| 1. |
- 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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| 2. |
- Debatin, Franziska, et al.
(författare)
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An Isoreticular Family of Microporous Metal-Organic Frameworks Based on Zinc and 2-Substituted Imidazolate-4-amide-5-imidate : Syntheses, Structures and Properties
- 2012
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 18:37, s. 11630-11640
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Tidskriftsartikel (refereegranskat)abstract
- We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-14 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.
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| 3. |
- Klechikov, Alexey, et al.
(författare)
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Graphite oxide swelling in molten sugar alcohols and their aqueous solutions
- 2018
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Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 140, s. 157-163
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Tidskriftsartikel (refereegranskat)abstract
- Graphite oxides (GO) are intercalated rapidly by one to several layers of solvent when immersed in liquid but the GO solvates are typically unstable on air due to solvent evaporation. Here we study swelling of GO in solvents (sugar alcohols) with melting temperature point above ambient. Using in situ synchrotron radiation XRD experiments we demonstrated GO swelling in molten xylitol and sorbitol. The expanded GO structure intercalated with one layer of xylitol or sorbitol is preserved upon solidification of melt and cooling back to ambient conditions. The structure of solid solvates of GO with xylitol and sorbitol is based on non-covalent interaction and pristine GO can be recovered by washing in water. Intercalation of xylitol and sorbitol into GO structure in aqueous solutions yields similar but less ordered structure of GO/sugar alcohol solid solvates. Very similar inter-layer distance was observed for GO intercalated by sugar alcohols in melt and for GO immersed in sugar solutions. This result shows that sugar alcohols penetrate into GO inter-layer space without hydration shell forming 2D layers with orientation parallel to graphene oxide sheets. Therefore, hydration diameter of molecules should not be considered as decisive factor for permeation through graphene oxide inter-layers in multilayered membranes.
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| 4. |
- 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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| 5. |
- 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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| 6. |
- Mercier, Guillaume, et al.
(författare)
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Porous Graphene Oxide/Diboronic Acid Materials : Structure and Hydrogen Sorption
- 2015
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:49, s. 27179-27191
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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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| 7. |
- Quesnel, Etienne, et al.
(författare)
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Graphene-based technologies for energy applications, challenges and perspectives
- 2015
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Ingår i: Current Opinion in Chemical Engineering. - : IOP Publishing. - 2211-3398. ; 2:3, s. 1-16
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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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| 8. |
- Sun, Jinhua, et al.
(författare)
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Porous graphite oxide pillared with tetrapod-shaped molecules
- 2017
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Ingår i: Carbon. - : Elsevier. - 0008-6223 .- 1873-3891. ; 120, s. 145-156
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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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