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Talyzin, Aleksandr V.ORCID iD iconorcid.org/0000-0002-3320-8487
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Publications (10 of 87) Show all publications
Iakunkov, A., Skrypnychuk, V., Nordenström, A., Shilayeva, E. A., Korobov, M., Prodana, M., . . . Talyzin, A. V. (2019). Activated graphene as a material for supercapacitor electrodes: effects of surface area, pore size distribution and hydrophilicity. Physical Chemistry, Chemical Physics - PCCP, 21(32), 17901-17912
Open this publication in new window or tab >>Activated graphene as a material for supercapacitor electrodes: effects of surface area, pore size distribution and hydrophilicity
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2019 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 21, no 32, p. 17901-17912Article in journal (Refereed) Published
Abstract [en]

Activated reduced graphene oxide (a-rGO) is a material with a rigid 3D porous structure and high specific surface area (SSA). Using variation of activation parameters and post-synthesis mechanical treatment we prepared two sets of materials with a broad range of BET (N2) SSA ∼1000–3000 m2 g−1, and significant differences in pore size distribution and oxygen content. The performance of activated graphene as an electrode in a supercapacitor with KOH electrolyte was correlated with the structural parameters of the materials and water sorption properties. a-rGO is a hydrophobic material as evidenced by the negligibly small BET (H2O) SSA determined using analysis of water vapor sorption isotherms. However, the total pore volume determined using water vapor sorption and sorption of liquid water is almost the same as the one found by analysis of nitrogen sorption isotherms. Ball milling is found to provide an improved bulk density of activated graphene and collapse of all pores except the smallest ones (<2 nm). A decrease in the activation temperature from 850 °C to 550 °C is found to result in materials with a narrow micropore size distribution and increased oxygen content. Elimination of mesopores using ball milling or a lower activation temperature provided materials with better specific capacitance despite a significant decrease (by ∼30%) of the BET (N2) SSA. The best gravimetric and volumetric capacitances in KOH electrolyte were achieved not for samples with the highest value of the BET (N2) SSA but for materials with 80–90% of the total pore volume in micropores and an increased BET (H2O) SSA. Comparing the performance of electrodes prepared using rGO and a-rGO shows that a more hydrophilic surface is favorable for charge storage in supercapacitors with KOH electrolyte.

Place, publisher, year, edition, pages
RSC Publishing, 2019
Keywords
graphene, energy storage, supercapacitors
National Category
Condensed Matter Physics
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-162087 (URN)10.1039/c9cp03327k (DOI)000481777100040 ()31380541 (PubMedID)
Available from: 2019-08-13 Created: 2019-08-13 Last updated: 2019-10-21Bibliographically approved
Iakunkov, A., Sun, J., Rebrikova, A., Korobov, M., Klechikov, A., Vorobiev, A., . . . Talyzin, A. V. (2019). Swelling of graphene oxide membranes in alcohols: effects of molecule size and air ageing.. Journal of Materials Chemistry A, 7, 11331-11337
Open this publication in new window or tab >>Swelling of graphene oxide membranes in alcohols: effects of molecule size and air ageing.
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2019 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 7, p. 11331-11337Article in journal (Refereed) Published
Abstract [en]

Swelling of Hummers graphene oxide (HGO) membranes in a set of progressively longer liquid alcohols (methanol to 1-nonanol) was studied using synchrotron radiation XRD after air ageing over prolonged periods of time. Both precursor graphite oxides and freshly prepared HGO membranes were found to swell in the whole set of nine liquid alcohols with an increase of interlayer spacing from ∼7 Å (solvent free) up to ∼26 Å (in 1-nonanol). A pronounced effect of ageing on swelling in alcohols was found for HGO membranes stored in air. The HGO membranes aged for 0.5–1.5 years show progressively slower swelling kinetics, a non-monotonic decrease of saturated swelling in some alcohols and complete disappearance of swelling for alcohol molecules larger than hexanol. Moreover, the HGO membranes stored under ambient conditions for 5 years showed a nearly complete absence of swelling in all alcohols but preserved swelling in water. In contrast, precursor graphite oxide powder showed unmodified swelling in alcohols even after 4 years of ageing. Since the swelling defines the size of permeation channels, the ageing effect is one of the important parameters which could explain the strong variation in reported filtration/separation properties of GO membranes. The time and conditions of air storage require standardization for better reproducibility of results related to performance of GO membranes in various applications. The ageing of GO membranes can be considered not only as a hindrance/degradation for certain applications, but also as a method to tune the swelling properties of HGO membranes for better selectivity in sorption of solvents and for achieving better selective permeability.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Materials Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:umu:diva-160413 (URN)10.1039/C9TA01902B (DOI)000472225200050 ()
Funder
EU, Horizon 2020, 785219The Kempe Foundations
Available from: 2019-06-18 Created: 2019-06-18 Last updated: 2019-07-18Bibliographically approved
diva2:1191014
Open this publication in new window or tab >>A Molecular Pillar Approach To Grow Vertical Covalent Organic Framework Nanosheets on Graphene: Hybrid Materials for Energy Storage
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2018 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 57, no 4, p. 1034-1038Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
John Wiley & Sons, 2018
National Category
Condensed Matter Physics
Research subject
nanomaterials
Identifiers
urn:nbn:se:umu:diva-145739 (URN)10.1002/anie.201710502 (DOI)000428208700030 ()29210484 (PubMedID)
Available from: 2018-03-16 Created: 2018-03-16 Last updated: 2018-06-09Bibliographically approved
Klechikov, A., You, S., Lackner, L., Sun, J., Iakunkov, A., Rebrikova, A., . . . Talyzin, A. V. (2018). Graphite oxide swelling in molten sugar alcohols and their aqueous solutions. Carbon, 140, 157-163
Open this publication in new window or tab >>Graphite oxide swelling in molten sugar alcohols and their aqueous solutions
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2018 (English)In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 140, p. 157-163Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
graphene, graphene oxide, swelling
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-151276 (URN)10.1016/j.carbon.2018.08.033 (DOI)000450120200016 ()
Funder
EU, Horizon 2020Swedish Research CouncilÅForsk (Ångpanneföreningen's Foundation for Research and Development)The Kempe Foundations
Available from: 2018-08-31 Created: 2018-08-31 Last updated: 2018-12-20Bibliographically approved
Chumakova, N. A., Rebrikova, A. T., Talyzin, A. V., Paramonov, N. A., Vorobiev, A. K. & Korobov, M. V. (2018). Properties of Graphite Oxide Powders and Membranes as Revealed by Electron Paramagnetic Resonance Spectroscopy. The Journal of Physical Chemistry C, 122(39), 22750-22759
Open this publication in new window or tab >>Properties of Graphite Oxide Powders and Membranes as Revealed by Electron Paramagnetic Resonance Spectroscopy
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2018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 39, p. 22750-22759Article in journal (Refereed) Published
Abstract [en]

The spin probe technique was used to study graphite oxide (GO) powders swelled in polar liquids (CH3CN, CH3OH, and H2O) and liquid-free GO membranes (GOM). The nitroxide radicals TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) and TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl) readily penetrated into the interplane space of GO from the solution. Electron paramagnetic resonance (EPR) spectra of these radical probes were sensitive to molecular mobility and orientation ordering within the internal space of GO. The radicals embedded in swelled GO were in two states with different rotational mobilities. The small fraction of radicals located in the interplane space of GO and detected in the broad range of temperatures was in the state of fast rotation, similar to the same radicals dissolved in bulk liquids, thus providing experimental evidence of formation of a liquid-like media within the interplane space of GO. Such mobile media may be responsible for the unusual permeation properties of GOM, which is reported in the literature. Second, less-mobile fraction of radicals was found to be immobilized at the internal surface of GO and was sensitive to phase transformations in the swelled GO structures. The transformations were detected as anomalies at temperature dependences of rotational mobility of radicals. The detected dependence of EPR spectra of probe radicals on orientation of GOM, relative to the direction of magnetic field in the EPR spectrometer, was used for quantitative characterization of orientation alignment of GO planes within the membranes. Such an approach may serve as an elegant method to estimate the relative quality of membranes and other GO-layered structures.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-152981 (URN)10.1021/acs.jpcc.8b07221 (DOI)000446926400057 ()
Available from: 2018-11-01 Created: 2018-11-01 Last updated: 2018-11-01Bibliographically approved
Klechikov, A., Sun, J., Vorobiev, A. & Talyzin, A. V. (2018). Swelling of Thin Graphene Oxide Films Studied by in Situ Neutron Reflectivity. The Journal of Physical Chemistry C, 122(24), 13106-13116
Open this publication in new window or tab >>Swelling of Thin Graphene Oxide Films Studied by in Situ Neutron Reflectivity
2018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 24, p. 13106-13116Article in journal (Refereed) Published
Abstract [en]

Permeation of multilayered graphene oxide (GO) membranes by polar solvents is known to correlate with their swelling properties and amount of sorbed solvent. However, quantitative estimation of sorption using standard (e.g., gravimetric) methods is technically challenging for few nanometers thick GO membranes/films exposed to solvent vapors. Neutron reflectivity (NR) was used here to evaluate the amount of solvents intercalated into the film which consists of only ∼31.5 layers of GO. Analysis of NR data recorded from the GO film exposed to vapors of polar solvents provides information about change of film thickness due to swelling, amount of intercalated solvent, and selectivity in sorption of solvents from binary mixtures. A quantitative study of GO film sorption was performed for D2O, d-methanol, ethanol, dimethyl sulfoxide (DMSO), acetonitrile, dimethylformamide (DMF), and acetone. Using isotopic contrast, we estimated selectivity in sorption of ethanol/d-methanol mixtures by the GO film. Estimation of sorption selectivity was also performed for D2O/DMF, D2O/DMSO, and D2O/acetonitrile binary mixtures. Sorption of polar solvents was compared for the thin GO film, micrometer thick free standing GO membranes, and graphite oxide powders.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
Keywords
graphene, graphene oxide, swelling
National Category
Physical Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:umu:diva-151273 (URN)10.1021/acs.jpcc.8b01616 (DOI)000436381600057 ()2-s2.0-85047617225 (Scopus ID)
Funder
EU, Horizon 2020
Available from: 2018-08-31 Created: 2018-08-31 Last updated: 2018-10-31Bibliographically approved
Talyzin, A., Mercier, G., Klechikov, A., Hedenström, M., Johnels, D., Wei, D., . . . Moons, E. (2017). Brodie vs Hummers graphite oxides for preparation of multi-layered materials. Carbon, 115, 430-440
Open this publication in new window or tab >>Brodie vs Hummers graphite oxides for preparation of multi-layered materials
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2017 (English)In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 115, p. 430-440Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
graphite, oxide
National Category
Condensed Matter Physics
Research subject
Physics
Identifiers
urn:nbn:se:umu:diva-130949 (URN)10.1016/j.carbon.2016.12.097 (DOI)000395601300045 ()
Available from: 2017-02-01 Created: 2017-02-01 Last updated: 2018-06-09Bibliographically approved
Klechikov, A., Sun, J., Hu, G., Zheng, M., Wågberg, T. & Talyzin, A. V. (2017). Graphene decorated with metal nanoparticles: Hydrogen sorption and related artefacts. Microporous and Mesoporous Materials, 250, 27-34
Open this publication in new window or tab >>Graphene decorated with metal nanoparticles: Hydrogen sorption and related artefacts
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2017 (English)In: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 250, p. 27-34Article in journal (Refereed) Published
Abstract [en]

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.

Keywords
Graphene, Hydrogen storage, Graphene oxide, Nanoparticles, Decoration
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-135589 (URN)10.1016/j.micromeso.2017.05.014 (DOI)000405045800004 ()
Funder
EU, Horizon 2020
Available from: 2017-05-31 Created: 2017-05-31 Last updated: 2018-06-09Bibliographically approved
Ajuria, J., Arnaiz, M., Botas, C., Carriazo, D., Mysyk, R., Rojo, T., . . . Goikolea, E. (2017). Graphene-based lithium ion capacitor with high gravimetric energy and power densities. Journal of Power Sources, 363, 422-427
Open this publication in new window or tab >>Graphene-based lithium ion capacitor with high gravimetric energy and power densities
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2017 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 363, p. 422-427Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
Tin oxide, Reduced graphene oxide, Activated graphene, Supercapacitor, Electric double layer pacitor, Lithium ion capacitor
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:umu:diva-140646 (URN)10.1016/j.jpowsour.2017.07.096 (DOI)000411544300049 ()
Available from: 2017-10-17 Created: 2017-10-17 Last updated: 2018-06-09Bibliographically approved
Klechikov, A., Sun, J., Baburin, I. A., Seifert, G., Rebrikova, A. T., Avramenko, N. V., . . . Talyzin, A. V. (2017). Multilayered intercalation of 1-octanol into Brodie graphite oxide. Nanoscale, 9(20), 6929-6936
Open this publication in new window or tab >>Multilayered intercalation of 1-octanol into Brodie graphite oxide
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2017 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 9, no 20, p. 6929-6936Article in journal (Refereed) Published
Abstract [en]

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.

National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:umu:diva-136327 (URN)10.1039/c7nr01792h (DOI)000402034400038 ()28509924 (PubMedID)
Funder
EU, Horizon 2020, 696656
Available from: 2017-06-30 Created: 2017-06-30 Last updated: 2018-06-09Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0002-3320-8487

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