification from amorphous carbon, side-wall hydrogenation, and partial unzipping of SWCNTs. Some graphene nanoribbons (GNRs) were synthesized as the result of SWCNTs unzipping. A surprising ability of hydrogen to penetrate inside SWNTs and to react with encapsulated fullerene C60 was demonstrated.
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| 33. |
- Luzan, Serhiy, 1985-, et al.
(författare)
-
Reaction of C60 with Hydrogen gas : In Situ monitoring and pathways
- 2011
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 115:23, s. 11484-11492
-
Tidskriftsartikel (refereegranskat)abstract
- Kinetics and pathways of C60 reaction with hydrogen gas were studied in a broad temperature interval and over extended periods of time. Specifically, hydrogenation was monitored in situ at high temperature and high hydrogen pressure conditions using the gravimetric method. The shape of gravimetric curve was found to depend on hydrogenation temperature: at 350–400 °C saturation of the sample weight was achieved, whereas at 420–440 °C the sample weight reached the maximum and decreased upon prolonged hydrogenation. The weight decrease is due to fullerene cage fragmentation with formation of light hydrocarbons evaporating from the sample. Hydrogenation products were studied by X-ray diffraction, MALDI TOF and APPI FT-ICR mass spectrometry, liquid chromatography, and elemental analysis. Hydrogenation pathways (from C60H18 up to C60H56) and possible mechanisms of hydrogenation-induced fragmentation of fulleranes are discussed.
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| 34. |
- Luzan, Serhiy, 1985-, et al.
(författare)
-
Thermal decomposition of C60H18
- 2009
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 113:30, s. 13133-13138
-
Tidskriftsartikel (refereegranskat)abstract
- Products of thermal dehydrogenation of C 60H18(which mainly occurs at 450-600°C) were studied by XRD, Raman, IR and mass spectrometry. IR spectra indicate that dehydrogenation resulted in partial recovery of pristine C 60. XRD data indicate that the cell parameter of the face-centered cubic structure, which is higher for C 60H18(14.55 Å) than for C60(14.17 Å), remained higher following heat treatment, and heating at>500° C caused further expansion (to 14.78 Å). The increase in the cell parameter correlates with the beginning of partial fullerene cage collapse (corroborated by IR, Raman and MS data) and is suggested to result from “self-doping”.
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| 35. |
- Martin, Natalia M., et al.
(författare)
-
High-temperature reactions of C60 with polycyclic aromatic hydrocarbons
- 2010
-
Ingår i: Chemical Physics. - : Elsevier. - 0301-0104 .- 1873-4421. ; 368:1-2, s. 49-57
-
Tidskriftsartikel (refereegranskat)abstract
- Fullerenes are proposed as a precursor for preparation of nanocarbon materials using controlled collapse of cage structure by high temperature reaction with polycyclic aromatic hydrocarbons. The chemical modification of C60 by reaction with anthracene and coronene was studied over a broad temperature interval. The products of the reaction were characterized by X-ray diffraction, and Raman and IR spectroscopy. Mono- and multi-adducts of C60 with anthracene were obtained in the temperature interval 290–400 °C. Above 400 °C the C60 adducts are not stable and decompose back to C60 and anthracene. No chemical adducts of C60 with coronene were found below 500 °C. Above this temperature fullerite structure was found to expand reflecting interaction with coronene melt and vapor. The reactions of C60 with anthracene and C60 with coronene at temperatures above 650 °C resulted in fullerene cage collapse and formation of nanocarbons. These nanocarbons were found to store up to 0.45 wt% of hydrogen at ambient temperatures despite negligible surface area.
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| 36. |
- Mercier, Guillaume, et al.
(författare)
-
Porous Graphene Oxide/Diboronic Acid Materials : Structure and Hydrogen Sorption
- 2015
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:49, s. 27179-27191
-
Tidskriftsartikel (refereegranskat)abstract
- Solvothermal reaction of graphite oxide (GO) with benzene-1,4-diboronic acid (DBA) was reported previously to result in formation of graphene oxide framework (GOP) materials. The theoretical structure of GOFs consists of graphene layers separated by benzene-diboronic "pillars" with similar to 1 nm slit pores thus providing the opportunity to use it as a model material to verify the effect of a small pore size on hydrogen adsorption. A set of samples with specific surface area (SSA) in the range of similar to 50-1000 m(2)/g were prepared using variations of synthesis conditions and GO/DBA proportions. Hydrogen storage properties of GOF samples evaluated at 293 and 77 K were found to be similar to other nanocarbon trends in relation to SSA values. Structural characterization of GO/DBA samples showed all typical features reported as evidence for formation of a framework structure such as expanded interlayer distance, increased temperature of thermal exfoliation, typical features in FTIR spectra, etc. However, the samples also exhibited reversible swelling in polar solvents which is not compatible with the idealized GOF structure linked by benzenediboronic molecular pillars. Therefore, possible alternative nonframework models of structures with pillars parallel and perpendicular to GO planes are considered.
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| 37. |
- Nordenstrom, Andreas, et al.
(författare)
-
Thermally reduced pillared GO with precisely defined slit pore size
- 2020
-
Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 10:12, s. 6831-6839
-
Tidskriftsartikel (refereegranskat)abstract
- Graphene oxide (GO) pillared with tetrakis(4-aminophenyl)methane (TKAM) molecules shows a narrow distribution of pore size, relatively high specific surface area, but it is hydrophilic and electrically not conductive. Analysis of XRD, N-2 sorption, XPS, TGA and FTIR data proved that the pillared structure and relatively high surface area (similar to 350 m(2) g(-1)) are preserved even after thermal reduction of GO pillared with TKAM molecules. Unlike many other organic pillaring molecules, TKAM is stable at temperatures above the point of GO thermal reduction, as demonstrated by TGA. Therefore, gentle annealing results in the formation of reduced graphene oxide (rGO) pillared with TKAM molecules. The TKAM pillared reduced graphene oxide (PrGO/TKAM) is less hydrophilic as found using dynamic vapor sorption (DVS) and more electrically conductive compared to pillared GO, but preserves an increased interlayer-distance of about 12 angstrom (compared to similar to 7.5 angstrom in pristine GO). Thus we provide one of the first examples of porous rGO pillared with organic molecules and well-defined size of hydrophobic slit pores. Analysis of pore size distribution using nitrogen sorption isotherms demonstrates a single peak for pore size of similar to 7 angstrom, which makes PrGO/TKAM rather promising for membrane and molecular sieve applications.
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| 38. |
- Nordenström, Andreas, et al.
(författare)
-
Intercalation of dyes in graphene oxide thin films and membranes
- 2021
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:12, s. 6877-6885
-
Tidskriftsartikel (refereegranskat)abstract
- Intercalation of dyes into thin multilayered graphene oxide (GO) films was studied by neutron reflectivity and X-ray diffraction. Methylene blue (MB) penetrates the interlayer space of GO in ethanol solution and remains intercalated after the solvent evaporation, as revealed by the expansion of the interlayer lattice and change in chemical composition. The sorption of MB by thin GO films is found to be significantly stronger compared to the sorption of Crystal violet (CV) and Rose bengal (RB). This effect is attributed to the difference in the geometrical shape of planar MB and essentially nonflat CV and RB molecules. Graphite oxides and restacked GO films are found to exhibit different methylene blue (MB) sorptions. MB sorption by precursor graphite oxide and thin spin-coated films of GO is significantly stronger compared to freestanding micrometer-thick membranes prepared by vacuum filtration. Nevertheless, the sorption capacity of GO membranes is sufficient to remove a significant part of the MB from diluted solutions tested for permeation in several earlier studies. High sorption capacity results in strong modification of the GO structure, which is likely to affect permeation properties of GO membranes. Therefore, MB is not suitable for testing size exclusion effects in the permeation of GO membranes. It is not only hydration or solvation diameter but also the exact geometrical shape of molecules that needs to be taken into account considering size effects for penetration of molecules between GO layers in membrane applications.
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| 39. |
- Quesnel, Etienne, et al.
(författare)
-
Graphene-based technologies for energy applications, challenges and perspectives
- 2015
-
Ingår i: Current Opinion in Chemical Engineering. - : IOP Publishing. - 2211-3398. ; 2:3, s. 1-16
-
Tidskriftsartikel (refereegranskat)abstract
- Here we report on technology developments implemented into the Graphene Flagship European project for the integration of graphene and graphene-related materials (GRMs) into energy application devices. Many of the technologies investigated so far aim at producing composite materials associating graphene or GRMs with either metal or semiconducting nanocrystals or other carbon nanostructures (e.g., CNT, graphite). These composites can be used favourably as hydrogen storage materials or solar cell absorbers. They can also provide better performing electrodes for fuel cells, batteries, or supercapacitors. For photovoltaic (PV) electrodes, where thin layers and interface engineering are required, surface technologies are preferred. We are using conventional vacuum processes to integrate graphene as well as radically new approaches based on laser irradiation strategies. For each application, the potential of implemented technologies is then presented on the basis of selected experimental and modelling results. It is shown in particular how some of these technologies can maximize the benefit taken from GRM integration. The technical challenges still to be addressed are highlighted and perspectives derived from the running works emphasized.
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| 40. |
- Rezania, B., et al.
(författare)
-
Hydration of bilayered graphene oxide
- 2014
-
Ingår i: Nano letters (Print). - : American Chemical Society (ACS). - 1530-6984 .- 1530-6992. ; 14:7, s. 3993-3998
-
Tidskriftsartikel (refereegranskat)abstract
- The hydration of graphene oxide (GO) membranes is the key to understand their remarkable selectivity in permeation of water molecules and humidity-dependent gas separation. We investigated the hydration of single GO layers as a function of humidity using scanning force microscopy, and we determined the single interlayer distance from the step height of a single GO layer on top of one or two GO layers. This interlayer distance grows gradually by approximately 1 A upon a relative humidity (RH) increase in the range of 2 to similar to 80% and the immersion into liquid water increases the interlayer distance further by another 3 A. The gradual expansion of the single interlayer distance is in good agreement with the averaged distance measured by X-ray diffraction on multilayered graphite oxides, which is commonly explained with an interstratification model. However, our experimental design excludes effects connected to interstratification. Instead we determine directly if insertion of water into GO occurs strictly by monolayers or the thickness of GO layers changes gradually. We find that hydration with up to 80% RH is a continuous process of incorporation of water molecules into single GO layers, while liquid water inserts as monolayers. The similarity of hydration for our bilayer and previously reported multilayered materials implies GO few and even bilayers to be suitable for selective water transport.
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| 41. |
- Skrypnychuk, Vasyl, 1986-, et al.
(författare)
-
Aqueous activated graphene dispersions for deposition of high-surface area supercapacitor electrodes
- 2020
-
Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 11:8, s. 3032-3038
-
Tidskriftsartikel (refereegranskat)abstract
- High-surface area activated graphene has a three-dimensional porous structure that makes it difficult to prepare dispersions. Here we report a general approach that allows the preparation of stable water-based dispersions/inks at concentrations of ≲20 mg/mL based on activated graphene using environmentally friendly formulations. Simple drying of the dispersion on the substrate allows the preparation of electrodes that maintain the high specific surface area of the precursor material (∼1700 m2/g). The electrodes are flexible because of the structure that consists of micrometer-sized activated graphene grains interconnected by carbon nanotubes (CNTs). The electrodes prepared using activated graphene demonstrate performance superior to that of reduced graphene oxide in supercapacitors with KOH and TEA BF4/acetonitrile electrolytes providing specific capacitance values of 180 and 137 F/g, respectively, at a specific current of 1 A/g. The high surface area of activated graphene in combination with the good conductivity of CNTs allows an energy density of 35.6 Wh/kg and a power density of 42.2 kW/kg to be achieved. The activated graphene dispersions were prepared in liter amounts and are compatible with most industrial deposition methods.
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| 42. |
- Skrypnychuk, Vasyl, 1986-
(författare)
-
Vertical charge transport in conjugated polymers
- 2017
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Conjugated polymers are novel organic electronic materials highly important for organic photovoltaic applications. Charge transport is one of the key properties which defines the performance of conjugated polymers in electronic devices.This work aims to explore the charge transport anisotropy in thin films of P3HT, one of the most common conjugated polymers. Using X-ray diffraction techniques and charge transport measurements, the relation between vertical charge transport through thin P3HT films and structure of the films was established.It was shown that particular orientations of crystalline domains of P3HT, namely face-on and chain-on, are beneficial for vertical charge transport. These orientations provide the efficient pathways for the charges to be transported vertically, either via π-π stacking interaction between the adjacent conjugated chains, or via the conjugated chain backbones. It was also demonstrated that particular orientations of crystallites are favourable for the formation of interconnected percolated pathways providing enhanced vertical charge transport across the film.Deposition of P3HT on most commonly used silicon substrates typically results in the formation of mostly edge-on orientation of crystallites which is unfavourable for vertical charge transport. Nanoimprint lithography was demonstrated as a powerful processing method for reorienting the edge-on crystalline domains of P3HT into chain-on (vertical) orientation. It is also shown that thin P3HT films with preferentially face-on orientations of crystallites can be deposited on graphene surface by spin coating.Using patterning of thin P3HT films by nanoimprint lithography, unprecedentedly high average vertical mobilities in the range of 3.1-10.6 cm2 V-1 s-1 were achieved in undoped P3HT.These results demonstrate that charge transport in thin films of a relatively simple and well-known conjugated polymer P3HT can be significantly improved using optimization of crystallinity,orientation of crystallites, polymer chain orientation and alignment in the films.
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| 43. |
- Sun, Jinhua, et al.
(författare)
-
A Molecular Pillar Approach To Grow Vertical Covalent Organic Framework Nanosheets on Graphene : Hybrid Materials for Energy Storage
- 2018
-
Ingår i: Angewandte Chemie International Edition. - : John Wiley & Sons. - 1433-7851 .- 1521-3773. ; 57:4, s. 1034-1038
-
Tidskriftsartikel (refereegranskat)abstract
- Hybrid 2D–2D materials composed of perpendicularly oriented covalent organic frameworks (COFs) and graphene were prepared and tested for energy storage applications. Diboronic acid molecules covalently attached to graphene oxide (GO) were used as nucleation sites for directing vertical growth of COF-1 nanosheets (v-COF-GO). The hybrid material has a forest of COF-1 nanosheets with a thickness of 3 to 15 nm in edge-on orientation relative to GO. The reaction performed without molecular pillars resulted in uncontrollable growth of thick COF-1 platelets parallel to the surface of GO. The v-COF-GO was converted into a conductive carbon material preserving the nanostructure of precursor with ultrathin porous carbon nanosheets grafted to graphene in edge-on orientation. It was demonstrated as a high-performance electrode material for supercapacitors. The molecular pillar approach can be used for preparation of many other 2D-2D materials with control of their relative orientation.
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| 44. |
- Sun, Jinhua, et al.
(författare)
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Exactly matched pore size for the intercalation of electrolyte ions determined using the tunable swelling of graphite oxide in supercapacitor electrodes
- 2018
-
Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 10:45, s. 21386-21395
-
Tidskriftsartikel (refereegranskat)abstract
- The intercalation of solvent molecules and ions into sub-nanometer-sized pores is one of the most disputed subjects in the electrochemical energy storage applications of porous materials. Here, we demonstrate that the temperature- and concentration-dependent swelling of graphite oxide (GO) can be used to determine the smallest pore size required for the intercalation of electrolyte ions into hydrophilic pores. The structure of Brodie graphite oxide (BGO) in acetonitrile can be temperature-switched between the ambient one-layer solvate with an interlayer distance of approximate to 8.9 angstrom and the two-layer solvate (approximate to 12.5 angstrom) at low temperature, thus providing slit pores of approximately 2.5 and 6 angstrom. Using in situ synchrotron radiation X-ray diffraction (XRD) and the temperature dependence of capacitance in supercapacitor devices, we found that solvated tetraethylammonium tetrafluoroborate (TEA-BF4) ions do not penetrate into both the 2.5 and 6 angstrom slit pores formed by BGO interlayers. However, increasing the electrolyte concentration results in the formation of a new phase at low temperature. This phase shows a distinct interlayer distance of approximate to 15-16.6 angstrom, which corresponds to the insertion of partly desolvated TEA-BF4 ions. Therefore, the remarkable ability of the GO structure to adopt variable interlayer distances allows for the determination of pore sizes that are optimal for solvated TEA-BF4 ions (about 9-10 angstrom). The intercalation of TEA-BF4 ions into the BGO structure is also detected as an anomaly in the temperature dependence of supercapacitor performance. The BGO structure remains to be expanded, even after the removal of acetonitrile, adopting an interlayer distance of approximate to 10 angstrom.
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| 45. |
- Sun, Jinhua, et al.
(författare)
-
Porous graphite oxide pillared with tetrapod-shaped molecules
- 2017
-
Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 120, s. 145-156
-
Tidskriftsartikel (refereegranskat)abstract
- Porous pillared graphene oxide (GO) materials were prepared using solvothermal reaction of Hummers GO with solution of Tetrakis(4-aminophenyl)methane (TKAm) in methanol. The intercalation of TKAm molecules between individual GO sheets, performed under swelling condition, results in expansion of inter-layer distance of GO from ∼7.5 Å to 13-14 Å. Pillaring GO with bulky, rigid 3D shaped TKAm molecules could be an advantage for the preparation of stable pillared structures compared to e.g. aliphatic or aromatic diamines. Insertion of TKAm molecules into inter-layer space of GO results in formation of interconnected network of sub-nanometer slit pores. The expanded GO structure prepared with optimized GO/TKAm composition shows Specific Surface Area (SSA) up to 660 m2/g which is among the highest reported for GO materials pillared using organic spacers. Modelling of GO structures pillared with TKAm molecules shows that maximal SSA of about 2300 m2/g is theoretically possible for realistic concentration of pillaring molecules in GO interlayers. Hydrogen sorption by pillared GO/TKAm is found to follow standard correlation with SSA both at ambient and liquid nitrogen temperatures with highest uptakes of 1.66 wt% achieved at 77 K and 0.25 wt% at 295 K. Our theoretical simulations show that pillared GO structures do not provide improvement of hydrogen storage beyond well-established physisorption trends even for idealized materials with subnanometer pores and SSA of 2300–3700 m2/g.
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| 46. |
- Sundqvist, Bertil, et al.
(författare)
-
Complex hydrides studied by Raman spectroscopy and thermal conductivity measurements under high pressure
- 2006
-
Ingår i: Hydrogen Storage Technologies. - Warrendale : Materials Research Society. ; , s. 7-12
-
Konferensbidrag (refereegranskat)abstract
- The pressure-temperature phase diagrams of alkali metal alanates and borohydrides are of large current interest, and we have recently studied phase transformations under pressure in several of these materials. We here report Raman studies of KBH4 under pressure at room temperature, showing a phase transition near 6 GPa. Although no structural information is yet available, the similarity between KBH4 and NaBH4 suggests the new structure is orthorhombic. We also report studies on LiBH4 showing that the high pressure phase of this material is metastable to zero pressure below 200 K.
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| 47. |
- Sundqvist, Bertil, et al.
(författare)
-
Low temperature phase diagram of NH3BH3
- 2011
-
Ingår i: Materials Research Society Symposium Proceedings. - : Cambridge University Press.
-
Konferensbidrag (refereegranskat)abstract
- The pressure-temperature (p-T) phase diagram of NH3BH3 has been investigated by thermal conductivity measurements up to 1.5 GPa at temperatures between 100 and 300 K, and the phase boundaries between the three known structural phases have been identified. The transformation between the room temperature tetragonal I4mm phase and the low temperature orthorhombic Pmn21 phase (Tc = 218 K at p = 0) shows only a small hysteresis. The transformation into the high pressure orthorhombic Cmc21 phase (at 1.0 GPa near 292 K) has a very strong hysteresis, up to Δp = 0.5 GPa, and below 230 K a fraction of this phase is metastable even at atmospheric pressure.
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| 48. |
- Sundqvist, Bertil, et al.
(författare)
-
Phase transitions in hydrogen storage compounds under pressure
- 2007
-
Ingår i: Journal of Physics Condensed Matter, vol. 19, issue 42. - Bristol : Intitute of Physics. ; , s. 425201-
-
Konferensbidrag (refereegranskat)abstract
- Solid, hydrogen-rich compounds, such as alkali metal hydrides, MAH4, where M is an alkali metal and A is boron or aluminium, may be used for hydrogen storage. We briefly review recent high-pressure work in this field aimed at exploring the phase behaviour, and especially the possibility to find highly dense new structures. In particular we present experimental data on the structure, lattice dynamics, phase diagrams, and thermal properties obtained by us and others by Raman scattering, x-ray diffraction, and thermal conductivity measurements under pressure between 100 and 400 K. From these data and the results of theoretical calculations we map observed structural phases and phase transitions in the pressure–temperature plane for the materials that have so far been investigated under pressure.
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| 49. |
- Szabó, Tamás, et al.
(författare)
-
Stability and dye inclusion of graphene oxide/polyelectrolyte layer-by-layer self-assembled films in saline, acidic and basic aqueous solutions
- 2017
-
Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 111, s. 350-357
-
Tidskriftsartikel (refereegranskat)abstract
- We demonstrate that a simple spectrophotometric method can be efficiently applied for the characterization of structural and chemical stability and adsorption properties of composite graphene oxide (GO) films in various solutions. The immersion stability of GO layer-by-layer (LbL) self-assembled with a polycation into ultrathin multilayered films was studied in water and in concentrated salty, acidic and basic solutions by UV-visible spectroscopy. These films were found to retain both their chemical stability and physical integrity in water, salt and HCl solutions with a slight rearrangement of the nanoscale structure as shown by the change in their visible spectrum. However, immersion into NaOH solutions above molar concentration led to the deconstruction of the multilayer structure by base-induced deoxygenation of GO. The adsorption of methylene blue on polymer/GO LbL films of various thicknesses revealed that the multilayers are largely impermeable towards this cationic dye.
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| 50. |
- Talyzin, Alexandr, 1969-, et al.
(författare)
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Brodie vs Hummers graphite oxides for preparation of multi-layered materials
- 2017
-
Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 115, s. 430-440
-
Tidskriftsartikel (refereegranskat)abstract
- Graphite oxides synthesized by one and two step Brodie oxidation (BGO) and Hummers (HGO) methods were analyzed by a variety of characterization methods in order to evaluate the reasons behind the difference in their properties. It is found that the Brodie method results in a higher relative amount of hydroxyl groups and a more homogeneous overall distribution of functional groups over the planar surface of the graphene oxide flakes. The higher number of carbonyl and carboxyl groups in HGO, detected by several methods, including XPS, NMR and FTIR, unavoidably results in defects of the graphene "skeleton", holes and overall disruption of the carbon-carbon bond network, stronger deviation from planar flake shape and poor ordering of the graphene oxide layers. It is also suggested that functional groups in HGO are less homogeneously distributed over the flake surface, forming some nanometer-sized graphene areas. The presence of differently oxidized areas on the GO surface results in inhomogeneous solvation and hydration of HGO and effects of inter- and intra-stratification. The proposed interpretation of the data explains the higher mechanical strength of multi-layered BGO membranes/papers, which are also less affected by humidity changes, thus providing an example of a membrane property superior to that of HGO. (C) 2016 Published by Elsevier Ltd.
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